Acrylic ester compound and usage thereof

专利摘要:
PURPOSE: Provided are an acrylic ester compound, a manufacturing method thereof and a sulfur-containing compound used as a synthetic intermediate thereof. Furthermore, provided are a polymerizable composition containing the acrylic ester compound, a cured article obtained by polymerizing the polymerizable composition and an optical component. CONSTITUTION: The acrylic ester compound is represented by the formula(1), wherein, R1 and R2 represent independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent, respectively; R3 represents a hydrogen atom or an alkyl group; A represents a divalent organic group; and X represents a sulfur atom or an oxygen atom; provided that when X is an oxygen atom, R1 represents an aromatic residue that may have a substituent.
公开号:KR20020023673A
申请号:KR1020010058845
申请日:2001-09-22
公开日:2002-03-29
发明作者:오쿠마타다시；이마이마사오；나카무라미츠오；오츠지아츠오
申请人:사토 아키오；미쯔이카가쿠 가부시기가이샤；
IPC主号:

专利说明:

Acrylic ester compound and its use {ACRYLIC ESTER COMPOUND AND USAGE THEREOF}
[1] The present invention relates to an acrylic ester compound, a method for producing the same, and a sulfur-containing compound used as a synthetic intermediate thereof. Moreover, this invention relates to the polymeric composition containing an acrylic acid ester compound, the hardened | cured material obtained by superposing | polymerizing this polymeric composition, and an optical component.
[2] The acrylic ester compound of the present invention is a novel compound having a specific dithiolan ring structure in a molecule and useful as a monomer for a photocurable polymerizable composition. The optical part obtained by hardening this polymeric composition has the favorable optical characteristic, a thermal characteristic, and a mechanical characteristic, is excellent in productivity, and has a high refractive index. In addition, various types of plastic lenses represented by corrective spectacle lenses, substrate materials for optical information recording media, plastic substrate materials for liquid crystal cells, transparent coating materials such as antireflection coating, optical fiber coating materials, LED sealing materials, dental materials, etc. useful.
[3] Inorganic glass has excellent transparency and many physical properties and at the same time has low optical anisotropy, and thus is widely used in the field of transparent optical materials. However, due to various problems such as being heavy, easy to break, and low productivity, development of an optical component resin (organic optical material) to replace inorganic glass has been in progress in recent years.
[4] As this resin for optical parts, transparency is an important characteristic. Currently, resins for industrial optical parts with sufficient transparency include polymethyl methacrylate (PMMA), bisphenol A polycarbonate (BPA-PC), polystyrene (PS), methyl methacrylate-styrene copolymer (MS), and styrene. Acrylonitrile copolymer (SAN), poly (4-methylpentene-1) (TPX), polycycloolefin (COP), poly (diethylene glycol bisallylcarbonate) (EGAC), polythiourethane (PTU), etc. This is known.
[5] PMMA is excellent in transparency and weather resistance, and also excellent in moldability. However, there is a disadvantage in that the refractive index nd is 1.49 small and the absorbency is high.
[6] BPA-PC has excellent transparency, heat resistance, and impact resistance, and has a high refractive index, but its chromatic aberration is large, thereby limiting its field of use.
[7] PS and MS are excellent in moldability and transparency, and have low water absorption and high refractive index, but are inferior in impact resistance, weather resistance and heat resistance, and thus are rarely used in the resin field for optical parts.
[8] SAN has a relatively high refractive index and a good balance of mechanical properties, but has low heat resistance (heat deformation temperature: 80 to 90 ° C) and is rarely used as an optical component resin.
[9] TPX and COP have excellent transparency, low water absorption and heat resistance, but have a low refractive index (nd = 1.47 to 1.53), and are inferior in impact resistance, gas barrier properties and dyeing properties.
[10] EGAC is a thermosetting resin having diethylene glycol bisallylcarbonate as a monomer and is mostly used for general-purpose spectacle lenses. In addition, although transparency and heat resistance are excellent, there are disadvantages in that chromatic aberration is very low, impact resistance is inferior, and low refractive index (nd = 1.50).
[11] PTU is a thermosetting resin obtained by the reaction of a diisocyanate compound and a polythiol compound, and is most commonly used for ultra high refractive index spectacle lenses. In addition, since the material has excellent transparency, impact resistance, and high refractive index and low chromatic aberration, it is a very good material, but has only one drawback of long thermal polymerization time (1 to 3 days). There is a problem.
[12] In order to improve the productivity and to carry out polymerization curing in a short time, several methods, namely, a method of obtaining an optical lens by photopolymerization using an acrylic acid ester compound containing a bromine atom or a sulfur atom as a polymerizable compound (for example, Japanese Patent Application Laid-Open No. 63-248811, Japanese Patent Laid-Open No. 3-217412, etc.), a method for obtaining an optical lens using a (meth) acrylic acid ester compound having a sulfur-containing aliphatic ring structure (for example, Japan Korean Patent Laid-Open No. 3-215081 has been proposed.
[13] However, according to these methods, when the obtained resin was used as an optical material, it was not satisfactory enough. That is, for example, since the viscosity of the polymerizable compound (monomer) is high and the fluidity is low, when the filtration or injection into the mold reduces the work efficiency, the polymerization can be performed in a short time, but the refractive index or Abbe If the number is not high enough, or used as a spectacle lens, the lens having a high refractive index tends to be damaged by falling back or having a high density. Therefore, there has been a strong demand for the development of materials that can overcome these problems.
[14] As described above, conventional resins for optical parts have excellent characteristics, but each of them has a drawback to overcome. Under these circumstances, development of an optical component resin excellent in high refractive index, workability and productivity, and excellent in transparency, thermal properties, and mechanical properties is urgently desired.
[15] SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of resins for optical parts, and to provide resins for optical parts of high refractive index which are excellent in workability and productivity, and excellent in transparency, thermal properties and mechanical properties.
[16] MEANS TO SOLVE THE PROBLEM The present inventors reached | attained this invention as a result of earnestly examining in order to solve the said subject. That is, this invention is following General formula (1):
[17]
[18] (Wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent; R ₃ is a hydrogen atom or an alkyl group; A is A divalent organic group; X is a sulfur atom or an oxygen atom; provided that when X is an oxygen atom, R ₁ is an aromatic moiety which may have a substituent.
[19] In addition, this invention relates to the polymeric composition containing the acrylic ester compound represented by the said General formula (1), the hardened | cured material obtained by superposing | polymerizing this polymeric composition, and the optical component which consists of this hardened | cured material.
[20] Moreover, this invention is a manufacturing method of the acrylic acid ester compound represented by said General formula (1), The following General formula (2):
[21]
[22] (Wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent; A is a divalent organic group; X is a sulfur atom) Or an oxygen atom, provided that when X is an oxygen atom, R ₁ is an aromatic moiety which may have a substituent to esterify the sulfur-containing compound to form an acrylic ester. It is about a method. Particularly, the present invention relates to a process for forming the halopropionic acid compound by reacting a compound represented by the above formula (2) with halopropionic acid or a halide thereof, followed by esterification for forming the acrylic acid ester by dehydrohalogenation. The present invention relates to a method for producing an acrylic acid ester compound.
[23] Moreover, this invention relates to the sulfur containing compound represented by the said General formula (2) useful as a raw material of an acrylic acid ester compound.
[24] The acrylic ester compound of the present invention is very useful for use in optical materials, dental materials, and the like as monomers for photocurable polymerizable compositions. The optical component obtained by hardening the said polymerizable composition can superpose | polymerize, harden, and shape | mold in a short time (high productivity), and are excellent in thermal characteristics and a mechanical characteristic, and have high refractive index. The optical component is useful for various plastic lenses represented by corrective spectacle lenses, substrate materials for optical information recording media, plastic substrate materials for liquid crystal cells, coating materials for optical fibers, and the like.
[25] In addition, according to the present invention, it is possible to provide a sulfur-containing compound represented by the general formula (2) which is very useful as a raw material of the acrylic acid ester compound.
[26] Hereinafter, the present invention will be described in detail by preferred embodiments.
[27] The acrylic ester compound represented by the general formula (1) of the present invention is a novel compound characterized by having a specific dithiolan ring structure.
[28] In said general formula (1), R <_1> and R <_2> are respectively independently a hydrogen atom, the alkyl group which may have a substituent, the aromatic alkyl group which may have a substituent, or the aromatic residue which may have a substituent. Here, for the "aromatic alkyl group" and the "aromatic moiety", in the former case, a bond having an aromatic ring is formed through an alkyl group, and in the latter case, a direct bond is formed at a member of the aromatic ring. In other words, this means that the aromatic ring in these groups may be a heterocyclic ring having aromaticity and containing a hetero atom.
[29] However, when X in General formula (1) is an oxygen atom, R <_1> represents the aromatic residue which may have a substituent.
[30] When R ₁ or / and R ₂ is an alkyl group which may have a substituent, examples of the substituent contained in this alkyl group include an alkoxy group, an alkoxyalkoxy group, an aralkyloxy group, an aryloxy group, an aryloxyalkoxy group, an alkylthio group, and an alkyl group. A thioalkylthio group, an aralkylthio group, an arylthio group, or an arylthioalkylthio group etc. are mentioned.
[31] When R <_1> and / or R <_2> is an aromatic alkyl group or aromatic residue which may have a substituent, it is preferable that the aromatic ring in an aromatic alkyl group or aromatic residue is substituted. At this time, examples of the substituent include an alkyl group, an alkoxy group, an alkoxyalkoxy group, an aralkyloxy group, an aryl group, an aryloxy group, an aryloxyalkyloxy group, an alkylthio group, an alkylthioalkylthio group, an aralkylthio group, an arylthio group or An arylthio alkylthio group, a halogen atom, etc. are mentioned.
[32] As an aromatic ring in the aromatic alkyl group or aromatic residue which R <_1> and / or R <_2> may have a substituent, aromatic hydrocarbons, such as benzene, naphthalene, anthracene, and phenanthrene, or thiophene, pyridine, pyrrole, furan, (gamma)- And a ring such as a heterocyclic ring having aromaticity such as pyran, γ-thiopyran, thiazole, imidazole, pyrimidine, 1,3,5-triazine, indole, quinoline, and purine.
