Composition Having Refractive Index Sensitively Changeable by Radiation and Method for Forming Refra

专利摘要:
The present invention (A) a decomposable compound, (B) a non-decomposable compound having a refractive index lower than that of the decomposable compound (A) (C) Sensitizing radiation dissociation and And (D) a stabilizer. When the radiation-sensitive composition of the present invention is irradiated with radiation through a pattern mask, the component (C) and the component (A) of the radiation-irradiated portion are decomposed to form a difference in refractive index between the irradiated portion and the non- And a pattern having a different refractive index is formed.
公开号:KR20020092921A
申请号:KR1020027005491
申请日:2001-08-24
公开日:2002-12-12
发明作者:이사오 니시무라；노부오 벳쇼；아쯔시 구마노；쯔또무 시모까와；겐지 야마다
申请人:제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive refractive index-changeable composition and a refractive index variation method,
[2] At present, there is a great demand for a refractive index distribution type optical molded article composed of different refractive index areas, which is called a multimedia society. Examples of such optical fibers include an optical fiber for carrying information, an optical diffraction grating having a periodic refractive index change, an optical memory in which information is recorded by a region having a different refractive index, and a light integrating circuit having a fine refractive index pattern. , A light control element, a light modulation element, and an optical transmission element.
[3] Herein, the refractive index distribution type optical forming article refers to a case where the refractive index is continuously distributed in a molded body such as a GI type optical fiber (hereinafter referred to as a GRIN optical molded article), a refractive index distribution such as an optical diffraction grating, an SI type optical waveguide, When the shape is discontinuous, it means all.
[4] The GRIN optical molded article has attracted attention as a next-generation optical molded article. For example, a GI type optical fiber whose refractive index is reduced parabolically from the central axis of the optical fiber core to the periphery allows a large amount of information to be transmitted, and the GRIN lens having a continuously changing refractive index in the lens has a refractive power A reading lens used in a copying machine or the like, a spherical lens for connecting fibers, or a microlens, etc., by utilizing features such as not having a spherical aberration.
[5] There have been many proposals as to the method for producing the GRIN optical molded article as described above. For example, a method of dispersing a low molecular weight or monomer in a polymer and continuously distributing the concentration thereof to obtain a GI type optical fiber is disclosed in JP-A-9-133813, JP-A-8-336911, JP-A-8-337609, JP-A-3-192310, JP-A-5-60931, WO93 / 19505, and WO94 / 04949. Further, Japanese Patent Laid-Open No. 62-25705 discloses a method of copolymerizing two or more kinds of vinyl monomers having different refractive indexes and reaction ratios with light to obtain a GI rod-shaped optical molded article or optical fiber. Japanese Patent Application Laid-Open No. 7-56026 discloses a method of forming a polymer A having a photoreactive functional group and diffusing a compound B having a lower refractive index than A in A to form a concentration distribution of B, B to obtain a refractive index distribution.
[6] In addition, some methods for producing GRIN optical molded articles relating to inorganic materials have been proposed. For example, thallium having a high refractive index is added to a rod-shaped glass containing silicon or lead as a main component, and the glass is immersed in a melt containing potassium having a low refractive index to form a concentration distribution of potassium by ion exchange, .
[7] The GRIN lens can be similarly obtained by applying the above method to a short rod, that is, a lens-shaped optical molded article. Alternatively, the GI type rod produced by the above method may be roundly cut.
[8] Further, as a manufacturing method of an optical molded article having a fine pattern of refractive index such as the above-described optical diffraction grating, optical integrated circuit and the like, there is known a technique of inducing a photochemical reaction in a molded body by light irradiation, thereby obtaining a change in refractive index. For example, in the case of an inorganic material, a method of producing an optical diffraction grating by irradiating a glass doped with germanium with light and changing the refractive index can be mentioned. In the case of an organic material, a technique in which a refractive index change is induced by irradiating laser light to a material in which a small molecule, which is known as a photochromic reaction or photobleaching, is dispersed in a polymer, is used as an optical diffraction grating, 7-92313, and the like. Further, in recent years, application of this technique to the production of a GRIN optical formed article has been proposed by Japanese Patent Laid-Open No. 9-178901. This method gives a continuous refractive index distribution in the depth direction to the irradiation by utilizing the fact that the irradiated light is absorbed and the strength is weakened.
[9] However, the refractive index distribution obtained by the above-described conventional materials has a maximum refractive index difference of only about 0.001 to 0.02, and it is also possible to achieve a remarkable refractive index distribution for the purpose of prevention of optical loss and suppression of malfunction of a circuit it's difficult.
[10] Further, once the refractive index distribution is formed and used under the condition that light near the wavelength used to change the refractive index is passed, the phenomenon that the refractive index is gradually changed and deteriorates can not be prevented.
[1] The present invention relates to a radiation-sensitive refractive-index-changing composition, a method of forming a refractive index pattern, a refractive index pattern and an optical material. More specifically, the present invention relates to a novel radiation-sensitive refractive-index-changing composition, a method of forming a refractive index pattern, a refractive index pattern, and an optical material, which are applied to optical electronics and a display field.
[24] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an apparatus for irradiating light when a lens is formed from the refractive index-changing composition of the present invention. FIG.
[25] Fig. 2 is a schematic view of an apparatus for performing light irradiation when a diffraction grating is formed from the refractive-index-changing composition of the present invention.
[26] In the present invention, the " refractive index pattern " means a refractive index distribution-type material composed of regions having different refractive indexes.
[27] Hereinafter, each component of the refractive index changing material used in the refractive index pattern forming method of the present invention will be described in detail.
[28] (A) a decomposable compound
[29] The decomposable compound (A) used in the present invention may be an acid decomposable compound or a base decomposable compound, and the refractive index thereof is preferably from 1.5 to 1.9. The weight average molecular weight of the decomposable compound (A) is preferably 100 to 500,000, more preferably 100 to 300,000.
[30] Examples of the acid-decomposable compound include compounds having at least one structure selected from the group consisting of the structures represented by the following formulas (1) to (8). These compounds may be used alone or in combination of two or more.
[31]
[32] Wherein R ¹ is an alkylene group, an alkylene arylene alkylene group or an arylene group, and R ² is an alkylene group, an alkylene arylene alkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group.
[33]
[34] Wherein M is Si or Ge, R ³ is an alkylene group, an alkylenearylenealkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group, and R ⁴ is an oxygen atom, an alkylene group, an alkylenearylene alkyl R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and m is an integer of 0 to 2.
[35]
[36] In the formulas, R ⁹ and R ¹⁰ are each independently an alkylene group, an alkylene arylene alkylene group, an arylene group, an alkylsilylene group or an alkyl damylene group.
[37]
[38] Wherein R ¹¹ is an oxyalkylene group or a single bond, and R ¹² is a hydrogen atom, an alkyl group, an alkylene arylene alkylene group or an aryl group.
[39]
[40] Wherein R ¹³ is a hydrogen atom, an alkyl group or an aryl group.
[41]
[42] Wherein R ¹⁴ is an alkylene group or a structure represented by the following general formula (6-1), (6-2) or (6-3).
[43]
[44] In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, An alkylthio group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxyl group having 1 to 6 carbon atoms, a halogenated alkylthio group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, A mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms.
[45] -OR ¹⁹ -O-
[46] Wherein R < ¹⁹ > is an alkylene group.
[47] -NH-R < ²⁰ > -NH-
[48] In the formula, R ²⁰ is an alkylene group.
[49]
[50] In the formula, R ²¹ is an alkylene group, an alkylene arylene alkylene group, or an arylene group.
[51]
[52] R ²² , R ²³ , R ²⁴ and R ²⁵ independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, An alkylthio group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxyl group having 1 to 6 carbon atoms, a halogenated alkylthio group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, A mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms.
[53] Examples of the base-decomposable compound include compounds having at least one structure selected from the group consisting of structures represented by any one of the following formulas (9) to (12). These compounds may be used alone or in combination of two or more.
[54]
[55] Wherein, R ²⁶ is an alkylene group, an aralkyl group and the alkylene group or arylene group, R ²⁷ is an alkylene group, an aralkyl group, an arylene group, alkylene-arylene-alkyl group, an alkylsilyl group or alkyl low milren group, R ^28, R ²⁹ , R ³⁰ and R ³¹ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and i and j are each independently 0 or 1.
[56]
[57] In the formula, R ³² is an alkylene group, an aralkylene group or an arylene group, and R ³³ is an alkylene group, an aralkylene group, an arylene group, an alkylenearylene alkylene group, an alkylsilylene group or an alkylgermylene group.
[58]
[59] In the formula, R ³⁴ and R ³⁵ each independently represent an alkylene group, an aralkylene group, an arylene group, an alkylene arylene alkylene group, an alkylsilylene group, or an alkyl lowerylene group.
[60]
[61] In the formula, R ³⁶ and R ³⁷ each independently represent an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.
[62] Examples of the above-mentioned all alkylene arylene alkylene groups include, independently, for example, a structure represented by the following general formula (13) or (14).
[63]
[64] Wherein, R ^38, R ^39, R ⁴⁰ and R ⁴¹ are each independently represents a hydrogen atom, an aryl-chain alkyl group or having 6 to 10 carbon atoms having from 1 to 6, R ^42, R ^43, R ⁴⁴ and R ⁴⁵ is A halogen atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group, a thioalkyl group, an alkyl ester group, an alkylthioester group, an aryl group, a cyano group or a nitro group independently from each other.
[65]
[66] Wherein, R ^46, R ^47, R ⁴⁸ and R ⁴⁹ are each independently represents a hydrogen atom, a C 1 -C 6 linear alkyl group or a C 6 -C 10 aryl, R ^50, R ^51, R ^52, R ^53, R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group, a thioalkyl group, an alkylester group, an alkylthioester group, represents a nitro group, a ¹ is _{-S-, -O-, -SO 2 -,} -CO-, -COO-, -OCOO-, -CH 2 - or -C (R ⁵⁸⁾ ₂ - represents the, R ⁵⁸ Is a chain alkyl group having 1 to 6 carbon atoms.
[67] As the above-mentioned all of the arylene groups, for example, there can be mentioned a structure represented by the following general formula (15) independently.
[68]
[69] Wherein R ⁵⁹ to R ⁶⁶ independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydroxy group, a mercapto group, an alkoxy group, a thioalkyl group, an alkylester group, an alkylthioester group, an aryl group, a cyano group or a nitro group , a ² is _{-S-, -O-, -SO 2 -,} -CO-, -COO-, -OCOO-, -CH 2 - or -C (R ⁶⁷⁾ ₂ - represents a, R ⁶⁷ is C 1 To 6
[70] Examples of the above alkylsilylene groups include, independently of each other, for example, a structure represented by the following general formula (16).
[71]
[72] In the formulas, R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, A ³ is -O-, an alkylene group or an arylene A represents 0 or an integer of 1
[73] Examples of the above alkylgermylene group include, independently of each other, for example, a structure represented by the following general formula (17).
[74]
[75] In formula (17), R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, A ⁴ is -O-, an alkylene group or aryl B represents an integer of 0 or 1;
[76] In the above formulas (16) and (17), each of the alkylene groups is independently a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and examples thereof include methylene, 1,2-ethylene, 1,10-decamethylene, and the like, and these hydrogen atoms may be replaced by, for example, a chlorine atom, a bromine atom, a hydroxyl group, a mercapto group, an alkoxy group, a thioalkyl group, an alkyl ester group, an alkylthioester group, Or a cyano group.
[77] The alkyl group, the alkoxy group, the thioalkyl group, the alkyl ester group and the alkyl thioester group of the above all alkyl groups are preferably, for example, straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, The atom may be substituted with a chlorine atom, a bromine atom, a hydroxy group, a mercapto group, an alkoxy group, a thioalkyl group, an alkyl ester group, an alkylthioester group, an aryl group or a cyano group.
[78] Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group or a biphenyl group, and the hydrogen atoms thereof may be substituted with a substituent selected from the group consisting of a chlorine atom, a bromine atom, a hydroxy group, a mercapto group, an alkoxy group, a thioalkyl group, A thioester group, a cyano group or a nitro group.
[79] In the formulas (6-1) and (8), the chain alkyl group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include a methyl group, ethyl group, n-propyl group, Butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group and texyl group.
[80] The alkoxyl group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, Butoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, and texyloxy group.
[81] The alkylthio group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i- Tert-butylthio group, t-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, tecityl group and the like.
[82] Examples of the halogenated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a chloromethyl group, a 2-chloroethyl group, a 3- chloropropyl group, a 1- chloromethylethyl group, A chloromethylpentyl group, a 4-chloromethylpentyl group, a 4-chloromethylpentyl group, a 2-chloromethylpentyl group, a 3-chloromethylbutyl group, A bromomethyl group, a 2-bromomethyl propyl group, a 5-bromomethyl group, a 3-bromoethyl group, a 1- Bromomethylpentyl, 4-bromomethylpentyl, 2-bromoethylbutyl, and the like are exemplified by the same or different substituents selected from the group consisting of methyl, ethyl, propyl, .
[83] Examples of the halogenated alkoxyl group having 1 to 6 carbon atoms include trifluoromethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, chloromethoxy group, 2-chloroethoxy group, 3-chloropropoxy group, Chloromethyl ethoxy group, 4-chlorobutoxy group, 2-chloromethyl propoxy group, 5-chloropentyloxy group, 3-chloromethylbutoxy group, 2- , 3-chloromethylpentyloxy group, 4-chloromethylpentyloxy group, 2-chloroethylbutoxy group, bromomethoxy group, 2-bromoethoxy group, 3- Bromomethylpropoxy group, 2-bromoethyloxy group, 2-bromoethyloxy group, 2-bromoethyloxy group, 2-bromoethyloxy group, 3-bromomethylpentyloxy group, 4-bromomethylpentyloxy group, 2-bromoethylbutoxy group and the like.
[84] Examples of the halogenated alkylthio group having 1 to 6 carbon atoms include trifluoromethylthio group, pentafluoroethylthio group, heptafluoropropyltithio group, chloromethylthio group, 2-chloroethylthio group, 3-chloropropylthio group, Chloromethylpropylthio, 2-chloromethylpropylthio, 5-chloropentylthio, 3-chloromethylbutylthio, 2-chloroethylpropylthio, 6-chloromethylbutylthio, - chlorohexylthio, 3-chloromethylpentylthio, 4-chloromethylpentylthio, 2-chloroethylbutylthio, bromomethylthio, 2-bromoethylthio, 3-bromopropylthio, Bromomethylpropylthio, 5-bromopentylthio, 3-bromomethylbutylthio, 2-bromoethylpropylthio, 3-bromomethylbutylthio, 2- Thio, 6-bromohexylthio, 3-bromomethylpentylthio, 4-bromomethylpentylthio, 2-bromoethylbutyl And the like can be imported.
[85] Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 1-hydroxymethylethyl group, a 4-hydroxybutyl group, , 5-hydroxypentyl group, 3-hydroxymethylbutyl group, 2-hydroxyethylpropyl group, 6-hydroxyhexyl group, 3-hydroxymethylpentyl group, 4-hydroxymethylpentyl group, And a butyl group.
[86] Examples of the mercaptoalkyl group having 1 to 6 carbon atoms include mercaptoalkyl groups such as a mercaptomethyl group, a 2-mercaptoethyl group, a 3-mercaptopropyl group, a 1-mercaptomethylethyl group, a 4-mercaptobutyl group, Mercaptopropyl group, 3-mercaptopropyl group, 3-mercaptomethylbutyl group, 2-mercaptoethylpropyl group, 6-mercaptohexyl group, 3-mercaptomethylpentyl group, Butyl group and the like.
[87] Examples of the hydroxyalkoxyl group having 1 to 6 carbon atoms include a hydroxymethoxy group, a 2-hydroxyethoxy group, a 3-hydroxypropoxy group, a 1-hydroxymethylethoxy group, a 4-hydroxybutoxy group, 2-hydroxymethylpropoxy group, 2-hydroxymethylpropoxy group, 5-hydroxypentyloxy group, 3-hydroxymethylbutoxy group, 2-hydroxyethylpropoxy group, , 4-hydroxymethylpentyloxy group, 2-hydroxyethylbutoxy group and the like.
[88] Examples of the mercaptoalkylthio group having 1 to 6 carbon atoms include mercaptoethylthio group, 2-mercaptoethylthio group, 3-mercaptopropylthio group, 1-mercaptomethylethylthio group, 4-mercaptobutyl group Mercaptopropylthio group, 3-mercaptopropylthio group, 3-mercaptopropylthio group, 3-mercaptopropylthio group, 3-mercaptopropylthio group, Tritiated, 4-mercaptomethylpentylthio, 2-mercaptoethylbutylthio, and the like.
[89] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cumenyl group and a 1-naphthyl group.
[90] Examples of the aralkyl group having 7 to 11 carbon atoms include benzyl, -Methylbenzyl, phenethyl, naphthylmethyl and the like.
[91] A method for producing an acid-decomposable compound having, for example, a repeating unit represented by the above formulas (1) to (7) in the present invention is known.
[92] The method for producing the compound having the structure represented by Formula 1 is described in Polymer Bull., 1. 199 (1978), JP-A 62-136638, EP 225,454, US 806,597, Japanese Patent Application Laid-Open Nos. 4-303843 and 7-56354, and the like.
[93] A method for producing a compound having the structure represented by the above formula (2) is disclosed in, for example, Macromolecules 29, 5529 (1996), Polymer 17, 1086 (1976) and Japanese Patent Application Laid-open No. 60-37549.
[94] The method for preparing the compound having the structure represented by the general formula (3) is described in Electrochem. Soc., Solid State Sci. Technol., 133 (1) 181 (1986)], [J. Imaging Sci., 30 (2) 59 (1986) and Macromol. Chem., Rapid Commun., 7, 121 (1986).
[95] The method for producing the compound having the structure represented by the above formula (4) is described in U.S. Patent No. 3,894,253, JP-A-62-190211, JP-A-2-146544, Macromol. A-1,8, 2375 (1970), U.S. Patent No. 4,247,611, European Patent No. 41,657, Japanese Patent Laid-open Publication No. 63-97945, Polymer Sci. Japanese Patent Application Laid-Open No. 57-31674, Japanese Patent Application Laid-Open No. 64-3647, and Japanese Patent Laid-Open Publication No. 56-17345.
[96] The method for preparing the compound having the structure represented by the formula (5) is described in Prepr. Eur. Disc Meet. Polymer Sci., Strasbourg, p 106 (1978) and Macromol. Chem., 179, 1689 (1978).
[97] The method for producing the compound having the structure represented by the above formula (6) is disclosed in, for example, U.S. Patent No. 3,894,253, U.S. Patent No. 3,940,507, and JP-A-62-190211.
[98] The method for preparing the compound having the structure represented by the above formula (7) is described in J. Med. Am. Chem. Soc., 54, 1579 (1932)], J. Polym. Sci., 29, 343 (1958)], [J. Polym. Sci., Part A, Polym. Chem., 25, 3373 (1958)], Macromolecules, 25, 12 (1992), Macromolecules, 20,705 (1997), Macromolecules, 21, 1925 (1998), Macromol. Chem., Rapid Commun., 11, 83 (1990).
[99] The compound having the structure represented by the formula (8) can be prepared by cationically polymerizing or anionically polymerizing a compound represented by the following formula (8-1) in a solvent in the presence of a molecular weight modifier, if necessary.
[100]
[101] The definition of R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ is a group selected from the same group as the group defined by R ²² , R ²³ R ²⁴ and R ²⁵ in Chemical Formula 8.
[102] The compound represented by the formula (8) may be at least one compound selected from the group consisting of a compound represented by the following formula (8-2), a compound represented by the following formula (8-3) and other different monomers, 1 < / RTI > In this case, the total amount of at least one compound selected from the group consisting of a compound represented by the following general formula (8-2), a compound represented by the following general formula (8-3), and other different monomers is the same as the total amount of the compound 100 parts by weight to 100 parts by weight.
[103]
[104] Wherein, R ²⁰⁵ is a hydrogen atom or an alkyl group having 1 to ^{10, R 206, R 207,} R 208, R 209 and R ²¹⁰ are independently of each other a hydrogen atom, a linear alkyl group, a chlorine atom, a bromine group having 1 to 6 carbon atoms An alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A hydroxyalkyl group having 1 to 6 carbon atoms, a mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 6 to 10 carbon atoms An aryl group and an aralkyl group having 7 to 11 carbon atoms, or any two of R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ may bond together to form a 4- to 7-membered ring together with the carbon atom to which they are bonded. May be formed
[105]
[106] In the formulas, R ²¹¹ and R ²¹² independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a mercaptoalkyl group having 1 to 10 carbon atoms, (Polypropylene glycol) propyl group having 1 to 5 propyleneoxy repeating units, a repeating unit having a repeating unit of 1 to 10, an aralkyl group having 7 to 11 carbon atoms, an (ethyleneglycol) ethyl group having 1 to 5 ethyleneoxy repeating units, (Polyethylsulfide) ethyl group having 1 to 5 carbon atoms, and (polypropylene sulfide) propyl group having 1 to 5 repeating units.
[107] Examples of other monomers include glyoxal, succinaldehyde, glutaraldehyde, maleic aldehyde, 1,8-octanedialdehyde, m-phthalaldehyde, p-phthalaldehyde, 2,3-naphthalenedicarboxylic aldehyde, 2 , 3-anthracene dicarboxylic aldehyde, 9,10-anthracene dicarboxylic aldehyde, 4,4'-bisbenzaldehyde, 2,5-dimethoxy-1,4-dicarboxylic aldehyde, 2,2 ' Bis (2-formylphenyl) ether, 6,6'-dihydroxy-5,5'-dimethoxy- [1,1 ' -Biphenyl] -3,3'-dicarboxylic aldehyde, salicylaldehyde chromium complex, aluminum formyl acetate, (1,1 ', 3', 1 ") - 2-hydroxybenzene-1,3,5-tricarbaldehyde, 1,2,4,5-tetra (p-formylphenyl ) Three or more aldehydes in one molecule such as benzene . ≪ / RTI >
[108] The hydrogen atoms of these compounds may be substituted with an alkoxyl group having from 1 to 10 carbon atoms, a halogenated alkyl group having from 1 to 10 carbon atoms, a halogenated alkoxyl group having from 1 to 10 carbon atoms, a halogenated alkylthio group having from 1 to 10 carbon atoms, a hydroxy group having from 1 to 10 carbon atoms An alkyl group, a mercaptoalkyl group having 1 to 10 carbon atoms, a hydroxyalkoxyl group having 1 to 10 carbon atoms, a mercaptoalkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, (Polyethylene glycol) ethyl group having 1 to 5 carbon atoms, a (propylene glycol) propyl group having 1 to 5 carbon atoms, and the like can be used.
[109] The cationic polymerization and / or anionic polymerization for producing the compound having the structure represented by the formula (8) can be performed using an anionic polymerization catalyst, a coordination anion polymerization catalyst, or a cationic polymerization catalyst. Representative examples of the anionic polymerization catalyst or the coordination anion polymerization catalyst include alkali metals such as sodium and lithium; alkyl metal compounds such as s-butyllithium; Alkali metal complexes such as sodium / naphthalene; Alkali metal alkoxides such as sodium methoxide; amines such as n-butylamine, diethylamine; Quaternary ammonium salts such as ammonium stearate and tetrabutylammonium acetate; Quaternary organotin compounds such as dibutyltin dilaurate, tributyltin chloride, and diethyltin dilaurate.
[110] Representative examples of the cation polymerization catalyst include tin tetrachloride, tin tetrabromide, titanium tetrachloride, aluminum trichloride, zinc chloride, boron trifluoride, boron trifluoride diethyl etherate, perchloric acid, acetyl perchlorate, p- toluenesulfonic acid, Triethyl aluminum, diethyl aluminum chloride, and the like.
[111] Examples of the polymerization solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated aliphatic hydrocarbons such as methylene chloride, ethylene chloride, and carbon tetrachloride; Halogenated aromatic hydrocarbons such as chlorobenzene, orthodichlorobenzene and the like can be used. These organic solvents may be used singly or in combination of two or more. It is preferable that such an organic solvent is sufficiently dehydrated and purified.
[112] The molecular weight regulator optionally arbitrarily coexisting at the time of preparing the polymer is preferably used in a uniformly dissolved or dispersed form in the reaction system, and alcohol, carboxylic acid, or the like can be used.
[113] As the alcohol, for example, methyl alcohol, ethyl alcohol, hexyl alcohol, cyclohexyl alcohol, benzyl alcohol and the like can be used. As the carboxylic acid, for example, formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, . The amount of the molecular weight regulator to be used is controlled depending on the molecular weight of the target polymer and the like, and can be easily determined experimentally.
[114] The reaction temperature is preferably set at a temperature between -200 DEG C and 50 DEG C, but in consideration of the solidification point and the boiling point of the organic solvent, it is more preferable that the temperature is in the range of -100 DEG C to 30 DEG C in many cases. The reaction time is not particularly limited, but can be suitably set within a range of usually 100 hours or less. After a predetermined polymerization time, for example, the obtained reaction mixture is filtered, and the obtained solid matter is washed with ion-exchanged water and then vacuum-dried to obtain the desired compound having the structure represented by the above general formula (8) . In addition, since the hydroxyl group at the molecular end of the hemiacetal type formed by the above polymerization reaction has a slight lack of thermal stability, if necessary, a method of blocking the polyacetal polymer such as esterification, etherification or urethanization Stability can be improved by blocking the molecular ends according to known methods.
[115] Further, for example, a process for producing a base-decomposable compound having the repeating units represented by the above formulas (9) to (12) is also known.
