Optical Material Containing Functional Fluoropolymer

专利摘要:
The present invention relates to an organic composition suitable for optical materials such as optical communication, comprising a functional group-containing fluoropolymer and rare earth metal ions, wherein the functional group-containing fluoropolymer has at least one ketone structure in the side chain, 1290 to 1320 nm and 1530 to 1570 nm, and The maximum absorption coefficient in each wavelength band of 600 to 900 nm is 1 cm -1 or less, and rare earth metal ions include erbium (Er) ions, thulium (Tm) ions, praseodymium (Pr) ions, holmium (Ho) ions, Provided is an optical material containing at least one functional group-containing fluoropolymer selected from the group consisting of neodymium (Nd) ions and europium (Eu) ions.
公开号:KR20030085546A
申请号:KR10-2003-7011628
申请日:2002-03-06
公开日:2003-11-05
发明作者:다까유끼 아라끼；요시또 다나까；유조 고마쯔；요시히또 안도
申请人:다이킨 고교 가부시키가이샤；
IPC主号:

专利说明:

Optical material containing a functional group containing fluoropolymer {Optical Material Containing Functional Fluoropolymer}
[2] Optical communication systems using fiber optic networks enable high capacity and high speed data transmission. In general, a quartz optical fiber is used as the optical fiber. Recently, however, in plastics optical fiber (POF), a POF called a wideband (400 Mbps at 100 m transmission), low loss GI (Graded Index) type has been developed, and the construction of an optical network in each home will be established in the future. Is also being considered. In each fiber, the wavelength band of light used for transmission is different, mainly 1300 nm band and 1500 nm band in quartz system, and 650 nm band is mainly used in plastic (acrylic).
[3] However, in optical communication systems, whether optical fibers are quartz or plastic, losses caused during propagation, branching, connection, and switching cause attenuation of optical signals. Attenuation of the optical signal is particularly problematic when long distance transmission is performed. Thus, an optical amplifier is needed to compensate for the attenuation of the optical signal.
[4] As an optical amplifier for an optical communication system using a quartz-based optical fiber network, for example, "Optical amplification and its application by Er doped optical fiber", Nakazawa Masataka, Application Physics Vol. 59, No. 9, pp.1175 -1192 (1990), there is a so-called fibrous optical amplifier. This applies the excitation by the light ray in the visible to near-infrared region of the electron in an erbium (Er) cation atom, and the fluorescence generation phenomenon of wavelength about 1500 nm.
[5] On the other hand, as a light-emitting body, it is practically used for the inorganic glass which contained rare-earth metal ion, the electronic device for laser beams, etc. However, since the manufacture is complicated and the machining is difficult, the use is limited. Moreover, although the polymer composition is proposed by Unexamined-Japanese-Patent No. 64-26583, luminous intensity is low.
[6] However, an optical amplifier (EDFA) with an Er doped fiber requires an optical fiber for amplification of 20 to 30 m in length to obtain a gain of 30 dB (1000 times). The reason is, for example, that the fibrous optical amplifier for the 1550 nm band is doped with erbium ions (Er ³⁺ ) to the quartz-based fiber. If the doping amount is increased, a cluster is formed according to the association of the doping ions. It is because it will fall. Therefore, the amplification effect is obtained by reducing the doping amount to 10 to 1000 ppm and then lengthening the fiber length. As described above, in the fiber type optical amplifier (glass system), there is a limit in shortening the working length of the optical amplifier. That is, there is a limit to miniaturization and low price of the optical amplifier.
[7] Moreover, since a base material is an inorganic glass material, toughness and moldability did not necessarily satisfy.
[8] In addition, in the case of a fibrous optical amplifier (glass system), it is difficult to realize a planar optical amplifier. This is detrimental to the case of constructing an optical integrated circuit by an optical amplifier and other optical elements.
[9] Inorganic devices as light emitters are also difficult to manufacture and difficult to process.
[10] On the other hand, addition of the rare earth element cation to organic polymer materials is also examined. For example, Japanese Patent Laid-Open No. 5-86189 discloses a polysiloxane in which rare earth metal ions obtained by using chlorosilanes having an organic group and chlorides of rare earth elements as raw materials are inserted in a polymer chain. Japanese Unexamined Patent Publication (Kokai) No. 5-88026 discloses a material containing a complex having excellent solubility and oxidation resistance of an rare earth metal ion in an organic solvent such as an acetylacetone complex in polyacrylate or polysiloxane. In addition, the Polymer Society Preview Vol. 43 (1) and 29 (1994) synthesize rare earth element cation salts of polymerizable organic acids such as acrylic acid and methacrylic acid, and polymerize or copolymerize such rare earth cation supported monomers to increase the cation concentration to about 10% by weight. Material is reported. By these methods, a rare earth element cation can be added in high concentration with respect to the organic polymer material excellent in moldability. However, there are drawbacks such as that the synthesis method is complicated, and can be an economical constraint in industrial applications, and that the resin used is limited to a resin having a relatively low heat resistance.
[11] In addition, in order to increase the dispersibility of the rare earth metal ions in the resin, it is necessary to contain carboxylic acid groups in a high proportion in the structure of the polymer constituting the acrylic resin. It could not be used as an optical material reluctant to exist.
[12] Moreover, heat resistance was also inadequate, and the fall of amplification characteristic generate | occur | produced in the manufacturing process of an optical amplification type element, or under use environment.
[13] In addition, when the 1300 nm band and the 1500 nm band are used as the wavelength of the light source, since the carbon-hydrogen and oxygen-hydrogen bonds in the organic material have absorption in this region, there is an inherent drawback that the light transmittance is lowered. . Therefore, studies have been made to replace such hydrogen atoms with deuterium (D) or fluorine. As a result, the transparency could be improved to some extent, but in the case of deuterium substitution, the absorbency of the material did not change, and in the case of fluorine substitution, the dispersibility of rare earth metal ions was remarkably decreased when substituted to such an extent that it had an effect on transparency. Or the solubility of the solvent was lowered. In addition, the glass transition point did not improve in fluorine substitution, and the problem of heat resistance was not solved. Moreover, there existed a problem, such as light resistance of the polymer used also in the application to the light emitting body using such a light emission phenomenon.
[14] As described above, not all problems in the field of light amplifying materials and light emitting materials have been solved, but new light amplifying materials and light emitting materials are required to solve the above problems.
[1] The present invention relates to an optical material comprising a functional group-containing fluoropolymer. More specifically, the present invention relates to a composition useful as an optical material and a material suitable for a field using light amplification techniques or luminescence phenomena used in the field of optical communication.
[29] 1 is a process chart for manufacturing the optical amplification device or light emitting device of the present invention.
[30] Best Mode for Carrying Out the Invention
[31] (I) functional group containing fluoropolymer used for the fluororesin composition of this invention is represented by following General formula (1) as above-mentioned, and contains 0.1-100 mol% of structural unit M and 0-99.9 mol% of structural unit A. It is a fluoropolymer.
[32] <Formula 1>
[33]
[34] In the formula, the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the following formula (2), and the structural unit A is a structural unit derived from the monomer copolymerizable with the structural unit M.
[35] <Formula 2>
[36]
[37] Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf has 1 to 5 moieties of> C═O, a fluorine-containing alkylene group having 1 to 50 carbon atoms excluding carbon of C═O or an ether bond having 2 to 100 carbon atoms excluding carbon of C═O It is a fluorine-containing alkylene group having a, a is an integer of 0 to 3, b and c are the same or different and 0 or 1.
[38] That is, the homopolymer of the structural unit M derived from the fluorine-containing ethylenic monomer which has one or more ketone structures which can form a complex or a salt with a rare earth metal ion in a side chain, or its fluorine-containing ethylenic monomer structural unit M is essential. It is a copolymer made as a component.
[39] In the present invention, the structural unit M in the functional group-containing fluoropolymer (I) of the general formula (1) is preferably a structural unit derived from the fluorine-containing ethylenic monomer represented by the structural unit M1 represented by the following general formula (3).
[40]
[41] In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , Rf, a and c are the same as above.
[42] The polymer containing the structural unit M1 has a particularly high transparency in the near infrared region (hereinafter also referred to as "near infrared transparency") and is not limited to a homopolymer containing only the structural unit M1, Also in a copolymer, since near-infrared transparency can be improved, it is preferable.
[43] Moreover, as one of the more preferable specific examples of structural unit M1, the structural unit derived from the fluorine-containing ethylenic monomer represented by the structural unit M2 represented by following formula (4) is mentioned.
[44]
[45] In formula, Rf is the same as the above.
[46] Structural unit M2 is a structural unit derived from the fluorine-containing allyl ether which has one or more ketone structures, and can not only improve near-infrared transparency, but also have good polymerizability, and especially homopolymerization and other fluorine-containing ethylenic monomers, It is preferable because the copolymerizability of is good.
[47] Moreover, as another preferable specific example of structural unit M1, the structural unit derived from the fluorine-containing ethylenic monomer represented by the structural unit M3 represented by following formula (5) is mentioned.
[48]
[49] In formula, Rf is the same as the above.
[50] Structural unit M3 is a structural unit derived from the fluorine-containing vinyl ether which has one or more ketone structures, and is preferable at the point which can improve near-infrared transparency and the copolymerization with another fluorine-containing ethylene-type monomer is favorable.
[51] In the functional group-containing fluoropolymer (I) of the general formula (1) used in the present invention, Rf contained in the structural units M, M1, M2 and M3 has 1 to 5 moieties of> C = O as described above, and C A fluorine-containing alkylene group having 1 to 50 carbon atoms excluding carbon of = O or a fluorine-containing alkylene group having ether bonds of 2 to 100 carbon atoms excluding carbon of C = O.
[52] The site | part of> C = O in Rf has the ability to form a complex or a salt with (II) rare earth metal ions, and can obtain a stable structure with (II) rare earth metal ions. Therefore, in the composition of the present invention, (II) rare earth metal ions and (I) functional group-containing fluoropolymers are easily formed by ion exchange reaction between, for example, rare earth metal salts in solution and (I) functional group-containing fluoropolymer molecules. It is assumed to form a stable structure.
[53] As a first example of preferred Rf,
[54] [Wherein, Y ¹ is H, OH, R ¹ or OR ² (wherein R ¹ and R ² are the same or different and are a hydrocarbon group having 1 to 10 carbon atoms), and Rf ¹ is a fluorine having 1 to 50 carbon atoms. Containing alkylene group or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
[55] As a 1st preferable specific example of Rf,
[56] Can be mentioned.
[57] In addition, as a 2nd example of preferable Rf,
[58] (Wherein Rf ² is a fluorine-containing alkylene group having 1 to 49 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 99 carbon atoms, and Rf ³ is a fluorine-containing alkyl group having 1 to 49 carbon atoms or an ether bond having 2 to 99 carbon atoms) Rf ² is a fluorine-containing alkylene group, at the same time, when Rf ³ is a fluorine-containing alkyl group, the total carbon number of Rf ² and Rf ³ is 50 or less, and any one of Rf ² and Rf ³ is an ether bond And in the case of a fluorine-containing alkylene group or a fluorine-containing alkyl group having the same, the total carbon number of Rf ² and Rf ³ is 100 or less).
[59] As a specific example of said 2nd Rf,
[60] Etc. can be mentioned.
[61] Moreover, as a 3rd example of preferable Rf,
[62] [Wherein X ⁶ is H or D (deuterium), X ⁷ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or a halogen atom, and Y ¹ is H, D, OH, OD, R ¹ or OR ² , wherein R ¹ and R ² are the same or different, and some or all of the hydrocarbon groups having 1 to 10 carbon atoms or their hydrogen atoms are deuterium or halogen atoms And Rf ⁴ is a fluorine-containing alkylene group having 1 to 49 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 99 carbon atoms.
[63] As a specific example of this third Rf,
[64] Etc. can be mentioned.
[65] Moreover, as a 4th example of preferable Rf,
[66] [Wherein X ⁶ is H or D (deuterium), X ⁷ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ⁵ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having ether bonds having 2 to 98 carbon atoms, and Rf ⁶ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or an ether bond having 2 to 98 carbon atoms Is an alkyl group, Rf ⁵ is a fluorine-containing alkylene group, and at the same time, when Rf ⁶ is a fluorine-containing alkyl group, the total carbon number of Rf ⁵ and Rf ⁶ is 49 or less, and any one of Rf ⁵ and Rf ⁶ has an ether bond; In the case of an alkylene group or a fluorine-containing alkyl group, the total carbon number of Rf ⁵ and Rf ⁶ is 99 or less].
[67] As a specific example of the fourth Rf,
[68] Etc. can be mentioned.
[69] As a fifth example of preferred Rf,
[70] [Wherein X ⁶ is H, D or a halogen atom, Y ¹ and Y ² are the same or different and H, D, OH, OD, R ¹ or OR ² (where R ¹ and R ² are the same or Or different, a hydrocarbon group having 1 to 10 carbon atoms or some or all of hydrogen atoms thereof are substituted with deuterium or halogen atoms, and Rf ⁷ is a fluorine-containing alkylene group having 1 to 49 carbon atoms or an ether bond having 2 to 99 carbon atoms; It is fluorine-containing alkylene group which has.
[71] As a specific example of the fifth Rf,
[72] Etc. can be mentioned.
[73] In addition, as a 6th example of preferable Rf,
[74] [Wherein X ⁶ is H, D or a halogen atom, Rf ⁸ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ⁹ and Rf ¹⁰ are the same; Or a different fluorine-containing alkyl group having 1 to 48 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 98 carbon atoms, Rf ⁸ is a fluorine-containing alkylene group, and at the same time, both Rf ⁹ and Rf ¹⁰ are fluorine-containing alkyl groups. and Rf ^8, Rf ⁹ and 49 or less carbon atoms, the sum of Rf ^10, Rf ^8, Rf ⁹ and Rf ¹⁰ in the case of one or two of an alkyl group containing a fluorine-containing alkylene group or fluorine having an ether bond, the Rf ^8, Rf ⁹ And the total carbon number of Rf ¹⁰ is 99 or less.
[75] As a specific example of said 6th Rf,
[76] Etc. can be mentioned.
[77] In addition, as a 7th example of preferable Rf,
[78] [Wherein X ⁶ is H, D or a halogen atom, Y ¹ is H, D, OH, OD, R ¹ or OR ² , wherein R ¹ and R ² are the same or different and have 1 to 10 carbon atoms; A hydrocarbon group or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms), Rf ¹¹ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, Rf ¹² is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 98 carbon atoms, Rf ¹¹ is a fluorine-containing alkylene group, and at the same time, when Rf ¹² is a fluorine-containing alkyl group, Rf ¹¹ and Rf ¹² The total carbon number is 49 or less, and when either of Rf ¹¹ and Rf ¹² is a fluorine-containing alkylene group or fluorine-containing alkyl group having an ether bond, the total carbon number of Rf ¹¹ and Rf ¹² is 99 or less).
[79] As a specific example of the seventh Rf,
[80] Etc. can be mentioned.
[81] In the (I) functional group-containing fluoropolymer of the general formula (1) used in the present invention, -Rf ^2- , -Rf ^4- , -Rf ^5- , -Rf ⁷ contained in the Rf groups of the structural units M, M1, M2 and M3 -, -Rf ⁸ -and -Rf ^11- (hereinafter collectively referred to as "Rf ⁿ group") are a fluorine-containing alkylene group having 1 to 49 carbon atoms or an ether bond having 2 to 99 carbon atoms. . This Rf ⁿ group may be bonded to a fluorine atom to a carbon atom to be included, and is generally a fluorine-containing alkylene group having a fluorine atom and a hydrogen atom or a chlorine atom or a fluorine-containing alkylene group having an ether bond. It is preferable to contain a lot (high fluorine content), and the fluorine content is 50% or more, preferably 70% or more, and more preferably perfluoroalkylene group or ether bond with respect to the molecular weight excluding the oxygen atom of the Rf ⁿ group. It is a perfluoroalkylene group which has. Because of these, the transparency of the near-infrared region of the (I) functional group-containing fluoropolymer can be increased, and in particular, even if the functional group content is increased for the purpose of increasing the content of the (II) rare earth metal ion, the near-infrared transparency can be maintained in a high state. desirable.
[82] When the carbon number of the Rf ⁿ group is too large, the solubility of the (I) functional group-containing fluoropolymer in the solvent may decrease in the case of the fluorine-containing alkylene group, and in the case of the fluorine-containing alkylene group having an ether bond, the (I) functional group The glass transition point and mechanical properties of the containing fluoropolymer itself and its cured product may be lowered, which is not preferable. 1-20 are preferable and, as for carbon number of a fluorine-containing alkylene group, 1-10 are more preferable. 2-30 are preferable and, as for carbon number of the fluorine-containing alkylene group which has an ether bond, 2-20 are more preferable.
[83] As a preferable specific example of Rf ⁿ group,
[84] Etc. can be mentioned.
[85] As described above, the structural unit M constituting the (I) functional group-containing fluoropolymer used in the present invention is preferably a structural unit M1, and the structural unit M1 is also preferably a structural unit M2 and a structural unit M3. Next, the specific example of structural unit M2 and M3 is demonstrated.
[86] As a specific example which is preferable as a monomer which provides structural unit M2, when a ketone group containing part (for example, above-mentioned 1st-7th Rf) is represented by Rf ',
[87]
[88]
[89] (Where n is an integer of 1 to 30).