[33] Substituents R ₁ and R ₂ in the general formula (1) independently have a hydrogen atom, a linear or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a combination of the linear alkyl group and a cyclic alkyl group, and a substituent. It is preferable that it is a C4-C20 aromatic alkyl group which may have a C5-C20 aromatic alkyl group which may have, and a substituent. Substituents R ₁ and R ₂ are each a hydrogen atom, a linear or cyclic alkyl group having 1 to 8 carbon atoms which may have a substituent or a combination of the linear alkyl group and a cyclic alkyl group, and an aromatic having 5 to 12 carbon atoms. It is preferable that it is a C4-C12 aromatic residue which may have an alkyl group or a substituent.
[34] Examples of the substituents R ₁ and R ₂ are
[35] Hydrogen atom; Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group, cyclohexyl group Linear, branched or cyclic alkyl groups such as cyclohexylmethyl group; Substituted or unsubstituted aromatic alkyl groups, such as a benzyl group, 4-methylbenzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, (beta) -phenylethyl group; Phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-phenylphenyl group, 4-phenoxyphenyl group, 3-phenoxy Phenyl group, 2-phenoxyphenyl group, 4-methylthiophenyl group, 3-methylthiophenyl group, 2-methylthiophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3-bro Substituted or unsubstituted aromatics such as a mophenyl group, 2-bromophenyl group, α-naphthyl group, β-naphthyl group, 2-furyl group, 3-furyl group, thiophen-2-yl group and thiophen-3-yl group Residues; and the like.
[36] As the substituent R ₁ and / or R ₂ , a hydrogen atom, a methyl group, a benzyl group, a β-phenylethyl group, a phenyl group, a thiophen-2-yl group, a thiophen-3-yl group, a 4-phenylphenyl group, an α-naphthyl group or β Naphthyl group is more preferable.
[37] In view of the effects of the present invention, as the substituent R ₁ , a phenyl group, a thiophen-2-yl group, a thiophen-3-yl group, a 4-phenylphenyl group, an α-naphthyl group or a β-naphthyl group are particularly preferable.
[38] In General formula (1), R <_3> represents a hydrogen atom or an alkyl group.
[39] The substituent R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.
[40] In General formula (1), A is a divalent organic group.
[41] The organic group A is preferably an alkylene group which may contain an oxygen atom or a sulfur atom, more preferably an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, still more preferably the following formula (a) :
[42]
[43] Is represented by.
[44] In the formula (a), B is an alkylene group having 1 to 3 carbon atoms, preferably methylene group, 1,2-ethylene group, trimethylene group or propylene group (1-methyl-1,2-ethylene group) to be.
[45] In the formula (a), Y is an oxygen atom or a sulfur atom, preferably a sulfur atom.
[46] In said formula (a), m is an integer of 1-3, Preferably it is an integer of 1-2, More preferably, it is 1.
[47] In said formula (a), n is an integer of 0-3, Preferably it is an integer of 0-2, More preferably, it is 0 or 1, More preferably, it is zero.
[48] In the general formula (1), X is an oxygen atom or a sulfur atom, preferably a sulfur atom.
[49] In order to obtain the various desired effects of the present invention, in the general formula (1), any one of R ₁ or R ₂ is preferably an aromatic moiety which may have a substituent, more preferably X is a sulfur atom. , R ₁ is an aromatic moiety which may have a substituent, and R ₂ is a hydrogen atom.
[50] As the acrylic ester compound represented by the general formula (1), for example,
[51] 4-acryloylthiomethyl-1,3-dithiolane,
[52] 2-methyl-4-acryloylthiomethyl-1,3-dithiolane,
[53] 2-ethyl-4-acryloylthiomethyl-1,3-dithiolane,
[54] 2-n-propyl-4-acryloylthiomethyl-1,3-dithiolane,
[55] 2-n-butyl-4-acryloylthiomethyl-1,3-dithiolane,
[56] 2-phenyl-4-acryloylthiomethyl-1,3-dithiolane,
[57] 2- (4'-methylphenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[58] 2- (3'-methylphenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[59] 2- (2'-methylphenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[60] 2- (4'-tert-butylphenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[61] 2- (4'-methoxyphenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[62] 2- (4-phenylphenyl) -4-acryloylthiomethyl-1,3-dithiolane,
[63] 2- (4'-phenoxyphenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[64] 2- (4'-methylthiophenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[65] 2- (2,4,6-trimethylthiophenyl) -4-acryloylthiomethyl-1,3-dithiolane,
[66] 2- (4'-chlorophenyl) -4-acryloylthiomethyl-1, 3-dithiolane,
[67] 2- (4'-bromophenyl) -4-acryloylthiomethyl-1,3-dithiolane,
[68] 2- (α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane,
[69] 2- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane,
[70] 2,2-dimethyl-4-acryloylthiomethyl-1,3-dithiolane,
[71] 2-methyl-2-phenyl-4-acryloylthiomethyl-1,3-dithiolane,
[72] 2,2-diphenyl-4-acryloylthiomethyl-1,3-dithiolane,
[73] 4- (2-acryloylthioethyl) -1,3-dithiolane,
[74] 4- (3-acryloylthiopropyl) -1,3-dithiolane,
[75] 4- (2-methyl-2-acryloylthioethyl) -1,3-dithiolane,
[76] 4-acryloylthiomethylthiomethyl-1,3-dithiolane,
[77] 4- (2-acryloylthioethylthio) methyl-1,3-dithiolane,
[78] 4- (3-acryloylthiopropylthio) methyl-1,3-dithiolane,
[79] 4- (2-methyl-2-acryloylthioethylthio) methyl-1,3-dithiolane,
[80] 4- [2- (acryloylthiomethylthio) ethyl] -1,3-dithiolane,
[81] 4- [2- (2-acryloylthioethylthio) ethyl] -1,3-dithiolane,
[82] 4- [2- (3-acryloylthiopropylthio) ethyl] -1,3-dithiolane,
[83] 4- [2- (2-methyl-2-acryloylthioethylthio) ethyl] -1,3-dithiolane,
[84] 4- [3- (acryloylthiomethylthio) propyl] -1,3-dithiolane,
[85] 4- [3- (2-acryloylthioethylthio) propyl] -1,3-dithiolane,
[86] 4- [3- (3-acryloylthiopropylethylthio) propyl] -1,3-dithiolane,
[87] 4- [3- (2-methyl-2-acryloylthioethylthio) propyl] -1,3-dithiolane,
[88] 4- [2-methyl-2- (acryloylthiomethylthio) ethyl] -1,3-dithiolane,
[89] 4- [2-methyl-2- (2-acryloylthioethylthio) ethyl] -1,3-dithiolane,
[90] 4- [2-methyl-2- (3-acryloylthiopropylthio) ethyl] -1,3-dithiolane,
[91] 4- [2-methyl-2- (2-methyl-2-acryloylthioethylthio) ethyl] -1,3-dithiolane,
[92] 2- (4-methylphenyl) -4- (2-acryloylthioethyl) -1,3-dithiolane,
[93] 2-α-naphthyl-4- (3-acryloylthiopropyl) -1,3-dithiolane,
[94] 2-phenyl-4- (acryloylthiomethylthio) methyl-1,3-dithiolane,
[95] 2- (4-methoxyphenyl) -4- (2-acryloylthioethylthio) methyl-1,3-dithiolane,
[96] 2- (4-bromophenyl) -4- (2-acryloylthiopropylthio) methyl-1,3-dithiolane,
[97] 2- (thiophen-2-yl) -4- (2-methyl-2-acryloylthioethylthio) -methyl-1,3-dithiolane,
[98] 2-furyl-4- [2- (2-acryloylthioethylthio) ethyl] -1,3-dithiolane,
[99] 2- (4-methylthiophenyl) -4- [3- (acryloylthiomethylthio) propyl] -1,3-dithiolane,
[100] 2-β-naphthyl-4- [2-methyl-2- (acryloylthiomethylthio) ethyl] -1,3-dithiolane,
[101] 2-methyl-4-acryloyloxymethyl-1,3-dithiolane,
[102] 2-phenyl-4-acryloyloxymethyl-1,3-dithiolane,
[103] 2- (4'-methylphenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[104] 2- (4'-methoxyphenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[105] 2- (4-phenylphenyl) -4-acryloylmethyl-1,3-dithiolane,
[106] 2- (4'-phenoxyphenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[107] 2- (4'-methylthiophenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[108] 2- (2,4,6-trimethylthiophenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[109] 2- (4'-chlorophenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[110] 2- (4'-bromophenyl) -4-acryloyloxymethyl-1,3-dithiolane,
[111] 2- (α-naphthyl) -4-acryloyloxymethyl-1,3-dithiolane,
[112] 2- (β-naphthyl) -4-acryloyloxymethyl-1,3-dithiolane,
[113] 2-methyl-2-phenyl-4-acryloyloxymethyl-1,3-dithiolane,
[114] 2,2-diphenyl-4-acryloyloxymethyl-1,3-dithiolane,
[115] 2- (4-methylphenyl) -4- (2-acryloyloxyethyl) -1,3-dithiolane,
[116] 2-α-naphthyl-4- (3-acryloyloxypropyl) -1,3-dithiolane,
[117] 2-phenyl-4- (acryloyloxymethylthio) methyl-1,3-dithiolane,
[118] 2- (4-methoxyphenyl) -4- (2-acryloyloxyethylthio) methyl-1,3-dithiolane,
[119] 2- (4-bromophenyl) -4- (2-acryloyloxypropylthio) methyl-1,3-dithiolane,
[120] 2- (thiophen-2-yl) -4- (2-methyl-2-acryloyloxyethylthio) methyl-1,3-dithiolane,
[121] 2-furyl-4- [2- (2-acryloyloxyethylthio) ethyl] -1,3-dithiolane,
[122] 2- (4-methylthiophenyl) -4- [3- (acryloyloxymethylthio) propyl] -1,3-dithiolane,
[123] 2-β-naphthyl-4- [2-methyl-2- (acryloyloxymethylthio) ethyl] -1,3-dithiolane,
[124] 4-methacryloylthiomethyl-1,3-dithiolane,
[125] 2-methyl-4-methacryloylthiomethyl-1, 3-dithiolane,
[126] 2-ethyl-4-methacryloylthiomethyl-1, 3-dithiolane,
[127] 2-n-propyl-4-methacryloylthiomethyl-1, 3-dithiolane,
[128] 2-n-butyl-4-methacryloylthiomethyl-1, 3-dithiolane,
[129] 2-phenyl-4-methacryloylthiomethyl-1,3-dithiolane,
[130] 2- (4'-methylphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[131] 2- (3'-methylphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[132] 2- (2'-methylphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[133] 2- (4'-tert-butylphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[134] 2- (4'-methoxyphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[135] 2- (4'-phenylphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[136] 2- (4'-phenoxyphenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[137] 2- (4'-methylthiophenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[138] 2- (2,4,6-trimethylthiophenyl) -4-methacryloylthiomethyl-1,3-dithiolane,