[116] The method for preparing the compound having the structure represented by the formula (9) is described in Macromol. Chem., Rapid Commun., 5, 151 (1984)], [Macromol. Chem., 189, 2229 (1988), Macromol. Chem., 187, 2525 (1986)], [Polym. J., 22, 803 (1990).
[117] The method for preparing the compound having the structure represented by the above formula (10) is described in J. Med. Polym. Sci., 47, 1523 (1993)], [J. App1. Polym. Sci., 35, 85 (1985)], [J. Polym. Sci., Polym. Chem. Ed., 22, 1579 (1984)], [J. Polym. Sci., Polym. Chem. Ed., 14, 655 (1976), J. Polym. Sci., Polym. Chem. Ed., 17, 2429 (1979).
[118] The method for preparing the compound having the structure represented by the formula (11) is described in J. Med. Macromol. Sci.-Chem., A9, 1265 (1975).
[119] The method for preparing the compound having the structure represented by the above formula (12) is described in Polym. Bull., 14, 85 (1985), Macromol. Chem., 189, 1323 (1988).
[120] (B) a non-degradable compound
[121] The non-decomposable compound (B) used in the present invention is a material which is stable to an acid or a base, and preferably has high optical transparency. The refractive index of the component (B) can be arbitrarily set and adjusted to a preferable value depending on the application. It is particularly preferable that the refractive index n _B of the compound (B) is smaller than the refractive index n _A of the polymer A and particularly satisfies the relationship of the following formula (1).
[122] n _A -n _B ≥0.05
[123] The non-decomposable compound (B) may be a non-degradable polymer.
[124] Examples of the non-degradable polymer (B) include acrylic resin, urethane resin, polyester resin, polycarbonate resin, norbornene resin, styrene resin, polyether sulfone resin, silicone resin, polyamide resin, polyimide resin, polysiloxane Based resin, a polybutadiene-based resin, a vinyl ether-based resin, and a vinyl ester-based resin. The preferred non-degradable polymer (B) to be used depending on the refractive index of the decomposable polymer (A) to be used may be selected arbitrarily. Particularly, for the purpose of increasing the difference in refractive index between (A) the decomposable polymer and the purpose of reducing the transmission loss with a long optical path length, the non-decomposable polymer (B) in which the hydrogen atom of the resin stream is replaced with a fluorine atom is suitably used There is a case.
[125] More specific examples of the non-degradable polymer (B) include the following polymers. The numbers in parentheses are the values of the refractive index by the d line.
[126] For example, polyvinylidene fluoride (1.42), polydimethylsiloxane (1.43), polytrifluoroethylmethacrylate (1.44), polyoxypropylene (1.45), polyvinylisobutyl ether (1.45) (1.45), polyoxyethylene (1.46), polyvinylbutyl ether (1.46), polyvinyl pentyl ether (1.46), polyvinylhexyl ether (1.46) 1.47), cellulose acetate phthalate (1.46 to 1.49), poly (4-fluoro-2-trifluoromethylstyrene) (1.46), polyvinyloctyl ether (1.46), poly (vinyl 2-ethylhexyl ether) 1.46), polyvinyldecyl ether (1.46), poly (2-methoxyethyl acrylate) (1.46), polybutyl acrylate (1.46), polybutyl acrylate (1.47), poly (t- butyl methacrylate) (1.46), polyvinyldodecyl ether (1.46), poly (3-ethoxypropyl acrylate) (1.47), polyoxycarbonyltetramethylene (1.47), poly (1.47), polyvinyl acetate (1.47), polyvinyl methyl ether (1.47), polyethylacrylate (1.47), ethylene-vinyl acetate copolymer (1.47 to 1.50) (1.47 to 1.49), cellulose acetate propionate (1.47), benzyl cellulose (1.47 to 1.58), phenol-formaldehyde resin (1.47 to 1.70), cellulose triacetate (1.47), poly (3-methoxypropyl acrylate) (1.47), poly (2-ethoxyethyl acrylate) (1.47), polymethyl acrylate (1.47 to 1.48), poly isopropyl methacrylate (1.47), poly (1-decene) (1.47), polypropylene (atactic, density of ^{0.8575 g / cm 3) (1.47} ), poly (vinyl sec- butyl ether) (isotactic) (1.47 ), Poly (dodecyl methacrylate (1.47), polyoxyethylene oxy succinoyl (1.47), poly (1.47), poly (ethylene succinate) polytetradecyl methacrylate (1.47), ethylene-propylene copolymer (EPR-rubber) (1.47-1.48), polyhexadecyl methacrylate (1.48), polyvinyl formate (1.48 to 1.50), cellulose acetate (1.48 to 1.50), cellulose triacetate (1.48 to 1.50), polyvinyl pyrrolidone (1.48 to 1.49), polyoxymethylene (1.48), polyvinyl butyral (1.48 to 1.49), poly (n-hexyl methacrylate) (1.48), poly (n-butyl methacrylate) (1.48), poly (2-ethoxyethyl methacrylate) (1.48), polyoxyethylene oxymaleoyl (1.48), (polyethylene maleate) poly (n-propyl methacrylate ) (1.48), poly (3,3,5-trimethylcyclohexyl methacrylate) (1.49), polyethyl methacrylate (1.49), poly (2-nitro-2-methylpropyl methacrylate) (1.49), polytriethylcarbyl methacrylate (1.49), poly (1,1-diethylpropyl methacrylate) ), Poly methyl methacrylate (1.49), poly (2-decyl-1,3-butadiene) (1.49), polyvinyl alcohol (1.49 to 1.53), polyethyl glycolate methacrylate Methyl cyclohexyl methacrylate) (1.49), poly (cyclohexyl α-ethoxy acrylate) (1.50), methyl cellulose (low viscosity) (1.50), poly (4-methylcyclohexyl methacrylate) ), Poly decamethylene glycol dimethacrylate (1.50), polyurethane (1.50 to 1.60), poly (1,2-butadiene) (1.50), polyvinyl formal (1.50) (1.50), cellulose nitrate (1.50 to 1.51), poly (sec-butyl -Chloroacrylate) (1.50), poly (2-heptyl-1,3-butadiene) , Poly (ethyl [alpha] -chloroalk Relate) (1.50), poly (2-isopropyl-1,3-butadiene (1.50), poly (2-methylcyclohexyl methacrylate) (1.50), polypropylene (density of ^{0.9075 g / cm 3) (1.50} ) , Polyisobutene (1.51), polybornyl methacrylate (1.51), poly (2-t-butyl-1,3-butadiene) (1.51), polyethylene glycol dimethacrylate (1.51), polycyclohexylmethacrylate (1.51), poly (cyclohexanediol-1,4-dimethacrylate) (1.51), butyl rubber (unvulcanized) (1.51), polytetrahydrofurfuryl methacrylate) (1.51) car (β) (1.51), polyethylene ionomer (1.51), polyoxyethylene (high molecular weight) (1.51 to 1.54), polyethylene (density ^{0.914 g / cm 3) (1.51} ), ( density of 0.94 to 0.945 g / cm ³ ) (1.52 to 1.53), (density of ^{0.965 g / cm 3) (1.55} ), poly (1-methylcyclohexyl methacrylate) (1.51), poly (2-hydroxyethyl methacrylate) (1.51), poly Vinyl chloroacetate (1.51), polybutene (isotactic) (1.51), polyvinyl methacrylate (1.51), poly (N-butyl-methacrylamide) (1.51), guttaferca ( ) (1.51), terpene resin (1.52) Poly (2-chloroethyl methacrylate) (1.52), cell (1.51 to 1.53), poly (methyl -Chloroacrylate) (1.52) ) (1.52), poly (2-chlorocyclohexyl methacrylate) (1.52), poly (1,3-butadiene) (35% cis; 56% TRANS 1.5180; 7% 1,2-content), natural rubber (1.52), polyallyl methacrylate (1.52), polyvinyl chloride + 40% dioctyl phthalate (1.52), polyacrylonitrile (1.52), polymethacrylonitrile (1.52), poly (1,3-butadiene) (cis-rich) (1.52), butadiene-acrylonitrile copolymer (1.52), polymethylisopropenyl ketone (1.52), polyisoprene (1.52 to 1.54), poly (N- (2-methoxyethyl) methacrylamide) (1.52), poly (2,3-dimethylbutadiene) (methyl rubber) (1.53) , Vinyl chloride-vinyl acetate copolymer (95/5 to 90/10) (1.53 to 1.54), polyacrylic acid (1.53), poly (1,3-dichloropropyl methacrylate) (1.53) (1.53), polyacrylic acid (1.53), poly (1-vinyl-2-pyrrolidone) (1.53), chlorinated rubber (1.53 to 1.55), nylon 6; Nylon 6,6; Styrene copolymer (about 30% styrene) (1.53), block copolymer poly (cyclohexyl a-chloroacrylate) (1.53), poly (2-chloroethyl alpha Styrene copolymer (about 75/25) (1.54), poly (2-aminoethyl methacrylate) (1.54), polyfurfuryl methacrylate (1.54), polybutyl (1.54), poly (1-phenyl-n-amyl methacrylate) (1.54), poly (N-methyl-methacrylamide) (1.54), cellulose (1.54), polyvinyl chloride (1.54 to 1.55), urea formaldehyde resin (1.54 to 1.56), poly (sec-butyl -Bromoacrylate) (1.54), poly (cyclohexyl -Bromoacrylate) (1.54), polydihydroabietic acid (1.54), polybietate (1.546), polyethylmercaptoethyl methacrylate (1.55), poly (N-allyl methacrylamide (1.55), poly (1-phenylethyl methacrylate) (1.55), polyvinyl furan (1.55), poly (2-vinyltetrahydrofuran) (1.55), poly (p-methoxybenzyl methacrylate) (1.55), polyisopropyl methacrylate (1.55), poly (p-isopropylstyrene) (1.55), polychloroprene (1.55 to 1.56) (1.56), poly (p, p'-xylylenedimethacrylate) (1.56), poly (1-phenylallyl methacrylate) (1.56 (1.56), poly (2-phenylethyl methacrylate) (1.56), poly (oxycarbonyloxy-1,4-phenylene-1-propyl (1.56), styrene-maleic anhydride copolymer (1.56), poly (1-phenylcyclohexyl methacrylate) (1.56), poly (oxy Carbonyloxy-1,4-phenylene-1,3-dimethyl-butylidene-1, (1.57), poly (4-phenylene) (1.57), poly (methyl -Bromoacrylate) (1.57), polybenzyl methacrylate Poly (m-cresyl methacrylate) (1.57), styrene-acrylonitrile copolymer (about 75/25) (1.57), poly (oxycarbonyloxy- (1.57), poly (o-methoxyphenyl methacrylate) (1.57), polyphenyl methacrylate (1.57), poly (o-cresyl methacrylate) (1.57), polydialyl (1.57), poly (2,3-dibromopropyl methacrylate) (1.57), poly (oxycarbonyloxy-1,4-phenylene-1-methyl-butylidene- (1.57), poly (oxy-2,6-dimethylphenylene) (1.58), polyoxyethylene terephthaloyl (amorphous) (1.58), polyethylene terephthalate (1.51-1.64), polyvinyl benzoate 1.58), poly (oxycarbonyloxy-1,4-phenylenebutylidene-1,4-phenylene) (1.58), poly Ethyl methacrylate) (1.58), poly (o-chlorobenzyl methacrylate) (1.58), poly (oxycarbonyloxy-1,4-phenylene-sec-butylidene- (1.58), polyoxypentaerythritol triphosphate (1.58), poly (m-nitrobenzyl methacrylate) (1.58), poly (oxycarbonyloxy- Poly (4-methoxy-2-methylstyrene) (1.59), poly (o-methylstyrene) (1.59) (1.59), polystyrene (1.59), poly (oxycarbonyloxy-1,4-phenylene cyclohexylidene-1,4-phenylene) (1.59), poly (o-methoxystyrene) (1.59), poly (oxycarbonyloxy-1,4-phenylene ethylidene-1,4-phenylene) (1.59), poly (p-bromophenyl methacrylate) (1.60), poly (N-benzylmethacrylamide) (1.60), poly (p-methoxystyrene) (1.60), polyvinylidene chloride (1.60 to 1.63), polysulfide (1.6 to 1.7), poly (o-chlorodiphenylmethyl methacrylate) (1.60), poly (oxycarbonyloxy-1,4- (2,6-dichloro) phenylene isopropylidene, 4- (1,6-dichloro) phenylene) (1.61), poly (oxycarbonyloxybis (1,4- (3,5-dichlorophenylene))) polypentachlorophenyl methacrylate (1.61), poly (1.61), poly (phenyl α-bromoacrylate) (1.61), poly (p-divinylbenzene) (1.62), poly (N-vinylphthalimide) (1.63), poly ( -Naphthylcarbyl methacrylate) (1.63), polysulfone (1.63), poly ( -Naphthylmethacrylate) Poly ( -Naphthyl methacrylate) (1.64), poly (oxycarbonyloxy-1,4-phenylenediphenyl-methylene-1,4-phenylene) (1.65 ), Polyvinylphenyl sulfide (1.66), butylphenol formaldehyde resin (1.66), urea-thiourea-formaldehyde resin (1.66), polyvinyl naphthalene (1.68), naphthalene-formaldehyde resin (1.70), phenol-formaldehyde resin (1.70), and polypentabromophenyl methacrylate (1.71).
[127] Of these, the d-line refractive index is preferably 1.6 or less, more preferably 1.5 or less.
[128] The weight average molecular weight of the non-decomposable compound (B) is preferably 100 to 500,000, more preferably 100 to 200,000.
[129] As the non-decomposable compound (B), a compound represented by the following general formula (18), a hydrolyzate thereof or a condensate thereof is similarly used.
[130] R ²¹³ _n Si (OR ²¹⁴ ) _4-n
[131] In the formulas, R ²¹³ and R ²¹⁴ may be the same or different and each is a monovalent organic group and n is an integer of 0 to 2.
[132] Examples of the monovalent organic group in Formula 18 include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group preferably has 1 to 5 carbon atoms. The alkyl group may be in the form of a chain or in a branched form, and the hydrogen atom may be substituted with a halogen atom such as a fluorine atom . Examples of the aryl group in the above formula (18) include a phenyl group and a naphthyl group. In Formula 18, it is preferable that n is 1 or 2.
[133] Specific examples of the alkylalkoxysilane represented by Formula 18 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyl Butoxysilane, tri-sec-butoxysilane, methyltri-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane , Ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri- N-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyl Butoxy silane, isopropyl tri-tert-butoxy silane, isopropyl tri-isopropoxy silane, isopropyl tri-n-butoxy silane, isopropyl tri- Butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-propyltrimethoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, Butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, butyltrimethoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltriisopropoxysilane, tert- - Butoxy Butyl tri-sec-butoxysilane, tert-butyl tri-tert-butoxysilane, tert-butyltriphenoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltriethoxysilane, butoxysilane, cyclohexyltriethoxysilane, n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltri-sec-butoxysilane, cyclohexyltri- , Norbornyltrimethoxysilane, norbornyltriethoxysilane, norbornyltri-n-propoxysilane, norbornyltriisopropoxysilane, norbornyltri-n-butoxysilane, norbornene N-butyl-sec-butoxysilane, norbornyltri-tert-butoxysilane, norbornyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri- Triisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert- Butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-sec-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di- Butoxysilane, dimethyl di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, di Diethyl di-sec-butoxysilane, diethyl di-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di- Di-n-propyl di-n-butoxysilane, di-n-propyl di-n-propyl silane, di- Butoxysilane, di-n-propyl di-tert-butoxysilane, di-n-propyldiphenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyl di- Silane, di Butoxy silane, diisopropyl di-sec-butoxysilane, diisopropyl di-isopropoxy silane, diisopropyl di-n-butoxy silane, diisopropyl di- butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldihydroxypropylsilane, di-n-butyldiisopropoxysilane, di- Di-n-butyldimethoxysilane, di-sec-butyldimethoxysilane, di-n-butyldimethoxysilane, di- butyl diethoxy silane, di-sec-butyl di-n-propoxy silane, di-sec-butyl diisopropoxy silane, di- Di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-sec-butyldimethoxysilane, di- butyl di-n-propoxysilane, di-tert-butyl diisopropoxysilane, di-tert-butyl di-n-butoxysilane, di- Di-tert-butyldiphenoxysilane, di-tert-butyldimethoxysilane, dicyclohexyldiethoxysilane, di-tert-butyldimethoxysilane, di- -Butyl di-n-propoxysilane, dicyclohexyl diisopropoxy silane, dicyclohexyl di-n-butoxy silane, dicyclohexyl di-sec-butoxysilane, dicyclohexyldi- Silane, dicyclohexyldiphenoxysilane, di-tert-butyldimethoxysilane, dinorbornyldiethoxysilane, di-tert-butyldi-n-propoxysilane, dinorbornyldiisopropoxysilane, dino N-butoxysilane, dinorbornyldi-sec-butoxysilane, dinorbornyldi-tert-butoxysilane, dinorbornyldiphenoxysilane, diphenyldimethoxysilane, diphenyldi -Epoxy silane, diphenyl di-n-propoxy silane, diphenyl diisopropoxy silane, diphenyl di-n-butoxy silane, diphenyl di-sec-butoxysilane, diphenyl di- Gt; Aminopropyltrimethoxysilane, -Aminopropyltriethoxysilane, -Glycidyloxypropyltrimethoxysilane, -Glycidyloxypropyltriethoxysilane, -Trimethoxysilane, -Trimethoxysilane, Ethoxysilane, -Trifluoropropyltrimethoxysilane, -Trifluoropropyltriethoxysilane, and the like. Further, a compound in which some or all of these hydrogen atoms are substituted with fluorine atoms can be mentioned. These alkylalkoxysilanes may be used alone or in combination of two or more.
[134] Among the compounds represented by the general formula (18), it is particularly preferable to use n = 1 alkyltrialkoxysilane. Of these, methyltrimethoxysilane and methyltriethoxysilane are preferably used, and the use of methyltrimethoxysilane and / or methyltriethoxysilane in a proportion of 70 mol% or more of the total alkylalkoxysilane , A cured product having a balance of heat resistance and refractive index is obtained, which is more preferable. The hydrolyzate and the condensate thereof are more preferable than the compound represented by the above-mentioned formula (18). When the component (B) is a condensate of the compound represented by the above formula (18), the weight average molecular weight in terms of polystyrene is preferably 500 to 100,000.
[135] The hydrolysis reaction and the condensation reaction in the case of using the hydrolyzate and / or condensate of the compound represented by the above general formula (18) as the component (B) are carried out in the presence of water and an appropriate catalyst as described below.
[136] Specifically, the compound represented by the formula (18) is dissolved in an appropriate organic solvent, and water is intermittently or continuously added to the solution. At this time, the catalyst may be dissolved or dispersed in the organic solvent in advance, or may be dissolved or dispersed in the added water.
[137] The temperature for carrying out the hydrolysis reaction and / or the condensation reaction is usually 0 to 100 占 폚, preferably 15 to 80 占 폚.
[138] The water for carrying out the hydrolysis and / or condensation of the compound represented by the above general formula (18) is not particularly limited, but it is preferable to use ion exchange water.
[139] The amount of water to be used is preferably 0.25 to 3 moles, particularly 0.3 to 2.5 moles, per 1 mole of the total of the groups represented by R < ²¹⁴ > O- in the compound represented by the formula (18).
[140] Examples of the catalyst for carrying out the hydrolysis and / or condensation of the compound represented by the general formula (18) include metal chelate compounds, organic acids, inorganic acids, organic bases and inorganic bases.
[141] Specific examples of the metal chelate compound used as the catalyst include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (Acetylacetonate) titanium, tri-tert-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono Bis (acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (Acetyl acetonate) titanium, di-sec-butoxy bis (acetyl acetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris Butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium (Ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethyl acetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, Titanium, di-sec-butoxy-bis (ethylacetoacetate) titanium, di- t-butoxy bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris Butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, (Ethyl acetoacetate) titanium, tris (acetylacetonate) titanium, mono (acetylacetonate) titanium, bis (acetylacetonate) And the like;
[142] Tri-n-butoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri- (Acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di-tert-butoxy mono (acetylacetonate) zirconium, n-butoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di- (Acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris Mono-i-propoxy tris (Acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium (Ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) (Ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, diethoxy Bis (ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis Acetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris Ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis Zirconium chelate compounds such as bis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
[143] Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethyl acetoacetate) aluminum, and the like.
[144] Specific examples of the organic acid used as the catalyst include organic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, But are not limited to, sebacic acid, gallic acid, butyric acid, malic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p- Benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid.
[145] Concrete examples of the inorganic acid used as the catalyst include, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
[146] Specific examples of the organic base used as the catalyst include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmono Ethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclo-nonane, diazabicyclo-undecene, tetramethylammonium hydroxide and the like.
[147] Examples of the inorganic base used as the catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
[148] Among them, a metal chelate compound, an organic acid or an inorganic acid is preferably used as a catalyst, and a titanium chelate compound or an organic acid is more preferable.
[149] These compounds may be used singly or in combination of two or more.
[150] The amount of the catalyst to be used is usually in the range of 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the compound represented by the above formula (18) in terms of SiO ₂ .
[151] Further, it is preferable to carry out the removal treatment of the remaining water and the alcohols generated as reaction by-products after the hydrolysis and / or condensation of the compound represented by the above-mentioned general formula (18).
[152] (B) is preferably 10 parts by weight to 95 parts by weight, more preferably 10 parts by weight to 90 parts by weight, and more preferably 20 parts by weight to 90 parts by weight, relative to 100 parts by weight of the total of the components (A) and (B) And particularly preferably 20 parts by weight to 70 parts by weight. When the amount of the component (B) is less than 10 parts by weight, the refractive index-changing material tends to become weak. When the amount is more than 90 parts by weight, the obtained refractive index difference tends to be small.
[153] (C) Sensitizing Radiation Release
[154] The (C) radiation sensitive decomposition release agent used in the present invention may be a radiation-sensitive acid generator or a radiation-sensitive base generator. In this case, when the acid-decomposable polymer (A) is used as the decomposable polymer, a radiation-sensitive acid generator (C) is used as the radiation-sensitive decomposer, and when the base-decomposable polymer (A) As the radiation-decomposing agent, it is preferable to use a radiation-sensitive base generator.
[155] As the radiation-sensitive acid generator, for example, trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, sulfonic acid esters and the like can be used.
[156] Examples of the trichloromethyl-s-triazine stream include 2,4,6-tris (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -4,6-bis (trichloromethyl) -s- (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s (Trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl) bis (trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) -4,6-bis (trichloro Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4-methoxy- - styryl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (2-methoxy-p-styryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxy- - styryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (3-methylthio-p-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) ) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis Trichloromethyl) -s-triazine, and the like.
[157] The diaryl iodonium salts include, for example, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoromethane sulfonate, diphenyl iodo Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluenesulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, di Phenyl iodonium hexyltris (p-chlorophenyl) borate, diphenyl iodonium hexyltris (3-trifluoromethylphenyl) borate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, 4-methoxyphenyl Phenyl iodonium hexafluorophosphate, 4-methoxyphenyl phenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodo Thionyl trifluoroacetate, 4-methoxy (2,6-difluorophenyl) borate, 4-methoxyphenylphenyl iodonium hexyl tris (p-chlorophenyl) boron tris Phenyl) borate, 4-methoxyphenylphenyl iodonium hexyltris (3-trifluoromethylphenyl) borate, bis (4-tert- butylphenyl) iodonium tetrafluoroborate, bis ), Iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbutyltris (2,6- difluorophenyl) ) Iodonium hexyltris (p-chlorophenyl) borate, and bis (4-tert-butylphenyl) iodonium hexyltris (3-trifluoromethylphenyl) The.
[158] The triarylsulfonium salts include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethane Triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium butyltris (2,6-difluorophenyl) borate, triphenylsulfonium hexyltris (p- Triphenylsulfonium hexyltris (3-trifluoromethylphenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphate , 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, Toxic 4-methoxyphenyldiphenylsulfonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium hexyltris (p-chlorophenyl) ) Borate, 4-methoxyphenyldiphenylsulfonium hexyltris (3-trifluoromethylphenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluoro Phosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenylsulfonium butyltris (2,6-difluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium hexyltris (p-chlorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium hexyl tris (3-trifluoromethylphenyl) borate, 4-hydroxy-1-naphthalenyl) dimethylsulfonium tetrafluoroborate, 4-hydroxy-1-naphthalenyldimethylsulfonium hexafluorophosphate, 4 1-naphthalenyldimethylsulfonium hexafluoroarsenate, 4-hydroxy-1-naphthalenyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthalenyl dimethyl Naphthalenyldimethylsulfonium p-toluenesulfonate, 4-hydroxy-1-naphthalenyldimethylsulfonium butyltris (2,6-difluoro Phenylborate, 4-hydroxy-1-naphthalenyldimethylsulfonium hexyltris (p-chlorophenyl) borate, 4-hydroxy-1-naphthalenyldimethylsulfonium hexyltris (3-trifluoromethylphenyl) Borate, and the like.
[159] The quaternary ammonium salts include, for example, tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphonate, tetramethylammonium hexafluoroarsenate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium tetrafluoroborate, Tetramethylammonium p-toluenesulfonate, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyl Tris (3-trifluoromethylphenyl) borate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hexafluoroarsenate, tetrabutylammonium trifluoromethanesulfonate, tetra Butyl ammonium trifluoroacetate, tetrabutylammonium-p-toluenesulfonate (P-chlorophenyl) borate, tetrabutylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyltrimethylammonium (tetrabutylammonium) butyltris Benzyltrimethylammonium hexafluorophosphate, benzyltrimethylammonium hexafluoroarsenate, benzyltrimethylammonium trifluoromethanesulfonate, benzyltrimethylammonium trifluoroacetate, benzyltrimethylammonium p-toluene, benzyltrimethylammonium pentafluorophosphate, Benzyltrimethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyltrimethylammonium hexyltris (p-chlorophenyl) borate, benzyltrimethylammonium butyltris (2,6- difluorophenyl) borate, benzyltrimethylammonium hexyltris Phenylammonium tetrafluoroborate, benzyldimethylphenylammonium hexafluorophosphate , Benzyldimethylphenylammonium hexafluoroarsenate, benzyldimethylphenylammonium trifluoromethanesulfonate, benzyldimethylphenylammonium trifluoroacetate, benzyldimethylphenylammonium-p-toluenesulfonate, benzyldimethylphenylammonium butyltris ( Benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, N-cinnamylidenemethylphenylammonium tetra N-cinnamylideneethylphenylammonium hexafluorophosphate, N-cinnamylideneethylphenylammonium hexafluoroarsenate, N-cinnamylideneethylphenylammonium trifluoromethanesulfonate, N < RTI ID = 0.0 & - cinnamylmethylidenemethylphenylammonium trifluoroacetate, N-cinnamylideneethylphenylammonium p-toluenesulfonate, N-cinnamylideneethylphenylcarbamate, (P-chlorophenyl) borate, N-cinnamylideneethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, N-trimethylphenylammonium hexyltris ) Borate, and the like.
[160] The sulfonic acid esters include, for example, -Hydroxymethylbenzoin-p-toluenesulfonic acid ester, -Hydroxymethylbenzoin-trifluoromethanesulfonic acid ester, -Hydroxymethylbenzoin-methanesulfonic acid ester , Pyrogallol-tri (trifluoromethanesulfonic acid) ester, pyrogallol-trimethanesulfonic acid ester, 2,4-dinitrobenzyl-p-toluenesulfonic acid ester, 2,4-dinitrobenzyl-methanesulfonic acid ester, 2,4-dinitrobenzyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, 4-dinitrobenzyl- Dinitrobenzyl-methanesulfonic acid ester, 2,6-dinitrobenzyl-1,2-diisobutylbenzenesulfonic acid ester, 2,6-dinitrobenzyl-methanesulfonic acid ester, -Naphthoquinonediazide-5-sulfonic acid ester, 2-nitrobenzyl-p-toluenesulfonic acid ester, 2-nitrobenzyl-trifluoromethanesulfonic acid ester, 2-nitrobenzyl-methanesulfonic acid ester, 2-nitrobenzyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4-nitrobenzyl- Esters, 4-nitrobenzyl-trifluoromethanesulfonic acid ester, 4-nitrobenzyl-methanesulfonic acid ester, 4-nitrobenzyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, N-hydroxynaphthalene Hydroxynaphthalimide-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-methanesulfonic acid ester, N-hydroxy-5-norbornene-2, 5-norbornene-2,3-dicarboxyimide-trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2 , 3-dicarboxyimide-methanesulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonic acid ester, and 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester.