[90] More specifically,
[91]
[92] (Wherein, n is an integer from 0 to 30, Rf ^1, Rf ² is a perfluoroalkyl alkyl group having 1 to 5 carbon atoms), and the like.
[93] As a specific example as a monomer which provides structural unit M3, when a ketone group containing part is represented by Rf ',
[94] Etc. can be mentioned.
[95] More specifically,
[96]
[97] (Wherein m is an integer of 0 to 30, n is an integer of 1 to 3, and Rf ¹ and Rf ² are perfluoroalkyl groups having 1 to 5 carbon atoms).
[98] In addition to these structural units M2 and M3, as a preferable specific example of the monomer which comprises the structural unit M of the (I) functional group containing fluoropolymer, a ketone group containing part (for example, said 1st-7th Rf) is used, for example. Rf ′
[99]
[100] Here, Rf ⁿ is the same as the above, etc. are mentioned.
[101] More specifically,
[102]
[103] Here, Rf 'is the same as the above.
[104] (I) functional group containing fluoropolymer used by this invention WHEREIN: Structural unit A is an arbitrary component, if it is a monomer copolymerizable with structural unit M, M1, M2, or M3, it will not specifically limit, The target (I) It can select suitably according to the required characteristic etc. of a functional group containing fluoropolymer.
[105] As structural unit A, the following structural units can be illustrated, for example.
[106] ① a structural unit derived from a fluorine-containing ethylenic monomer having a functional group having no> C═O moiety
[107] They are preferable at the point which can provide adhesiveness with respect to a base material, and the solubility to a solvent, especially a general purpose solvent, maintaining transparency in the near-infrared region of a functional group containing fluoropolymer and its hardened | cured material, In addition, a crosslinkability etc. It is preferable in that it can give the function of. A preferred fluorine-containing ethylenic monomer for the structural unit having a functional group, to a structural unit represented by the formula (6), particularly CH ₂ = CFCF ₂ ORf ¹³ -Z ¹ (wherein, Rf ¹³ and Z ¹ are the same as for Preferred are structural units derived from
[108]
[109] Wherein X ¹¹ , X ¹² and X ¹³ are the same or different and are H or F, X ¹⁴ is H, F or CF ₃ , h is an integer from 0 to 2, i is 0 or 1, and Rf ¹³ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, and Z ¹ is -OH, -CH ₂ OH, -SO ₃ H, a sulfonic acid derivative, an epoxy group, a cyano group It is 1 or more types chosen from.
[110] More specifically,
[111]
[112] Structural units derived from fluorine-containing ethylenic monomers such as (wherein Z ¹ is the same as above) are preferably mentioned.
[113] Also,
[114] Structural units derived from CF ₂ = CFORf ¹³ -Z ¹ , wherein Rf ¹³ and Z ¹ are the same as above, may be preferably exemplified, and more specifically,
[115]
[116] And structural units derived from monomers such as (wherein Z ¹ is the same as above).
[117] In addition, as a functional group containing fluorine-containing ethylenic monomer
[118]
[119] (Wherein Z ¹ is the same as described above, and Rf ²⁰ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms);
[120]
[121] (Wherein Z ¹ is the same as above) and the like.
[122] ② structural units derived from fluorine-containing ethylenic monomers containing no functional groups
[123] These are preferable at the point that the refractive index of a functional group containing fluoropolymer or its hardened | cured material can be kept low, and further low refractive index can be made. In addition, the mechanical properties of the polymer, the glass transition point and the like can be adjusted by selecting the monomer, and in particular, the glass transition point can be increased by copolymerizing with the structural unit M, which is preferable.
[124] As a structural unit of this fluorine-containing ethylenic monomer (2), what is represented by following General formula (7) is preferable.
[125]
[126] Wherein X ¹⁵ , X ¹⁶ and X ¹⁸ are the same or different and are H or F, X ¹⁷ is H, F or CF ₃ , h1, i1 and j are the same or different and are 0 or 1, Z ² is H, F or Cl, and Rf ¹⁴ is a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group containing an ether bond having 2 to 100 carbon atoms.
[127] As a specific example,
[128]
[129] Structural units derived from monomers such as these are preferable.
[130] (3) structural units of aliphatic rings having fluorine
[131] The introduction of these structural units 3 is preferable in that transparency can be enhanced, lower refractive index can be obtained, and a functional group-containing fluoropolymer having a high glass transition point can be obtained.
[132] As a structural unit (3) of a fluorine-containing aliphatic ring, it is preferable to represent with following formula (8).
[133]
[134] Wherein X ¹⁹ , X ²⁰ , X ²³ , X ²⁴ , X ²⁵ and X ²⁶ are the same or different and are H or F, X ²¹ and X ²² are the same or different and are H, F, Cl or CF ₃ Rf ¹⁵ is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 10 carbon atoms, n2 is an integer of 0 to 3, and n1, n3, n4 and n5 are the same or Different and an integer of 0 or 1.
[135] For example
[136]
[137] There may be mentioned a structural unit represented by (wherein, Rf ^15, X ²¹ and X ²² are the same also as defined above).
[138] Specifically
[139]
[140] (Wherein X ¹⁹ , X ²⁰ , X ²³ and X ²⁴ are the same as above).
[141] As another fluorine-containing aliphatic cyclic structural unit, for example
[142] Etc. can be mentioned.
[143] (4) structural units derived from ethylenic monomers containing no fluorine
[144] The structural unit (4) derived from the ethylenic monomer which does not contain fluorine in the range which does not deteriorate refractive index (high refractive index) may be introduce | transduced.
[145] This is preferable because the solubility in a general purpose solvent can be improved or compatibility with an additive, for example, a photocatalyst and the hardening | curing agent added as needed can be improved.
[146] As a specific example of a non-fluorine ethylenic monomer,
[147] α-olefins:
[148] Ethylene, propylene, butene, vinyl chloride, vinylidene chloride, etc.
[149] Vinyl ether or vinyl ester monomers:
[150] CH ₂ = CHOR, CH ₂ = CHOCOR, where R is a hydrocarbon group of 1 to 20 carbon atoms, etc.
[151] Allyl monomers:
[152] CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH ₂ OH, CH ₂ = CHCH ₂ COOH, CH ₂ = CHCH ₂ Br, etc.
[153] Allyl ether monomer:
[154]
[155] Acrylic or methacrylic monomers:
[156] In addition to acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, maleic anhydride, maleic acid, maleic acid ester, etc. are mentioned. It is more preferable from the viewpoint of near-infrared transparency that the hydrogen atom of these non-fluorine-type ethylenic monomers was partially or fully substituted by the deuterium atom.
[157] ⑤ structural units derived from alicyclic monomers
[158] As a copolymerization component of the structural unit M, More preferably, In addition to the structural unit of the structural unit M and the above-mentioned fluorine-containing ethylenic monomer or non-fluorine ethylenic monomer (3, above), an alicyclic type as a 3rd component Since monomer structural unit (5) can also be introduce | transduced and high glass transition point and high hardness can be aimed at, it is preferable.
[159] As a specific example of the alicyclic monomer ⑤,
[160] Where m is an integer from 0 to 3, A, B, C and D are the same or different and are H, F, Cl, COOH, CH ₂ OH or a perfluoroalkyl group having 1 to 5 carbon atoms, etc. Norbornene derivatives,
[161]
[162] Alicyclic monomers, such as these, The derivative which introduce | transduced a substituent into these, etc. are mentioned.
[163] In the (I) functional group containing fluoropolymer used for the composition of this invention, it is represented by following General formula (20), The fluoropolymer containing 0.1-100 mol% of structural unit M and 0-99.9 mol% of structural unit A is not described in literature. New polymers.
[164]
[165] In the formula, the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the following formula (21), and the structural unit A is a structural unit derived from the monomer copolymerizable with the structural unit M.
[166]
[167] Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf ^x is a group represented by the following formula (22), (23), (24), (25) or 26 (26), a is an integer of 0 to 3, b and c are the same or different, and are 0 or 1.
[168] Examples of Rf ^x include the following.
[169]
[170] Wherein X ⁶ is H or D, X ⁷ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or a halogen atom, and Y ¹ is H, D, OH, OD, R ¹ or OR ² , wherein R ¹ and R ² are the same or different and some or all of the hydrocarbon groups having 1 to 10 carbon atoms or their hydrogen atoms are substituted with deuterium or halogen atoms Rf ⁴ is a fluorine-containing alkylene group having 1 to 49 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 99 carbon atoms.
[171]
[172] Wherein X ⁶ is H or D, X ⁷ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or a halogen atom, and Rf ⁵ is 1 carbon atom A fluorine-containing alkylene group having from 48 to 48 or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, Rf ⁶ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a fluorine-containing alkyl group having ether bonds having 2 to 98 carbon atoms, Rf ⁵ is a fluorine-containing alkylene group, and when Rf ⁶ is a fluorine-containing alkyl group, the total carbon number of Rf ⁵ and Rf ⁶ is 49 or less, and any one of Rf ⁵ and Rf ⁶ has an ether bond or a fluorine-containing alkylene group or fluorine; If a phosphorus-containing group has a carbon number of 99 or less in total of Rf ⁵ and Rf ^6.
[173]
[174] Wherein X ⁶ is H, D or a halogen atom, Y ¹ and Y ² are the same or different and H, D, OH, OD, R ¹ or OR ² where R ¹ and R ² are the same or Different from each other, a hydrocarbon group having 1 to 10 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ⁷ is a fluorine-containing alkylene group having 1 to 49 carbon atoms or an ether bond having 2 to 99 carbon atoms. It is a fluorine-containing alkylene group which has.
[175]
[176] Wherein X ⁶ is H, D or a halogen atom, Rf ⁸ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ⁹ and Rf ¹⁰ are the same or Or a different fluorine-containing alkyl group having 1 to 48 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 98 carbon atoms, Rf ⁸ is a fluorine-containing alkylene group, and Rf ⁹ and Rf ¹⁰ are both fluorine-containing alkyl groups; ^The total carbon number of ⁸ , Rf ⁹ and Rf ¹⁰ is 49 or less, and when one or two of Rf ⁸ , Rf ⁹ and Rf ¹⁰ are a fluorine-containing alkylene group or a fluorine-containing alkyl group having an ether bond, Rf ⁸ , Rf ⁹ and The total carbon number of Rf ¹⁰ is 99 or less.
[177]
[178] Wherein X ⁶ is H, D or a halogen atom, Y ¹ is H, D, OH, OD, R ¹ or OR ² , wherein R ¹ and R ² are the same or different and have from 1 to 10 carbon atoms A hydrocarbon group or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms), Rf ¹¹ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, Rf ¹² is a group having a carbon number of 1 to 48 and a fluorine-containing alkyl group or fluorine-containing alkyl group having ether bond having 2 to 98, Rf ¹¹ is a containing alkylene group fluorine, if at the same time an alkyl group that Rf ¹² containing fluorine is Rf ¹¹ and Rf ¹² The total carbon number is 49 or less, and when either of Rf ¹¹ and Rf ¹² is a fluorine-containing alkylene group or fluorine-containing alkyl group having an ether bond, the total carbon number of Rf ¹¹ and Rf ¹² is 99 or less.
[179] As the structural unit M in the general formula (20), the structural units M1, M2 and M3 represented by the following general formulas (27), (28) and (29), respectively, are preferable.
[180] Structural unit M1 derived from the fluorine-containing ethylenic monomer represented by the structural unit M1 represented by following formula (27).
[181]
[182] ^{Wherein, X 1, X 2, X} 3, X 4, X 5, Rf x, a and c are as defined in the general formula 21.
[183] Moreover, the structural unit M2 derived from the fluorine-containing ethylenic monomer represented by the structural unit M2 represented by following formula (28).
[184]
[185] In formula, Rf ^x is the same as the above.
[186] In particular, the structural unit M3 derived from the fluorine-containing ethylenic monomer represented by the structural unit M3 represented by the following general formula (29).
[187]
[188] In formula, Rf ^x is the same as the above.
[189] As a specific example of the monomer which provides the structural unit M in General formula (20), although it overlaps with the illustration in the above-mentioned (I) functional group containing fluoropolymer, the following are mentioned non-limitingly.
[190]
[191]
[192] (Where n is an integer of 0 to 30, and Rf ¹ , Rf ² are perfluoroalkyl groups having 1 to 5 carbon atoms),
[193]
[194] (Wherein m is an integer of 0 to 30, n is an integer of 1 to 3, Rf ¹ , Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms),
[195]
[196]
[197] Where Rf 'is as defined above.
[198] In addition, the fluorine-containing ethylenic monomer represented by following formula (30) which is a monomer which provides the structural unit M represented by general formula (20) is a novel compound not described in literature. Moreover, the above-mentioned thing can be illustrated as a specific example of this novel monomer.
[199]
[200] Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf ^x is a group represented by Formula 22, 23, 24, 25 or 26, a is an integer of 0 to 3, b and c are the same or different and 0 or 1.
[201] The present invention also provides a composition comprising (I) a functional group-containing fluoropolymer and (II) rare earth metal ions, wherein (I) the functional group-containing fluoropolymer contains a portion of the polymer represented by the following formula (10) in the polymer: It also relates to a composition.
[202] <Formula 10>
[203]
[204] Wherein X ³⁰ is H or D (deuterium), X ³¹ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ³⁰ Is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ³¹ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a ether bond having 2 to 98 carbon atoms. Rf ³⁰ is a fluorine-containing alkylene group, and at the same time, when Rf ³¹ is a fluorine-containing alkyl group, the total carbon number of Rf ³⁰ and Rf ³¹ is 49 or less, and either of Rf ³⁰ and Rf ³¹ is a fluorine-containing alkyl having an ether bond. when the group or fluorine-containing alkyl group has a carbon number of 99 or less in total of Rf ³⁰ and Rf ^31.
[205] As a specific example of the structural site | part represented by Formula (10),
[206] Etc. can be mentioned. In addition, in the following description, the structural unit represented by General formula (10) is called structural unit M. FIG.
[207] In the (I) functional group-containing fluoropolymer used in the present invention, the combination and composition ratio of the structural unit M (M1, M2, M3) and the structural unit A are based on the above-mentioned examples. Advantage, hardness, etc.), function (transparency, refractive index), etc. can be variously selected.
[208] In the functional group-containing fluoropolymer (I) used in the present invention, the structural unit M (M1, M2, M3) is included as an essential component, and the structural unit M itself provides a function of providing transparency in the near infrared region ( II) It has the characteristic of forming a stable structure by forming a complex or a salt with rare earth metal ions. Therefore, the (I) functional group containing fluoropolymer can maintain high transparency in a near-infrared region, even if it is a composition containing many structural units M and extremely polymers consisting only of structural unit M (100 mol%). Moreover, it is also preferable at the same time to form a complex or salt with (II) rare earth metal ion, and to form a stable structure.
[209] In addition, in the case of the copolymer containing the structural unit M and the structural unit A of the functional group-containing fluoropolymer (I), by selecting the structural unit A from the above examples, the hardness is higher, the glass transition point is high, and the near infrared transparency is high. A polymer can be obtained.
[210] (I) When the functional group-containing fluoropolymer is a copolymer of the structural unit M and the structural unit A, the content of the structural unit M may be 0.1 mol% or more based on the total structural units constituting the (I) functional group-containing fluoropolymer, but (II In order to obtain a stable structure with a rare earth metal ion, it is preferable to set it as 2.0 mol% or more, Preferably it is 5 mol% or more, More preferably, it is 10 mol% or more.
[211] In particular, in order to form a highly efficient light amplifying material or light emitting material, it is preferable to contain 10 mol% or more, preferably 20 mol% or more and further 50 mol% or more. An upper limit is less than 100 mol%.
[212] Since the transparency of the (I) functional group-containing fluoropolymer used in the present invention does not decrease even when the proportion of the structural unit M is increased ((II) when the coordination sites of the rare earth metal ions are increased), the use of optical amplification materials in particular in the near infrared region is used. And light-emitting materials for use in the near-infrared region from visible light.
[213] In addition, the (I) functional group-containing fluoropolymer requires amorphous combinations of the structural unit M and the structural unit A when high transparency, such as an optical amplifying material and optical material in the visible region, in the near infrared region, is required for optical communication applications. It is important to have a combination and composition that can be. Here, amorphous is a property in which the endothermic peak based on melting is not observed or the amount of heat of fusion is 1 J / g or less when measured under conditions of a temperature rising rate of 10 ° C./min in DSC analysis (ASTM D3418-99). Indicates.
[214] Moreover, as for the fluorine content rate of (I) functional group containing fluoropolymer, 25 weight% or more is preferable.
[215] When the fluorine content is low, transparency in the near infrared region is lowered. In addition, when the fluorine content is low, the absorbency is also increased, so that it cannot be substantially used as an optical material for optical communication. As an optical amplification material and a light emitting material use, the most preferable fluorine content rate is 40 weight% or more. Although the upper limit of a fluorine content rate changes with the composition of (I) fluoropolymer, it is a fluorine content rate when all hydrogen atoms are substituted by the fluorine atom, and it is about 75 weight%.
[216] The (I) functional group-containing fluoropolymer used in the present invention preferably has a maximum absorbance coefficient of 1 cm ⁻¹ or less in a specific communication band (1290 to 1320 nm or 1530 to 1570 nm or 600 to 900 nm). It is not suitable for the optical amplification material used for optical communication to show a higher absorbance coefficient than this.
[217] The rare earth metal ion (II) which is another component in the fluorine resin composition of this invention is mix | blended in order to give a resin composition a function which gives light functionality, ie, an optical amplification action and a light emission effect.