[139] 2- (4'-chlorophenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[140] 2- (4'-bromophenyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[141] 2- (α-naphthyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[142] 2- (β-naphthyl) -4-methacryloylthiomethyl-1, 3-dithiolane,
[143] 2,2-dimethyl-4-methacryloylthiomethyl-1,3-dithiolane,
[144] 2-methyl-2-phenyl-4-methacryloylthiomethyl-1,3-dithiolane,
[145] 2,2-diphenyl-4-methacryloylthiomethyl-1,3-dithiolane,
[146] 4- (2-methacryloylthioethyl) -1,3-dithiolane,
[147] 4- (3-methacryloylthiopropyl) -1,3-dithiolane,
[148] 4- (2-methyl-2-methacryloylthioethyl) -1,3-dithiolane,
[149] 4-methacryloylthiomethylthiomethyl-1, 3-dithiolane,
[150] 4- (2-methacryloylthioethylthio) methyl-1,3-dithiolane,
[151] 4- (3-methacryloylthiopropylthio) methyl-1,3-dithiolane,
[152] 4- (2-methyl-2-methacryloylthioethylthio) methyl-1,3-dithiolane,
[153] 4- [2- (2-methacryloylthiomethylthio) ethyl] -1,3-dithiolane,
[154] 4- [2- (2-methacryloylthioethylthio) ethyl] -1,3-dithiolane,
[155] 4- [2- (3-methacryloylthiopropylthio) ethyl] -1,3-dithiolane,
[156] 4- [2- (2-methyl-2-methacryloylthioethylthio) ethyl] -1,3-dithiolane,
[157] 4- [3- (methacryloylthiomethylthio) propyl] -1,3-dithiolane,
[158] 4- [3- (2-methacryloylthioethylthio) propyl] -1,3-dithiolane,
[159] 4- [3- (3-methacryloylthiopropylthio) propyl] -1,3-dithiolane,
[160] 4- [3- (2-methyl-2-methacryloylthioethylthio) propyl] -1,3-dithiolane,
[161] 4- [2-methyl-2- (methacryloylthiomethylthio) ethyl] -1,3-dithiolane,
[162] 4- [2-methyl-2- (2-methacryloylthioethylthio) ethyl] -1,3-dithiolane,
[163] 4- [2-methyl-2- (3-methacryloylthiopropylthio) ethyl] -1,3-dithiolane,
[164] 4- [2-methyl-2- (2-methyl-2-methacryloylthioethylthio) ethyl] -1,3-dithiolane,
[165] 2- (4-methylphenyl) -4- (2-methacryloylthioethyl) -1,3-dithiolane,
[166] 2-α-naphthyl-4- (3-methacryloylthiopropyl) -1,3-dithiolane,
[167] 2-phenyl-4- (methacryloylthiomethylthio) methyl-1,3-dithiolane,
[168] 2- (4-methoxyphenyl) -4- (2-methacryloylthioethylthio) methyl-1,3-dithiolane,
[169] 2- (4-bromophenyl) -4- (2-methacryloylthiopropylthio) methyl-1,3-dithiolane,
[170] 2- (thiophen-2-yl) -4- (2-methyl-2-methacryloylthioethylthio) methyl-1,3-dithiolane,
[171] 2-furyl-4- [2- (2-methacryloylthioethylthio) ethyl] -1,3-dithiolane,
[172] 2- (4-methylthiophenyl) -4- [3- (methacryloylthiomethylthio) propyl] -1,3-dithiolane,
[173] 2-β-naphthyl-4- [2-methyl-2- (methacryloylthiomethylthio) ethyl] -1,3-dithiolane,
[174] 2-methyl-4-methacryloyloxymethyl-1,3-dithiolane,
[175] 2-phenyl-4-methacryloyloxymethyl-1,3-dithiolane,
[176] 2- (4'-methylphenyl) -4-methacryloyloxymethyl-1, 3-dithiolane,
[177] 2- (4'-methoxyphenyl) -4-methacryloyloxymethyl-1, 3-dithiolane,
[178] 2- (4'-phenylphenyl) -4-methacryloyloxymethyl-1, 3-dithiolane,
[179] 2- (4'-phenoxyphenyl) -4-methacryloyloxymethyl-1, 3-dithiolane,
[180] 2- (4'-methylthiophenyl) -4-methacryloyloxymethyl-1, 3-dithiolane,
[181] 2- (2,4,6-trimethylthiophenyl) -4-methacryloyloxymethyl-1,3-dithiolane,
[182] 2- (4'-chlorophenyl) -4-methacryloyloxymethyl-1, 3-dithiolane,
[183] 2- (4'bromophenyl) -4-methacryloyloxymethyl-1,3-dithiolane,
[184] 2- (α-naphthyl) -4-methacryloyloxymethyl-1,3-dithiolane,
[185] 2- (β-naphthyl) -4-methacryloyloxymethyl-1,3-dithiolane,
[186] 2-methyl-2-phenyl-4-methacryloyloxymethyl-1,3-dithiolane,
[187] 2,2-diphenyl-4-methacryloyloxymethyl-1,3-dithiolane,
[188] 2- (4-methylphenyl) -4- (2-methacryloyloxyethyl) -1, 3-dithiolane,
[189] 2-α-naphthyl-4- (3-methacryloyloxypropyl) -1,3-dithiolane,
[190] 2-phenyl-4- (methacryloyloxymethylthio) methyl-1,3-dithiolane,
[191] 2- (4-methoxyphenyl) -4- (2-methacryloyloxyethylthio) methyl-1,3-dithiolane,
[192] 2- (4-bromophenyl) -4- (2-methacryloyloxypropylthio) methyl-1,3-dithiolane,
[193] 2- (thiophen-2-yl) -4- (2-methyl-2-methacryloyloxyethylthio) methyl-1,3-dithiolane,
[194] 2-furyl-4- [2- (2-methacryloyloxyethylthio) ethyl] -1,3-dithiolane,
[195] 2- (4-methylthiophenyl) -4- [3- (methacryloyloxymethylthio) propyl] -1,3-dithiolane,
[196] 2-β-naphthyl-4- [2-methyl-2 (methacryloyloxymethylthio) ethyl] -1,3-dithiolane, etc. are mentioned, but this invention is not limited to these.
[197] It is preferable that the acrylic acid ester compound represented by General formula (1) of this invention is manufactured by the various esterification method in which reaction itself is known using the sulfur containing compound represented by General formula (2) as a raw material. That is, the acrylic ester compound represented by the general formula (1) is prepared by applying various known esterification methods represented by the following representative method examples to the sulfur-containing compound represented by the general formula (2):
[198] (1) A method of obtaining (meth) acrylic acid ester by reacting (meth) acrylic acid (for example, (meth) acrylic acid, its acid halide or ester derivative thereof, etc.) (for example, JP-A-64) -26613, SO 64-31759, SO 63-188660, etc.);
[199] (2) halopropionic acids (e.g., 3-chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid, etc.) or a halide thereof; Dehalogenation to obtain a halopropionic acid ester, thereby obtaining acrylic esters (for example, JP-A-10-204056, JP-A 2-172968, JP-A 2-172969, JP 4-29967) Method assigned to a call publication).
[200] Formula (2) is as follows:
[201]
[202] Wherein R ₁ , R ₂ , A and X are as defined above.
[203] In the said method, the method as described in said (2) is more preferable as a method of manufacturing the acrylic acid ester compound represented by General formula (1) of this invention.
[204] Also in this method, after the method represented by the following reaction formula, that is, the halopropionic acid ester compound (3) shown below is obtained by reacting an acid halide of a sulfur-containing compound represented by the general formula (2) with halopropionic acids, Even more preferable is a method for producing an acrylic ester compound represented by the general formula (1) by dehydrohalation of this halopropionic acid ester compound (3) in the presence of a base.
[205]
[206] Wherein R ₁ , R ₂ , R ₃ , A and X are the same as described above, and Z ₁ and Z ₂ are each independently a chlorine atom or a bromine atom.
[207] Hereinafter, the method will be described in more detail.
[208] First, the method of obtaining the halopropionic acid ester compound (3) by reacting the sulfur-containing compound represented by the general formula (2) with the acid halide of the halopropionic acids will be described in detail.
[209] In the case of this reaction, an acid halide of halopropionic acids (for example, 3-chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methyl) acting on the sulfur-containing compound represented by the general formula (2) The amount of propionic acid, 3-bromo-2-methylpropionic acid, etc.) is not particularly limited, but is usually 0.1 to 5 moles, preferably 0.2 to 3 moles, more preferably 0.5 to 1 mole per 1 mole of sulfur-containing compound. 2 moles. The usage-amount of the acid halide of halopropionic acid becomes like this. Especially preferably, it is 0.8-1.5 mol.
[210] The reaction may be carried out in a solvent or in a solvent inert to the reaction. The solvent used is not particularly limited as long as it is an inert solvent. Moreover, you may perform the said reaction in water, a predetermined organic solvent, or its mixture, for example. As an organic solvent, Hydrocarbon solvents, such as n-hexane, benzene, and toluene; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ester crab solvents such as ethyl acetate and butyl acetate; Ether solvents such as diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, chlorobenzene and o-chlorobenzene; And polar solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. You may use these solvent individually or in combination of 2 or more types.
[211] Although reaction temperature does not have a restriction | limiting in particular, Usually, it is -78-150 degreeC, Preferably it is -20-120 degreeC, More preferably, it is 0-100 degreeC.
[212] The reaction time also depends on the reaction temperature, but is usually from minutes to 100 hours, preferably from 30 minutes to 50 hours, more preferably from 1 hour to 20 hours. In addition, it is also possible to stop a reaction at arbitrary reaction rates, confirming a reaction rate by well-known analytical means (for example, liquid chromatography, gas chromatography, thin layer chromatography, IR, etc.).
[213] Such reaction may be performed without removing a catalyst by-product, such as hydrogen halide (for example, hydrogen chloride), from a reaction system, or using a dehalogenated hydrogen agent.
[214] As the dehalogenated hydrogen agent, for example, triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo Organic bases such as [5.4.0] undeca-7-ene (DBU) or inorganic bases such as sodium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide, and the like. .