[161] Among these compounds, the trichloromethyl-s-triazine derivatives include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s- triazine, 2- (4-methoxyphenyl) (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-.beta.- (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-ylmethyl) (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2- (4-methylphenyl) ethenyl] -bis Methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine;
[162] The diaryl iodonium salts include diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, or 4-methoxy Phenyl phenyl iodonium trifluoroacetate;
[163] Examples of the triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate;
[164] Examples of the quaternary ammonium salts include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate , Benzyldimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate;
[165] Sulfonic acid esters include 2,6-dinitrobenzyl-p-toluenesulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-p-toluenesulfonic acid ester, N -Hydroxynaphthalimide-trifluoromethanesulfonic acid ester can be preferably used.
[166] As the radiation-sensitive base generator, those described in JP-A-4-330444, "Polymer" p 242-248, Vol. 46 (6) (1997), U.S. Patent No. 5,627,010, etc. are suitably used . However, the function is not limited to these as long as it generates bases by irradiation of radiation.
[167] Preferred examples of the radiation-sensitive base generator in the present invention include optically active carbamates such as triphenylmethanol, benzylcarbamate and benzoincarbamate; Amides such as O-carbamoyl hydroxyl amide, O-carbamoyl oxime, aromatic sulfonamide, alpha-lactam and N- (2-allylethynyl) amide, and other amides; Oxime ester, -Amino acetophenone, and cobalt complexes.
[168] Examples of the radiation-sensitive base generator include compounds represented by the following general formulas (19) to (29).
[169]
[170] Wherein R ⁷⁶ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, a nitro group, a hydroxy group, an aryl group, a fluorine atom, a chlorine atom or a bromine atom, k is an integer from O to 3, R ⁷⁷ is an alkyl group or an aryl group, a hydrogen atom, a C 1 -C 6, R ⁷⁸ and R ⁷⁹ are each independently a hydrogen atom , An alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ⁷⁸ and R ⁷⁹ may combine with each other to form a cyclic structure having 5 to 6 carbon atoms, together with the nitrogen atom to which they are bonded.
[171]
[172] Wherein R ⁸⁰ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, a nitro group, a hydroxy group, an aryl group, R ⁸¹ is an alkyl group or an aryl group, a hydrogen atom, a group having 1 to 6 carbon atoms and R ⁸² and R ⁸³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ⁸² and R ⁸³ May be bonded to each other to form a cyclic structure having 5 to 6 carbon atoms as a single bond with the nitrogen atom to which they are bonded.
[173]
[174] Wherein, R ⁸⁴ is an alkyl group or aryl group having 1 to 6 carbon atoms, are bonded to each other R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ⁸⁵ and R ⁸⁶ May be combined with the nitrogen atom to which they are bonded to form a cyclic structure having 5 to 6 carbon atoms.
[175]
[176] In the formula, R ⁸⁷ and R ⁸⁸ are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms.
[177]
[178] In the formulas, R ⁸⁹ , R ⁹⁰ and R ⁹¹ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group.
[179]
[180] R ⁹² represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, a nitro group, a hydroxy group, R ⁹⁴ , R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group; R ⁹³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group;
[181]
[182] Wherein R ⁹⁷ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidinyl group, a nitro group, a hydroxy group, and an aryl group, R ⁹⁸ and R ⁹⁹ each independently represent a hydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an aryl group, R ¹⁰⁰ and R ^{101 and} R ¹⁰¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ¹⁰⁰ and R ¹⁰¹ are bonded to each other to form a cyclic structure having 5 to 6 carbon atoms You may.
[183]
[184] Wherein R ¹⁰² and R ¹⁰³ each independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, , a hydroxy group, a mercapto group, or an aryl group, R ¹⁰⁴ to R ¹⁰⁷ each independently represent a hydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an aryl group And A < ⁵ > is a bivalent atomic group formed by excluding two hydrogen atoms bonded to one or two nitrogen atoms of a monoalkylamine, piperazine, aromatic diamine or aliphatic diamine.
[185]
[186] Wherein R ¹⁰⁸ and R ¹⁰⁹ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a piperidyl group, , a hydroxy group, a mercapto group, or an aryl group, R ¹¹⁰ and R ¹¹¹ are each independently a hydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an aryl group And R ¹¹² to R ¹¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group, or R ¹¹² and R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ are bonded to each other to form a nitrogen atom A ⁶ may be an alkylene group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group or a single bond.
[187]
[188] Wherein R ¹¹⁶ to R ¹¹⁸ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkynyl group having 1 to 6 carbon atoms, 6 > is an alkoxy group or an aryl group.
[189]
[190] In the formula, L is at least one member selected from the group consisting of ammonia, pyridine, imidazole, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, propylenediamine, 1,2-cyclohexanediamine, Amine, m is an integer of 2 to 6, R ¹¹⁹ is an aryl group, and R ¹²⁰ is an alkyl group having 1 to 18 carbon atoms.
[191] In the above general formulas (19) to (29), the alkyl group may be linear, branched or cyclic. Also, examples of the aryl group include an alkenyl group such as a vinyl group and a propenyl group; An alkynyl group such as an acetylenyl group; A halogen atom, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, an azide group, a dialkylamino group, An alkoxy group or a thioalkyl group.
[192] Among these radiation-sensitive base generators, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-carbamoylhydroxylamide, o-carbamoyloxime, [[(2,6-dinitrobenzyl) (Methylthiobenzoyl) -1-methyl-1-morpholinoethane, ((2-nitrobenzyl) oxy] carbonyl] Benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamine cobalt (III) tris (triphenylmethyl borate) -2-dimethylamino-1- (4-morpholinophenyl) -butane, and the like.
[193] The above-mentioned (C) radiation-sensitive decomposition release agent is preferably used in an amount of 0.01 part by weight or more, more preferably 0.05 part by weight or more, based on 100 parts by weight of the total of the (A) decomposable polymer and the (B) non-decomposable compound. When the amount of the component (C) is 0.01 part by weight or less, the sensitivity to irradiation light tends to be lowered. The upper limit value is preferably 30 parts by weight, more preferably 20 parts by weight.
[194] (D) stabilizer
[195] The stabilizer (D) used in the present invention has a function of stabilizing the decomposable polymer (A) remaining in the refractive index change material after irradiation with radiation to impart stability to an acid or a base. With this stabilization process, the refractive index pattern formed by the method of the present invention does not deteriorate without causing a change in the refractive index even under the condition that light near the wavelength used for changing the refractive index passes through.
[196] Examples of the stabilizer (D) include amino compounds, epoxy compounds, thioran compounds, oxetane compounds, alkoxymethylated melamine compounds, alkoxymethylated glycoluril compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated urea compounds, isocyanate compounds , Cyanate compounds, oxazoline compounds, oxazine compounds and silyl compounds (halogenated silyl compounds, other silyl compounds).
[197] Examples of the amino compound include ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, triphenylamine, tribenzylamine, aniline, ethylenediamine, diethylene tri Amine, triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-propane-2-ol, 2,2 ', 2 "-triaminotriethylamine, 1,4-diamino-2,2,2-trichlorohexane, , 3,3-tetrafluoropentane, 1,5-diamino-2,2,3,3,4,4-hexafluoropentane, melamine, benzoguanamine, acetoguanamine, acryloguanamine, para Amine, amidol, m-phenylenediamine, p-phenylenediamine , p, p'-diaminodiphenylmethane, diaminodiphenylsulfone, 1,8-diaminonaphthalene, 3,5-diamino-1,2,4-triazole, Diaminobenzidine, bis (4-aminophenyl) ether, m-xylylenediamine, p-xylylenediamine, 1, 2,4,5-benzene tetramine, 2,4-diamino-1,3,5-triazine, 4,4'-diaminobenzophenone, 3,3 ', 4,4'-tetraaminobenzophenone , Triaminobenzene, 4,4'-thiodianiline, 2,3,5,6-tetrabromo-p-xylylenediamine, 2,3,5,6-tetrachloro-p-xylylenediamine , 4,5-methylenedioxy-1,2-phenylenediamine, 2,2'-bis (5-aminopyridyl) sulfide and the like.
[198] Examples of the epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, and cyclic aliphatic epoxy resins. Bisphenol A type epoxy compounds, aliphatic polyglycidyl Ether, and the like.
[199] Examples of such commercially available products include the following. As the bisphenol A type epoxy resin, Epicot 1001, Copper 1002, Copper 1003, Copper 1004, Copper 1007, Copper 1009, Copper 1010, Copper 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) (Manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN 201 and 202 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like were used as phenol novolak type epoxy resins, EOCN-1025, EOCN-1025 and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.) as cresol novolak type epoxy resins, ERL-4299, ERL-4221, ERL-4231, ERL-4234, ERL-4234, ERL-4231, and ERL-4231 as the cyclic aliphatic epoxy resin. Examples of the cyclic aliphatic epoxy resin include CY175, CY177 and CY179 ARDITE CY-182, CY-192 and CY-184 (manufactured by CIBA-GEIGY AG), Epiclon (trade name) manufactured by Showa Denko K.K., 200, 400 (or more, Dynet (Available from Yuka Shell Epoxy Co., Ltd.), ED-5661, and ED-5662 (manufactured by Seraniz Coatings Co., Ltd.) Examples of the cidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and Epiol TMP (manufactured by NIPPON BUSINESS CO., LTD.).
[200] In addition to the above, there may be mentioned phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, (Nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidyl aniline, 3- [2- Perfluorohexyl) ethoxy] -1,2-epoxypropane and the like can be suitably used as an epoxy compound.
[201] As the thiocyanate compounds, epoxy groups of the above epoxy compounds can be used, for example, as described in J. Org. Chem., 28, 229 (1963) and substituted with an ethylene sulfide group can be used.
[202] As the oxetane compound, bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (trade name "XDO" Methyl-phenyl] methane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [ Methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like can be enumerated .
[203] The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound are each selected from the group consisting of a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol compound Group into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.
[204] Examples of such commercially available products include Cymel 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper 266, Copper Copper 267, Copper Copper 238, Copper Copper 1141, Copper Copper Copper 202, Nixa Rock Mx-750, Mx-032, Mx-706 and Mx-708 (manufactured by Mitsui Cyanamid Co., Ltd.) , Copper Mx-40, copper Mx-31, copper Ms-11, copper Mw-30 (manufactured by Sangwa Chemical Co., Ltd.).
[205] Examples of the isocyanate compound include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene- 3,3'-dimethoxybiphenylene-4,4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, di Phenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthylene Diisocyanate, cyclobutylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, Diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane, cyclo (Methyl isocyanate), cyclohexane-1,4-bis (methyl isocyanate), isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane- Diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester, Terminal isocyanate-free polymer obtained by reacting a stoichiometric excess of diisocyanate with a bifunctional active hydrogen-containing compound, and the like.
[206] In some cases, the diisocyanate may be used in combination with, for example, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane- Triisocyanate, triphenylmethane-2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4" -triisocyanate, diphenylmethane- Diphenylmethane-2,5,2 ', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methyl isocyanate), 3,5- 1,3,5-tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2'-triisocyanate , Dicyclohexylmethane-2,4,4'-triisocyanate, or the like, or the stoichiometry of such an organic polyisocyanate having three or more functionalities It may be used in combination with terminal isocyanate prepolymer obtained by a reaction with the excess amount and functionality of two or more multi-functional active hydrogen containing compound.
[207] Examples of the cyanate compound include 1,3-dicyanate benzene, 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-, 1,4-, 1,6-, , 2,6-, or 2,7-dicyanate naphthalene, 1,3,6-tricanate naphthalene, 2,2'- or 4,4'-dicyanate biphenyl, bis (4-cyanate phenyl) methane Bis (4-cyanate phenyl) propane, 2,2'-bis (3,5-dichloro-4-cyanate phenyl) propane, 2,2- Bis (4-cyanate phenyl) ether, bis (4-cyanate phenyl) thioether, bis (4-cyanate phenyl) sulfone, 1,1,1,3,3,3-hexafluoro-2,2 Polyisocyanate compounds of benzene polynucleer obtained from the reaction of bis (4-cyanate phenyl) propane, tris (4-cyanate phenyl) phosphite, tris (4-cyanate phenyl) For example, Japanese Unexamined Patent Publication No. 45-11712 and No. 55-9433) And so on. The divalent cyanate ester compounds derived from bisphenols such as 2,2-bis (4-cyanate phenyl) propane are particularly preferred because they are easy to obtain and provide good moldability and final cured properties do. Also useful is a polycyanate obtained by reacting an initial condensate of phenol and formaldehyde with cyanogen halide.
[208] Examples of the oxazoline compound include 2,2'-bis (2-oxazoline), 4-furan-2-ylmethylene- Bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4-isopropenyl- ) Butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl- 2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylenebis (4-tert- , 2,2'-methylenebis (4-phenyl-2-oxazoline), and the like.
[209] Examples of the oxazine compound include 2,2'-bis (2-oxazine), 4-furan-2-ylmethylene- Dihydro-2-oxadyl) benzene, 1,3-bis (4,5-dihydro-2-oxadyl) benzene, 2,3- ) Butane, 2,2'-bis-4-benzyl-2-oxazine, 2,6-bis (isopropyl- 2-oxazine), 2,2'-isopropylidenebis (4-phenyl-2-oxazine), 2,2'-methylenebis (4-tert- , 2,2'-methylenebis (4-phenyl-2-oxazine), and the like.
[210] Examples of the halogenated silyl compound include tetrahalogenosilanes such as tetrachlorosilane, tetrabromosilane, tetraiodosilane, trichlorobromosilane and dichlorodibromosilane, methyltrichlorosilane, methyldichlorobromosilane, cyclohexyltrichloro Monoalkyltrihalogenosilanes such as silane, silane and the like, monoaryltrihalogenosilanes such as phenyltrichlorosilane, naphthyltrichlorosilane, 4-chlorophenyltrichlorosilane and phenyldichlorobromosilane, phenoxy trichloro Monoaryloxytrihalogenosilanes such as silane and phenoxydichlorobromosilane, monoalkoxytrihalogenosilanes such as methoxytrichlorosilane and ethoxy trichlorosilane, dimethyldichlorosilane, methyl (ethyl) dichloro Dialkyldihalogenosilanes such as silane and methyl (cyclohexyl) dichlorosilane, and monoalkylmonoars such as methyl (phenyl) dichlorosilane Diaryldihalogenosilanes such as lidihalogenosilanes and diphenyldichlorosilane, diaryloxydihalogenosilanes such as diphenoxydichlorosilane, monoalkyl monoarylsilanes such as methyl (phenoxy) dichlorosilane and the like Monoaryl monoaryloxydihalogenosilanes such as phenyl (phenoxy) dichlorosilane and the like, dialkoxydihalogenosilanes such as diethoxydichlorosilane, methyl (ethoxy) dichloro Monoaryl monoethoxy dichlorosilanes such as phenyl (ethoxy) dichlorosilane and the like; monoalkyl monoethoxy dichlorosilanes such as trimethyl chlorosilane, dimethyl (ethyl) chlorosilane and dimethyl (cyclohexyl) Dialkyl monoaryl monohalogenosilanes such as dimethyl (phenyl) chlorosilane and the like, monoalkyldiaryl monohalogenosilanes such as methyl (diphenyl) chlorosilane and the like, triphenoxycyclo Room Monoalkyldiaryloxymonohalogenosilanes such as methyl (diphenoxy) chlorosilane and the like, monoaryldiaryloxy such as phenyl (diphenoxy) chlorosilane and the like Dialkyl monoaryloxymonohalogenosilanes such as dimethyl (phenoxy) chlorosilane and the like, diarylmonoaryloxymonohalogenosilanes such as diphenyl (phenoxy) chlorosilane and the like, Monoalkyl monoaryl monoaryloxy monohalogenosilanes such as methyl (phenyl) (phenoxy) chlorosilane and the like, triethoxy monohalogenosilanes such as triethoxy chlorosilane, and tetra Oligomers of the above compounds such as pentamers, and the like.
[211] Examples of the silyl compounds other than the above include hexamethyldisilazane, t-butyldimethylchlorosilane, bis (trimethylsilyl) trifluoroacetamide, diethylaminotrimethylsilane, trimethylsilanol, hexamethyldisiloxane, Hexyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, triethoxysilane, tripropylsilane, triethylsilanol, tripropylsilanol, tributylsilanol, trimethylethoxysilane, trimethylethoxysilane, tri Bis (hydroxybutyl) tetramethyldisiloxane, 1,3-bis (hydroxypropyl) tetramethyldisiloxane, gamma -butyrolactone, (Aminoethyl) - - aminopropyltrimethoxysilane, N- (Aminoethyl) - - aminopropyltrimethoxysilane, N- Phenyl-gamma -aminopropyl - aminopropyltrimethoxysilane, -Dibutylaminopropyltrimethoxysilane, -Ureidopropyltriethoxysilane, N- (N-vinylbenzylaminoethyl) - - amino Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma -glycidoxypropyltriethoxysilane, gamma -glycidoxypropyltriethoxysilane, gamma -glycidoxypropyltriethoxysilane, gamma- Mercaptopropyltrimethoxysilane, gamma -chloropropyltrimethoxysilane, trimethylchlorosilane, hexamethyldisilazane, N-trimethylsilylimidazole, bis (trimethylsilyl) silane, ) Urea, trimethylsilylacetamide, bistrimethylsilylacetate Trimethylsilyl isocyanate, trimethylmethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, t-butyldimethylchlorosilane, t-butyldiphenyl N-hexyltrimethoxysilane, n-hexadecyltrimethoxysilane, 1-hexyltrimethoxysilane, 1-hexyltrimethoxysilane, 1-hexyltrimethoxysilane, , 6-bis (trimethoxysilyl) hexane, dimethylsilyldiisocyanate, methylsilyltriisocyanate, phenyltrimethoxysilane, diphenyldimethoxysilane, and phenylsilyltriisocyanate.
[212] As the stabilizer (D) used in the present invention, an amino compound, an epoxy compound, a thiane compound, an oxetane compound, an oxazoline compound, an oxazine compound, a silyl compound, an isocyanate compound and a cyanate compound are preferable, Among them, an amino compound, an epoxy compound, a thiane compound, an oxetane compound, an oxazoline compound and an oxazine compound are more preferably used. Among them, particularly preferred are ethylenediamine, phenylglycidyl ether, 3-phenoxypropylene sulfide, 3,3,3-trifluoropropylenoxide, hexamethyldisilazane, -Aminopropylmethoxysilane, Glycidoxypropyltrimethoxysilane, methylsilyltriisocyanate and the like are preferably used.
[213] These (D) stabilizers may be used alone or in combination of two or more. The amount of the component (D) to be used may be excessively used so that the residual portion of the decomposable polymer (A) sufficiently reacts. Usually, 10 parts by weight or more, preferably 30 parts by weight or more, based on 100 parts by weight of the component (A) There is a number.
[214] If the amount of the component (D) is less than 10 parts by weight, the reaction becomes insufficient and the stability of the refractive index changing material may become insufficient.
[215] Further, the catalyst can be used together with the stabilizer (D). The use of the catalyst promotes the reaction between the component (D) and the residual portion of the degradable polymer (A).
[216] Examples of such catalysts include acid catalysts, base catalysts, and fourth onium salts.
[217] Examples of the acid catalyst include organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid, or inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. Examples of the base catalyst include sodium carbonate, potassium carbonate, Alkali metal carbonates such as sodium carbonate; Alkali metal bicarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate or lithium hydrogen carbonate; Alkali metal acetates such as sodium acetate; Alkali metal hydrides such as lithium hydride, sodium hydride or potassium hydride; Alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide or lithium methoxide; Mercaptan alkaline metals such as methyl mercaptan sodium or ethyl mercaptan sodium; N, N-dimethylaniline, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylaniline, Diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,8-diazabicyclo [5.4.0] undec-7 - organic amines such as benzene (DBU); Alkyllithiums such as methyllithium, ethyllithium or butyllithium; And lithium alkylamides such as lithium diisopropylamide or lithium dicyclohexylamide, and the fourth onium salts include, for example, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutyl Ammonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, cetyltrimethylammonium bromide, tetrapropylammonium bromide, benzyltriethylammonium chloride, and others. It is also possible to use 18-crown-6-ether as a catalyst in combination with salts such as potassium chloride, potassium bromide, potassium iodide, cesium chloride, potassium phenoxide, sodium phenoxide and potassium benzoate.
[218] Among these, preferred catalysts include p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium t-butoxide, triethylamine, DBU, tetrabutylammonium bromide, tetrabutylphosphonium bromide, 18- Seeds.
[219] When the amino compound, the alkoxymethylated melamine compound, the alkoxymethylated glycoluril compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated urea compound and the halogenated silyl compound are used as the component (D), the amount of the catalyst (D) An amount of not more than 2 mol based on the equivalent is preferably used.
[220] When an epoxy compound, thioran compound, oxetane compound, isocyanate compound, cyanate compound, oxazoline compound, oxazine compound or other silyl compound is used as the component (D), 0.2 mol The following amounts are preferably used.
[221] The number of equivalents of the component (D) is a value obtained by multiplying the amount (mol) of the component (D) by the number of reactive groups contained in the component (D) As shown below.
[222] For amino compounds; Number of nitrogen atoms
[223] For epoxy compounds; Number of epoxy groups
[224] For a thiocyanate compound; Number of ethylene sulfide groups
[225] For oxetane compounds; Number of oxetanyl groups
[226] In the case of an alkoxymethylated melamine compound, an alkoxymethylated glycoluril compound, an alkoxymethylated benzoguanamine compound and an alkoxymethylated urea compound; The number of alkoxymethyl groups
[227] For isocyanate compounds; Number of isocyanate groups
[228] For cyanate compounds; Number of cyanate groups
[229] In the case of oxazoline compounds: the number of oxazolyl groups
[230] In the case of an oxazine compound; The number of oxadiyl groups
[231] Halogenated silyl compounds; The number of halogen atoms bonded to silicon atoms
[232] Other silyl compounds; Number of silicon atoms
[233] ≪ Other components >
[234] The refractive index-changing composition used in the present invention may contain other additives insofar as the object of the present invention is not impaired. Examples of such additives include ultraviolet absorbers, sensitizers, surfactants, heat resistance improvers, and adhesion improvers.
[235] Examples of the ultraviolet absorber include ultraviolet absorbers such as benzotriazoles, salicylates, benzophenones, substituted acrylonitriles, xanthines, coumarins, flavones, and carrageenan compounds. Specific examples thereof include Tinuvin 234 (2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, manufactured by Ciba Specialty Chemicals, Tinuvin 571 (3-t-butyl-5- (2H-benzotriazole-2-yl) -4- hydroxyphenyl) propionate-polyethylene glycol ), 1,7-bis (4-hydroxy-3-methoxyphenyl) -1,6-heptadiene-3,5-dione, dibenzylideneacetone and the like.
[236] By adding the ultraviolet absorber, the amount of acid or base generated from the component (C) can be gradually reduced as the depth of the surface of the irradiated portion in the refractive index-changing composition of the present invention becomes deeper, which is useful as a GRIN forming means. The use ratio of such an ultraviolet absorber is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the total of the components (A) and (B).
[237] Examples of the sensitizer include coumarins having substituents at positions 31 and / or 71, flavones, dibenzalacetones, dibenzalcyclohexanes, kerites, xanthines, thioxanthines, Phthalocyanines, acridines, anthracenes, and the like can be used.
[238] The use ratio of the sensitizer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the total of the components (A) and (B).
[239] Further, the surfactant can be added to improve coating properties, for example, to prevent striping or to improve developability.
[240] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene olefin ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and the like Nonionic surfactants such as polyethylene glycol dialkyl esters such as polyoxyethylene aryl ethers, polyethylene glycol dilaurate and polyethylene glycol distearate; Megafac F171, DongF172 and DongF173 (all manufactured by Dainippon Ink and Chemicals, Inc.), Fluoride FC430 and DongF431 (all manufactured by Shin-Etsu Chemical Co., Ltd.), EF301 and EF352 SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (all available from Asahi Kagaku Co., Ltd., Fluorochemical surfactants commercially available under the trade names of Nippon Kayaku Co., Ltd .; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymer Polyflow No. 57, and 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like can be used.
[241] The use ratio of such a surfactant is preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the component (A) and the component (B).
[242] The adhesion aid may be added in order to improve adhesion with the substrate, and a silane coupling agent or the like is preferably used.
[243] As the heat resistance improving agent, an unsaturated compound such as a polyhydric acrylate may be added.
[244] In the refractive index changing material used in the present invention, an antistatic agent, a storage stabilizer, a halation inhibitor, a defoaming agent, a pigment, a thermal acid generator and the like may be added as necessary.
[245] <Formation of Refractive Index Pattern>
[246] In the present invention, by using the above-described refractive index-changing composition, a refractive index pattern can be formed, for example, as follows.
[247] First, the composition is prepared by dissolving or dispersing the refractive-index-varying composition in a solvent such that the concentration of the solid component is 5 to 70% by weight. And may be used after filtration with a filter having a pore size of about 0.1 to 10 mu m, if necessary.
[248] Thereafter, this composition is coated on the surface of a substrate such as a silicon wafer and subjected to pre-baking to remove the solvent to form a coating film of the refractive index-changeable composition. Subsequently, the formed coating film is irradiated with a part of the irradiated radiation through, for example, a pattern mask, and then heating is carried out, whereby a difference in refractive index between the irradiated portion and the non-irradiated portion of the refractive index changeable composition is formed.