[218] (II) rare earth metal ions used in the present invention include erbium (Er) ions, thulium (Tm) ions, praseodymium (Pr) ions, holmium (Ho) ions, neodymium (Nd) ions, and europium (Eu) ions. One or more types selected from the group can be mentioned. The fluororesin composition of the present invention contains (II) rare earth metal ions in the form of a cation, but the rare earth metal cations may be single or mixed in plural kinds.
[219] The valence of the rare earth metal cation is not limited and is usually used as a divalent or trivalent cation, and is usually formulated in the form of a rare earth metal compound or a complex. As a rare earth metal compound, Halides, such as a chloride, bromide, and iodide; Salts, such as nitrate, perchlorate, bromate, acetate, sulfate, and phosphate, are preferable at the point that the dispersibility with respect to the (I) functional group containing fluoropolymer is favorable. Moreover, binitrate, bisulfate, chelate, and a complex can also be used. For example, sulfonamide, sulfonimide, (beta) -diketone, sulfonic acid, phosphoric acid, etc. are mentioned. Especially, these fluorine-containing compounds are preferable.
[220] Examples of halides or salts containing rare earth metal ions preferred in the present invention include praseodymium chloride, praseodymium bromide, praseodymium iodide, praseodymium nitrate, praseodymium perchlorate, praseodymium bromide, praseodymium acetate, praseodymium sulfate, and praseodymium phosphate; Neodymium salts such as neodymium chloride, neodymium bromide, neodymium iodide, neodymium nitrate, neodymium perchlorate, neodymium bromide, neodymium acetate, neodymium sulfate, and neodymium phosphate; Europium chloride, europium bromide, europium iodide, europium nitrate, europium perchlorate, europium bromide, europium acetate, europium sulfate, europium phosphate, etc. And erbium salts such as erbium acetate, erbium sulfate and erbium phosphate.
[221] Moreover, as a complex containing a preferable rare earth metal ion, for example, tris (dibenzoylmethed) erbium (III), tris (benzoyltrifluoroacetonato) erbium (III), and tris (hexafluoroacetonato) ) Erbium (III), tris (dibenzoylmethed) erbium (III), tris (benzoyltrifluoroacetonato) erbium (III), tris (hexafluoroacetonato) erbium (III), tris (di Benzoylmethed) neodymium (III), tris (benzoyltrifluoroacetonato) neodymium (III), tris (hexafluoroacetonato) neodymium (III), etc., and these include tetrakis (hexafluoro) It may also be a tetrakis complex such as acetonato) neodymium (III). Nd [C ₈ F ₁₇ SO ₂ NSO ₂ C ₈ F ₁₇ ] ₃ , Nd [C ₄ F ₉ SO ₂ NSO ₂ C ₄ F ₉ ] ₃ , Nd [C ₆ F ₅ SO ₂ NSO ₂ C ₆ F ₅ ] ₃ , Nd [C ₄ F ₉ SO ₂ NSO ₂ C ₆ F ₅ ] ₃ , Nd [C ₄ F ₉ SO ₂ NSO ₂ C ₈ F ₁₇ ] ₃ , Nd [C ₆ F ₁₃ SO ₂ NSO ₂ C ₆ F ₁₃ ] ₃ , Nd [C ₂ F ₅ SO ₂ NSO ₂ C ₂ F ₅ ] ₃ , Nd [CF ₃ SO ₂ NSO ₂ CF ₃ ] ₃ , Nd [C ₄ F ₉ SO ₂ NCOC ₃ F ₇ ] ₃ , Nd [C ₄ F ₉ SO ₂ NCOCF ₃ ] ₃ , Nd [O ₃ SC ₈ F ₁₇ ] ₃ , Nd [O ₃ SCF ₃ ] ₃ , and the like.
[222] Among them, in the use of optical amplifiers for optical communication, praseodymium salts, neodymium salts and erbium salts having a fluorescence generating ability in the near infrared region, complexes thereof, and the like are particularly preferable. Among them, preferable signals are preferable for optical fibers of inorganic glass such as silica glass. Most preferred are neodymium salts, praseodymium salts and erbium salts and complexes thereof having the ability to generate fluorescence having a wavelength of about 1300 nm to 1550 nm. Moreover, the europium salt and its complex are most preferable for amplification of the 650 nm band which is a visible wavelength range used when an organic polymer material is used as an optical fiber. In the use as a light emitting element, a blue luminescence thorium salt, a green luminescence terbium salt, and a red luminescence europium salt are preferable.
[223] It is preferable that the fluororesin composition of this invention contains 0.001-25 weight% of (II) rare earth metal ions (weight% as an ion and the content of (II) rare earth metal ions are the same below). Although it depends on the kind of (II) rare earth metal ion and (I) functional group containing fluoropolymer to be used, etc., when the content of (II) rare earth metal ion is less than 0.001 weight%, preferable properties, such as a target optical amplification effect, are not exhibited. On the other hand, when it exceeds 25 weight%, the dispersibility of rare earth metal ions may worsen, and all are unpreferable. When used as an optical communication component such as an optical amplifier or an optical waveguide or a light emitting element, the content of the rare earth metal ions is preferably selected in the range of 0.01 to 20 wt% in terms of fluorescence intensity, and more preferably 0.1 to 15 wt%. 0.5 to 10% by weight is most preferred. In addition, the content of the rare earth metal ions can be quantitatively measured by burning an organic component in an electric furnace at a temperature of about 600 ° C. and quantitating the ash, or by physicochemical methods such as fluorescence X-ray analysis.
[224] When the fluorine resin composition of the present invention is used in optical communication, the absorbance coefficient of each wavelength band of each communication band, i.e., 600 to 900 nm, 1290 to 1320 nm, and 1530 to 1570 nm, must be 1 cm ^-1 or less. . If the absorbance coefficient exceeds 1 cm ⁻¹ in this wavelength range, the optical signal itself is absorbed and hardly acts as an optical amplifier. Therefore, as described above, the functional group-containing fluoropolymer (I) is required to have an absorbance coefficient of 1 cm ⁻¹ or less in all wavelength ranges of 600 to 900 nm, 1290 to 1320 nm, and 1530 to 1570 nm. In addition, since the composition containing (II) rare earth metal ions exhibits a sensitive absorption of the rare earth itself at a specific wavelength, the absorbance coefficient of the composition may exceed 1 cm ⁻¹ at that wavelength. That is, the characteristic absorption wavelength of rare earth metal ions is, for example, 980 nm or 1480 nm in erbium, 820 nm in neodymium, 1017 nm in praseodymium, and the like. When used as a visible light emitting material, one that is transparent in the visible band is preferable.
[225] In an optical amplifier such as an optical fiber amplifier that serves to restore attenuation of communication light, an excitation light (pump light) that effectively excites rare earth metal ions that generate fluorescence of a communication light wavelength is continuously passed continuously at a constant time, By the induced emission phenomenon, the same fluorescence as this pulse waveform is generated to act as an amplifying action. Therefore, when using the fluorine resin composition of this invention as an optical amplifier use, it is necessary to have the fluorescence generation ability in the excitation light derived from (II) rare earth metal ion.
[226] In addition, the light emitting element contains rare earth metal ions that generate fluorescence from the visible light to the wavelength of the near infrared band, and irradiates the excitation light to obtain light emission of a desired wavelength. Therefore, when using the fluorine resin composition of this invention as a light emitting use, it is necessary to have the fluorescence generation ability in the excitation light derived from (II) rare earth metal ion.
[227] From such a viewpoint, the fluororesin composition used for the light amplifying material or the light emitting material is a (I) functional group-containing fluoropolymer to be used,
[228] (a) a specific functional group-containing fluoropolymer of Formula 1 having at least one ketone structure in the side chain,
[229] (b) the maximum absorbance coefficient in each wavelength range of 1290 to 1320 nm and / or 1530 to 1570 nm and / or 600 to 900 nm is 1 cm ⁻¹ or less,
[230] (c) Rare earth metal ions are selected from the group consisting of erbium (Er) ions, thulium (Tm) ions, praseodymium (Pr) ions, holmium (Ho) ions, neodymium (Nd) ions, and europium (Eu) ions It may be a fluorine resin composition as described above.
[231] The fluorine resin composition of this invention can be manufactured by containing (II) rare earth metal ion in the (I) functional group containing fluoropolymer. (II) There is no restriction | limiting in particular in the method of including rare earth metal ion in the (I) functional group containing fluoropolymer. (II) dissolving or dispersing the compound or complex containing rare earth metal ions in a (I) functional group-containing fluoropolymer, or (I) an ionic bond, a coordinating bond to a functional group (especially a ketone group) of the functional group-containing fluoropolymer, It is also possible to carry (II) rare earth metal ions by inclusion.
[232] For example, (1) After adding the compound and complex containing the said (II) rare earth metal ion to the functional group containing fluorine monomer which provides structural unit M, by well-known synthesis methods, such as a melt polymerization method and an anion polymerization method, I) A method for producing a functional group-containing fluoropolymer, (2) (I) a solvent after dissolving the functional group-containing fluoropolymer in a solvent and then adding and mixing the compound or complex containing the (II) rare earth metal ion Or (3) a method of melt kneading a compound or complex containing the (I) functional group-containing fluoropolymer and the above (II) rare earth metal ions.
[233] Among these, the method of said (2) is the most preferable at the point that the dispersibility of the compound containing a rare earth metal ion in a functional group containing fluoropolymer, or a complex is favorable. A particularly preferable method is a method in which a functional group-containing fluoropolymer is dissolved in a compound or complex solution containing the rare earth metal ions, and the resulting homogeneous solution is heated to distill off the solvent. In addition, the composition of a solution or dispersion state can also be used as a source of the solution in an optical element formation process, without distilling a solvent off.
[234] Therefore, the (I) functional group-containing fluoropolymer is preferably soluble in an organic solvent, particularly a general purpose solvent, and is soluble in at least one general purpose solvent among, for example, a ketone solvent, an acetate ester solvent, an alcohol solvent, and an aromatic solvent. Or soluble in a mixed solvent containing one or more of the above general purpose solvents. Solvent solubility can be suitably adjusted by selecting the kind of structural unit M, content rate, and the kind of copolymerization structural unit A used as needed.
[235] If it is soluble in a general-purpose solvent, when forming an optical element such as an optical amplification element using the composition of the present invention, spin coating or dip coating is possible when producing a film on a substrate, and particularly high film thickness control is required. In the case of forming the single mode waveguide, a material excellent in film formation and homogeneity can be provided, which is advantageous in terms of productivity in forming optical elements such as optical amplification elements.
[236] As such a solvent, For example, Cellosolve type solvents, such as a methyl cellosolve, an ethyl cellosolve, a methyl cellosolve acetate, an ethyl cellosolve acetate; Diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutylate, ethyl acetoacetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, 3-methoxy Ester solvents such as ethyl propionate, methyl 2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate; Propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether ; Ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone and 2-heptanone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; Aromatic hydrocarbons, such as toluene and xylene, 2 or more types of these mixed solvents, etc. are mentioned.
[237] Moreover, in order to improve the solubility of (I) functional group containing fluoropolymer, you may use a fluorine-type solvent as needed.
[238] As the fluorine-based solvent, for example, CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro ( _2- butyltetra Hydrofuran), methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, etc.
[239]
[240] Fluorine alcohols such as these;
[241] Benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF ₂ CFClCF ₂ CFCl ₂ and the like.
[242] These fluorine-based solvents may be used alone or as a mixed solvent of fluorine-based solvents or at least one of non-fluorine and fluorine-based solvents.
[243] Among these, a ketone solvent, an acetate ester solvent, an alcohol solvent, an aromatic solvent, etc. are preferable from a viewpoint of paintability, productivity of application | coating, etc. as mentioned above.
[244] The (I) functional group containing fluoropolymer of this invention may have a hardening site | part in the range which does not impair transparency in the near infrared region. The curing site is not particularly limited as long as it is a site forming a bond with itself or another kind of crosslinking site or a crosslinking agent, and the like, and may be a polymerizable group such as a vinyl group, acryloyl group, or an epoxy group; A curing group for causing a condensation reaction such as a combination of an acid chloride and a hydroxyl group in addition to the silanol group and the trifluorovinyl group; Curing group which produces addition reactions, such as a combination of a cyano group, an amino group, and -OCN group; The chemical structure which decomposes | disassembles by light irradiation, such as an iodine terminal structure, a bromine terminal structure, an azide structure, a thermal initiator, etc., and produces | generates active species, such as a radical, carbene, and nitrene, etc. are mentioned.
[245] The curing site may be present in the (I) functional group-containing fluoropolymer, but is preferably present in the polymer side chain and / or at the polymer backbone end. In addition, this hardening site | part may be contained in Rf 'which is the ketone group containing part mentioned above.
[246] Among these curing sites, a polymerizable curing group is preferable in view of good reaction efficiency, and a curing group having an addition polymerizable carbon-carbon double bond is particularly preferable. In addition, carbon-carbon double bonds are preferably present at the polymer side chain ends. As a kind of addition polymerization reaction, it may be any of radical polymerization, cationic polymerization, and anionic polymerization.
[247] The following are mentioned as a specific example of the hardening machine which has the addition polymeric carbon-carbon double bond which exists in a polymer side chain terminal.
[248]
[249] Although the fluororesin composition of this invention can be obtained only by (I) functional group containing fluoropolymer and (II) rare earth metal ion, when (I) functional group containing fluoropolymer has a hardening site, it is (III) an active energy ray hardening initiator (III-1) An optical radical generator or (III-2) photo-acid generator can be further added, and it can also be set as the photocurable composition.
[250] (III) The active energy ray curing initiator, for example, radiates radicals, cations (acids) and the like by irradiating electromagnetic waves in the wavelength region of 350 nm or less, that is, active energy rays such as ultraviolet rays, electron beams, X rays, and γ rays. It generates, and functions as a catalyst which initiates hardening (crosslinking reaction) through the hardening site | part of a fluoropolymer, and what generate | occur | produces a radical and a cation (acid) by ultraviolet-ray, especially what produces a radical is used.
[251] (I) When the functional group-containing fluoropolymer has a curing site, according to the fluorine resin composition for the optical amplifying material or the light emitting material of the present invention, the curing reaction can be easily initiated by the active energy ray and heated at a high temperature. It is not necessary to use it, and since curing reaction is possible at a relatively low temperature, heat resistance is low, and it is preferable in that it can be applied also to a base material which is easily deformed, decomposed, or colored by heat, for example, a transparent resin substrate.
[252] The (III) active energy ray curing initiator in the composition of the present invention is (I) the kind of curing site (radical reactivity or cation (acid) reactivity) in the functional group-containing fluoropolymer, the kind of active energy ray to be used (wavelength region, etc.) And the irradiation strength and the like are appropriately selected.
[253] Generally, the following can be illustrated as an initiator (photo radical generator) which hardens the (I) functional group containing fluoropolymer which has a radical reactivity hardening site | part using the active energy ray of an ultraviolet-ray region.
[254] Acetophenone series:
[255] Acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, etc.
[256] Benzoin series:
[257] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.
[258] Benzophenone series:
[259] Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.
[260] Thioxanthones:
[261] Thioxanthone, chloro thioxanthone, methyl xanthone, diethyl thioxanthone, dimethyl thioxanthone, etc.
[262] Etc:
[263] Benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.
[264] Moreover, photoinitiation adjuvant, such as amines, sulfones, sulfin, can also be added as needed.
[265] Moreover, the following can be illustrated as an initiator (photoacid generator) which hardens the (I) functional group containing fluoropolymer which has a cation (acid) reactive hardening site | part.
[266] Onium salt:
[267] Iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt, etc.
[268] Sulfone compounds:
[269] β-ketoesters, β-sulfonylsulfones and α-diazo compounds thereof
[270] Sulfonic acid esters:
[271] Alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate, etc.
[272] Etc:
[273] Sulfonimide compounds, diazomethane compounds, etc.
[274] In addition, as a radical reactive curing site | part, for example, a chemical formula
[275] What is represented by these etc. is a hardening site | part of cation-reactive, For example, a chemical formula Etc. are shown.
[276] As described above, when the (I) functional group-containing fluoropolymer has a curing site, the fluororesin composition used for the light amplifying material or the light emitting material of the present invention may contain (I) the functional group-containing fluoropolymer and (II) rare earth metal ions. (III) an active energy ray curing initiator is added as needed to form a curable fluorine-containing resin composition, and a curing agent may be further added to the coating solution for fluorine-containing resin composition for coating containing a solvent described later. have.
[277] As a hardening | curing agent, what has one or more carbon-carbon unsaturated bonds, and what can superpose | polymerize with a radical or an acid is preferable, Specifically, Cationically polymerizable monomers, such as radically polymerizable monomers, such as an acryl-type monomer, and a vinyl ether monomer, are mentioned. Can be. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.
[278] These so-called curing agents having carbon-carbon unsaturated bonds react with radicals or cations generated by the reaction of an active energy ray curing initiator in the composition of the present invention with active energy rays such as light, and the (I) functional group in the composition of the present invention. When it has a carbon-carbon double bond as a hardening site of a containing fluoropolymer, bridge | crosslinking can be achieved by copolymerization with a carbon-carbon double bond.