[215] The amount of the dehalogenated hydrogen agent is not particularly limited, but is 0.05 to 10 moles, preferably 0.1 to 5 moles, more preferably 0.5 to 3 moles with respect to 1 mole of the sulfur-containing compound represented by the general formula (2). to be.
[216] Next, the method for producing an acrylic ester compound represented by the general formula (1) of the present invention by dehydrohalogenating the halopropionic acid ester compound (3) in the presence of a base will be described in detail.
[217] Examples of the base used for this reaction include methylamine, dimethylamine, triethylamine, pyridine, picoline, aniline, dimethylaniline, diethylaniline, toluidine, anisidine, 1,4-diazabicyclo [2.2 .0] organic bases such as octane (DABCO), 1,8-diazabicyclo [5.4.0] undeca-7 yen (DBU) or sodium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide And inorganic bases such as calcium hydroxide and magnesium oxide.
[218] The amount of the base to be used is not particularly limited, but is 0.05 to 10 mol, preferably 0.1 to 5 mol, more preferably 0.5 to 3 mol with respect to 1 mol of the halopropionic acid ester compound (3).
[219] The reaction may be performed in a solvent or in a solvent that is inert to the reaction. The solvent used is not particularly limited as long as it is an inert solvent. Moreover, you may perform the said reaction in water, a predetermined organic solvent, or its mixture, for example.
[220] As an organic solvent, Hydrocarbon solvents, such as n-hexane, benzene, toluene, and xylene; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ester solvents such as ethyl acetate and butyl acetate; Ether solvents such as diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, chlorobenzene and o-dichlorobenzene; And polar solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. You may use these solvent individually or in combination of 2 or more types.
[221] Although reaction temperature does not have a restriction | limiting in particular, Usually, it is -78-150 degreeC, Preferably it is -20-120 degreeC, More preferably, it is 0-100 degreeC.
[222] The reaction time also depends on the reaction temperature, but is usually from minutes to 100 hours, preferably from 30 minutes to 50 hours, more preferably from 1 hour to 20 hours. In addition, you may stop a reaction at arbitrary reaction rates, confirming a reaction rate by well-known analytical means (for example, liquid chromatography, gas chromatography, thin layer chromatography, IR, etc.).
[223] In the above reaction path, after the esterification reaction of halopropionic acid in the first step, the halopropionic acid ester compound represented by the general formula (3), which is an intermediate, is once taken out and then dehalogenated in the second step. The method may be adopted, or a one-step method may be adopted in which the dehalogenation reaction is carried out in one-pot without removing the halopropionic acid ester compound.
[224] When manufacturing the acrylic ester compound represented by General formula (1) of this invention, it is preferable to use a polymerization inhibitor in order to prevent superposition | polymerization of a product after reaction or during reaction.
[225] As a polymerization inhibitor, various well-known compounds, such as 4-methoxy phenol, 2, 6- di-tert- butyl cresol, hydroquinone, phenothiazine, are mentioned, for example.
[226] The amount of the polymerization inhibitor is not particularly limited, but is usually 0.001 to 5% by weight, preferably 0.05 to 3% by weight, and more preferably 0.01 to 1% by weight based on the raw material mixture or the reaction product in the reaction system.
[227] After the reaction, the acrylic acid ester compound represented by the general formula (1) of the present invention as a reaction product is subjected to post-treatment by a known operation and treatment method (for example, neutralization, solvent extraction, washing, separation, solvent evaporation, etc.). Conduct and isolate. The acrylic acid ester compound represented by the general formula (1) obtained by the above method is further separated and purified by a known method (for example, distillation, recrystallization, chromatography, activated carbon treatment, etc.), if necessary, to obtain high purity. You may isolate as a compound of.
[228] The sulfur-containing compound represented by the general formula (2) of the present invention is a novel compound and is a synthetic intermediate for an acrylic ester compound represented by the general formula (1) of the present invention as described above.
[229] In the formula _{(2), R 1, R} 2, A and X are the same as R _1, R _2, A and X in the formula (1) described previously.
[230] As a sulfur-containing compound represented by General Formula (2) of the present invention, for example,
[231] 4-mercaptomethyl-1,3-dithiolane,
[232] 2-methyl-4-mercaptomethyl-1,3-dithiolane,
[233] 2-ethyl-4-mercaptomethyl-1,3-dithiolane,
[234] 2-n-propyl-4-mercaptomethyl-1,3-dithiolane,
[235] 2-n-butyl-4-mercaptomethyl-1,3-dithiolane,
[236] 2-phenyl-4-mercaptomethyl-1,3-dithiolane,
[237] 2- (4'-methylphenyl) -4-mercaptomethyl-1,3-dithiolane,
[238] 2- (3'-methylphenyl) -4-mercaptomethyl-1,3-dithiolane,
[239] 2- (2'-methylphenyl) -4-mercaptomethyl-1,3-dithiolane,
[240] 2- (4'-tert-butylphenyl) -4-mercaptomethyl-1,3-dithiolane,
[241] 2- (4'-methoxyphenyl) -4-mercaptomethyl-1,3-dithiolane,
[242] 2- (4'-phenylphenyl) -4-mercaptomethyl-1,3-dithiolane,
[243] 2- (4'-phenoxyphenyl) -4-mercaptomethyl-1,3-dithiolane,
[244] 2- (4'-methylthiophenyl) -4-mercaptomethyl-1,3-dithiolane,
[245] 2- (2,4,6-trimethylthiophenyl) -4-mercaptomethyl-1,3-dithiolane,
[246] 2- (4'-chlorophenyl) -4-mercaptomethyl-1,3-dithiolane,
[247] 2- (4'-bromophenyl) -4-mercaptomethyl-1,3-dithiolane,
[248] 2- (α-naphthyl) -4-mercaptomethyl-1,3-dithiolane,
[249] 2- (β-naphthyl) -4-mercaptomethyl-1,3-dithiolane,
[250] 2,2-dimethyl-4-mercaptomethyl-1,3-dithiolane,
[251] 2-methyl-2-phenyl-4-mercaptomethyl-1,3-dithiolane,
[252] 2,2-diphenyl-4-mercaptomethyl-1,3-dithiolane,
[253] 4- (2-mercaptoethyl) -1,3-dithiolane,
[254] 4- (3-mercaptopropyl) -1,3-dithiolane,
[255] 4- (2-methyl-2-mercaptoethyl) -1,3-dithiolane,
[256] 4-mercaptomethylthiomethyl-1,3-dithiolane,
[257] 4- (2-mercaptoethylthio) methyl-1,3-dithiolane,
[258] 4- (3-mercaptopropylthio) methyl-1,3-dithiolane,
[259] 4- (2-methyl-2-mercaptoethylthio) methyl-1,3-dithiolane,
[260] 4- [2- (mercaptomethylthio) ethyl] -1,3-dithiolane,
[261] 4- [2- (2-mercaptoethylthio) ethyl] -1,3-dithiolane,
[262] 4- [2- (3-mercaptopropylthio) ethyl] -1,3-dithiolane,
[263] 4- [2- (2-methyl-2-mercaptoethylthio) ethyl] -1,3-dithiolane,
[264] 4- [3- (mercaptomethylthio) propyl] -1,3-dithiolane,
[265] 4- [3- (2-mercaptoethylthio) propyl] -1,3-dithiolane,
[266] 4- [3- (3-mercaptopropylthio) propyl] -1,3-dithiolane,
[267] 4- [3- (2-methyl-2-mercaptoethylthio) propyl] -1,3-dithiolane,
[268] 4- [2-methyl-2- (mercaptomethylthio) ethyl] -1,3-dithiolane,
[269] 4- [2-methyl-2- (2-mercaptoethylthio) ethyl] -1,3-dithiolane,
[270] 4- [2-methyl-2- (3-mercaptopropylthio) ethyl] -1,3-dithiolane,
[271] 4- [2-methyl-2- (2-methyl-2-mercaptoethylthio) ethyl] -1,3-dithiolane,
[272] 2- (4-methylphenyl) -4- (2-mercaptoethyl) -1,3-dithiolane,
[273] 2-α-naphthyl-4- (3-mercaptopropyl) -1,3-dithiolane,
[274] 2-phenyl-4- (mercaptomethylthio) methyl-1,3-dithiolane,
[275] 2- (4-methoxyphenyl) -4- (2-mercaptoethylthio) methyl-1,3-dithiolane,
[276] 2- (4-bromophenyl) -4- (2-mercaptopropylthio) methyl-1,3-dithiolane,
[277] 2- (thiophen-2-yl) -4- (2-methyl-2-mercaptoethylthio) methyl-1,3-dithiolane,
[278] 2-furyl-4- [2- (2-mercaptoethylthio) ethyl] -1,3-dithiolane,
[279] 2- (4-methylthiophenyl) -4- [3- (mercaptomethylthio) propyl] -1,3-dithiolane,
[280] 2-β-naphthyl-4- [2-methyl-2- (mercaptomethylthio) ethyl] -1,3-dithiolane,
[281] 2-methyl-4-hydroxymethyl-1,3-dithiolane,
[282] 2-phenyl-4-hydroxymethyl-1,3-dithiolane,
[283] 2- (4'-methylphenyl) -4-hydroxymethyl-1,3-dithiolane,
[284] 2- (4'-methoxyphenyl) -4-hydroxymethyl-1,3-dithiolane,
[285] 2- (4-phenylphenyl) -4-hydroxymethyl-1,3-dithiolane,
[286] 2- (4'-phenoxyphenyl) -4-hydroxymethyl-1,3-dithiolane,
[287] 2- (4'-methylthiophenyl) -4-hydroxymethyl-1,3-dithiolane,
[288] 2- (2,4,6-trimethylthiophenyl) -4-hydroxymethyl-1,3-dithiolane,
[289] 2- (4'-chlorophenyl) -4-hydroxymethyl-1,3-dithiolane,
[290] 2- (4'-bromophenyl) -4-hydroxymethyl-1,3-dithiolane,
[291] 2- (α-naphthyl) -4-hydroxymethyl-1,3-dithiolane,
[292] 2- (β-naphthyl) -4-hydroxymethyl-1,3-dithiolane,
[293] 2-methyl-2-phenyl-4-acryloyloxymethyl-1,3-dithiolane,
[294] 2,2-diphenyl-4-hydroxymethyl-1,3-dithiolane,
[295] 2- (4-methylphenyl) -4- (2-hydroxyethyl) -1,3-dithiolane,
[296] 2-α-naphthyl-4- (3-hydroxypropyl) -1,3-dithiolane,
[297] 2-phenyl-4- (hydroxymethylthio) methyl-1,3-dithiolane,
[298] 2- (4-methoxyphenyl) -4- (2-hydroxyethylthio) methyl-1,3-dithiolane,
[299] 2- (4-bromophenyl) -4- (2-hydroxypropylthio) methyl-1,3-dithiolane,
[300] 2- (thiophen-2-yl) -4- (2-methyl-2-hydroxyethylthio) methyl-1,3-dithiolane,
[301] 2-furyl-4- [2- (2-hydroxyethylthio) ethyl] -1,3-dithiolane,
[302] 2- (4-methylthiophenyl) -4- [3- (hydroxymethylthio) propyl] -1,3-dithiolane,
[303] 2-β-naphthyl-4- [2-methyl-2- (hydroxymethylthio) ethyl] -1,3-dithiolane and the like, but the present invention is not limited to these exemplary compounds.