[249] An acid or a base is produced from the radiation-sensitive decomposing agent of the component (C) by irradiation with radiation, and the acid or base acts on the component (A) to decompose the component (A). This decomposition mainly volatilizes during heating after irradiation. As a result, a difference in refractive index occurs between the irradiated portion and the irradiated portion.
[250] Further, the component (A) and the component (D), which remain without reacting with an acid or a base upon heating, react with each other to stabilize the formed refractive index pattern.
[251] As the solvent for preparing the solution containing the refractive-index-changing composition for use in the present invention, the components of (A), (B), (C), (D) and other additives optionally added are uniformly dissolved Those that do not react with each component are used.
[252] Specific examples thereof include alcohols such as methanol, ethanol, propanol, iso-propanol, butanol, ethylene glycol and propylene glycol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether: propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol Propylene glycol monoalkyl ethers such as butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanal; And
[253] Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxy propylacetate, butyl propoxyacetate, methyl butoxyacetate, Methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 3-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-methoxypropionate, Ethoxypropionate, methyl 3-propoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Esters such as ethyl butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate;
[254] (Trifluoromethyl) benzene, hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane, octafluorodecalin, 1 &lt; RTI ID = 0.0 &gt; , 1,2-trichloro-1,2,2-trifluoroethane, and the like.
[255] Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, ketones, esters and diethylene glycols are preferable in terms of solubility, reactivity with each component, and ease of forming a coating film Lt; / RTI &gt;
[256] A high boiling solvent may be used together with the above solvent. Examples of the high boiling point solvents that can be used in combination include N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, dimethyl sulfoxide, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caproic acid, , Diethyl maleate, -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.
[257] The refractive-index-changing composition used in the present invention is molded into various shapes in consideration of its use in irradiation with radiation. For example, a rod type, a fiber type, a long plate type, a spherical type, a film type, a lens type, and the like. A commonly used method can also be used for the molding method. For example, injection molding, compression molding, blow molding, extrusion, box-frame polymerization, stretching, stretching, heat cooling, CVD, sintering and scanning can be used. The spin coating method, slit method, bar coating method, solvent casting method, LB method, spray method, roll coating method, convex printing method, screen printing method and the like can also be used depending on the use of the optical formed article.
[258] In this molding process, it is preferable to carry out heat treatment (hereinafter referred to as " pre-baking "). The heating conditions vary depending on the composition of the material of the present invention, the kind of each additive, and the like, but it is preferably 30 to 200 DEG C, more preferably 40 to 150 DEG C, and is heated using a hot plate, an oven, .
[259] As the radiation used for the irradiation treatment, ultraviolet rays such as a wide-wavelength light source such as i-line at 365 nm wavelength, h-line at 404 nm, g-line at 436 nm or xenon lamp, a KrF excimer laser with a wavelength of 248 nm, Ultraviolet rays such as ArF excimer lasers, charged particle beams such as X rays or electron rays such as synchrotron radiation, visible rays, and such mixed rays. Among these, ultraviolet light and visible light are preferable. Although the roughness varies depending on the irradiation wavelength and the like, it is preferable that the irradiation intensity is 0.1 mW / cm ² to 100 mW / cm ² with the best reaction efficiency. Such radiation can be patterned by irradiating the radiation through the pattern mask to the radiation-sensitive refractive index change material. The patterning accuracy is affected by the light source used, but it is possible to manufacture an optical component having a refractive index change distribution having a resolution of about 0.2 탆.
[260] In the present invention, it is preferable to perform a heat treatment (exposure baking (PEB) after irradiation) after exposure. For the heating thereof, the same apparatus as the above-described prebaking can be used, and the conditions can be arbitrarily set. The heating temperature is preferably 30 to 150 占 폚, more preferably 30 to 130 占 폚. It is also preferable to carry out a heat treatment for stabilization in which the component (A) and the component (D), which are continuously or separately remained after the irradiation with the radiation, are reacted. The heat treatment for stabilization is preferably 35 to 200 DEG C, more preferably 10 DEG C or more higher than the PEB temperature, and most preferably 20 DEG C or more higher than the PEB temperature.
[261] Further, the component (C) remaining in the non-irradiated portion may be decomposed to perform re-exposure treatment to further enhance the stability of the material.
[262] The re-exposure treatment can be carried out, for example, by irradiating the entire surface of the pattern with the same exposure amount of radiation having the same wavelength as the radiation used in the process of changing the refractive index.
[263] The stability of the material can be further improved by further performing heat treatment as desired. At this time, at the time of heating, the same apparatus as that for prebaking at the time of material molding can be used, and the conditions can be arbitrarily set.
[264] According to the present invention, the refractive index pattern forming method of the present invention comprises irradiating a refractive index-varying composition containing the component (A), the component (B) and the component (C) with radiation through a pattern mask and then (D) And the like.
[265] The treatment with the stabilizer (D) is preferably carried out after baking after exposure.
[266] (D) The stabilizer has a function of stabilizing the decomposable compound (A) remaining in the refractive index change material after irradiation with radiation to impart stability to an acid or a base. With this stabilization process, the refractive index pattern formed by the method of the present invention does not change and does not deteriorate even when used under the condition that light near the wavelength used for changing the refractive index passes through.
[267] As the stabilizer (D), in addition to the above specific examples, a low boiling point compound such as ammonia or triethylamine may also be used.
[268] In the stabilization treatment, a suitable method may be employed for contacting the refractive index-changing composition after irradiation with radiation and the stabilizer (D). For example, the component (D) and the catalyst i may be dissolved in a suitable solvent Or the component (D) can be brought into contact with the refractive index-modifiable composition in the state of 100% of the component (D) when the component (D) is a liquid or a gas under the contact conditions.
[269] When the solvent is used in the reaction between the stabilizer (D) and the component (A), it is preferred that the solvent (D) and the optionally added catalyst are dissolved, and the component (A) is not dissolved. If these solvents are selected, roughness does not occur on the resulting refractive index pattern surface.
[270] These solvents include, for example, water; Alcohols such as methanol, ethanol, iso-propanol, n-propanol, n-butanol, isobutanol, tert-butanol, cyclohexanol, ethylene glycol, propylene glycol and diethylene glycol; Ethers such as diethyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether and propylene glycol ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; Ketones such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl amyl ketone, and 4-hydroxy-4-methyl-2-pentanone; Hydroxypropionate, ethyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy-2-hydroxypropionate, Methoxypropionate, butyl 2-ethoxypropionate, butyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-hydroxypropionate, Esters such as butyl propoxypropionate, butyl 3-methoxypropionate, butyl 3-ethoxypropionate, butyl 3-propoxypropionate, and butyl 3-butoxypropionate; (Trifluoromethyl) benzene, hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane, octafluorodecalin, 1 &lt; RTI ID = 0.0 &gt; , 1,2-trichloro-1,2,2-trifluoroethane, and the like.
[271] Among these solvents, water, alcohols, glycol ethers, ethylene glycol alkyl ether acetates and fluorine atom-containing solvents are preferably used.
[272] The reaction temperature at the time of the reaction between the stabilizer (D) and the remaining part of the decomposable compound (A) can be generally from 0 to 130 캜, and the reaction time is usually from 10 seconds to 1 hour.
[273] Further, the component (C) remaining in the non-irradiated portion may be decomposed to perform re-exposure treatment to further enhance the stability of the material.
[274] It is to be understood that the matters not described in the refractive index pattern forming method including the stabilization treatment are applied to the above-described refractive index pattern forming method as well as the modifications obvious to those skilled in the art.
[275] According to the present invention, in the refractive index pattern forming method of the present invention, the refractive index-changing composition comprising the component (A), the component (B) and the component (C) is irradiated with a radiation through a pattern, Can be carried out by decomposing the decomposable compound (A).
[276] The heating is preferably carried out at a temperature of 10 ° C or more higher than the baking temperature after the irradiation with the radiation. For example, a temperature of 170 DEG C or higher is preferable, and a temperature of 200 DEG C or higher is more preferable.
[277] The decomposable compound (A) remaining in the unexposed portion of the heating furnace by heating is removed by decomposition or sublimation, and is preferably substantially free of pores.
[278] It should be understood that the matters not described in the above-mentioned method of forming a refractive index pattern in the case of not including the component (D) apply to the related matters of the above-mentioned pattern formation method as it is or under changes apparent to those skilled in the art.
[279] As described above, the refractive index pattern of the present invention formed by various methods is preferably such that the refractive index of the irradiated portion (first region) is smaller than the refractive index of the non-irradiated portion (second region). This difference can be arbitrarily adjusted by adjusting the kinds and contents of the component (A) and the component (B) in the refractive index-changing composition used in the present invention. For example, the maximum value of the refractive index difference can be set to a value larger than 0.02.
[280] The refractive index pattern of the present invention has or does not have voids in the irradiation portion.
[281] When the irradiated portion has a void, the porosity thereof is preferably 10 to 99.9%, more preferably 15 to 99.9%, and particularly preferably 20 to 99.9%.
[282] The modulus of elasticity of the irradiated portion and the unirradiated portion is preferably 0.3 GPA or more and 1 GPA or more, more preferably 0.5 GPa or more and 3 GPa or more, respectively.
[283] The modulus of elasticity of the irradiated portion is preferably smaller than that of the irradiated portion.
[284] Further, the refractive index pattern of the present invention can be used under the condition that light near a wavelength used for changing the refractive index is changed as described above, and there is no change in refractive index and does not cause deterioration, so that it is used in optical electronics and display fields Is very useful as an optical material.
[285] The refractive index pattern of the present invention is very useful as an optical material used in optical electronics and display fields because it has a sufficiently large refractive index difference and a refractive index difference formed thereon is stable to light and heat. The refractive index pattern of the present invention can be used for optical fibers such as other photo arrays, various lenses, photocouplers, photo interrupters, polarized beam splitters, holograms, single mode / multimode optical fibers, bundle fibers, various light guides, single core / multi core / Optical discs such as optical discs, connectors, optical isolators, polarizers, photo diodes / phototransistors / photo ICs / CCD image sensors / CMOS image sensors / optical fiber sensors, optical fiber compasses, CD / LD / PD / DVD, Waveguides, optical touch panels, diffraction gratings, light guide plates, optical diffusion plates, antireflection plates, and optical encapsulants.
[286] <Manufacturing Method of Optical Parts>
[287] The photosensitive refractive index-changing composition is molded into various shapes in consideration of its application in light irradiation.
[288] For example, a rod type, a fiber type, a long plate type, a spherical type, a film type, a lens type, and the like. The molding method may also be a commonly used method. For example, injection molding, compression molding, blow molding, extrusion, box-frame polymerization, stretching, stretching, heat cooling, CVD, sintering, . The spin coating method, slit method, bar coating method, solvent casting method, LB method, spray method, roll coating method, convex printing method, screen printing method and the like can also be used depending on the use of the optical formed article.
[289] As the light used for the light irradiation treatment, ultraviolet rays such as a wide-wavelength light source such as an i-line with a wavelength of 365 nm, an h-line with a wavelength of 404 nm, a g-line with a wavelength of 436 nm or a xenon lamp, a KrF excimer laser with a wavelength of 248 nm, Ultraviolet rays such as ArF excimer lasers, charged particle beams such as X rays or electron rays such as synchrotron radiation, visible rays, and such mixed rays. Of these, ultraviolet light and visible light are preferable. The roughness depends on the irradiation wavelength and the like, but it is preferable to set the irradiation intensity to 0.1 mW / cm ² to 100 mW / cm ² with the best reaction efficiency. It is possible to pattern the radiation-sensitive refractive index-varying composition by irradiating such radiation through a pattern mask. The patterning accuracy is affected by a light source or the like used, but it is possible to manufacture an optical component having a refractive index change distribution having a resolution of about 0.2 탆.
[290] In the present invention, it is preferable to perform heat treatment after exposure (hereinafter referred to as " post-exposure baking "). The heating conditions vary depending on the mixing composition of the material of the present invention, the kind of each additive, and the like, but preferably 30 to 200 ° C, more preferably 40 to 150 ° C .; heating using a hot plate, can do.
[291] The difference between the maximum refractive index and the minimum refractive index in the refractive index profile of the optical component of the present invention can be set arbitrarily according to the use as described above. For example, the difference may be 0.02 or more, Or more and 0.08 or more.
[292] As a specific example, a method of forming an optical fiber, a lens, an optical waveguide, a diffraction grating, a hologram element, and a recording medium will be described in detail below.
[293] &Lt; Method of forming optical fiber &
[294] The optical fiber can be formed by an appropriate method, but it can be done, for example, by the following method.
[295] The photosensitive refractive index-changing composition for forming an optical fiber can be used in a state in which it is dissolved in a suitable solvent. As the solvent used herein, a solvent having a boiling point of 50 ° C to 200 ° C may be used, and the solid content concentration in the solution may be 50 to 80%. This solution is defoamed using a fiber stock solution, and then a fiber shape is formed by heat elongation, laser irradiation elongation, extrusion or the like. In this case, the pore diameter may be 0.1 to 1.0 mm, and the drawing speed may be 0.1 to 1, OOO m / min.
[296] Next, the optical fiber of the present invention can be formed by irradiating the fiber formed as described above uniformly in the form of a ring in the form of an optical fiber, a reflector or the like, uniformly around the fiber toward the center, and then baking after exposure. The baking temperature after baking at this time may be set to 50 to 200 占 폚, and the baking time may be set to about 1 to 30 minutes. As the heating heat source, an appropriate heat source such as an infrared lamp may be used.
[297] At this time, it is possible to form a GI type optical fiber having a refractive index decreasing in a parabolic shape from the central axis to the periphery by adjusting the irradiation amount of light and selecting the wavelength and using the ultraviolet absorbing agent.
[298] As described above, the fiber drawing device, the irradiation device, and the heating device can be continuous processes. Thus, it is possible to continuously produce a GI type optical fiber or the like.
[299] &Lt; Method of Forming Lens >
[300] The lens of the present invention can be formed by an appropriate method, but it can be done, for example, by the following method.
[301] (1) A method of forming a GRIN lens having a concave lens capability
[302] The photosensitive refractive index-changing composition used for forming the lens can be used in a state in which it is dissolved in a suitable solvent. The solvent used herein may be a solvent having a boiling point of from 50 to 200 DEG C. The solid content concentration in the solution may be from 50 to 80%. The solution is formed into a disk shape of a desired shape by hot pressing or the like.
[303] Then, the GRIN lens having the concave lens ability can be formed by irradiating light such that the central portion of the original plate has a large exposure amount and the exposure amount decreases toward the circumferential portion, and then post-exposure baking is performed. For example, the irradiation apparatus shown in Fig. 1 may be used. The irradiating apparatus of Fig. 1 is equipped with a fastening 2 freely openable and closable in front of the disk-shaped specimen 1, irradiating only the parallel light of the light source while slowly opening the fastening 2 in a closed state, By adjusting the shutter speed so that the tightening 2 is opened, the above-described exposure state is realized.
[304] As the heating conditions for baking after exposure, it is possible to employ about 50 seconds to 200 占 폚 for about 1 second to 30 minutes.
[305] (2) Method of forming GRIN lens having convex lens ability
[306] A GRIN lens having a convex lens capability can be obtained by irradiating light to the disk-shaped specimen same as the above (1) so that the exposure amount of the circular portion of the disk becomes large and the exposure amount becomes smaller toward the center portion, and then baking after exposure.
[307] Such an exposure state can be realized, for example, when light is uniformly incident on only the side surface in a state in which the upper and lower portions of the cylinder are shielded from light. An optical fiber or a reflector can be used for uniform light irradiation on the side surface.
[308] The baking after the exposure can employ the same conditions as in the above (1).
[309] &Lt; Method of forming optical waveguide &
[310] The optical waveguide of the present invention can be formed by an appropriate method, but the following method can be used, for example.
[311] The photosensitive refractive index-changing composition for forming the optical waveguide can be used in a state in which it is dissolved in a suitable solvent (liquid A). As the solvent to be used at this time, a solvent having a boiling point of 50 ° C to 200 ° C may be used, and the solid content concentration in the solution may be 20 to 60%.
[312] Separately from this solution, a composition solution to which a thermal acid generator and / or photoacid generator is added to component (B) is adjusted (liquid B). The solid concentration in the solution may be 20 to 60%, and the solvent may have a boiling point of about 50 to 200 캜.
[313] First, a liquid B is coated on a suitable substrate such as silicon or glass, and the solvent is removed to form a coating film having a thickness of about 1 to 50 mu m. This coating film becomes a lower clad layer. As a coating method at this time, an appropriate method such as spin coating or slit coater can be used, and as the solvent removing condition, heating can be performed at 50 to 150 DEG C for about 1 minute to 30 minutes.
[314] Next, the solution A is applied onto the lower clad layer formed above, and the solvent is removed to form an intermediate layer having a thickness of about 1 to 50 mu m. The coating method and solvent removal conditions can be the same as described above.
[315] Subsequently, light is irradiated using a photomask in which the pattern of the waveguide is shielded from the core portion, and post-exposure baking is performed. At this time, the unexposed portion becomes the core portion and the exposed portion becomes the side cladding layer. The baking condition after exposure may be about 50 to 200 占 폚 for about 1 second to 30 minutes.
[316] Subsequently, the optical waveguide can be formed by applying the liquid B again, removing the solvent, and forming the upper clad layer having a thickness of about 1 to 50 탆. Since the optical waveguide obtained in this case contains the thermal acid generator at the upper and lower portions, diffusion of the acid occurs slightly at the interface between the core layer and the upper and lower clad layers. Accordingly, the interface between the core layer and the cladding layer can have a structure in which the refractive index gradually changes even in the upper, side, and lower portions, and the obtained optical waveguide becomes a GI type.
[317] &Lt; Method of Forming Recording Medium &
[318] The recording medium of the present invention can be formed by a suitable method, but it can be done, for example, by the following method.
[319] The photosensitive refractive index-changing composition for forming a recording medium may be used in a state in which it is dissolved in a suitable solvent. As the solvent to be used, a solvent having a boiling point of 50 ° C to 200 ° C may be used, and a solid content concentration in the solution may be 5 to 50% .
[320] This solution is coated on a substrate such as a flat plastic substrate, on which a suitable metal such as aluminum is deposited to a thickness of about 60 nm, and the solvent is removed to form a coating film having a thickness of about 0.1 to 10 mu m. As a coating method at this time, an appropriate method such as spin coating or slit coater can be used, and for solvent removal, heating can be performed at 50 to 150 DEG C for about 1 to 30 minutes.
[321] Thereafter, the optical recording medium can be formed by irradiating light through a photomask having a pitch width of about 0.2 탆 to about 0.5 탆 at a track pitch of 1.6 탆, and then performing post-exposure baking. The post-exposure baking conditions at this time may be, for example, 50 to 200 占 폚 for 1 second to 30 minutes.
[322] &Lt; Method of forming diffraction grating >
[323] The diffraction grating of the present invention can be formed by an appropriate method, but it can be done, for example, by the following method.
[324] The photosensitive refractive index-changing composition for forming the diffraction grating can be used in a state in which it is dissolved in a suitable solvent. As the solvent to be used at this time, a solvent having a boiling point of 50 ° C to 200 ° C may be used, and the solid content concentration in the solution may be 20 to 60%.
[325] This solution was coated on a suitable substrate surface such as glass and the solvent was removed to form a thin film having a thickness of about 1 to 50 mu m. As a coating method, an appropriate method such as spin coating or slit coater can be employed, and as the solvent removing method, heating can be carried out at 50 ° C to 150 ° C for about 1 minute to 30 minutes.
[326] The diffraction grating can be formed by irradiating the coating film with light in a slit shape and then baking after exposure. As a method of irradiating the slit-shaped light, for example, a method as shown in Fig. 2 can be used. Fig. 2 shows a method in which parallel irradiation light is reflected by a reflector arranged diagonally and irradiated onto a film-like coating film. An interference pattern formed from direct light and reflected light is irradiated onto the coating film. At the same time as the irradiation, the sample is moved at a speed of about 0.1 to 100 mu m / min in the direction of the arrow in the figure, so that a diffraction grating having an arbitrary period at 0.3 mu m or more can be formed. This method can provide a dense refractive index distribution.
[327] A method of irradiating a coating film formed as described above with a plurality of radiation beams in different directions to interfere with each other or a method of irradiating light through a slit can be used as an alternative method of irradiating slit type light. In any of the methods, a diffraction grating having a desired period can be formed by changing the irradiation angle of the light or the angle of the mirror.
[328] The post-exposure baking condition may be, for example, heating at 50 to 200 캜 for 1 second to 30 minutes.
[329] &Lt; Hologram element forming method >
[330] The hologram element of the present invention can be formed by an appropriate method, but the following method can be used, for example.
[331] The photosensitive refractive index-changing composition for forming the hologram element can be used in a state in which it is dissolved in a suitable solvent. As the solvent used herein, a solvent having a boiling point of 50 ° C to 200 ° C may be used, and the solid content concentration in the solution may be 20 to 60%.
[332] This solution was applied onto the surface of a suitable substrate such as glass and the solvent was removed to form a thin film having a thickness of about 1 to 50 mu m. As a coating method, an appropriate method such as spin coating or slit coater can be employed, and as the solvent removal method, heating can be performed at 50 to 150 DEG C for about 1 minute to 30 minutes.
[333] By irradiating the coating film with an interference pattern and baking after exposure, the recording medium (hologram) can be made into a holographic technique. That is, the image of the object can be recorded on the coating film by interfering with the signal light transmitted through the object to be recorded and the reference light directly obtained from the same light source to irradiate the coating film and change the refractive index.
[334] The post-exposure baking condition may be, for example, heating at 50 to 200 캜 for about 1 to 30 minutes.
[11] DISCLOSURE OF THE INVENTION <
[12] The present invention has been made in view of the above-described circumstances in the prior art. That is, an object of the present invention is to provide an optical material which can change the refractive index of a material in a simple and comfortable manner and at the same time has a sufficiently large difference in refractive index, and can provide a stable refractive index pattern or optical material A radiation-sensitive, a refractive index, and a variable composition.