[279] Examples of monofunctional acrylic monomers include epoxy groups, in addition to acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, α-fluoroacrylic acid, α-fluoroacrylic acid esters, maleic acid, maleic anhydride, maleic acid esters, (Meth) acrylic acid ester which has a hydroxyl group, a carboxyl group, etc. are illustrated.
[280] Especially, in order to maintain the near-infrared transparency of hardened | cured material high, the acrylate-type monomer which has a fluoroalkyl group is preferable, For example, A compound represented by (wherein X is H, CH ₃ or F, and Rf is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms) is preferable.
[281] Specifically
[282]
[283] (Wherein X is H, CH ₃ or F, n is an integer of 1 to 5), and the like.
[284] Generally as a polyfunctional acryl-type monomer, the compound which substituted the hydroxyl group of polyhydric alcohols, such as diol, a triol, and tetraol, with an acrylate group, a methacrylate group, and the (alpha)-fluoroacrylate group is known.
[285] Specific polyhydric alcohols, such as 1, 3- butanediol, 1, 4- butanediol, 1, 6- hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, and dipentaerythritol The compound in which two or more hydroxyl groups were substituted by any of an acrylate group, a methacrylate group, and the (alpha)-fluoroacrylate group is mentioned.
[286] In addition, polyfunctional acrylic monomers in which two or more hydroxyl groups in a polyhydric alcohol having a fluorine-containing alkyl group or a fluorine-containing alkylene group are substituted with an acrylate group, a methacrylate group and an α-fluoroacrylate group can also be used. It is preferable at the point which can maintain high near-infrared transparency of hardened | cured material.
[287] As a specific example
[288]
[289] (Wherein Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms),
[290]
[291] (Wherein Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms, R is H or an alkyl group having 1 to 3 carbon atoms),
[292]
[293] (Wherein Rf 'is a fluorine-containing alkylene group having 1 to 40 carbon atoms, R is H or an alkyl group having 1 to 3 carbon atoms) and at least two hydroxyl groups in the fluorine-containing polyhydric alcohol represented by the formula The thing of the structure substituted by the group, the methacrylate group, or the (alpha)-fluoroacrylate group is mentioned preferably.
[294] Moreover, especially when these illustrated monofunctional and polyfunctional acryl-type monomers are used for the composition of this invention as a hardening | curing agent, especially the (alpha)-fluoroacrylate compound is preferable at the point that hardening reactivity is favorable.
[295] In the fluorine resin composition for the optical amplifying material or the luminescent material of the present invention, the amount of the active energy ray curing initiator added depends on the content of the curing site in the (I) fluoropolymer, whether or not the curing agent is used and the amount of the curing agent used. It is appropriately selected depending on the initiator used, the type of active energy ray and the amount of irradiation energy (strength and time, etc.), but when no curing agent is used, (I) 0.01 to 30 parts by weight, and 0.05 to 100 parts by weight of the fluoropolymer To 20 parts by weight, most preferably 0.1 to 10 parts by weight.
[296] More specifically, (I) 0.05-50 mol% with respect to content (molar number) of the hardening site | part contained in a fluoropolymer, Preferably it is 0.1-20 mol%, Most preferably, it is 0.5-10 mol%.
[297] When using a hardening | curing agent, (I) 0.05-50 mol% with respect to the total number of moles of content (molar number) of the hardening site | part contained in a fluoropolymer, and the mole number of the carbon-carbon unsaturated bond of a hardening | curing agent, Preferably it is 0.1-20 mol %, Most preferably, it is 0.5-10 mol%.
[298] Various additives can also be mix | blended with the composition of this invention as needed in addition to the compound mentioned above.
[299] As such an additive, a leveling agent, a viscosity modifier, a light stabilizer, a water absorbing agent, a pigment, dye, a reinforcing agent, etc. are mentioned, for example.
[300] The present invention also relates to an optical element using the fluorine resin composition described above in the core portion, that is, an optical amplifying element and a light emitting element.
[301] As a method for producing an optical element, that is, an optical amplifying element or a light emitting element using the fluorine resin composition of the present invention, a fluorine resin composition is dissolved in a suitable solvent to prepare a coating liquid, and the coating liquid is applied onto a predetermined substrate. By forming a film of the fluorine composition of the present invention, and then patterning the film into the shape of an optical amplifying part or a light emitting part by a method, a method of forming an optical amplifying part or a light emitting part can be used.
[302] Additives, such as an active energy ray hardening initiator, a hardening | curing agent, a leveling agent, an optical stabilizer, may be contained in the coating liquid containing the composition of this invention for forming the pattern of this light amplification part and a light emitting part. Moreover, as a solvent which prepares a coating liquid, if it melt | dissolves or disperse | distributes the composition of this invention uniformly, it will not specifically limit, Especially the said general purpose solvent which melt | dissolves (I) functional group containing fluoropolymer uniformly is preferable.
[303] An optical amplification element is a kind of optical waveguide device generally having a core portion and a covering portion, and refers to an element whose signal intensity is amplified while an optical signal passes through a core portion of an optical waveguide formed on a substrate. In this optical amplifying element, it is necessary to form the core part with a material having an optical amplifying effect.
[304] The optical amplifying element of the present invention is constructed by constructing a core portion (optical waveguide portion having an optical amplifying effect) from the fluorine resin composition containing the rare earth metal ions of the present invention described above.
[305] In order to use the fluorine resin composition of this invention as a core part of an optical amplification element, a suitable coating material is required. As the material for the coating part, it is necessary to use a material having a lower refractive index than the material of the core part. When the fluororesin composition of the present invention is used as the core part, the material for the coating part is not particularly limited and existing organic materials can be used. Of course, the above-mentioned (I) functional group containing fluoropolymer can also be used without mix | blending rare earth metal ion.
[306] The light emitting element of the present invention is, for example, an EL element, a polymer light emitting diode, a light emitting diode, a fiber laser, a laser element, an optical fiber, a liquid crystal backlight, an optical detector, and the like, and a large display, an illumination, a liquid crystal, an optical disk, a laser printer, a medical device It is applied to laser, laser processing, printing and copying equipment.
[307] In the case of a light emitting element composed of a core portion and a coating portion, the light emitting material of the present invention is used in the core portion similarly to the optical amplification element, and a conventional organic material, for example, the aforementioned (I) functional group-containing fluoropolymer is used for the coating portion. You can use it as it is.
[308] The optical amplification element and the light emitting element of the present invention can be produced by a conventionally known manufacturing method, except that the fluororesin composition of the present invention is used as the core portion.
[309] The general manufacturing process of an optical waveguide device (optical amplifying element and light emitting element) is shown in FIG. First, the lower coating layer 2 is formed on the substrate 1. This coating layer 2 uses a material having a low refractive index with respect to the core layer 3. Next, the fluororesin composition of the present invention is formed as the core layer 3 on the lower coating layer 2. Furthermore, the mask pattern 4 of an optical waveguide is formed on the core layer 3 by the photolithography method. The core layer 3 on which the mask pattern 4 is formed is etched using the Reactive Ion Etching (RIE) method to form the core pattern 5 of the optical waveguide. After removing the mask, the upper coating layer 6 is formed on the core pattern 5 of the optical waveguide to form an optical waveguide (optical amplifying element and light emitting element).
[310] In addition, the optical amplifying element and the light emitting element of the present invention can construct a more versatile optical circuit by integrating with other optical elements. As another optical element, arbitrary things, such as an optical switch, an optical filter, and an optical branching element, are mentioned. In particular, the optical branching element connected to the optical amplification element of this invention and the core part output terminal of this optical amplification element, and including the N branch waveguide (N is an integer of 2 or more) comprised of the same material as the said core part is integrated in the same board | substrate. The optical circuit provided with is preferable because it can be a branching element with little optical loss.
[15] The present inventors have intensively studied to achieve this object, and as a result, they have discovered a novel functional group-containing fluoropolymer having a ketone structure in the side chain, and using this functional group-containing fluoropolymer, combining rare earth metal ions therewith Optical materials, i.e., light amplifying materials and light emitting materials, and find that it is particularly useful to combine rare earth metal ions with specific fluoropolymers having a ketone structure at the side chain ends as optical materials, namely light amplifying materials and light emitting materials. It was.
[16] Based on this fact, the present inventors came to complete the following this invention.
[17] The present invention comprises (I) a functional group-containing fluoropolymer and (II) rare earth metal ions, and (I) the functional group-containing fluoropolymer is represented by the following general formula (1), wherein the structural unit M is 0.1 to 100 mol%, and the structural unit A is The fluorine resin composition used for the optical material which is a fluoropolymer containing 0-99.9 mol%, ie, an optical amplification material, and a luminescent material. Since the optical material based on the present invention, that is, the light amplifying material and the light emitting material has a functional group, despite the high fluorine content, the dispersibility of the rare earth metal ions is excellent, the amplification rate, the light emission intensity are high, and the light resistance and the heat resistance are excellent. . Moreover, since the refractive index is low, the characteristics as the light emitting body are improved.
[18]
[19] In the formula, the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the following formula (2), and the structural unit A is a structural unit derived from the monomer copolymerizable with the structural unit M.
[20]
[21] Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf has 1 to 5 moieties of> C═O, a fluorine-containing alkylene group having 1 to 50 carbon atoms excluding carbon of C═O or an ether bond having 2 to 100 carbon atoms excluding carbon of C═O It is a fluorine-containing alkylene group having a, a is an integer of 0 to 3, b and c are the same or different and 0 or 1.
[22] Moreover, the (I) functional group containing fluoropolymer may be a fluoropolymer which contains the site | part represented by following formula (10) in a polymer.
[23]
[24] Wherein X ³⁰ is H or D (deuterium), X ³¹ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ³⁰ Is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ³¹ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a ether bond having 2 to 98 carbon atoms. Rf ³⁰ is a fluorine-containing alkylene group, and at the same time, when Rf ³¹ is a fluorine-containing alkyl group, the total carbon number of Rf ³⁰ and Rf ³¹ is 49 or less, and either of Rf ³⁰ and Rf ³¹ is a fluorine-containing alkyl having an ether bond. when the group or fluorine-containing alkyl group has a carbon number of 99 or less in total of Rf ³⁰ and Rf ^31.
[25] Moreover, the (I) functional group containing fluoropolymer may have a hardening site | part in a polymer.
[26] As such a fluororesin composition, it is an optical material containing (I) functional group containing fluoropolymer and (II) rare earth metal ion, ie, an optical amplification material and a light emitting material composition, The said (I) functional group containing fluoropolymer has a fluorine content rate of 25 It is preferably an amorphous fluoropolymer which is at least% by weight, preferably at least 40% by weight, having at least one ketone structure in the side chain, 1290-1320 nm and / or 1530-1570 nm and / or 600-900 It is preferable that the maximum value of absorbance coefficient in each wavelength range of nm is 1 cm <^-1> or less, and (II) rare earth metal ion is erbium (Er) ion, thulium (Tm) ion, praseodymium (Pr) ion, holmium (Ho) The fluorine resin composition which is 1 or more types chosen from the group which consists of a) ion, neodymium (Nd) ion, and europium (Eu) ion is preferable.
[27] Moreover, (III) active energy ray hardening initiator can be further added and it can also be set as a curable fluororesin composition.
[28] The present invention also relates to an optical element, that is, an optical amplifying element and a light emitting element, comprising a fluorine resin composition used for such an optical material, that is, an optical amplifying material and a light emitting material.
[311] Next, although this invention is demonstrated based on an Example, this invention is not limited only to this Example.
[312] Synthesis Example 1 (Synthesis of Homopolymer of Fluorine-containing Allyl Ether Having COOH Group)
[313] 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid in a 100 ml glass four-necked flask equipped with a stirring device and a thermometer: 20.0 g and 8.5 g of 8.0 wt% of a perfluorohexane solution was added thereto, followed by nitrogen substitution, followed by stirring at 30 ° C. for 5 hours under a nitrogen stream, whereby a high viscosity solid was produced.
[314] The obtained solid dissolved in acetone was poured into perfluorohexane, separated, and dried in vacuo to give 15.09 g of a colorless transparent polymer.
[315] This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis. The polymer was composed only of the structural units of the fluorine-containing allyl ether, and was a fluorine-containing polymer having a carboxyl group at the side chain terminal. In addition, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 7000, and the weight average molecular weight was 9000.
[316] Synthesis Example 2 (Synthesis of Copolymer of Fluorine-containing Allyl Ether Having COOH Group)
[317] 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid in a 100 ml glass four-necked flask equipped with a stirring device and a thermometer: 10.1 g and 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-methyl nonenoate: Add 9.6 g and stir well 2.0 g of 8.0% by weight of a perfluorohexane solution was added to the mixture, followed by nitrogen substitution. The mixture was stirred at 20 캜 for 20 hours under a nitrogen stream, whereby a high viscosity solid was produced.
[318] The obtained solid was dissolved in acetone, poured into HCFC225 / n-hexane = 1/1 solution, separated, and dried in vacuo to obtain 13.2 g of a colorless transparent polymer.
[319] This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis. As a result, it was a fluorine-containing polymer containing structural units of the carboxyl group-containing fluorine-containing allyl ether and the fluorine-containing allyl ether having a methyl ester structure.
[320] The composition ratio was calculated | required at 42:58 (molar ratio) by NMR.
[321] In addition, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 9000, and the weight average molecular weight was 13000.
[322] Synthesis Example 3 (Synthesis of fluorine-containing allyl ether having a COCl group)
[323] 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid (422 g, 1.0 mol): SOCl ₂ (143 g, 1.2 mol) was added dropwise at 80 ° C while stirring a mixed liquid of dimethylformamide (7.4 g, 0.1 mol) into a reaction vessel. Thereafter, the reaction solution was heated to 100 ° C and stirred for 6 hours. The distillation unit was mounted in a reaction vessel, and SOCl ₂ was distilled off from the reaction solution under reduced pressure, and then the pressure was increased to further increase 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid. The crude product of chloride was taken out. The liquid was washed with concentrated sulfuric acid, distilled under reduced pressure at 60 mmHg, and 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid chloride shown below having a boiling point of 50 ° C. Was obtained (441 g, 0.91 mol, yield 91%).
[324]
[325] Synthesis Example 4 (Synthesis of fluorine-containing allyl ether having a CO group)
[326] 60% sodium hydride (1.9 g, 48 mmol) was suspended in THF (100 mL), and hexafluoroacetylacetone (10.0 g, 48 mmol) was added dropwise at 0 ° C. After stirring for 10 minutes at 0 ° C, the mixture was further stirred for 20 minutes at room temperature. Thereafter, the reaction solution was cooled to −78 ° C., and copper iodide (25 g, 131 mmol) was added at that temperature, followed by further stirring at −78 ° C. for 10 minutes and at −30 ° C. for 10 minutes. The reaction solution was cooled again to -78 ° C, and 9H, 9H-perfluoro-2,5-dimethyl-3,6-dioxa-8-nonenoic acid chloride (17.6 g, 40 mol) was added dropwise over 1 hour. It was. The reaction mixture was allowed to react until the temperature reached 10 ° C. over 6 hours. The reaction solution was filtered through celite, and ether was added to the obtained liquid, washed with 1N hydrochloric acid, followed by water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and distilled to give 3H, 12H, 12H-perfluoro-5,8-dimethyl-6,9-dioxa-3-trifluoroacetyl-11 shown below at 0.5 mmHg and 60 ° C. -Dodecene-2,4-dione (14.3 g, 23.3 mmol, yield 58%) was obtained.
[327]
[328] Synthesis Example 5 (Synthesis of Homopolymer of Fluorine-containing Allyl Ether Having a CO Group)
[329] In a 100 ml glass sand dune flask with a stirring device and a thermometer, 3H, 12H, 12H-perfluoro-5,8-dimethyl-6,9-dioxa-3-trifluoroacetyl-11-dodecene-2 4-dione: 10.0 g and 5.3 g of a 8.0 wt% perfluorohexane solution was added to the mixture, followed by sufficiently nitrogen substitution, followed by stirring at 30 ° C. for 5 hours under a nitrogen stream, whereby a high viscosity solid was produced.
[330] The obtained solid dissolved in acetone was poured into perfluorohexane, separated, and dried in vacuo to give 7.3 g of a colorless transparent polymer.