[304] In the general formula (2), the compound in which X is an oxygen atom is preferably produced by a known method (for example, a method disclosed in the Journal of Chemical Society, pp415-419 (1966) or the like).
[305] That is, for example, in the general formula (2), a compound in which R ₁ = hydrogen atom, R ₂ = hydrogen atom, A is a -CH ₂ -group and X is an oxygen atom is known from formalin in the presence of an acid catalyst. It manufactures by making it react with 2, 3- dimercaptopropanol which is a compound.
[306] By the same method, in the said General formula (2), the sulfur containing compound whose X is an oxygen atom is a protonic acid or Lewis with respect to the dimercapto compound represented by following formula (4) for the carbonyl group containing compound represented by following formula (5). Prepared by working in the presence of an acid catalyst such as acid:
[307]
[308] Wherein R ₁ , R ₂ , A and X are as defined above.
[309] In the general formula (2) of the present invention, the sulfur-containing thiol compound in which X is a sulfur atom is reacted by a known method using a sulfur-containing hydroxy compound in which X is an oxygen atom in general formula (2) as a raw material. By converting the hydroxyl group in the molecule to a thiol group.
[310] That is, for example, in order to convert the hydroxy compound in which X is an oxygen atom to a thiol (mercapto) compound in which X is a sulfur atom in the general formula (2), a known method, for example, the Journal of American Chemical Society , Vol. 68, pp 2103-2104 (1946), Journal of Organic Chemistry, Vol. It is preferable to carry out by the method as described in 27, pp93-95 (1962), Organic Synthesis, V, pp401-403 (1963) and the like.
[311] Therefore, in the general formula (2) of the present invention, the thiol compound in which X is a sulfur atom is reacted with a hydroxy compound in which X is an oxygen atom, hydrogen chloride, hydrogen bromide and the like in the general formula (2) of the present invention. After conversion to a halide, it is preferable that the halide is reacted with thiourea to obtain a thiuronium salt, which is then prepared by hydrolyzing the salt with a base such as aqueous ammonia or sodium hydroxide.
[312] Next, the polymeric composition containing the acrylic acid ester compound represented by General formula (1) of this invention is demonstrated in detail.
[313] The polymerizable compound of the present invention contains, as essential components, an acrylic ester compound represented by the general formula (1) of the present invention and a polymerization initiator. A polymerization initiator is a compound which can start superposition | polymerization of a polymeric compound by light and / or heat, and can use various well-known polymerization initiators demonstrated below.
[314] In the polymerizable composition of the present invention, the acrylic acid ester compound may be used alone or in combination of two or more different acrylic acid ester compounds contained in the general formula (1).
[315] Moreover, the polymerizable composition of this invention is a polymerizable composition (light and / or light) other than the acrylic ester compound represented by General formula (1) as needed in the range which does not impair the desired effect of this invention. Thermally polymerizable monomer or oligomer).
[316] The amount of the acrylic acid ester compound represented by the general formula (1) contained in the polymerizable composition is not particularly limited, but is usually 10% by weight or more, preferably 20% by weight or more, based on the total weight of the polymerizable composition. It is preferably at least 30% by weight, even more preferably at least 50% by weight.
[317] The polymerization initiator used in the polymerizable composition of the present invention is not particularly limited, but a known compound (thermal polymerization initiator) that initiates polymerization by heat or a compound (photopolymerization initiator) which initiates polymerization by irradiation of light may be used.
[318] As a photoinitiator, For example, benzophenone, 4-methylbenzo phenone,
[319] 4,4'-dichlorobenzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate,
[320] 4-phenylbenzophenone, 4- (4-methylphenylthio) benzophenone, 3,3-dimethyl-4-methylbenzophenone,
[321] 4- (1,3-acryloyl-1,4,7,10,13-pentaoxatridecyl) benzophenone,
[322] 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone,
[323] 4-benzoyl-N, N, N-methylbenzenemethanealuminum chloride,
[324] 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propaneamichloride,
[325] 4-benzoyl-N, N-dimethyl-N-[(2- (1-oxo-2-propenoxy) ethyl) -benzenemethanealuminum chloride,
[326] 4-benzoyl-N, N-dimethyl-N-[(2- (1-oxo-2-propenyloxy) ethyl) -benzenemethanealuminum bromide,
[327] 2-isopropylthioisopropyl thioxanthone,
[328] 4-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone,
[329] 2,4-diisopropyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycyxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo- 9H-Tioxanthone-2-yl-oxy) -N, N, N-trimethyl-1-propaneaminium chloride,
[330] Carbonyl compounds such as 2-benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline;
[331] Benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione (collectively camphorquinone),
[332] 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone,
[333] 1-chloroanthraquinone, 2-amylanthraquinone, 9,10-phenanthrenequinone,
[334] Dicarbonyl compounds such as methyl a-oxobenzene acetate;
[335] Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
[336] 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one,
[337] 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one,
[338] 1-hydroxycyclohexylphenyl ketone, dimethoxyacetophenone, diethoxyacetophenone,
[339] 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one,
[340] 1,1-dichloroacetophenone, N, N-dimethylaminoacetophenone,
[341] 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one,
[342] 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one
[343] 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime,
[344] Acetophenone compounds such as 3,6-bis (2-methyl-2-morpholinopropanoyl) -9-butylcarbazole;
[345] Benzoin and benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
[346] Benzoin ether compounds such as benzoin-n-butyl ether and benzoin isobutyl ether;
[347] 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
[348] Aryl phosphine oxide compounds such as bis (2,6-dichlorobenzoyl)-(4-n-propylphenyl) phosphine oxide;
[349] Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate
[350] 4-dimethylaminobenzoate-n-butoxyethyl ester,
[351] Isoamyl 4-dimethylaminobenzoate, benzoate-2-dimethylaminoethyl ester, 4,4'-bis (dimethylamino) benzophenone (ketone from Michler),
[352] 4,4'-bis (diethylamino) benzophenone,
[353] Aminocarbonyl compounds such as 2,5'-bis (4-dimethylaminobenzal) cyclopentanone;
[354] 2,2,2-trichloro-1- (4'-tert-butylphenyl) ethan-1-one,
[355] 2,2-dichloro-1- (4-phenoxyphenyl) ethan-1-one,
[356] α, α, α-tribromomethylphenylsulfone, 2,4,6-tris (trichloromethyl) triazine,
[357] 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) triazine,
[358] 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) triazine,
[359] 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) triazine,
[360] 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) triazine,
[361] 2,4-bis (trichloromethyl) -6- [2- (5-methylfuryl) ethylidine] triazine,
[362] Halogenated compounds such as 2,4-bis (trichloromethyl) -6- [2-furylethylidine] triazine;
[363] 9-phenylacridine, 2,2'-bis (-o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole,
[364] 2,2-azobis (2-aminopropane) dihydrochloride,
[365] 2,2-azobis [2- (imidazolidin-2-yl) propane] dihydrochloride,
[366] η-5-2-4- (cyclopentadienyl) (1,2,3,4,5,6, η)-(methylethyl) benzene] iron (II) hexafluorophosphate,
[367] And other known compounds such as bis (5-cyclogentadienyl) bis [2,6-difluoro-3- (1H-pyr-1-yl) -phenyl] titanium. You may use these individually or in combination of 2 or more types.
[368] The amount of the photopolymerizable initiator used is 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more, based on 100 parts by weight of the acrylic ester compound represented by the general formula (1). Preferably it is 0.2-5 weight part.
[369] As a thermal polymerization initiator, For example, peroxides, such as a benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, tert- butyl peroxy pivalate; Azo compounds, such as azobisisobutyronitrile, etc. are mentioned.
[370] The amount of the thermal polymerization initiator is usually 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the acrylic acid ester compound represented by the general formula (1), Even more preferably 0.2 to 5 parts by weight.