[13] Another object of the present invention is to provide a method of forming a fine hole pattern by forming fine holes by irradiating with radiation to stably maintain fine holes formed in such a manner and having a plurality of fine holes, Sensitive refractive index-changeable composition which provides a radiation-sensitive refractive index-changeable composition.
[14] It is another object of the present invention to provide a method of forming a refractive index pattern from the composition of the present invention.
[15] It is still another object of the present invention to provide a refractive index pattern or optical material produced by the method of the present invention.
[16] Other objects and advantages of the present invention will become apparent from the following description.
[17] MEANS FOR SOLVING THE PROBLEMS [
[18] According to the present invention, the above objects and advantages of the present invention are attained by firstly providing (A) a decomposable compound, (B) a non-decomposable compound having a refractive index lower than that of the decomposable compound (A), (C) Sensitive refractive index-changeable composition according to the present invention.
[19] The above objects and advantages of the present invention can be attained by the use of a radiation sensitive composition comprising (A) a decomposable compound, (B) a non-decomposable compound having a lower refractive index than the decomposable compound (A), (C) (A) is reacted with the stabilizing agent (D) of the unexposed portion by irradiating the composition with the refractive index-changeable composition and then heating it.
[20] The above objects and advantages of the present invention are achieved by a method for producing a refractive index-changing composition comprising (A) a decomposable compound, (B) a non-decomposable compound having a refractive index lower than that of the decomposable compound (A), and (C) (D) a stabilizing agent, and (D) the decomposing compound in the unexposed portion is reacted with the stabilizing agent.
[21] The above objects and advantages of the present invention are achieved by fourthly providing a pattern mask for a refractive index-changing composition containing (A) a decomposable compound, (B) a non-decomposable compound having a refractive index lower than that of the decomposable compound (A), and (C) Irradiating the resist with a radiation, and then heat-treating the resultant to decompose the decomposable polymer of the unexposed portion.
[22] The above objects and advantages of the present invention are achieved by a refractive index pattern formed by the method of forming a refractive index pattern.
[23] The above object and advantages of the present invention are achieved by an optical material formed by the above-described method of forming a refractive index pattern.
[335] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
[336] Hereinafter, the polystyrene reduced weight average molecular weight of the polymer was measured using GPC Chromatograph SYSTEM-21 manufactured by Showa Denko K.K.
[337] Synthesis Example of Component (A)
[338] &Lt; Synthesis Example 1 &
[339] 50 parts by weight of o-phthalaldehyde as a monomer and 500 parts by weight of tetrahydrofuran were placed in a 1 L flask, and the mixture was cooled to -78 占 폚. Thereto was added 1.0 part by weight of n-butyllithium (1.5 mol / l) n-hexane solution, and the mixture was stirred under nitrogen atmosphere at -78 캜 for 48 hours under cooling.
[340] To the obtained reaction solution, 0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added in a cooled state, followed by stirring at -78 캜 for 2 hours. The reaction solution was heated to 60 DEG C under reduced pressure, concentrated to 100 mL, and then put into 5 L of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, reprecipitated and refined with 5 L of ion-exchanged water, and vacuum dried at 50 占 폚 to obtain 45 parts by weight of the compound (A-1). The weight average molecular weight of the obtained compound was 26,000.
[341] &Lt; Synthesis Example 2 &
[342] 45 parts by weight of o-phthalaldehyde as a monomer, 5 parts by weight of benzaldehyde, and 500 parts by weight of tetrahydrofuran were placed in a 1 L flask, and the mixture was cooled to -78 占 폚. Thereto was added 1.0 part by weight of n-butyllithium (1.5 mol / l) n-hexane solution, and the mixture was stirred under nitrogen atmosphere at -78 캜 for 48 hours under cooling.
[343] To the obtained reaction solution, 0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added in a cooled state, followed by stirring at -78 캜 for 2 hours. The reaction solution was heated to 60 ° C under reduced pressure, the total amount was concentrated to 100 ml, and then continuously introduced into 5 L of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, reprecipitated with 5 L of ion-exchanged water and purified by vacuum drying at 50 DEG C to obtain 43 parts by weight of the compound (A-2). The weight average molecular weight of the obtained compound was 15,000.
[344] &Lt; Synthesis Example 3 &
[345] In a 1 L flask, 45 parts by weight of o-phthalaldehyde, 5 parts by weight of glutaraldehyde, and 500 parts by weight of tetrahydrofuran were placed in a reaction vessel purged with nitrogen and cooled to -78 占 폚. Thereto was added 1.0 part by weight of n-butyllithium (1.5 mol / l) n-hexane solution, and the mixture was stirred under nitrogen atmosphere at -78 캜 for 48 hours under cooling.
[346] To the obtained reaction solution, 0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added while cooling, followed by stirring at -78 占 폚 for 2 hours. The reaction solution was heated to 60 占 폚 under reduced pressure, the whole amount was concentrated to 100 ml, and then continuously introduced into 5 L of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, reprecipitated with 5 L of ion-exchanged water and purified by vacuum drying at 50 占 폚 to obtain 45 parts by weight of a compound (A-3). The weight average molecular weight of the obtained compound was 20,000.
[347] &Lt; Synthesis Example 4 &
[348] To a 1 L flask were added 25 parts by weight of 4-chloro-o-phthalaldehyde as a monomer and 500 parts by weight of methylene chloride into a nitrogen-purged reaction vessel and cooled to -78 ° C. 0.1 part by weight of a boron trifluoride ether complex was added thereto, and the mixture was stirred under cooling at -78 캜 for 48 hours under a nitrogen atmosphere.
[349] To the resultant reaction solution, 0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added while cooling, followed by stirring at -78 占 폚 for 2 hours. The reaction solution was heated to 60 占 폚 under reduced pressure, the whole amount was concentrated to 50 ml, and then continuously introduced into 3 L of ion-exchanged water for 5 minutes. The precipitate was redissolved in 30 parts by weight of tetrahydrofuran, reprecipitated and refined with 3 L of ion-exchanged water, and vacuum dried at 50 占 폚 to obtain 46 parts by weight of the compound (A-4). The weight average molecular weight of the obtained compound was 48,000.
[350] &Lt; Synthesis Example 5 &
[351] In a 1 L flask, 25 parts by weight of 4-bromo-o-phthalaldehyde as a monomer and 500 parts by weight of methylene chloride were placed in a nitrogen-purged reaction vessel and cooled to -78 deg. 0.1 part by weight of a boron trifluoride ether complex was added thereto, and the mixture was stirred under cooling at -78 캜 for 48 hours under a nitrogen atmosphere.
[352] To the obtained reaction solution, 0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added while cooling, and the mixture was stirred at -78 캜 for 2 hours. The reaction solution was heated to 60 占 폚 under reduced pressure, the whole amount was concentrated to 50 ml, and then continuously introduced into 3 L of ion-exchanged water for 5 minutes. The precipitate was redissolved in 30 parts by weight of tetrahydrofuran, reprecipitated and refined with 3 L of ion-exchanged water, and vacuum dried at 50 占 폚 to obtain 47 parts by weight of a compound (A-5). The weight average molecular weight of the obtained compound was 53,000.
[353] &Lt; Synthesis Example 6 &
[354] 50 parts of o-phthalaldehyde as a monomer and 500 parts of tetrahydrofuran were placed in a 1 L flask, and the mixture was cooled to -78 deg. Thereto was added 0.2 part of n-butyllithium (1.5 mol / l) n-hexane solution, and the mixture was stirred under cooling at -78 캜 for 48 hours under a nitrogen atmosphere.
[355] To the obtained reaction solution, 0.8 part by weight of acetic anhydride and 0.6 part by weight of pyridine were added while cooling, and then the mixture was stirred at -78 캜 for 2 hours. The reaction solution was heated to 60 占 폚 under reduced pressure, the whole amount was concentrated to 100 ml, and then continuously introduced into 5 L of ion-exchanged water for 10 minutes. The precipitate was redissolved in 50 parts by weight of tetrahydrofuran, reprecipitated with 5 L of ion-exchanged water and purified by vacuum drying at 50 占 폚 to obtain 45 g of a compound (A-6). The weight average molecular weight of the obtained compound was 110,000.
[356] &Lt; Synthesis Example 7 &
[357] In a 500 ml three-necked flask under argon atmosphere, 33.05 g of 1,4-benzenethiol and 66.06 g of 1,4-di (2-nitrovinyl) benzene were dissolved in 100 g of N-methylpyrrolidone. A solution of 1.55 g of N-methylmorpholine in 10 g of N-methylpyrrolidone was added thereto under ice-cooling for 1 hour with stirring. After completion of the addition, the reaction solution was allowed to stand at room temperature and polymerized for 24 hours. After completion of the polymerization, the solution was reprecipitated twice with tetrahydrofuran-methanol.
[358] The precipitated polymer was filtered off, and then vacuum dried at 50 DEG C to obtain 72.80 g of a compound (A-7). The weight average molecular weight of the obtained compound was 5,800.
[359] &Lt; Synthesis Example 8 &
[360] 49.84 g of terephthalic acid chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask under an argon atmosphere, to which 33.05 g of 1,4-benzenethiol and 16.83 g of potassium hydroxide were dissolved in 150 ml of ion- Followed by agitation and interfacial polycondensation. The reaction was allowed to proceed for 6 hours and then reprecipitated twice with tetrahydrofuran-methanol.
[361] The precipitated polymer was filtered off, and then dried at 50 캜 under vacuum to obtain 61.28 g of Compound (A-8). The weight average molecular weight of the obtained compound was 27,600.
[362] &Lt; Synthesis Example 9 &
[363] In a 500 ml three-necked flask under argon atmosphere, 33.05 g of 1,4-benzenethiol, 48.04 g of p-phenylenediisocyanate and 0.12 g of dibutyltin dichloride as a catalyst were dissolved in 200 g of dimethyl sulfoxide. After completion of the addition, the reaction solution was heated to 60 DEG C and polymerized for 24 hours. After completion of the polymerization, reprecipitation was performed twice with tetrahydrofuran-methanol. The precipitated polymer was filtered off, and then vacuum dried at 50 ° C to obtain 66.50 g of a compound (A-9). The weight average molecular weight of the obtained compound was 15,000.
[364] &Lt; Synthesis Example 10 &
[365] In a 1 L three-necked flask under argon atmosphere, 2.42 g of 4-nitro-1,3-phenylene dichloroformate was dissolved in 400 mL of chloroform, to which 33.05 g of 1,4-benzenethiol and 16.83 g of potassium hydroxide Dissolved in 200 ml of ion-exchanged water was added and stirred to perform interfacial polycondensation.
[366] The reaction was allowed to proceed for 6 hours and then reprecipitated twice with tetrahydrofuran-methanol.
[367] The precipitated polymer was filtered off, and then vacuum-dried at 50 DEG C to obtain 83.61 g of the compound (A-10). The weight average molecular weight of the obtained compound was 32,000.
[368] &Lt; Synthesis Example 11 &
[369] 49.84 g of terephthalic acid and 57.34 g of phenylmethyldichlorosilane were dissolved in 200 g of N-methylpyrrolidone in a 500 ml three-necked flask under an argon atmosphere. A solution of 23.73 g of pyridine in 50 g of N-methylpyrrolidone was added thereto under ice-cooling for 1 hour with stirring. After completion of the addition, the reaction solution was heated to 60 캜 and polymerized for 24 hours. After completion of the polymerization, the reaction solution was poured into 2 L of methanol, precipitated, dissolved again in 200 mL of N-methylpyrrolidone, added to 2 L of methanol, and reprecipitated and purified.
[370] The precipitated polymer was filtered off, and then vacuum-dried at 50 DEG C to obtain 70.80 g of a compound (A-11). The weight average molecular weight of the obtained compound was 26,000.
[371] &Lt; Synthesis Example 12 &
[372] In a 500 ml three-necked flask under argon atmosphere, 45.66 g of benzaldehyde dimethylacetal and 42.04 g of methoxyhydroquinone were dissolved in 100 g of diethylene glycol ethyl methyl ether. To this was added 0.06 g of p-toluenesulfonic acid dissolved in 10 g of diethylene glycol ethyl methyl ether, followed by polymerization at 100 占 폚 for 8 hours and then at 130 占 폚 for 1 hour while stirring. Methanol formed by the reaction at this time was polymerized while distilling off under reduced pressure.
[373] After completion of the polymerization, the reaction solution was poured into 2 L of methanol, precipitated, dissolved again in 100 mL of diethylene glycol ethyl methyl ether, and poured into 2 L of methanol to perform reprecipitation and purification. The precipitated polymer was filtered off, and then dried at 50 캜 under vacuum to obtain 47.93 g of a compound (A-12). The weight average molecular weight of the obtained compound was 5,800.
[374] &Lt; Synthesis Example 13 &
[375] 49.84 g of terephthalic acid and 57.34 g of phenylmethyldichlorosilane were dissolved in 200 g of N-methylpyrrolidone in a 500 ml three-necked flask under an argon atmosphere. A solution prepared by dissolving 47.46 g of pyridine in 50 g of N-methylpyrrolidone was added thereto under ice-cooling for 1 hour while stirring. After completion of the addition, the reaction solution was heated to 60 캜 and polymerized for 24 hours. After completion of the polymerization, the reaction solution was poured into 2 L of methanol, precipitated, dissolved again in 200 mL of N-methylpyrrolidone, put into 2 L of methanol, and reprecipitated and purified.
[376] The precipitated polymer was filtered off, and then vacuum-dried at 50 DEG C to obtain 80.01 g of a compound (A-13). The weight average molecular weight of the obtained compound was 31,200.
[377] &Lt; Synthesis Example 14 &
[378] Under an argon atmosphere, 61.51 g of terephthalic acid chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask, and 33.05 g of 1,4-benzenethiol and 33.66 g of potassium hydroxide were dissolved in 150 ml of ion- Followed by stirring and polycondensation at an interface. The reaction was allowed to proceed for 6 hours and then reprecipitated twice with tetrahydrofuran-methanol.
[379] The precipitated polymer was filtered off, and then vacuum dried at 50 DEG C to obtain 75.98 g of the compound (A-14). The weight average molecular weight of the obtained compound was 33,600.
[380] &Lt; Synthesis Example 15 &
[381] A 1 L flask was charged with 50 g of o-phthalaldehyde as a monomer and 500 g of tetrahydrofuran in a nitrogen-purged reaction vessel and cooled at -78 캜. To this was added 41.83 g of tert-butoxy potassium and the mixture was stirred under nitrogen atmosphere at -78 캜 for 48 hours under cooling.
[382] To the reaction solution obtained, 45.67 g of acetic anhydride and 35.38 g of pyridine were added in a cooled state, followed by stirring at -78 ° C for 2 hours. The reaction solution was heated to 60 DEG C under reduced pressure, concentrated to 100 mL, dissolved in 1 L of ethyl acetate, washed three times with ion-exchanged water, and the ethyl acetate was concentrated, followed by vacuum drying at 50 DEG C to obtain 45 g of compound (A-15). The obtained compound (A-15) had an initiator / monomer ratio of 1: 1 due to an integral ratio of protons derived from tert-butyl group of 1.2 to 1.3 ppm and proton of aromatic origin of 7.2 to 7.7 ppm by 1 H-NMR.
[383] &Lt; Synthesis Example 16 &
[384] 49.84 g of terephthalic acid chloride was dissolved in 150 ml of chloroform in a 500 ml three-necked flask under an argon atmosphere, to which 33.05 g of 1,4-benzenethiol and 16.83 g of potassium hydroxide were dissolved in 150 ml of ion- Followed by stirring and polycondensation at an interface. The reaction was allowed to proceed for 4 hours and then reprecipitated twice with tetrahydrofuran-methanol.
[385] The precipitated compound was filtered off, and then vacuum-dried at 50 ° C to obtain 56.55 g of a compound (A-16). The weight average molecular weight of the obtained compound was 7,600.
[386] (B)
[387] &Lt; Synthesis Example 1 &
[388] In a 1 L three-necked flask, 15.22 g of tetramethoxysilane and 27.24 g of methyltrimethoxysilane were dissolved in 100 g of ethylene glycol ethyl methyl ether, and the obtained mixed solution was heated to 60 DEG C with stirring by a magnetic stirrer. 5.20 g of ion-exchanged water was continuously added to the mixed solution for 1 hour. After reacting at 60 DEG C for 4 hours, the obtained reaction solution was cooled to room temperature. Thereafter, 9.20 g of methanol as a reaction by-product was distilled off under reduced pressure in the reaction solution. The solid content concentration of the obtained solution of the polymer (B-1) was 33.2%, and the weight average molecular weight of the polymer was 2,200.
[389] &Lt; Synthesis Example 2 &
[390] A stainless autoclave equipped with a 1.5 L internal stirrer was thoroughly purged with nitrogen gas, and then 500 g of ethyl acetate, 57.2 g of ethyl vinyl ether (EVE), 10.2 g of hydroxybutyl vinyl ether (HBVE) After 3 g of lauroyl peroxide was added and cooled to -50 ° C with dry ice methanol, oxygen in the system was again removed with nitrogen gas. Subsequently, 146 g of hexafluoropropylene (HFP) was added, and the temperature was elevated. The pressure at the time when the temperature in the autoclave reached 60 DEG C was 5.3 kgf / cm &lt; ^{2 &} gt ;. Thereafter, the reaction was continued under stirring at 60 DEG C for 20 hours. When the pressure dropped to 1.5 kgf / cm &lt; ² &gt;, the autoclave was water-cooled to stop the reaction. After reaching room temperature, the unreacted monomer was taken out and the autoclave was opened to obtain a polymer solution having a solid content concentration of 28.1%. The resulting polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum-dried at 50 DEG C to obtain 193 g of a fluorine-containing copolymer. The polymer (B-2) thus obtained had a weight average molecular weight of 17,000.
[391] &Lt; Synthesis Example 3 &
[392] In a 500 ml three-necked flask, 8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 g of diethylene glycol dimethyl ether were placed. Subsequently, 20 g of methacrylic acid, 30 g of glycidyl methacrylate, and 50 g of pentafluoroethyl methacrylate were charged and replaced with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 3 hours to obtain a solution of the polymer (B-3). The solid concentration of the obtained polymer solution was 31.0%, and the weight average molecular weight of the polymer was 12,000.
[393] &Lt; Synthesis Example 4 &
[394] In a 1 L three-necked flask, 50 g of methyltrimethoxysilane was added to 100 g of 1-ethoxy-2-propanol and dissolved. The obtained mixed solution was heated to 60 DEG C with stirring by a magnetic stirrer. 19.85 g of ion-exchanged water was continuously added thereto for 1 hour. After reacting at 60 DEG C for 4 hours, the obtained reaction solution was cooled to room temperature.
[395] Thereafter, methanol as a reaction by-product was removed from the reaction solution under reduced pressure, and the solution was concentrated to a solid concentration of 20 wt% to obtain a solution containing the compound (B-4). This compound (B-4) had a weight average molecular weight of 8,000.
[396] &Lt; Example 1 >
[397] 40 parts by weight of a compound (A-1) as a component (A) and 60 parts by weight of a co-condensate (molecular weight: 2,000) of a mixture of methyltrimethoxysilane and tetramethoxysilane (weight ratio 55: 5) And 1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as the component (C) were dissolved in diethylene glycol ethyl methyl Ether, and then filtered through a membrane filter having a pore size of 0.2 mu m to prepare a solution containing the photosensitive refractive index-changeable composition.
[398] &Lt; Formation of coating film &
[399] The solution was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 1.0 mu m.
[400] <Light irradiation treatment>
[401] The coating film thus obtained was subjected to light irradiation treatment with an exposure dose of 20 mJ / cm ² at an optimal focus depth by an NSR 1505i6A reduction projection exposure apparatus (NA = 0.45, λ = 365 nm, manufactured by Nikon Corporation) Thereby forming a difference in refractive index between the light portion and the unexposed portion. Then, post-exposure baking was performed on a hot plate at 120 ° C for 2 minutes.
[402] <Measurement of Refractive Index>
[403] The refractive index of the exposed and unexposed portions on the silicon substrate at room temperature was measured at 633 nm using an ellipsometer of Auto EL Ⅳ NIR Ⅲ (Rudolf Research). The results are shown in Table 1.
[404] <Evaluation of transparency>
[405] A glass substrate on which a photosensitive refractive index-changing composition was formed on the surface was obtained in the same manner as above except that a glass substrate "Corning 1737 (manufactured by Corning)" was used instead of the silicon substrate.
[406] Subsequently, the transmittance of the obtained glass substrate was measured using a spectrophotometer "150-20 double beam (manufactured by Hitachi, Ltd.)" at a wavelength of 400 to 800 nm. In this case, when the lowest transmittance exceeds 95%, the transmittance is good, and when the lowest transmittance is less than 95%, the transmittance is bad. The results are shown in Table 1.
[407] &Lt; Example 2 >
[408] The refractive index and the transparency were evaluated in the same manner as in Example 1 except that the amount of exposure was 300 mJ / cm ² in the light irradiation treatment. The results are shown in Table 1.
[409] &Lt; Example 3 >
[410] Except that 70 parts by weight of the compound (A-1) was used as the component (A) and 30 parts by weight of a condensate of methyltrimethoxysilane (molecular weight: 2,000) was used as the component (B) . The results are shown together in Table 1.
[411] <Example 4>
[412] Except that 15 parts by weight of the compound (A-1) was used as the component (A) and 85 parts by weight of a condensate of methyltrimethoxysilane (molecular weight: 2,000) was used as the component (B) . The results are shown together in Table 1.
[413] &Lt; Example 5 >
[414] Was evaluated in the same manner as in Example 1 except that 40 parts by weight of the compound (A-2) was used as the component (A). The results are shown together in Table 1.
[415] &Lt; Example 6 >
[416] The evaluation was conducted in the same manner as in Example 1 except that 40 parts by weight of the compound (A-3) was used as the component (A). The results are shown together in Table 1.
[417] &Lt; Example 7 >
[418] Was evaluated in the same manner as in Example 1 except that 40 parts by weight of the compound (A-4) was used as the component (A). The results are shown together in Table 1.
[419] &Lt; Example 8 >
[420] Was evaluated in the same manner as in Example 1 except that 40 parts by weight of the compound (A-5) was used as the component (A). The results are shown together in Table 1.
[421] &Lt; Example 9 >
[422] And 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate was used as the component (C). The results are shown together in Table 1.
[423] &Lt; Example 10 >
[424] And 1 part by weight of diphenyliodonium trifluoroacetate was used as the component (C). The results are shown together in Table 1.
[425] Exposure dose mJ / cm ² Refractive indexTransparency ExposureMineralsExposureMinerals Example 1201.421.5299.3%99.0% Example 23001.421.5299.3%99.0% Example 3201.421.5599.5%98.6% Example 4201.421.4799.2%99.1% Example 5201.421.5299.3%99.1% Example 6201.421.5199.3%99.2% Example 7201.421.5399.3%99.0% Example 8201.421.5699.3%98.6% Example 9201.421.5299.3%99.0% Example 10201.421.5299.3%99.0%
[426] &Lt; Example 11 >
[427] 50 parts by weight of the compound (A-7) as the component (A), 50 parts by weight of the polymer (B-1) as the component (B), 2-benzyl- (4-morpholinophenyl) -butan-1-one were dissolved in diethylene glycol ethyl methyl ether so as to have a total solids concentration of 20%, and then filtered with a membrane filter having a pore size of 0.2 m to obtain a composition solution Lt; / RTI &gt;
[428] <Formation of Coating Film> <Measurement of Refractive Index> and <Evaluation of Transparency> were performed in the same manner as in Example 1.
[429] <Irradiation Treatment and PEB Treatment>
[430] The coating film thus obtained was irradiated with NSR 1505i6A reduced projection radiation (manufactured by Nikon Corporation, NA = 0.45, = 365 nm) at an optimal focus depth. Subsequently, the PEB treatment was hammed for 2 minutes to form a difference in refractive index between the irradiated portion of the refractive index-changing composition and the unirradiated portion. The irradiation dose and the PEB treatment temperature are shown in Table 2.
[431] &Lt; Example 12 >
[432] Was evaluated in the same manner as in Example 11 except that 50 parts by weight of the compound (A-8) was used as the component (A). The results are shown together in Table 2.
[433] &Lt; Example 13 >
[434] Was evaluated in the same manner as in Example 11 except that 50 parts by weight of the compound (A-9) was used as the component (A). The results are shown together in Table 2.
[435] &Lt; Example 14 >
[436] Was evaluated in the same manner as in Example 11 except that 50 parts by weight of the compound (A-10) was used as the component (A). The results are shown together in Table 2.
[437] &Lt; Example 15 >
[438] And that 50 parts by weight of the compound (B-2) was used as the component (B). The results are shown together in Table 2.
[439] &Lt; Example 16 >
[440] Was evaluated in the same manner as in Example 11 except that 50 parts by weight of the compound (B-3) was used as the component (B). The results are shown together in Table 2.
[441] Radiation dose (mJ / cm ² )PEB treatment temperature (캜)Refractive indexTransparency Radiation irradiation partRadiation non-irradiation partRadiation irradiation partAircraft stern section Example 1801301.421.5599.3%99.0% Example 2801301.421.5898.9%98.6% Example 3801301.421.5799.1%98.9% Example 4801301.421.5699.2%99.0% Example 5801301.381.5299.3%99.1% Example 6801301.421.5599.3%99.1% Example 71301301.421.5599.3%99.0% Example 81501001.421.5599.3%99.0%
[442] &Lt; Example 17 >
[443] 50 parts by weight (solid content) of a polymer (B-1) containing 50 parts by weight of the compound (A-11) as the component (A) and the polymer (B- And 1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as component (C) were dissolved in diethylene glycol ethyl methyl ether so that the total solids concentration was 20% , And then filtered with a membrane filter having a pore size of 0.2 mu m to prepare a solution of the refractive index variable composition.
[444] &Lt; Formation of Coating Film >
[445] The above solution was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 1.0 mu m.
[446] &Lt; Formation of refractive index pattern >
[447] The coating film obtained as described above was irradiated with an irradiation dose of 50 mJ / cm ² at an optimal focusing depth by an NSR 1505i6A reduction projection irradiation apparatus (manufactured by Nikon Corporation, NA = 0.45, = 365 nm) . Subsequently, exposure was performed at 130 캜 for 2 minutes, and baking treatment was performed to form a refractive index pattern having a difference in refractive index between the irradiated portion and the non-irradiated portion. Hereinafter, with respect to the refractive index pattern formed here, the irradiation part is referred to as a " low refractive index part " and the non-irradiated part is referred to as a " high refractive index part &quot;.
[448] <3> Measurement of refractive index>