[331] This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, and found to be a fluoropolymer containing only the structural units of the fluorine-containing allyl ether and having a ketone group at the side chain terminal. In addition, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 3000, and the weight average molecular weight was 4000.
[332] Synthesis Example 6 (Comparative Synthesis Example)
[333] Compound which does not contain a functional group represented by the following formula in a 100 ml glass-necked flask equipped with a stirring device and a thermometer 10.0 g and 4.1 g of 8.0 wt% of a perfluorohexane solution was added to the mixture, followed by nitrogen substitution. The mixture was stirred at 30 ° C. for 6.5 hours under a nitrogen stream, whereby a high viscosity solid was produced.
[334] The obtained solid dissolved in acetone was poured into perfluorohexane, separated, and dried in vacuo to give 6.62 g of a colorless transparent polymer.
[335] This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis to find a fluorine-containing polymer containing only structural units of the fluorine-containing allyl ether. In addition, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 13000, and the weight average molecular weight was 20000.
[336] Example 1 (Preparation of Rare Earth Metal Containing Fluorine Resin Composition)
[337] Into a 100 ml glass four-necked flask equipped with a stirring device and a thermometer, 2.09 g of a homopolymer of fluorine-containing allyl ether having a COOH group obtained in Synthesis Example 1 and 15 g of methanol were added, followed by stirring with europium (III) tetrahydrate (Eu ( CH ₃ COO) ₃ .4H ₂ O) 0.62 g (1.54 mmol) dissolved in 8 g of water was added dropwise over 5 minutes. After dropping, stirring was continued for 2 hours, and then allowed to stand for 30 minutes to precipitate the resulting viscous solid. The supernatant methanol solution was removed along and the solid washed three times with acetone. Thereafter, the resultant was vacuum dried at 60 ° C. for 12 hours to obtain 1.93 g of a colorless transparent solid.
[338] Example 2 (Preparation of Rare Earth Metal-Containing Fluorine Resin Composition)
[339] Into a 100 ml glass four-necked flask equipped with a stirring device and a thermometer, 2.04 g of a homopolymer of fluorine-containing allyl ether having a COOH group obtained in Synthesis Example 1 and 15 g of methanol were added thereto, followed by stirring and erbium chloride hexahydrate (ErCl ₃ · 6H _2). 0) A solution of 0.61 g (1.61 mmol) dissolved in 3 g of methanol was added dropwise over 5 minutes. After dripping was continued for 2 hours, the solution was heated to 60 ° C while concentrating with an evaporator, and heating was continued for 1 hour. As a result, 2.19 g of a pale pink solid was obtained.
[340] Example 3 (Preparation of Rare Earth Metal Containing Fluorine Resin Composition)
[341] Into a 100 ml glass four-necked flask equipped with a stirring device and a thermometer, 2.05 g of a fluorine-containing allyl ether having a COOH group obtained in Synthesis Example 2 and 15 g of methanol were added thereto, followed by stirring with europium acetate (III) tetrahydrate (Eu ( CH ₃ COO) ₃ .4H ₂ O) 0.62 g (1.54 mmol) dissolved in 8 g of water was added dropwise over 5 minutes. After dropping, stirring was continued for 2 hours, and then allowed to stand for 30 minutes to precipitate the resulting viscous solid. The supernatant methanol solution was removed along and the solid washed three times with acetone. Then, it vacuum-dried at 60 degreeC for 12 hours and obtained 1.74 g of colorless transparent solids.
[342] Example 4 (Preparation of Rare Earth Metal Containing Fluorine Resin Composition)
[343] 2.00 g of a homopolymer of fluorine-containing allyl ether having a CO group obtained in Synthesis Example 5 and 15 g of methanol were added to a 100 ml glass-necked flask equipped with a stirring device and a thermometer, and stirred with europium (III) tetrahydrate (Eu ( CH ₃ COO) ₃ .4H ₂ O) 0.62 g (1.54 mmol) dissolved in 8 g of water was added dropwise over 5 minutes. After dropping, stirring was continued for 2 hours, and then allowed to stand for 30 minutes to precipitate the resulting viscous solid. The supernatant methanol solution was removed along and the solid washed three times with acetone. Thereafter, vacuum drying was carried out at 60 ° C. for 12 hours to obtain 2.03 g of a colorless transparent solid.
[344] <Comparative Example 1 (Production of Fluorine Resin Composition not Containing Functional Group)>
[345] 2.00 g of a homopolymer of fluorine-containing allyl ether containing no functional group obtained in Synthesis Example 6 and 15 g of methanol were added to a 100 ml glass-necked flask equipped with a stirring device and a thermometer, and stirred with europium acetate (III) tetrahydrate ( A solution of 0.62 g (1.54 mmol) of Eu (CH ₃ COO) ₃ .4H ₂ O) dissolved in 8 g of water was added dropwise over 5 minutes. After dropping, stirring was continued for 2 hours, and then allowed to stand for 30 minutes to precipitate the resulting viscous solid. The supernatant methanol solution was removed along and the solid washed three times with acetone. Then, when vacuum-dried at 60 degreeC for 12 hours, it was cloudy and could not be used for optical use.
[346] Reference Example 1 Evaluation of Physical Properties of Functional Group-Containing Fluoropolymer
[347] (1) Preparation of fluorine-containing resin composition
[348] The functional group-containing fluoropolymers obtained in Synthesis Examples 1, 2 and 5 were dissolved in methyl ethyl ketone (MEK) and adjusted to a polymer concentration of 50% by weight.
[349] (2) Film production of functional group-containing fluoropolymer
[350] The 50% MEK solution of the functional group-containing fluoropolymer was applied onto the PET film using an applicator so that the film thickness became a predetermined thickness, vacuum dried at 50 ° C. for 10 minutes, and then the casting film obtained from the PET film was peeled off to form a film thickness. A film having a thickness of about 1 mm and about 100 μm was obtained.
[351] (3) Measurement of physical properties of the film
[352] The following physical properties were evaluated about the obtained film.
[353] ① Measurement of absorbance coefficient
[354] The spectral transmittance curve of the film having a thickness of about 1 mm at a wavelength of 300 to 1700 nm was measured using a magnetic spectrophotometer (U-3410 manufactured by Hitachi Seisakusho Co., Ltd.). From the obtained spectrum, the value of the absorbance coefficient was computed according to the following formula.
[355] Absorbance factor = absorbance / sample film thickness
[356] The results are shown in Table 1.
[357] ② Measurement of refractive index
[358] Refractive index was measured for light of 550 nm wavelength at 25 ° C. for a film having a thickness of about 100 μm using an Abbe refractometer. The results are shown in Table 1.
[359] ③ Thermal Characteristics (DSC)
[360] When thermal properties were measured using a differential calorimeter (DSC-50, manufactured by Shimadzu Corporation) under conditions of a temperature increase rate of 10 ° C./min, no peak of clear crystal melting point was observed, and all films were amorphous. .
[361] ④ pyrolysis temperature
[362] It measured on the conditions of the temperature increase rate of 10 degree-C / min on the conditions of nitrogen atmosphere using the thermogravimeter (TGA-50 by Shimadzu Corporation), and evaluated by the temperature of 10% weight loss. The results are shown in Table 1.
[363]
[364] All of the obtained functional group containing fluoropolymers were materials provided with high transparency and heat resistance.
[365] Example 5 Evaluation of Physical Properties of Composition of Functional Group-Containing Fluoropolymer and Rare Earth Metal
[366] The following physical properties were evaluated about the fluororesin composition obtained in Examples 1-3.
[367] ① Measurement of fluorescence spectrum
[368] Absorbance spectrum of 300-1700 nm wavelength range was measured by the magnetic spectrophotometer (U-34110 by Hitachi Seisakusho Co., Ltd.), the absorption wavelength corresponding to the peak of absorbance was calculated | required, and the fluorescence measurement performed below is carried out. The excitation wavelength was taken. In the sample containing europium, the absorption wavelength derived from europium obtained by the above absorption spectrum measurement is an excitation wavelength, and is 300 to 700 µm in a wavelength range by a fluorescence photometer (F-3040 manufactured by Hitachi Seisakusho Co., Ltd.). The fluorescence spectrum of was measured. In samples containing erbium, it is known to generate fluorescence in the near infrared region near 1500 nm, and the presence or absence of near infrared fluorescence was observed by a near infrared camera (C-5840 manufactured by Hamamatsu Photonics Co., Ltd.). . The results are shown in Table 2.
[369] ② Measurement of refractive index
[370] The refractive index was measured with respect to the light of 550 nm wavelength at 25 degreeC using the Abbe refractometer. The results are shown in Table 2.
[371] ③ content of rare earth element cation
[372] About 2 g of the sample was correctly weighed and calculated from the weight fraction of the remaining difference which was completely incinerated in an electric furnace at 600 ° C. The results are shown in Table 2.
[373] ④ Measurement of fluorescence lifetime
[374] The emission lifetime (time taken for the emission intensity immediately after pulse excitation to decrease to 37%) of the sample of Example 1 was measured to be about 0.8 ms. Since the light emission lifetime is about 10 ⁴ to 10 ⁶ times longer than in the case of ordinary dye compounds (e.g., fluorescein, rhodamine, etc.), it is easy to form an inversion distribution state necessary for causing an optical amplification effect. It shows what can be.
[375] ⑤ durability test
[376] Although the sample of Example 1 was preserve | saved for 1 week in the environment of the temperature of 80 degreeC, and the humidity of 85%, transparency was not reduced at all.
[377]
[378] <Synthesis example 7 (synthesis of homopolymer of fluorine-containing allyl ether which has CO group)>
[379] 3H, 12H, 12H-perfluoro-5,8-dimethyl-6,9-dioxa-3-trifluoroacetyl-11-dodecene-2,4-dione in the same manner as in Synthesis example 5: 3.1 g and 1.3 g of 8 wt% of a perfluorohexane solution was added to the mixture, followed by nitrogen substitution. The mixture was stirred at 30 ° C. for 5 hours under a nitrogen stream, whereby a high viscosity solid was produced.
[380] The obtained solid dissolved in acetone was poured into perfluorohexane, separated, and dried in vacuo to obtain 1.6 g of a colorless transparent polymer.
[381] This polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, and it was a fluorine-containing polymer containing only the structural unit of the fluorine-containing allyl ether and having a ketone group at the side chain terminal. The fluorine content was 59 wt%. In addition, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 6000, and the weight average molecular weight was 7500.
[382] <Example 6>
[383] The polymer obtained in the synthesis example 7 was dissolved in MEK, and it was 5 weight%. Europium chloride was added to this solution, and it adjusted so that europium ion concentration might be 1 weight% with respect to a polymer. The solution was colorless and transparent. Casting according to conventional practice showed that the obtained polymer film was also colorless and transparent. When light of 394 nm which is an excitation wavelength of europium was irradiated, it emitted red.
[384] The area intensity of 615 nm light emission was measured at an excitation wavelength of 394 nm with a fluorescence spectrometer (F-4010 manufactured by Hitachi Seisakusho Co., Ltd.). When the intensity is 1, a high value of about 120 is shown.
[385] Comparative Example 2 (dispersibility of polymer having no functional group)
[386] Polymethyl methacrylate (acrylic pet from Mitsubishi Rayon Co., Ltd.) was dissolved in butyl acetate to obtain 5 wt%. Europium chloride was added to this solution, and the concentration was adjusted to 1% by weight relative to the polymer. The solution was colorless and transparent. However, casting according to customary practice gave the resulting polymer film cloudy.
[387] In addition, the area intensity of 615 nm light emission was measured with a fluorescence spectrometer (F-4010, manufactured by Hitachi Seisakusho Co., Ltd.) at an excitation wavelength of 394 nm. When the area intensity is 1, 1 or less shows a low value.
[388] Comparative Example 3 (Dispersibility for Fluorine-Based Polymers Having No Functional Group)
[389] Teflon AF1600 (Acrylate PET manufactured by DuPont, a fluorine-based polymer having no functional group) was dissolved in a fluorine-based solvent (FC-75 manufactured by 3M Corporation) to 5 wt%. Europium chloride was added to this solution, and the concentration was adjusted to 1% by weight relative to the polymer. The solution was cloudy and cast according to the customary, resulting in a cloudy polymer film.
[390] Synthesis Example 8 (Synthesis of Copolymer of Fluorine-containing Allyl Ether Having a CO Group and a hydroxyl Group)
[391] In a 100 ml glass sand dune flask with a stirring device and a thermometer, 3H, 12H, 12H-perfluoro-5,8-dimethyl-6,9-dioxa-3-trifluoroacetyl-11-dodecene-2 , 4-dione (CO group-containing fluorine-containing allyl ether): 10.0 g and perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-diosanonenol) (OH group-containing fluorine-containing allyl ether): Add 10.2 g and stir well, 9.8 g of 8.0 wt% of a perfluorohexane solution was added to the mixture, followed by nitrogen substitution. The mixture was stirred at 30 ° C for 5 hours under a nitrogen stream, whereby a high viscosity solid was produced.
[392] The obtained solid dissolved in acetone was poured into perfluorohexane, separated, and dried in vacuo to give 14.7 g of a colorless transparent polymer.
[393] The polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, and was a fluorine-containing polymer containing only the structural units of the fluorine-containing allyl ether and having a ketone group and a hydroxyl group at the side chain terminal. The composition ratio was CO group containing fluorine-containing allyl ether / OH group containing fluorine-containing allyl ether = 51/49 (mol%). In addition, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 3200, and the weight average molecular weight was 4200.
[394] Synthesis Example 9 (Synthesis of Copolymer of Fluorine-containing Allyl Ether Having CO Group and Curing Site)
[395] 5.1 g of a fluorine-containing allylether copolymer containing 80 ml of diethyl ether, a CO group and a hydroxyl group obtained in Synthesis Example 8 in a 200 ml four-necked flask equipped with a reflux cooler, a thermometer, a stirring apparatus, and a dropping funnel, and pyridine 2.1 g was added and ice-cooled to 5 ° C or lower.
[396] A solution of 2.0 g of α-fluoroacrylic acid fluoride CH ₂ = CFCOF dissolved in 20 ml of diethyl ether was further added dropwise over about 30 minutes while stirring under a nitrogen stream.
[397] After completion of the dropwise addition, the temperature was raised to room temperature, and stirring was further continued for 4.5 hours.
[398] After the reaction, the ether solution was placed in a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% sodium chloride, and washed with water, and then dried over anhydrous magnesium sulfate, and the ether solution was separated by filtration to remove CO and harden. The copolymer of fluorine-containing allyl ether which has a site | part was obtained.
[399] This ether solution was examined by ¹⁹ F-NMR analysis, and the conversion was almost 100%, and the fluorine content was 57% by weight. The absorption of carbon-carbon double bonds was observed at 1661 cm ⁻¹ by IR analysis. In addition, amorphousness was confirmed by analysis by DSC.
[400] <Example 7 (Production of Cured Film)>
[401] After adding MEK to the fluoropolymer (ether solution) which has the CO group and hardening site ((alpha) -fluoroacryloyl group) obtained by the synthesis example 9, ether is distilled off by an evaporator and the polymer concentration is adjusted to 50 weight%. It was. Europium chloride was added to this solution, and it adjusted so that europium ion concentration might be 5 weight% with respect to a polymer. Next, 0.1 g of 2-hydroxy-2-methylpropiophenone was added to 10 g of this solution as an active energy ray curing initiator.
[402] The solution was colorless and transparent. Furthermore, it applied on aluminum foil so that the film thickness might be about 100 micrometers using an applicator, and it vacuum-dried at 50 degreeC for 10 minutes. The film after drying was irradiated with the ultraviolet-ray at the intensity of 1000 mJ / cm <^2> U using the high pressure mercury lamp, and aluminum foil was melt | dissolved in diluted hydrochloric acid, and it was set as the sample film.
[403] The film thus obtained was colorless and transparent, and was radiated strongly in red when irradiated with light of 394 nm which is an excitation wavelength of europium.
[404] Example 8 (Manufacture of Optical Amplification Element)
[405] The optical amplification element was formed in the following order.
[406] The optical amplification element was manufactured using the fluororesin composition manufactured in Example 1 as a core part material, and using the fluoropolymer manufactured in the synthesis example 1 as a coating material.
[407] Each of these two materials was dissolved in methyl isobutyl ketone to obtain a solution. First, the coating material was applied to a plastic substrate or silicon substrate to a thickness of about 15 μm. After baking and drying this, the core part material was apply | coated to the thickness of about 8 micrometers on the film | membrane of a coating part material. Subsequently, the mask pattern was formed on the core layer by the photolithographic method using the photomask (4). The core layer on which the mask pattern was formed was etched using the RIE method to form a core pattern. The mask was removed and processed into a straight spherical pattern having a length of 50 mm, a width of 8 m, and a height of 8 m as the core portion. After the processing, the coating portion was coated on the core portion as described in FIG. 1 to manufacture an optical amplification element.
[408] Subsequently, the propagation loss of the manufactured optical amplification element was measured by passing light having a wavelength of 633 nm to the core portion. As a result, it was 0.3 dB / cm.
[409] Moreover, when the ultraviolet ray lamp was irradiated to the optical amplification element formed in this way and observed above the main surface of the optical amplification element, the red luminescent pattern peculiar to the linear Eu ion corresponding to the core part was observed. This indicates that only the core portion contains rare earth Eu ions necessary for the optical amplification action.
[410] According to the present invention, it is possible to obtain preferred light amplifying materials and light emitting materials which form a stable structure with rare earth metal ions by specific functional groups while maintaining transparency in the near infrared region from visible light. When using the fluorine resin composition of this invention, the outstanding optical amplification element and light emitting element can be manufactured by a comparatively simple process.