[371] As a polymeric compound used for the polymeric composition of this invention as a well-known polymeric compound other than the acrylic acid ester compound represented by General formula (1), it is a for example,
[372] Methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
[373] Ethylcarbitol (meth) acrylate, lauryl (meth) acrylate,
[374] Tetracyclododecyl (meth) acrylate, phenoxyethyl (meth) acrylate,
[375] Nonylphenoxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate,
[376] Isobornyl (meth) acrylate, N-n-butyl-O- (meth) acryloyloxy ethyl carbamate,
[377] Acryloyl morpholine, trifluoroethyl (meth) acrylate,
[378] Monofunctional acrylates such as tribromobenzyl (meth) acrylate and perfluorooctylethyl (meth) acrylate;
[379] Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
[380] Neopentylglycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate,
[381] Triethylene glycol di (meth) acrylate,
[382] Tripropylene glycol di (meth) acrylate,
[383] Polyethylene glycol di (meth) acrylate,
[384] Polypropylene glycol di (meth) acrylate,
[385] 2,2-bis (4-acryloxy phenyl) propane, 2,2-bis (4-methacryloyloxyphenyl) propane,
[386] Bis (4-acryloyloxyphenyl) methane, bis (4-methacryloyloxyphenyl) methane,
[387] 4,4'-bis (2-acryloyloxy) phenylsulfide,
[388] 4,4'-bis (2-methacryloyloxy) phenylsulfide,
[389] 2,2-bis (4-acryloyloxyethoxyphenyl) propane,
[390] 2,2-bis (4-methacryloyloxyethoxyphenyl) propane,
[391] 2,2-bis [4- (2-acryloyloxypropoxy) phenyl] propane,
[392] 2,2-bis [4- (2-methacryloyloxypropoxy) phenyl] propane,
[393] Bis (4-acryloyloxyethoxyphenyl) methane,
[394] Bis (4-methacryloyloxyethoxyphenyl) methane,
[395] Bis [4- (2-acryloyloxypropoxy) phenyl] methane,
[396] [4- (2-methacryloyloxypropoxy) phenyl] methane,
[397] 4,4'-bis (2-acryloyloxyethoxy) phenyl sulfide,
[398] 4,4'-bis (2-methacryloyloxyethoxy) phenyl sulfide,
[399] 4,4'-bis (2-acryloyloxypropoxy) phenyl sulfide,
[400] 4,4'-bis (2-methacryloyloxypropoxy) phenyl sulfide,
[401] 4,4'-bis (2-acryloyloxyethoxy) phenyl sulfone,
[402] 4,4'-bis (2-methacryloyloxyethoxy) phenyl sulfone,
[403] 4,4'-bis (2-acryloyloxypropoxy) phenyl sulfone,
[404] Bifunctional (meth) acrylates such as 4,4'-bis (2-methacryloyloxypropoxy) phenyl sulfone,
[405] Trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate,
[406] Pentaerythritol triacrylate, pentaerythritol tetraacrylate,
[407] Ditrimethylol tetraacrylate, dipentaerythritol hexaacrylate,
[408] 2- (meth) acryloyloxyethyl triisocyanurate,
[409] Polyfunctional acrylates such as (meth) acryloyloxypropyl tri (methoxy) silane;
[410] Phenyl glycidyl ether, ethylene glycol diglycidyl ether,
[411] Propylene glycol diglycidyl ether, resorcin diglycidyl ether,
[412] Hydroquinone diglycidyl ether,
[413] Bis (4-hydroxyphenyl) methane (collectively, bisphenol F) diglycidyl ether,
[414] 2,2-bis (4-hydroxyphenyl) propane (common name, bisphenol A) diglycidyl ether,
[415] 4,4'-bishydroxyphenylsulfide diglycidyl ether,
[416] 4,4'-bishydroxyphenylsulfone (common name bisphenol S) diglycidyl ether,
[417] 4,4'-biphenol diglycidyl ether,
[418] 3,3 ', 5,5'-tetramethyl-4,4'-biphenol diglycidyl ether,
[419] Epoxy (meth) acrylates obtained by reacting a (meth) acrylic acid compound with a monofunctional or bifunctional epoxy compound such as tris (2,3-epoxypropyl) isocyanurate;
[420] Epoxy (meth) acrylates obtained by making a (meth) acrylic acid compound react with epoxy resins, such as a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a phenol xsiloxane type epoxy resin, and a bisphenol-type epoxy resin;
[421] Vinyl compounds such as vinylbenzene, divinylbenzene, trivinylbenzene, isopropenylbenzene, diisopropenylbenzene, triisopropenylbenzene, N-vinylpyrrolidone and N-vinyl caprolactam;
[422] Various known polymerizable monomers such as allyl group-containing compounds such as ethylene glycol diallyl carbonate, trimellitic acid triallyl ester and triallyl isocyanurate; or
[423] Various well-known polymerizable oligomers, such as polyurethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates, etc. are mentioned.
[424] In order to acquire the effect of this invention, the usage-amount of these polymeric compounds is 300 weight part or less normally, Preferably it is 200 weight part or less with respect to 100 weight part of acrylic acid ester compounds represented by General formula (1). Preferably 100 parts by weight or less.
[425] Specifically, the polymeric compound of this invention uses the said well-known polymeric compound together as needed using the acrylic ester compound represented by General formula (1) of this invention, and also adds the said polymerization initiator. After mixing, it is obtained by mixing and dissolving. The polymerizable composition is used to remove insoluble matters, foreign matters and the like by filtration before depolymerization, and to degassing sufficiently under reduced pressure to polymerize and cure the polymerizable composition as necessary.
[426] In the case of producing the polymerizable composition, if desired, internal mold release agents, light stabilizers, UV absorbers, antioxidants, coloring pigments (for example, cyanine green, cyanine blue, etc.), dyes, flow control agents, inorganic fillers ( For example, it is also possible to add various well-known additives, such as talc, silica, alumina, barium sulfate, magnesium oxide, etc.).
[427] The optical component which consists of hardened | cured material and hardened | cured material of this invention is obtained by superposing | polymerizing and hardening the said polymeric composition. As the method of the present invention, various conventionally known methods are employed and preferably carried out. Typically, for example, the polymerizable composition obtained as described above is injected into a mold and then started by heat or light. And template polymerization using a radical polymerization reaction.
[428] The mold is composed of, for example, two mirror-polished molds through a gasket made of polyethylene, ethylene-vinylacetate copolymer, polyvinyl chloride, or the like. Examples of the mold include glass and glass; Plastic plates and glass; The mold which glass and the metal plate etc. were combined is mentioned. As the gasket, in addition to using the above soft thermosetting resin (polyethylene, ethylene-vinylacetate copolymer, polyvinyl chloride, etc.), two molds may be fixed with a polyester adhesive tape or the like. In addition, you may apply well-known processing methods, such as a mold release process, with respect to a mold.
[429] As the radical polymerization reaction, as described above, a method using a polymerization reaction by heat (thermal polymerization), a polymerization reaction by light such as ultraviolet rays (photopolymerization), a polymerization reaction by γ-rays, a method in which a plurality of these methods are combined, etc. Can be mentioned.
[430] In the case of polymerization by light, after completion of curing, the cured product obtained by releasing the mold or the optical part made of the cured product may be annealed to remove internal stress and distortion.
[431] Among these methods, the curing at the time of thermal polymerization requires several hours to several tens of hours, whereas the curing at the time of photopolymerization by ultraviolet irradiation or the like can be finished in only a few seconds to several minutes, thus improving the productivity in manufacturing the optical component of the present invention. In view of height, the photopolymerization method is preferable.
[432] In the case of thermal polymerization, the polymerization temperature is affected by the polymerization conditions such as the kind of polymerization initiator, but is not limited, but is usually 25 to 200 ° C, preferably 50 to 170 ° C.
[433] As the molding method of the optical lens, as described above, for example, a method of obtaining a lens by performing a mold polymerization by light or / and heat may be mentioned (for example, JP-A-60-135901). Hei 10-67736, Hei 10-130250, etc.).
[434] Therefore, in this method, after defoaming by the appropriate method the polymerizable composition containing the acrylic acid ester compound represented by General formula (1) of this invention manufactured by the above-mentioned method as needed, and then inject | pouring into a mold, Usually, it is preferable by the method of superposing | polymerizing by light irradiation. Moreover, in the case of superposition | polymerization by heat, it is preferable to carry out by the method of heating and polymerizing this composition gradually from low temperature to high temperature.
[435] The obtained optical lens may be annealed as necessary after curing. In addition, if necessary, for the purpose of antireflection, high hardness, improved friction resistance, antifogging or fashion, surface polishing, antistatic treatment, hard coating treatment, antireflection coating treatment, dyeing treatment, and dimming You may perform various well-known physical or chemical processes, such as a process (for example, photochromic lens process, etc.).
[436] As a method of forming a substrate of an optical disc or a magneto-optical disc, for example, a polymerizable composition containing an acrylic ester compound represented by the general formula (1) obtained by the above method is injected into a mold cavity of the disc substrate, This is polymerized by a radical polymerization method or the like and subjected to a post-heat treatment (Japanese Patent Application Laid-Open No. 58-130450, No. 58-137150, No. 62-280008, etc.), photopolymerization in a double-sided glass type. Conventionally known methods such as a method (Japanese Patent Application Laid-Open No. 60-202557) and a method of thermally polymerizing a liquid resin under reduced pressure after casting or injection (Japanese Patent Laid-Open No. 60-203414) Can be mentioned.
[437] The cured product obtained by photopolymerization of the polymerizable composition of the present invention and the optical component composed of the cured product require several minutes to several hours for polymerization and curing, and are made of conventional polydiethylene glycol diallylcarbonate and polythiourethane. Compared with the thermosetting resin for typical optical components, polymerization molding is possible in a short time, and there is an advantage that productivity is high.
[438] Moreover, the hardened | cured material and optical component of this invention are excellent in transparency, a mechanical characteristic, and a thermal characteristic compared with a well-known photopolymerizable monomer, and have the characteristic of high refractive index. As the use of the optical component, for example, various plastic lenses typified by corrective spectacle lenses, substrates for optical information recording media, plastic substrates for liquid crystal cells, optical fiber coating materials, and the like can be cited as specific forms.
[439] The (meth) acrylic acid ester compound represented by the general formula (1) of the present invention is a novel compound having a cyclic thioacetal structure in its molecule, and is very useful as a water support material monomer for an optical part such as a corrective spectacle lens. Compound.
[440] Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.
[441] (1) Synthesis of Sulfur-Containing Compound Represented by General Formula (2)
[442] Preparation Example 1 [Synthesis of 4-hydroxymethyl-1,3-dithiolane]
[443] The preparation was carried out according to the method described in the Journal of Chemical Society (C), p415-419 (1966). That is, after weighing and injecting 250 ml of 30% formaldehyde solution and 250 ml of dioxane into a 1-liter glass reactor equipped with a stirrer and a cooling tube, 186 g of 2,3-dimercaptopropanol was stirred with respect to the mixture. 1.5 mol) was added. After further adding 1 g of sulfuric acid, the resultant mixture was heated and stirred at 90 to 100 ° C. for 6 hours under a nitrogen atmosphere to react. After confirming that the raw materials disappeared by gas chromatography and the reaction was completed, the solvent was distilled off under reduced pressure. The solvent was distilled off from the organic layer extracted with chloroform and wash | cleaned with water, and 133 g (0.98 mol) of 4-hydroxymethyl- 1, 3- dithiolanes were obtained.
[444] Yield: 65%
[445] Purity:> 99% (area method by gas chromatography analysis)
[446] Boiling Point: 124-125 ° C / 266kPa (2mmHg)
[447] EI-MS: 136 (M).