[449] The refractive indexes of the low refractive index portion and the high refractive index portion of the refractive index pattern formed above were measured at 633 nm using an ellipsometer of Auto EL Ⅳ NIR Ⅲ (manufactured by Rudolf Research). The results are shown in Table 3.
[450] <Evaluation of transparency>
[451] A refractive index pattern was formed on a glass substrate in the same manner as in (1) and (2) except that a glass substrate "Corning 1737 (manufactured by Corning)" was used instead of the silicon substrate. Hereinafter, the refractive index pattern on the glass substrate formed here is also referred to as the " low refractive index portion ", and the " high refractive index portion "
[452] Subsequently, transmittance of each of the low refractive index portion and the high refractive index portion of the glass substrate having this refractive index pattern was measured at a wavelength of 400 to 800 nm using a spectrophotometer " 150-20 double beam (manufactured by Hitachi, Ltd.) ". At this time, when the lowest transmittance exceeds 95%, the transmittance is good, and when the lowest transmittance is less than 95%, the transmittance is bad. The results are shown in Table 3.
[453] <5) Stabilization processing>
[454] (Containing 0.1 mmol of tetrabutylammonium bromide as a reaction catalyst) of phenylglycidyl ether as a component (D) was heated to 100 占 폚, and the refractive index on the silicon substrate and the glass substrate The pattern was soaked at 100 DEG C for 2 minutes and then washed with very pure water for 1 minute.
[455] Subsequently, the entire surface of the pattern was re-exposed for 1 minute at 4.5 mW / cm ² without using a filter with a Canon PLA-501F, and then heated in an oven at 200 ° C for 10 minutes to stabilize the refractive index pattern.
[456] &Lt; Evaluation of refractive index and transparency >
[457] The refractive indices of the low refractive index portion and the high refractive index portion of the refractive index pattern on the silicon substrate subjected to the stabilization treatment were measured in the same manner as in (3) above. The results are shown in Table 4.
[458] The transparency of the low refractive index portion and the high refractive index portion of the refractive index pattern on the glass substrate subjected to the stabilization treatment was measured in the same manner as in the above (4). The results are shown in Table 4.
[459] <⑦ Evaluation of stability of refractive index pattern>
[460] The refractive index pattern on the silicon substrate and the refractive index pattern on the glass substrate subjected to the stabilization treatment were subjected to exposure treatment for 4.5 hours at 4.5 mW / cm ² for 30 minutes without using a filter in the Canon PLA-501F, Was carried out.
[461] The refractive indices of the low refractive index portion and the high refractive index portion were measured for the refractive index pattern on the silicon substrate subjected to this treatment in the same manner as in (3) above. The results are shown in Table 4.
[462] With respect to the refractive index pattern on the glass substrate subjected to the stabilization treatment, the transparency of the low refractive index portion and the high refractive index portion was measured in the same manner as in the above (4). The results are shown in Table 4.
[463] &Lt; Example 18 >
[464] 50 parts by weight of the compound (A-12) was used as the component (A), and the baking temperature after the exposure in the step 2 (formation of the refractive index pattern) was as shown in Table 3, The evaluation was conducted in the same manner as in Example 17, except that the kind of the component (D) and the stabilization treatment temperature were changed as shown in Table 4. The results are shown in Tables 3 and 4 together.
[465] &Lt; Example 19 >
[466] 50 parts by weight of the compound (A-1) was used as the component (A), the amount of irradiation in the step 2 (formation of the refractive index pattern) was as shown in Table 3, ) The evaluation was made in the same manner as in Example 17 except that the kind of the component and the stabilization treatment temperature were changed as shown in Table 4. The results are shown in Tables 3 and 4 together.
[467] &Lt; Example 20 >
[468] 50 parts by weight of the compound (A-8) as the component (A) and 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine as the component (C) Was evaluated in the same manner as in Example 17, except that the irradiation dose was set as shown in Table 3 and the kind of the component (D) in the step (5) (stabilization treatment) was changed as shown in Table 4. [ The results are shown in Tables 3 and 4 together.
[469] &Lt; Example 21 >
[470] Was evaluated in the same manner as in Example 17 except that a solution (corresponding to 50 parts by weight (solid content) of the polymer (B-2)) containing the polymer (B-2) The results are shown in Tables 3 and 4 together.
[471] &Lt; Example 22 >
[472] Except that 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate was used as the component (C), and the irradiation dose in the step (2) (formation of the refractive index pattern) was changed as shown in Table 3 And evaluated in the same manner as in Example 17. The results are shown in Tables 3 and 4 together.
[473] &Lt; Example 23 >
[474] Evaluation was made in the same manner as in Example 20, except that the irradiation dose in the step 2 (formation of the refractive index pattern) was changed as shown in Table 3. [ The results are shown in Tables 3 and 4 together.
[475] Refractive index pattern formation conditionsOptical properties before stabilization treatment Radiation dose (mJ / cm ² )Baking temperature after exposure (° C)Refractive indexTransparency The low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratio Example 1501301.421.5399.3%99.0% Example 2501201.421.5599.3%98.6% Example 3201301.421.5299.3%99.0% Example 4801301.421.5898.9%98.6% Example 5501301.421.5299.3%99.1% Example 6401301.421.5399.3%99.0% Example 7901301.421.5898.9%98.6%
[476] Stabilization treatment conditionsOptical properties after stabilization treatmentOptical properties after accelerated irradiation treatment Refractive indexTransparencyRefractive indexTransparency (D) Component typeTreatment temperatureThe low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratio Example 1D-1100 ℃1.421.5499.3%99.0%1.421.5499.3%99.0% Example 2D-220 ℃1.421.5599.3%98.7%1.421.5599.3%98.7% Example 3D-220 ℃1.421.5499.3%99.0%1.421.5499.3%99.0% Example 4D-3100 ℃1.421.5898.9%98.6%1.421.5898.9%98.6% Example 5D-1100 ℃1.421.5499.3%99.1%1.421.5499.3%99.1% Example 6D-1100 ℃1.421.5499.3%99.0%1.421.5499.3%99.0% Example 7D-3100 ℃1.421.5898.9%98.6%1.421.5898.9%98.6%
[477] In Table 4, the symbols of the component (D) indicate the following.
[478] D-1; Phenyl glycidyl ether (with 10 mol% tetrabutylammonium bromide)
[479] D-2; A 1% aqueous solution of p-xylenediamine
[480] D-3; 3-phenoxypropylene sulfide (added with 10 mol% tetrabutylammonium bromide) Example 24:
[481] 50 parts by weight of the compound (A-11) as the component (A)
[482] (Equivalent to 50 parts by weight (solid content) of the polymer (B-1)) containing the polymer (B-1)
[483] 1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as component (C) and 10 parts by weight of bisphenol A diglycidyl ether as component (D) The solution was dissolved in diethylene glycol ethyl methyl ether so that the total solids concentration was 20%, and then filtered with a membrane filter of 0.2 탆 pore size to prepare a solution of the refractive index-varying composition.
[484] Formation of a coating film, formation of a refractive index pattern, measurement of refractive index, evaluation of transparency, evaluation of refractive index and transparency were all the same as those of Example 17.
[485] <5) Stabilization processing>
[486] The refractive index pattern on the silicon substrate and the glass substrate formed in the same manner as described above and the refractive index pattern on the glass substrate were heated at 150 캜 for 2 minutes at a temperature at which the component (A) did not decompose and the components (A) and Followed by heat treatment.
[487] Subsequently, the canon PLA-501F was subjected to a re-exposure treatment at 4.5 mW / cm ² for 1 minute with respect to the entire surface of the pattern without using a filter, and further heated in an oven at 200 ° C for 10 minutes to stabilize the refractive index pattern Respectively.
[488] <7) Re-exposure and heat treatment>
[489] Each of the refractive index patterns subjected to the stabilization treatment was irradiated with radiation at 4.5 mW / cm &lt; ² &gt; for 1 minute on the entire surface of the pattern without using a filter in the Canon PLA-501F, And heated.
[490] <8) Evaluation of stability after re-exposure and heat treatment>
[491] The refractive index of the low refractive index portion and the refractive index of the high refractive index portion were measured and the stability of the refractive index for the re-exposure and heating was evaluated for the refractive index pattern on the silicon substrate subjected to the re-exposure and the heat treatment in the same manner as in <
[492] The transparency of the low refractive index portion and the high refractive index portion of the refractive index pattern on the glass substrate subjected to re-exposure and heat treatment was measured in the same manner as in < 4) Evaluation of transparency > The results are shown in Tables 5 and 6.
[493] &Lt; Example 25 >
[494] 50 parts by weight of the compound (A-12) was used as the component (A), and the baking temperature after the exposure in the step 2 (formation of the refractive index pattern) was as shown in Table 5, The evaluation was made in the same manner as in Example 24 except that the heating temperature was changed as shown in Table 6. [ The results are shown in Tables 5 and 6 together.
[495] &Lt; Example 26 >
[496] Evaluation was made in the same manner as in Example 24 except that 50 parts by weight of the compound (A-15) was used as the component (A) and the irradiation dose in the step (2) . The results are shown in Tables 5 and 6 together.
[497] &Lt; Example 27 >
[498] 50 parts by weight of the compound (A-16) as the component (A) and 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine as the component (C) Was evaluated in the same manner as in Example 24, except that the irradiation dose was changed as shown in Table 5. &lt; tb &gt; &lt; TABLE &gt; The results are shown in Tables 5 and 6 together.
[499] &Lt; Example 28 >
[500] Was evaluated in the same manner as in Example 24 except that a solution (corresponding to 50 parts by weight (solid content) of the polymer (B-2)) containing the polymer (B-2) The results are shown in Tables 5 and 6 together.
[501] &Lt; Example 29 >
[502] 10 parts by weight of 1,4-bis (4,5-dihydro-2-oxazolyl) benzene was used as the component (D), and the amount of irradiation in the step (formation of the refractive index pattern) Was evaluated in the same manner as in Example 24. [ The results are shown in Tables 5 and 6 together.
[503] Refractive index pattern formation conditionsOptical properties before stabilization treatment Radiation dose (mJ / cm ² )Baking temperature after exposure (° C)Refractive indexTransparency The low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratio Example 24501301.441.5399.3%99.0% Example 25501201.441.5599.3%98.6% Example 26201301.441.5299.3%99.0% Example 27801301.441.5898.9%98.6% Example 28501301.441.5299.3%99.1% Example 29401301.441.5399.3%99.0% Example 30901301.441.5898.9%98.6%
[504] Stabilization treatment conditionsOptical properties after stabilization treatmentOptical properties after accelerated irradiation treatment Refractive indexTransparencyRefractive indexTransparency Treatment temperatureThe low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratio Example 24200 ℃1.441.5399.1%98.8%1.441.5399.1%98.8% Example 25140 ° C1.441.5499.1%98.5%1.441.5499.1%98.5% Example 26150 ℃1.441.5299.1%98.8%1.441.5299.1%98.8% Example 27150 ℃1.441.5798.7%98.4%1.441.5798.7%98.4% Example 28150 ℃1.441.5299.1%98.9%1.441.5299.1%98.9% Example 29150 ℃1.441.5399.1%98.8%1.441.5399.1%98.8% Example 30150 ℃1.441.5798.4%98.4%1.441.5798.7%98.4%
[505] &Lt; Example 30 >
[506] 10 parts by weight of 1,4-bis (4,5-dihydro-2-oxazolyl) benzene was used as the component (D), and the amount of irradiation in the step (formation of the refractive index pattern) The evaluation was made in the same manner as in Example 27 except that The results are shown in Tables 5 and 6 together.
[507] &Lt; Example 31 >
[508] 50 parts by weight (solid content) of a solution (compound (B-4)) containing 50 parts by weight of the compound (A-11) as the component (A) and the compound (B- 1 part by weight of 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate as component (C) was dissolved in diethylene glycol ethyl methyl ether so as to have a total solids concentration of 20%, followed by filtration with a membrane filter of 0.2 μm in pore size Followed by filtration to prepare a refractive index variable composition.
[509] &Lt; Formation of coating film &
[510] The above solution was coated on a silicon substrate using a spinner, and then baked on a hot plate at 100 DEG C for 2 minutes to form a coating film having a thickness of 1.0 mu m.
[511] <Formation of refractive index pattern>, <stabilization treatment>, <measurement of refractive index> and <evaluation of transparency> were the same as those of Example 17.
[512] <Measurement of porosity by mercury porosimeter>
[513] The low refractive index portion of the refractive index pattern and the respective porosity of the high refractive index portion formed as described above were measured using a mercury porosimeter (Autopore 9200 manufactured by Shimadzu Corporation, minimum measurable pore size 34 Å).
[514] <Measurement of beam hole distribution by BJH method>
[515] The beam hole distribution of the low refractive index portion of the refractive index pattern formed above was measured by the BJH method using OMNISORP100 / 360 series manufactured by COULTER. Table 8 shows the number of pores of 100 nm or more.
[516] <Measurement of Beam Pore Size by Electron Microscope Observation>
[517] The beam pore size of each of the low refractive index portion and the high refractive index portion of the refractive index pattern formed above was measured by a transmission electron microscope observation to measure the number of beam holes having a diameter of 100 nm or more per 10 μm ² in an arbitrary observation range.
[518] &Lt; Example 32 >
[519] 50 parts by weight of the compound (A-12) was used as the component (A), the baking temperature after the exposure in the step 2 (formation of the refractive index pattern) was as shown in Table 7, ) Was evaluated in the same manner as in Example 31, except that the kind of the component (D) and the stabilization treatment temperature were changed as shown in Table 8. The results are shown in Tables 7 and 8 together.
[520] &Lt; Example 33 >
[521] 50 parts by weight of the compound (A-15) was used as the component (A), the irradiation dose in the step (2) (formation of the refractive index pattern) was as shown in Table 7, The kind of the component and the stabilization treatment temperature were evaluated in the same manner as in Example 31 except that the results are shown in Table 8. [ The results are shown in Tables 7 and 8 together.
[522] &Lt; Example 34 >
[523] (Formation of a refractive index pattern) was carried out by using 50 parts by weight of the compound (A-16) as the component (A) and 5 parts by weight of N- (2-nitrobenzyloxycarbonyl) pyrrolidine as the component (C) Was evaluated in the same manner as in Example 31 except that the irradiation dose was changed as shown in Table 7 and the kind of the component (D) in the step (3) (stabilization treatment) was changed as shown in Table 8. [ The results are shown in Tables 7 and 8 together.
[524] &Lt; Example 35 >
[525] Was evaluated in the same manner as in Example 31 except that a solution (corresponding to 50 parts by weight (solid content) of the compound (B-3)) containing the compound (B-3) as the component (B) was used. The results are shown in Tables 7 and 8 together.
[526] Refractive index pattern formation conditionsStabilization treatment conditions Radiation dose (mJ / cm ² )Baking temperature after exposure (° C)(D) Component speciesTreatment temperature Example 3180100D-180 Example 3280100D-220 Example 3360100D-220 Example 34100100D-180 Example 3580150D-180
[527] In Table 7, symbols of component (D) indicate the following.
[528] D-1; Phenyl glycidyl ether (with 10 mol% tetrabutylammonium bromide)
[529] D-2; A 1% aqueous solution of p-xylenediamine
[530] Refractive indexPorosityPublic distributionPore diameterTransmittance The low refractive index portionHigh-deflection ratioThe low refractive index portionHigh-deflection ratioThe low refractive index portionThe low refractive index portionThe low refractive index portionHigh-deflection ratio Example 311.311.5428%0%0098.5%98.1% Example 321.301.5530%0%0098.5%98.1% Example 331.271.5438%0%0098.5%98.2% Example 341.331.5822%0%0098.2%97.7% Example 351.371.5411%0%0098.5%98.0%
[531] Example 36 (Fabrication of GI type optical fiber (1)) [
[532] 50 parts by weight of a compound (A-6) as a component (A), 50 parts by weight of a condensate of methyltrimethoxysilane (weight average molecular weight = 18,000) as a component (B) 1 part by weight of thiophenyldiphenylsulfonium trifluoromethanesulfonate, and 2 parts by weight of 2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole 1.5 Were dissolved in methyl ethyl ketone so that the solid concentration of the whole was 70%. This solution was subjected to defoaming using the raw fiber solution and then extruded at a discharge port having a pore size of 1.0 mm at a rate of 1 m / min. A 250 mW ultra-high pressure mercury lamp (spot curing, manufactured by Ushio Inc.) 6.7 mW / cm ² ) was uniformly irradiated to the fibers around the fiber using a ring type light guide (inner diameter 55 mm) manufactured by Japan Pty. Co., Ltd., and then the fiber was heated at 200 ° C. for 5 seconds The fiber was heated at an irradiation width of 10 cm of the infrared lamp.
[533] The acid generated from the component (C) is widely distributed in the vicinity of the fiber surface and the decomposition of the component (A) is gradually reduced from the vicinity of the surface to the inside by heating, GI type optical fiber with a refractive index decreased in parabolic shape was fabricated. As measured by an interference refractometer, the maximum refractive index difference N at the center and periphery was 0.09.
[534] &Lt; Example 37 > (Production of GI type optical fiber (2)) [
[535] A GI type optical fiber was produced in the same manner as in Example 36 except that 50 parts by weight of the compound (A-5) was used as the component (A). The maximum refractive index difference N at the central portion and the periphery as measured by the interference refractometer was 0.11.
[536] Example 38 (Production of GI type optical fiber (3)) [
[537] GI type optical fiber was prepared in the same manner as in Example 36 except that 1 part by weight of 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine was used as the component (C) As measured by an interference refractometer, the maximum refractive index difference N at the center and periphery was 0.09.
[538] &Lt; Example 39 > (Preparation of GRIN lens (1)) [
[539] By cutting the GI type optical fibers produced in Examples 36 to 38 shortly, GRIN lenses having a refractive index continuously distributed from the center to the periphery were obtained.
[540] &Lt; Example 40 > (Preparation of GRIN lens (2)) [
[541] 50 parts by weight of a compound (A-2) as a component (A) and 50 parts by weight of a condensate of methyltrimethoxysilane (weight average molecular weight = 18,000) as a component (B) 1 part by weight of phenyldiphenylsulfonium trifluoromethanesulfonate, and 1.5 parts by weight of 2- (2-hydroxy-3,5-bis ( , - dimethylbenzyl) phenyl) -2H-benzotriazole as an ultraviolet absorber Was dissolved in methyl ethyl ketone so that the solid concentration of the whole was 70%, and then a disk-shaped sample having a diameter of 2 cm and a thickness of 5 mm was produced under reduced pressure in a hot press. Irradiation apparatus fastening the disk-shaped sample (1) attached to the free hardware (2) opening and closing in front of, and irradiation device (3) Wavelength 365 nm, ultraviolet ray 4 of illuminance 30 mW / cm ² emitted from As shown in Figure 1 The shutter speed was adjusted so that the tightening (2) was fully opened within 5 seconds, the irradiation was finished after 5 seconds, and the film was exposed at 120 DEG C for 2 minutes and then baked Respectively. As a result, a disc-shaped optical molded article in which the refractive index is continuously increased from the central portion to the peripheral portion was obtained. The difference in refractive index was 0.08, and it became a GRIN lens having a concave lens ability, which showed the possibility as a near vision lens for spectacles.
[542] &Lt; Example 41 > (Preparation of GRIN lens (3)) [
[543] Example 40 A disk-shaped sample was obtained in the same manner as in the front end. (Spot curing, manufactured by Ushio Electric Co., Ltd., i ray intensity: 6.7 mW / cm ² ) with a structure of 250 mW ultra-high pressure mercury lamp ) For 20 seconds using a light guide of a manufacturing ring type (inner diameter 55 mm), and baked after exposure at 120 ° C for 2 minutes. As a result, a disc-shaped optical molded article in which the refractive index is continuously lowered from the central portion to the peripheral portion was obtained. The refractive index difference was 0.08, and a GRIN lens having a convex lens ability was obtained.
[544] Example 42 (Fabrication of GI type optical waveguide)
[545] 50 parts by weight of a compound (A-2) as a component (A) and 50 parts by weight of a condensate of methyltrimethoxysilane (weight average molecular weight = 2,000) as a component (B) 1 part by weight of phenyldiphenylsulfonium trifluoromethanesulfonate was dissolved in diethylene glycol ethyl methyl ether so as to have a total solids concentration of 40% and then filtered with a membrane filter having an pore diameter of 1.0 탆 to obtain a photosensitive refractive index change A solution (S-1) containing the composition was prepared. Further, 100 parts by weight of a 5-condensate of methyltrimethoxysilane (weight average molecular weight = 2,000) used as the component (B) and 1 part by weight of SI-L150 (manufactured by San-Shin Kagaku Co., Ltd.) (S-2) was prepared by dissolving it in diethylene glycol ethyl methyl ether so that the solid concentration became 40%.
[546] First, the solution (S-2) of the coating by spin coating on the surface of the silicon substrate, and then dried at 70 ℃ for 10 min, wavelength 365 nm, illuminance for 5 seconds with UV light at 4.0 mW / cm ² on the entire surface irradiated To form a lower clad layer having a thickness of 10 mu m. Next, the solution (S-1) was applied on the lower clad layer by spin coating and dried at 70 DEG C for 10 minutes to form an intermediate layer having a thickness of 10 mu m. Then, a photomask Was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² for 10 seconds. Thereafter, post-exposure baking was performed at 120 캜 for 2 minutes. At this time, the unexposed portion becomes the core portion and the exposed portion becomes the side cladding layer. Continuing with yiwi by applying a solution (S-2) by spin coating, and dried at 70 ℃ for 10 minutes, forming an upper clad layer having a thickness of 10 ㎛, wavelength 365 nm, illuminance 4.0 UV mW / cm ² Was irradiated to the entire surface for 5 seconds, exposed at 120 DEG C for 2 minutes, and baked to produce an optical waveguide. The refractive index of light having a wavelength of 1550 nm of the upper, side, and lower cladding layers formed was 1.42. In contrast, the core layer had a refractive index of 1.50 at a wavelength of 1,550 nm and a maximum refractive index difference of 0.08. The optical waveguide obtained here contains a photoacid generator both in the upper and lower parts, and the interface between the core layer and the upper and lower clad layers generates diffusion of slightly generated acid. Accordingly, the refractive index distribution is generated at the interface between the core layer and the clad layer even at the top, side, and bottom, and the obtained optical waveguide becomes a GI type. The optical waveguide thus obtained was measured for the amount of light emitted from the other end thereof when light having a wavelength of 1,300 nm was incident from one end of the waveguide. The loss of the waveguide was found to be 0.1 dB / cm or less.
[547] Example 43 (Preparation of optical recording medium)
[548] 50 parts by weight of a compound (A-2) as a component (A), 50 parts by weight of a condensate having a molecular weight of methylene trimethoxysilane of 2,000 as a component (B), and 4-phenylthiophenyldiphenyl 1 part by weight of sulfonium trifluoromethanesulfonate was dissolved in diethylene glycol ethyl methyl ether so that the total solids concentration was 20%, and the solution was filtered through a membrane filter of 0.2 탆 pore size to obtain a photosensitive composition containing a photosensitive refractive index- Solution. This was coated with an aluminum reflection film by a spin coating method on a flat polycarbonate substrate deposited to a thickness of 60 nm by a sputtering method and dried at 80 DEG C for 2 minutes to form a refractive index change layer having a thickness of 1.0 mu m. Thereafter, ultraviolet irradiation at an intensity of 40 mW / cm ² was performed for 5 seconds through a mask having a track pitch of 1.6 탆 and a pitch of 0.5 탆 at a wavelength of 365 nm, followed by baking after exposure at 120 캜 for 2 minutes. Thus, the difference in refractive index between the exposed portion and the unexposed portion was 0.08 at 633 nm, which was sufficiently readable as an optical recording medium.
[549] Example 44 (Fabrication of optical integrated circuit)
[550] 50 parts by weight of a compound (A-2) as a component (A) and 50 parts by weight of a condensate of methyltrimethoxysilane (weight average molecular weight = 2,000) as a component (B) 1 part by weight of phenyldiphenylsulfonium trifluoromethanesulfonate was dissolved in diethylene glycol ethyl methyl ether so as to have a total solids concentration of 33% and then filtered with a membrane filter having an pore diameter of 1.0 탆 to obtain a photosensitive refractive index change A solution containing the composition was prepared. Was dried at 70 is applied by spin coating on a glass substrate surface, and ℃ for 10 minutes and then irradiated for 5 seconds in 100 ㎛ wavelength of 365 nm through a mask of width, intensity 4.0 mW / cm ² UV, 120 Lt; 0 &gt; C for 2 minutes and then baked. As a result, an optical integrated circuit having a refractive index pattern of 1 占 퐉 占 퐉 could be obtained.
[551] Example 45 (Fabrication of optical diffraction grating)
[552] Using the solution prepared in Example 42, a film type sample of 2 cm x 1 cm x 10 m was prepared. This sample was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² . As shown in Fig. 2, the irradiating light is converted into parallel light 9 by the irradiating device 8 and reflected by the reflector 7 located at 45 degrees to irradiate the sample 5 on the film 6 on the stage 6 Respectively. The sample is irradiated with the reflected light and the interference pattern formed from the light directly irradiated. Simultaneously with the irradiation, the sample was moved at a speed of 1 占 퐉 / min in the direction of the arrow in the figure, resulting in an optical diffraction grating having a period of 0.5 占 퐉.
[553] Example 46 (Production of hologram)
[554] Parallel light having a wavelength of 365 nm and an illuminance of 4.0 mW / cm ² was divided into two optical paths by a half mirror, one was passed through a transparent object to be a signal light and interfered with another reference light, and its interference pattern was the same as in Example 45 The optical molded article was irradiated. By observing the regenerated illumination light on the obtained optical molded article, it was possible to confirm the image of the recorded object with high resolving power.