权利要求:
Claims (41)
[1" claim-type="Currently amended] (I) a functional group-containing fluoropolymer and (II) a rare earth metal ion, and (I) the functional group-containing fluoropolymer is represented by the following general formula (1), wherein the structural unit M is 0.1 to 100 mol%, and the structural unit A is 0 to 99.9. The fluororesin composition which is a fluoropolymer containing mol%.
<Formula 1>

In the formula, the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the following formula (2), and the structural unit A is a structural unit derived from the monomer copolymerizable with the structural unit M.
<Formula 2>

Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf has 1 to 5 moieties of> C═O, a fluorine-containing alkylene group having 1 to 50 carbon atoms excluding carbon of C═O or an ether bond having 2 to 100 carbon atoms excluding carbon of C═O It is a fluorine-containing alkylene group having a, a is an integer of 0 to 3, b and c are the same or different and 0 or 1.
[2" claim-type="Currently amended] (I) a functional group-containing fluoropolymer and (II) a rare earth metal ion, and (I) the functional group-containing fluoropolymer is represented by the following general formula (1), wherein the structural unit M is 0.1 to 100 mol%, and the structural unit A is 0 to 99.9. The fluororesin composition used for the optical amplification material which is a fluoropolymer containing mol%.
<Formula 1>

In the formula, the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the following formula (2), and the structural unit A is a structural unit derived from the monomer copolymerizable with the structural unit M.
<Formula 2>

Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf has 1 to 5 moieties of> C═O, a fluorine-containing alkylene group having 1 to 50 carbon atoms excluding carbon of C═O or an ether bond having 2 to 100 carbon atoms excluding carbon of C═O It is a fluorine-containing alkylene group having a, a is an integer of 0 to 3, b and c are the same or different and 0 or 1.
[3" claim-type="Currently amended] (I) a functional group-containing fluoropolymer and (II) a rare earth metal ion, and (I) the functional group-containing fluoropolymer is represented by the following general formula (1), wherein the structural unit M is 0.1 to 100 mol%, and the structural unit A is 0 to 99.9. The fluororesin composition used for a luminescent material which is a fluoropolymer containing mol%.
<Formula 1>

In the formula, the structural unit M is a structural unit derived from the fluorine-containing ethylenic monomer represented by the following formula (2), and the structural unit A is a structural unit derived from the monomer copolymerizable with the structural unit M.
<Formula 2>

Wherein X ¹ and X ² are the same or different and are H or F, X ³ is H, F, CH ₃ or CF ₃ , X ⁴ and X ⁵ are the same or different and H, F or CF ₃ Rf has 1 to 5 moieties of> C═O, a fluorine-containing alkylene group having 1 to 50 carbon atoms excluding carbon of C═O or an ether bond having 2 to 100 carbon atoms excluding carbon of C═O It is a fluorine-containing alkylene group having a, a is an integer of 0 to 3, b and c are the same or different and 0 or 1.
[4" claim-type="Currently amended] The functional group-containing fluoropolymer according to any one of claims 1 to 3, wherein the functional group-containing fluoropolymer is a fluoropolymer in which the structural unit M in the formula (1) is a structural unit M1, and the structural unit M1 is a fluorine-containing compound represented by the following formula The fluororesin composition which is a structural unit derived from an ethylenic monomer.
<Formula 3>

In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , Rf, a and c are the same as above.
[5" claim-type="Currently amended] The functional group-containing fluoropolymer according to any one of claims 1 to 3 is a fluorine polymer in which the structural unit M in the general formula (1) is a structural unit M2, and the structural unit M2 is a fluorine-containing compound represented by the following general formula (4). The fluororesin composition which is a structural unit derived from an ethylenic monomer.
<Formula 4>