[448] Example 1 [4-mercaptomethyl-1,3-dithiolane: of the compound of the formula (2) wherein R ₁ = hydrogen atom, R ₂ = hydrogen atom, A = -CH ₂ -group and X = sulfur atom synthesis]
[449] 38.0 g (0.50 mol) of thiourea and 88 g of hydrobromic acid (corresponding to 0.5 mol of hydrogen bromide) were introduced into a glass 500 ml reactor equipped with a stirrer and a cooling tube. 68 g (0.50 mol) of 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1 was added dropwise to the mixture over 60 minutes at 60 ° C, and reacted at 80 ° C for 4 hours to obtain a thironium salt. . After analyzing the reaction solution by high performance liquid chromatography to confirm that the hydroxy compound as a raw material was lost, 300 g of 18% ammonia water was added dropwise to the reaction mixture at 50 DEG C over 10 minutes. Moreover, reaction was continued at 50 degreeC for 2 hours, and the thiuronium salt was hydrolyzed. Toluene 200g was added here, the toluene layer was separated and extracted, and it washed with water until the wastewater layer became neutral. Then, the toluene layer was taken out from the reaction system, and toluene was distilled off at 40 degreeC under reduced pressure, and the crude product of the yellow transparent liquid was obtained. The product was purified by silica gel column chromatography (using toluene as a solvent), to obtain 61 g (0.40 mol) of 4-mercaptomethyl-1,3-dithiolane, which is a colorless liquid represented by the following formula (2-1). Got it.
[450] Yield: 80%
[451] Purity:> 99% (area method by gas chromatography analysis)
[452] EI-MS: 152 (M).
[453] Example 2 [2-phenyl-4-hydroxymethyl-1,3-dithiolane: in formula (2), R ₁ = phenyl group, R ₂ = hydrogen atom, A = -CH ₂ -group and X = sulfur atom Synthesis of Phosphorus Compound]
[454] 50.0 g (0.40 mol) of 2,3-dimercaptopropanol, 0.44 g (0.004 mol) of 98% sulfuric acid and 80 g of dioxane were weighed and injected into a 1 L reactor made of glass equipped with a stirrer and a cooling tube. About 46.8 g (0.442 mol) of benzaldehydes were dripped over 25 minutes at 25 degreeC. The mixture was reacted under stirring to terminate the reaction at 70 ° C. for 5 hours, and the obtained mixture was poured into 500 g of water, followed by extraction with toluene. The organic layer (toluene solution) was washed, and separation with water was repeated until the water layer became neutral, and then the organic layer was taken out. Toluene was distilled off, the mixture was concentrated under reduced pressure, and n-hexane was added. The solution is left to stand, and the precipitated crystals are filtered out, and the crystals are washed with toluene / hexane (weight ratio = 60/40), and are represented by the following formula (2-2) as white crystals:
[455]
[456] 72.2 g of 2-phenyl-4-hydroxymethyl-1,3-dithiolane represented by the above were obtained.
[457] Yield: 85%
[458] Purity: 99% (calculated by Gas Chromatography Area Percentage)
[459] 270 MHz ¹ H-NMR δ (CDCl ₃ ): 2.25 (t, 1H), 3.40 to 4.20 (m, 5H), 5.65 (d, 1H), 7.20 to 7.55 (5H)
[460] EI-MS: 212 (M).
[461] Example 3 [2- (α-naphthyl) -4-hydroxymethyl-1,3-dithiolane: in formula (2), R ₁ = α-naphthyl group, R ₂ = hydrogen atom, A =- Synthesis of CH ₂ -group and X = Oxygen Atom]
[462] The following formula (2-3) was carried out in the same manner as in the method described in Example 2 except that α-formylnaphthalene was used instead of benzaldehyde in Example 2.
[463]
[464] 2- (α-naphthyl) -4-hydroxymethyl-1,3-dithiolane represented by was obtained.
[465] EI-MS: 262 (M)
[466] Example 4 [2- (β-naphthyl) -4-hydroxymethyl-1,3-dithiolane: in formula (2), R ₁ = β-naphthyl group, R ₂ = hydrogen atom, A = − Synthesis of CH ₂ -group and X = Oxygen Atom]
[467] The following formula (2-4) was carried out in the same manner as in the method described in Example 2 except that β-formylnaphthalene was used instead of benzaldehyde in Example 2.
[468]
[469] 2- (β-naphthyl) -4-hydroxymethyl-1,3-dithiolane represented by was obtained.
[470] EI-MS: 262 (M)
[471] Example 5 [2- (thiophen-2-yl) -4-hydroxymethyl-1,3-dithiolane: in formula (2), R ₁ = thiophen- ₂ -yl group, R ₂ = hydrogen atom , A = -CH ₂ -group and X = synthesis of a compound of oxygen atom]
[472] Except having used 2-formylthiophene instead of benzaldehyde in Example 2, it carried out similarly to the method of Example 2, and is following formula (2-5):
[473]
[474] 2- (thiophen-2-yl) -4-hydroxymethyl-1,3-dithiolane represented by was obtained.
[475] EI-MS: 218 (M)
[476] Example 6 [2-phenyl-4-mercaptomethyl-1,3-dithiolane: in formula (2), R ₁ = phenyl group, R ₂ = hydrogen atom, A = -CH ₂ -group and X = sulfur atom Synthesis of Phosphorus Compound]
[477] Example 1 except that 2-phenyl-4-hydroxymethyl-1,3-dithiolane prepared in Example 2 was used instead of 4-hydroxymethyl-1,3-dithiolane synthesized in Preparation Example 1. In the same manner as described, the following formula (2-6):
[478]
[479] 2-phenyl-4-mercaptomethyl-1,3-dithiolane represented by was obtained.
[480] 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.68 (dt, 1 H), 2.80 to 3.58 (m, 4H), 3.97 (dm, 1H), 5.65 (d, 1H), 7.20 to 7.53 (5H)
[481] EI-MS: 228 (M).
[482] Example 7 [2- (α-naphthyl) -4-mercaptomethyl-1,3-dithiolane: R ₁ = α-naphthyl group in Formula (2), R ₂ = hydrogen atom, A =- Synthesis of CH ₂ -group and X = sulfur atom]
[483] Instead of 4-hydroxymethyl-1,3-dithiolane synthesized in Preparation Example 1, 2- (α-naphthyl) -4-hydroxymethyl-1,3-dithiolane prepared in Example 3 was used. Except for the same method as described in Example 1, the following formula (2-7):
[484]
[485] 2- (α-naphthyl) -4-mercaptomethyl-1,3-dithiolane represented by was obtained.
[486] EI-MS: 278 (M).
[487] Example 8 [2- (β-naphthyl) -4-mercaptomethyl-1,3-dithiolane: in formula (2), R ₁ = β-naphthyl group, R ₂ = hydrogen atom, A = − Synthesis of CH ₂ -group and X = sulfur atom]
[488] Instead of 4-hydroxymethyl-1,3-dithiolane synthesized in Preparation Example 1, 2- (β-naphthyl) -4-hydroxymethyl-1,3-dithiolane prepared in Example 4 was used. Except for the same method as described in Example 1, the following formula (2-8):
[489]
[490] 2- (β-naphthyl) -4-mercaptomethyl-1,3-dithiolane represented by was obtained.
[491] EI-MS: 278 (M).
[492] Example 9 [2- (thiophen-2-yl) -4-mercaptomethyl-1,3-dithiolane: in formula (2), R ₁ = thiophen- ₂ -yl group, R ₂ = hydrogen atom , A = -CH ₂ -group and X = synthesis of sulfur atom
[493] 2- (thiophen-2-yl) -4-hydroxymethyl-1,3-dithiolane prepared in Example 5 instead of 4-hydroxymethyl-1,3-dithiolane synthesized in Preparation Example 1 Except having used similarly to the method described in Example 1, following formula (2-9):
[494]
[495] 2- (thiophen-2-yl) -4-mercaptomethyl-1,3-dithiolane represented by was obtained.
[496] EI-MS: 234 (M).
[497] (2) Synthesis of Acrylic Acid Ester Compound Represented by General Formula (1)
[498] Example 10 [4-acryloylthiomethyl-1,3-dithiolane: in formula (1), R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = hydrogen atom, A = -CH _2- Group and X = synthesis of sulfur atom
[499] 91.2 g (0.60 mol) of 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 was weighed and injected into a 500 ml reactor made of glass equipped with a stirrer and a cooling tube. 80.0 g (0.63 mol) of 3-chloropropionic acid chloride was added dropwise to the reactor at 40 ° C. over 15 minutes. After reacting for 8 hours at 40 DEG C while stirring, 200 g of toluene was added to the reaction mixture to dissolve the mixture. The mixture was then transferred to a separatory funnel and washed three times with 300 g of a 3% by weight aqueous sodium hydrogen carbonate solution. Subsequently, the mixture was washed with pure water 300 g until the water layer became neutral, and then the organic layer (toluene solution) was taken out. Toluene was distilled off under reduced pressure to obtain 119 g of 4- (3-chloropropionylthiomethyl) -1,3-dithiolane as a colorless transparent liquid.
[500] Subsequently, triethylamine was applied to a solution obtained by introducing 119 g (0.49 mol) of 4- (3-chloropropionylthiomethyl) -1,3-dithiolane and 200 g of acetone obtained in the manner described above into a glass 1 L reactor. 74 g (0.73 mol) was dripped at 25 degreeC over 1 hour. Then, after making it react for 6 hours by stirring at 25 degreeC, 400 g of toluene and 400 g of water were added with respect to the said reaction mixture, the toluene phase was separated and taken out. The toluene solution was washed with 5% by weight aqueous hydrogen chloride solution, and then washed with water until the water layer became neutral. Then, toluene was distilled off under reduced pressure to obtain a viscous colorless transparent liquid as the following formula (1-1):
[501]
[502] Obtained 99 g (0.48 mol) of 4- (2'-acryloylthiomethyl) -1,3-dithiolanes represented by the following.
[503] Yield: 80%
[504] Purity:> 99% (area method by liquid chromatography analysis)
[505] EI-MS: 206 (M).
[506] Example 11 [2-phenyl-4-acryloylthiomethyl-1,3-dithiolane: in formula (1), R ₁ = phenyl group, R ₂ = hydrogen atom, R ₃ = hydrogen atom, A =- Synthesis of CH ₂ -group and X = sulfur atom]
[507] 2-phenyl-4-mercaptomethyl-1,3-dithiolane prepared in Example 6 instead of 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material. Except having used (2-6), it carried out similarly to Example 10 and following formula (1-2):
[508]
[509] 2-phenyl-4-acryloylthiomethyl-1,3-dithiolane represented by was obtained.