权利要求:
Claims (14)
[1" claim-type="Currently amended] (A) a decomposable compound,
(B) a non-decomposable compound having a refractive index lower than that of the decomposable compound (A)
(C) Sensitizing radiation dissociation and
(D) a stabilizing agent.
[2" claim-type="Currently amended] The composition according to claim 1, wherein the maximum difference between the refractive index of the irradiated portion and the refractive index of the unradiated portion is 0.02 or more.
[3" claim-type="Currently amended] The composition according to claim 1 or 2, wherein the refractive index n _B of the non-decomposing compound (B) is in the relationship of the refractive index n _A of the decomposing compound (A)
&Quot; (1) &quot;
n _A -n _B ≥0.05
[4" claim-type="Currently amended] The positive resist composition according to any one of claims 1 to 3, wherein the decomposable compound is an acid decomposable compound, (B) the non-decomposable compound is an acid decomposable polymer, (C) the radiation- Jane composition.
[5" claim-type="Currently amended] The composition according to claim 4, wherein the acid-decomposable compound (A) contains at least one compound having at least one structure selected from the group consisting of structures represented by the following formulas (1) to (8).
&Lt; Formula 1 >

Wherein R ¹ is an alkylene group, an alkylene arylene alkylene group or an arylene group, and R ² is an alkylene group, an alkylene arylene alkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group.
(2)