In formula, Rf is the same as the above.
[6" claim-type="Currently amended] The functional group-containing fluoropolymer according to any one of claims 1 to 3, wherein the functional group-containing fluoropolymer is a fluoropolymer in which the structural unit M in the formula (1) is a structural unit M3, and the structural unit M3 is a fluorine-containing compound represented by the following formula (5): The fluororesin composition which is a structural unit derived from an ethylenic monomer.
<Formula 5>

In formula, Rf is the same as the above.
[7" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) [Wherein, Y ¹ is H, OH, R ¹ or OR ² (wherein R ¹ and R ² are the same or different and are a hydrocarbon group having 1 to 10 carbon atoms), and Rf ¹ is a fluorine having 1 to 50 carbon atoms. Containing alkylene group or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
[8" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) (Wherein Rf ² is a fluorine-containing alkylene group having 1 to 49 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 99 carbon atoms, and Rf ³ is a fluorine-containing alkyl group having 1 to 49 carbon atoms or an ether having 2 to 99 carbon atoms) A fluorine-containing alkyl group having a bond, Rf ² is a fluorine-containing alkylene group, and at the same time, when Rf ³ is a fluorine-containing alkyl group, the total carbon number of Rf ² and Rf ³ is 50 or less, and either of Rf ² and Rf ³ is an ether; A fluorine-containing alkylene group or a fluorine-containing alkyl group having a bond, wherein the total carbon number of Rf ² and Rf ³ is 100 or less;
[9" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) [Wherein X ⁶ is H or D (deuterium), X ⁷ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or a halogen atom, and Y ¹ is H, D, OH, OD, R ¹ or OR ² , wherein R ¹ and R ² are the same or different, and some or all of the hydrocarbon groups having 1 to 10 carbon atoms or their hydrogen atoms are deuterium or halogen atoms Substituted), and Rf ⁴ is a fluorine-containing alkylene group having 1 to 49 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 99 carbon atoms.
[10" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) [Wherein X ⁶ is H or D (deuterium), X ⁷ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or a halogen atom, and Rf ⁵ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having ether bonds having 2 to 98 carbon atoms, and Rf ⁶ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or an ether bond having 2 to 98 carbon atoms Is an alkyl group, Rf ⁵ is a fluorine-containing alkylene group, and at the same time, when Rf ⁶ is a fluorine-containing alkyl group, the total carbon number of Rf ⁵ and Rf ⁶ is 49 or less, and any one of Rf ⁵ and Rf ⁶ has an ether bond; In the case of an alkylene group or a fluorine-containing alkyl group, the total carbon number of Rf ⁵ and Rf ⁶ is 99 or less].
[11" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) [Wherein X ⁶ is H, D (deuterium) or a halogen atom, Y ¹ and Y ² are the same or different and H, D, OH, OD, R ¹ or OR ² (where R ¹ and R ² Is the same or different, a hydrocarbon group having 1 to 10 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ⁷ is a fluorine-containing alkylene group having 1 to 49 carbon atoms or 2 to 99 carbon atoms Fluorine-containing alkylene group having an ether bond].
[12" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) [Wherein X ⁶ is H, D (deuterium) or a halogen atom, Rf ⁸ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, Rf ⁹ and Rf ¹⁰ is the same or different and is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 98 carbon atoms, Rf ⁸ is a fluorine-containing alkylene group, and at the same time, both Rf ⁹ and Rf ¹⁰ are fluorine-containing alkyl groups In the case of Rf ⁸ , Rf ⁹ And Rf ^{10 It has} a total carbon number of 49 or less, and when one or two of Rf ⁸ , Rf ⁹ and Rf ¹⁰ is a fluorine-containing alkylene group or an fluorine-containing alkyl group having an ether bond Rf ⁸ , Rf ⁹ and Rf ^{10 have} a total carbon number of 99 or less].
[13" claim-type="Currently amended] The compound of any one of claims 1 to 6, wherein Rf in the formulas (2), (3), (4) and (5) [Wherein X ⁶ is H, D (deuterium) or a halogen atom, Y ¹ is H, D, OH, OD, R ¹ or OR ² (wherein R ¹ and R ² are the same or different and have carbon atoms) A hydrocarbon group of 1 to 10 or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ¹¹ is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkyl having an ether bond having 2 to 98 carbon atoms. If group and, Rf ¹² is a fluorine-containing alkyl group having ether bond with a carbon number of 1 to 48 fluorine-containing alkyl group or a carbon number of 2 to 98, and Rf ¹¹ contains an alkylene group of fluorine, while the alkyl group is Rf ¹² containing fluorine is Rf ¹¹ And the total carbon number of Rf ¹² is 49 or less, and when either of Rf ¹¹ and Rf ¹² is a fluorine-containing alkylene group or a fluorine-containing alkyl group having an ether bond, the total carbon number of Rf ¹¹ and Rf ¹² is 99 or less. Suzy Composition.
[14" claim-type="Currently amended] The fluororesin composition according to any one of claims 1 to 13, wherein (I) the functional group-containing fluoropolymer is an amorphous fluoropolymer having a fluorine content of 25% by weight or more.
[15" claim-type="Currently amended] The fluorine resin composition of Claim 14 whose fluorine content rate of (I) functional group containing fluoropolymer is 40 weight% or more.
[16" claim-type="Currently amended] The fluorine resin composition according to any one of claims 1 to 15, wherein the (I) functional group-containing fluoropolymer is a polymer having a maximum absorbance coefficient in a wavelength range of 1290-1320 nm of 1 cm ^-1 or less.
[17" claim-type="Currently amended] The fluorine resin composition according to any one of claims 1 to 16, wherein the (I) functional group-containing fluoropolymer is a polymer having a maximum absorbance coefficient in the wavelength range of 1530 to 1570 nm of 1 cm ^-1 or less.
[18" claim-type="Currently amended] The fluorine resin composition according to any one of claims 1 to 17, wherein the (I) functional group-containing fluoropolymer is a polymer having a maximum absorbance coefficient in the wavelength range of 600 to 900 nm of 1 cm ⁻¹ or less.
[19" claim-type="Currently amended] The method according to any one of claims 1 to 18, wherein (II) rare earth metal ions are erbium (Er) ions, thulium (Tm) ions, praseodymium (Pr) ions, holmium (Ho) ions, neodymium (Nd) ions And at least one fluorine resin composition selected from the group consisting of europium (Eu) ions.
[20" claim-type="Currently amended] A fluororesin composition comprising (I) a functional group-containing fluoropolymer and (II) rare earth metal ions, and (I) the functional group-containing fluoropolymer contains a site | part represented by following formula (10) in a polymer.
<Formula 10>

Wherein X ³⁰ is H or D (deuterium), X ³¹ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ³⁰ Is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ³¹ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a ether bond having 2 to 98 carbon atoms. Rf ³⁰ is a fluorine-containing alkylene group, and at the same time, when Rf ³¹ is a fluorine-containing alkyl group, the total carbon number of Rf ³⁰ and Rf ³¹ is 49 or less, and either of Rf ³⁰ and Rf ³¹ is a fluorine-containing alkyl having an ether bond. when the group or fluorine-containing alkyl group has a carbon number of 99 or less in total of Rf ³⁰ and Rf ^31.
[21" claim-type="Currently amended] Fluorine used for the optical amplification material containing (I) functional group containing fluoropolymer and (II) rare earth metal ion, and (I) functional group containing fluoropolymer contains the site | part represented by following formula (10) in a polymer Resin composition.
<Formula 10>

Wherein X ³⁰ is H or D (deuterium), X ³¹ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ³⁰ Is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ³¹ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a ether bond having 2 to 98 carbon atoms. Rf ³⁰ is a fluorine-containing alkylene group, and at the same time, when Rf ³¹ is a fluorine-containing alkyl group, the total carbon number of Rf ³⁰ and Rf ³¹ is 49 or less, and either of Rf ³⁰ and Rf ³¹ is a fluorine-containing alkyl having an ether bond. when the group or fluorine-containing alkyl group has a carbon number of 99 or less in total of Rf ³⁰ and Rf ^31.
[22" claim-type="Currently amended] A fluorine resin for use in a luminescent material, comprising (I) a functional group-containing fluoropolymer and (II) rare earth metal ions, and (I) the functional group-containing fluoropolymer contains a moiety represented by the following general formula (10) in the polymer: Composition.
<Formula 10>

Wherein X ³⁰ is H or D (deuterium), X ³¹ is H, D, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms or some or all of its hydrogen atoms are substituted with deuterium or halogen atoms, and Rf ³⁰ Is a fluorine-containing alkylene group having 1 to 48 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 98 carbon atoms, and Rf ³¹ is a fluorine-containing alkyl group having 1 to 48 carbon atoms or a ether bond having 2 to 98 carbon atoms. Rf ³⁰ is a fluorine-containing alkylene group, and at the same time, when Rf ³¹ is a fluorine-containing alkyl group, the total carbon number of Rf ³⁰ and Rf ³¹ is 49 or less, and either of Rf ³⁰ and Rf ³¹ is a fluorine-containing alkyl having an ether bond. when the group or fluorine-containing alkyl group has a carbon number of 99 or less in total of Rf ³⁰ and Rf ^31.
[23" claim-type="Currently amended] The fluororesin composition according to any one of claims 1 to 22, wherein (I) the functional group-containing fluoropolymer has a curing site.
[24" claim-type="Currently amended] The fluorine resin composition according to claim 23, wherein the curing site is present in the side chain of the (I) functional group-containing fluoropolymer and / or at the polymer main chain terminal.
[25" claim-type="Currently amended] The fluorine resin composition according to claim 23 or 24, wherein the curing site is a carbon-carbon double bond.
[26" claim-type="Currently amended] The fluorine resin composition according to any one of claims 23 to 25, wherein the curing site is a carbon-carbon double bond present at the polymer backbone terminal.
[27" claim-type="Currently amended] 27. The fluorine resin composition according to any one of claims 23 to 26, wherein the curing site is an ethylenic carbon-carbon double bond having radical reactivity.
[28" claim-type="Currently amended] The fluorine resin composition according to any one of claims 23 to 26, wherein the curing site is an ethylenic carbon-carbon double bond having cationic reactivity.
[29" claim-type="Currently amended] An optical amplifying element comprising a core portion and a covering portion, wherein the core portion comprises the fluororesin composition according to any one of claims 1 to 28.
[30" claim-type="Currently amended] A light emitting element in which part or all of the light emitting element comprises the fluororesin composition according to any one of claims 1 to 28.
[31" claim-type="Currently amended] An optical amplifying element comprising a core part and a covering part, wherein the core part comprises the fluorine resin composition according to any one of claims 1 to 28.
[32" claim-type="Currently amended] 29. The fluorine resin composition according to any one of claims 1 to 28, further comprising (III) an active energy ray curing initiator in addition to the (I) functional group-containing fluoropolymer and (II) rare earth metal ions.
[33" claim-type="Currently amended] 33. The fluorine resin composition according to claim 32, wherein the active energy ray hardener (III) is a radical radical generator (III-1).
[34" claim-type="Currently amended] 33. The fluorine resin composition according to claim 32, wherein (III) the active energy ray curing initiator is a (III-2) photoacid generator.
[35" claim-type="Currently amended] A fluorine-containing optical amplifying material formed by curing the fluorine resin composition according to any one of claims 32 to 34.
[36" claim-type="Currently amended] The fluorine-containing optical amplifying material according to claim 35, wherein the fluorine resin composition according to any one of claims 32 to 34 is photocured.
[37" claim-type="Currently amended] An optical amplifying element comprising a core part and a covering part, wherein the core part comprises the fluorine-containing optical amplifying material according to claim 35 or 36.
[38" claim-type="Currently amended] A fluorine-containing light emitting material obtained by curing the fluorine resin composition according to any one of claims 32 to 34.
[39" claim-type="Currently amended] The fluorine-containing light emitting material according to claim 38, wherein the fluorine resin composition according to any one of claims 32 to 34 is photocured.
[40" claim-type="Currently amended] A light emitting element in which part or all of the light emitting element comprises the fluorine-containing light emitting material according to claim 38 or 39.
[41" claim-type="Currently amended] A light emitting element comprising a core portion and a covering portion, wherein the core portion comprises the fluorine-containing light emitting material according to claim 38 or 39.

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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:
2001-03-08|Priority to JPJP-P-2001-00064771

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2001-03-08|Priority to JP2001064771

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2002-03-06|Application filed by 다이킨 고교 가부시키가이샤

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2002-03-06|Priority to PCT/JP2002/002057

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2003-11-05|Publication of KR20030085546A

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2006-04-18|Application granted

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2006-04-18|Publication of KR100571899B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00064771|2001-03-08|

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JP2001064771|2001-03-08|

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PCT/JP2002/002057|WO2002072696A1|2001-03-08|2002-03-06|Optical material containing functional fluoropolymer|