Wherein M is Si or Ge, R ³ is an alkylene group, an alkylenearylenealkylene group, an arylene group, an alkylsilylene group or an alkylgermylene group, and R ⁴ is an oxygen atom, an alkylene group, an alkylenearylene alkyl R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and m is an integer of 0 to 2.
(3)

In the formulas, R ⁹ and R ¹⁰ are each independently an alkylene group, an alkylene arylene alkylene group, an arylene group, an alkylsilylene group or an alkyl damylene group.
&Lt; Formula 4 >

Wherein R ¹¹ is an oxyalkylene group or a single bond, and R ¹² is a hydrogen atom, an alkyl group, an alkylene arylene alkylene group or an aryl group.
&Lt; Formula 5 >

Wherein R ¹³ is a hydrogen atom, an alkyl group or an aryl group.
(6)

In the formula, R ¹⁴ is a structure represented by the formula 6-1, 6-2 or 6-3 alkylene group.
(6-1)

In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, An alkylthio group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxyl group having 1 to 6 carbon atoms, a halogenated alkylthio group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, A mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms.
<Formula 6-2>
-OR ¹⁹ -O-
Wherein R &lt; ¹⁹ &gt; is an alkylene group.
<Formula 6-3>
-NH-R &lt; ²⁰ &gt; -NH-
In the formula, R ²⁰ is an alkylene group.
&Lt; Formula 7 >

In the formula, R ²¹ is an alkylene group, an alkylene arylene alkylene group or an arylene group.
(8)

R ²² , R ²³ , R ²⁴ and R ²⁵ independently represent a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a mercapto group, An alkylthio group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxyl group having 1 to 6 carbon atoms, a halogenated alkylthio group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, A mercaptoalkyl group having 1 to 6 carbon atoms, a hydroxyalkoxyl group having 1 to 6 carbon atoms, a mercaptoalkylthio group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms.
[6" claim-type="Currently amended] The positive resist composition according to any one of claims 1 to 3, wherein (A) the decomposable compound is a base decomposable compound, (B) the non-decomposable compound is a base non-degradable polymer, (C) &Lt; / RTI &gt;
[7" claim-type="Currently amended] The composition according to claim 6, which contains at least one compound having at least one structure selected from the group consisting of structures represented by the following formulas (9) to (12).
&Lt; Formula 9 >

Wherein, R ²⁶ is an alkylene group, an aralkyl group and the alkylene group or arylene group, R ²⁷ is an alkylene group, an aralkyl group, an arylene group, alkylene-arylene-alkyl group, an alkylsilyl group or alkyl low milren group, R ^28, R ²⁹ , R ³⁰ and R ³¹ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a thioalkyl group, and i and j are each independently 0 or 1.
&Lt; Formula 10 >

In the formula, R ³² is an alkylene group, an aralkylene group or an arylene group, and R ³³ is an alkylene group, an aralkylene group, an arylene group, an alkylenearylene alkylene group, an alkylsilylene group or an alkylgermylene group.
&Lt; Formula 11 >

In the formula, R ³⁴ and R ³⁵ each independently represent an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.
&Lt; Formula 12 >

In the formula, R ³⁶ and R ³⁷ each independently represent an alkylene group, an aralkylene group, an arylene group, an alkylenearylenealkylene group, an alkylsilylene group or an alkylgermylene group.
[8" claim-type="Currently amended] The method according to any one of claims 1 to 7, wherein (D) the stabilizer is selected from the group consisting of an amino compound, an epoxy compound, a thioran compound, an oxetane compound, an alkoxymethylated melamine compound, an alkoxymethylated glycoluril compound, an alkoxymethylated benzoguanamine compound , An alkoxymethylated urea compound, an isocyanate compound, a cyanate compound, an oxazoline compound, an oxazine compound, and a silyl compound.
[9" claim-type="Currently amended] The composition according to claim 1, further comprising (D) a stabilizer, and further comprising a catalyst for the reaction of (A) the decomposable compound and (D) the stabilizer.
[10" claim-type="Currently amended] (D) a radiation-sensitive refractive-index-changeable composition containing (A) a decomposable compound, (B) a non-decomposable compound, (C) a radiation- ) A stabilizer and (A) a decomposable compound.
[11" claim-type="Currently amended] (D) irradiating a radiation-sensitive composition comprising (A) a decomposable compound, (B) a non-decomposable compound having a lower refractive index than the decomposable compound (A) and (C) (A) decomposable compound in the unexposed portion is reacted with the stabilizer (D).
[12" claim-type="Currently amended] (A) a decomposable compound, (B) a non-decomposable compound having a refractive index lower than that of the decomposable compound (A), and (C) a refractive index-varying composition containing radiation-sensitive radiation decomposition are irradiated with radiation through a pattern mask, And decomposing the decomposable polymer of the light portion.
[13" claim-type="Currently amended] The method according to claim 10, 11, or 12, wherein the resulting refractive index pattern has or does not have voids in the exposed portion.
[14" claim-type="Currently amended] A refractive index pattern formed by the method according to any one of claims 10, 11, 12 or 13.

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同族专利:

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公开号 | 公开日

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US6828078B2|2004-12-07|

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CN1273869C|2006-09-06|

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AU8015701A|2002-03-13|

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AU2001280157B2|2005-08-11|

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CN1388919A|2003-01-01|

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US20030064303A1|2003-04-03|

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EP1235104A4|2008-10-01|

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WO2002019034A1|2002-03-07|

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CA2387716A1|2002-03-07|

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EP1235104A1|2002-08-28|

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KR100719426B1|2007-05-18|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-08-29|Priority to JPJP-P-2000-00258524

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2000-08-29|Priority to JP2000258524

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2000-09-01|Priority to JPJP-P-2000-00265483

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2000-09-01|Priority to JP2000265483

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2000-10-24|Priority to JPJP-P-2000-00324508

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2000-10-24|Priority to JP2000324508

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2000-11-13|Priority to JPJP-P-2000-00345764

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2000-11-13|Priority to JP2000345764

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2000-11-27|Priority to JP2000360075

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2000-11-27|Priority to JPJP-P-2000-00360075

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2001-01-26|Priority to JPJP-P-2001-00018765

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2001-01-26|Priority to JP2001018765

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2001-08-24|Application filed by 제이에스알 가부시끼가이샤

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2002-12-12|Publication of KR20020092921A

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2007-05-18|Application granted

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2007-05-18|Publication of KR100719426B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2000-00258524|2000-08-29|

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JP2000258524|2000-08-29|

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JPJP-P-2000-00265483|2000-09-01|

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JP2000265483|2000-09-01|

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JPJP-P-2000-00324508|2000-10-24|

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JP2000324508|2000-10-24|

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JPJP-P-2000-00345764|2000-11-13|

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JP2000345764|2000-11-13|

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JP2000360075|2000-11-27|

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JPJP-P-2000-00360075|2000-11-27|

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JPJP-P-2001-00018765|2001-01-26|

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JP2001018765|2001-01-26|