[510] 270 MHz ¹ H-NMR δ (CDCl ₃ ): 3.22 to 3.55 (m, 4H), 4.08 (dm, 1H), 5.68 to 5.77 (m, 2H), 6.35 to 6.40 (d, 2H), 7.25 to 7.55 ( 5H)
[511] EI-MS: 282 (M).
[512] The viscosity of this compound was measured and found to be 200 mPa · s (200 cPoise) or less. This compound could easily flow to a relatively low viscosity and was easy to handle during work hours such as filtration and permeation.
[513] Example 12 [2- (α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane: in formula (1), R ₁ = α-naphthyl group, R ₂ = hydrogen atom, R ₃ = synthesis of hydrogen atom, A = -CH ₂ -group and X = sulfur atom]
[514] 2- (α-naphthyl) -4-mercaptomethyl-1 prepared in Example 7 instead of 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material The following formula (1-3) was carried out in the same manner as in Example 10 except for using, 3-dithiolane (2-7):
[515]
[516] 2- (α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane represented by was obtained.
[517] EI-MS: 332 (M).
[518] Example 13 [2- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane: R ₁ = β-naphthyl group, R ₂ = hydrogen atom, R in general formula (1) ₃ = synthesis of hydrogen atom, A = -CH ₂ -group and X = sulfur atom]
[519] 2- (β-naphthyl) -4-mercaptomethyl-1 prepared in Example 8 instead of 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material The following formula (1-4) was carried out in the same manner as in Example 10 except for using, 3-dithiolane (2-8):
[520]
[521] 2- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane represented by was obtained.
[522] EI-MS: 332 (M).
[523] Example 14 [2- (thiophen-2-yl) -4-acryloylthiomethyl-1,3-dithiolane: in formula (1), R ₁ = thiophen- ₂ -yl group, R ₂ = Synthesis of a compound having a hydrogen atom, R ₃ = hydrogen atom, A = -CH ₂ -group and X = sulfur atom]
[524] 2- (thiophen-2-yl) -4-mercaptomethyl prepared in Example 9 instead of 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material. Except having used -1, 3- dithiolane (2-9), it carried out similarly to Example 10 and following formula (1-5):
[525]
[526] 2- (thiophen-2-yl) -4-acryloylthiomethyl-1,3-dithiolane represented by was obtained.
[527] EI-MS: 288 (M).
[528] Example 15 [2-phenyl-4-acryloyloxymethyl-1,3-dithiolane: in formula (1), R ₁ = phenyl group, R ₂ = hydrogen atom, R ₃ = hydrogen atom, A =- Synthesis of CH ₂ -group and X = sulfur atom]
[529] 2-phenyl-4-hydroxymethyl-1,3-dithiolane prepared in Example 2 instead of 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material Except having used (2-2), it carried out similarly to Example 10 and following formula (1-6):
[530]
[531] 2-phenyl-4-acryloyloxymethyl-1,3-dithiolane represented by was obtained.
[532] 270 MHz ¹ H-NMR δ (CDCl ₃ ): 3.30 to 3.55 (m, 2H), 4.00 to 4.55 (m, 3H), 5.75 (s, 1H), 5.85 to 5.90 (dd, 1H), 6.10 to 6.20 ( dd, 1H), 6.40-6.50 (d, 1H), 7.20-7.60 (5H)
[533] EI-MS: 266 (M).
[534] (3) Preparation of polymeric composition using acrylic ester compound represented by General formula (1), and manufacture of hardened | cured material by hardening the composition
[535] The physical property evaluation (transparency, thermal characteristic, mechanical characteristic) of the hardened | cured material or optical component (lens) manufactured by the Example and the comparative example was performed with the following method.
[536] Appearance: Color and transparency were visually evaluated.
[537] Refractive index and Abbe number: It measured at 20 degreeC using the Fulfrisch refractometer.
[538] Heat resistance: The glass transition temperature of the cured product was measured using TMA (needle penetration method).
[539] Impact resistance: A 28.7 g iron ball was dropped at a height of 127 cm at the center of a negative lens having a central thickness of 1.5 mm to investigate the presence of cracks.
[540] Example 16
[541] To 30 g of the acrylic acid ester compound (4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 10, 2-hydroxy-2-methyl-1-phenylpropan-1-one (as a photoinitiator) "Darocur-1173" (trademark of Chiba Special Chemicals Co., Ltd.) 150 mg was added, mixed well, and dissolved. The obtained liquid was defoamed under sufficiently reduced pressure, and then poured into a mold made of a glass mold and a gasket. The polymerization was carried out by irradiating ultraviolet light for 60 seconds using a metal halide lamp (80 W / cm). After completion of the polymerization, the resulting cured product was slowly cooled and removed from the mold.
[542] The obtained hardened | cured material was colorless and transparent. No optical distortion was observed. The refractive index nd was 1.660 and the Abbe number was 36 (v d).
[543] Examples 17-21
[544] Instead of the acrylic acid ester compound (4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 10, 2-hydroxy-2-methyl, using the acrylic acid ester compound prepared in Examples 11 to 15 Polymerization was carried out in the same manner as in Example 16, except that 2,4,6-trimethoxybenzoyl diphenylphosphine oxide (manufactured by BASF Corporation) was used as the photopolymerization initiator instead of -1-phenylpropan-1-one. The composition was prepared, and polymerization and curing were performed.
[545] The measurement results of the refractive index and the Abbe number of the cured product are shown in Table 1 below.
[546] ExampleAcrylic Ester Compound UsedRefractive index (nd)Abbe number (νd) 172-phenyl-4-acryloylthiomethyl-1,3-dithiolane (prepared in Example 11)1.68830.5 182- (α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane (prepared in Example 12)1.69329.5 192- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane (prepared in Example 13)1.69329.5 202- (thiophen-2-yl) -4-acryloylthiomethyl-1,3-dithiolane (prepared in Example 14)1.69529.5 212-phenyl-4-acryloyloxymethyl-1,3-dithiolane (made in Example 15)1.65332.2
[547] The polymerizable composition containing the acrylic acid ester compound of the present invention can be polymerized and cured for a short time by a polymerization reaction initiated by light irradiation, and the refractive index of the resulting cured product is very high.
[548] Example 22
[549] 24 g of the acrylic acid ester compound (2-phenyl-4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 11, 3 g of trimethylolpropane trimethacrylate and bisphenol A diglycidyl ether dimethacrylate 30 mg of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (manufactured by BASF Corporation) was added to the mixture obtained by mixing 3 g, and the obtained mixture was mixed well and dissolved to prepare a liquid composition having a low viscosity. . The obtained composition was sufficiently degassed under reduced pressure, and then injected into a mold made of a glass mold and a gasket. Moreover, after irradiating an ultraviolet-ray for 60 second using the metal halide lamp (120W / cm), superposition | polymerization was performed. Then, it cooled slowly to room temperature, hardened | cured material was taken out from the mold, and it heated and annealed at 130 degreeC for 2 hours in an inert oven.
[550] The obtained hardened | cured material was colorless and transparent, the optical distortion was not observed, the refractive index (nd) was 1.655, and Abbe number was 33 ((nu)).
[551] The glass transition temperature of the hardened | cured material was the level which can be practically utilized as a spectacle lens for visual correction, and was also excellent in impact resistance.
[552] Comparative Example 1
[553] 1,4-bis (2-methacryl) which is a conventionally known acrylic acid ester compound (Japanese Patent Laid-Open No. 3-217412) instead of an acrylic acid ester compound represented by the general formula (1) of the present invention as a polymerizable composition. A polymerizable composition was prepared in the same manner as in Example 22 except that 24 g of loyloxyethylthio) xylylene and 6 g of 2,2-bis (4-methacryloyloxyethoxyphenyl) propane were used. , The lens was produced.
[554] The lens was colorless and transparent, with a refractive index (nd) of 1.588 Abbe number of 39 (νd).
[555] Comparative Example 2
[556] 2-methacryloyloxymethyl-1,4 which is a conventionally well-known compound (Unexamined-Japanese-Patent No. 3-215801) instead of the acrylic ester compound represented by General formula (1) of this invention as a polymeric composition. Except having used dithiane, it carried out similarly to the method of Example 22, and obtained the hardened | cured material. The obtained hardened | cured material was colorless and transparent, the refractive index (nd) was 1.590, and Abbe number (vd) was 43.
[557] Comparative Example 3
[558] 6- which is a conventionally well-known compound (compound described on page 61 of Japanese Patent Application Laid-Open No. 2000-509075) instead of the acrylic ester compound represented by General formula (1) of this invention as a polymeric composition. Except having used 6 g of methacryloyloxy-1, 4- dithiacycloheptane, it carried out similarly to the method described in Example 22, the polymeric composition was obtained, and the hardened | cured material was produced. The obtained hardened | cured material was colorless and transparent, the refractive index (nd) was 1.545, and Abbe number (vd) was 43.5.
[559] As described above, the acrylic ester compound of the present invention has a low viscosity as compared with conventionally known monomers, and therefore, when the polymerizable composition is prepared and when the optical component is manufactured using the polymerizable composition, the fluidity and the processability during handling are excellent. .
[560] In addition, the polymerizable composition containing the acrylic ester compound of the present invention can be polymerized and cured in a short time by a compound (polymerization initiator) which initiates polymerization by light irradiation, thereby producing an optical component such as a cured product or a lens. It can be obtained efficiently. Moreover, the obtained hardened | cured material or a lens is excellent in practical physical properties, such as heat resistance and impact resistance, and has a high refractive index compared with the conventionally well-known acrylic acid ester compound.

权利要求:
Claims (10)
[1" claim-type="Currently amended] General formula (1) below:

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent; R ₃ is a hydrogen atom or an alkyl group; A is A divalent organic group; X is a sulfur atom or an oxygen atom, provided that when X is an oxygen atom, R ₁ is an aromatic moiety which may have a substituent.
[2" claim-type="Currently amended] A compound according to claim 1, wherein in formula (1), R ₁ is an aromatic moiety which may have a substituent, A is-(CH ₂ ) _m- (m is an integer of 1 to 3), and X is a sulfur atom Acrylic ester compound characterized in that.
[3" claim-type="Currently amended] A polymerizable composition comprising the acrylic acid ester compound according to claim 1 or 2.
[4" claim-type="Currently amended] It is obtained by superposing | polymerizing the polymeric composition of Claim 3, The hardened | cured material characterized by the above-mentioned.
[5" claim-type="Currently amended] An optical component comprising a cured product according to claim 4.
[6" claim-type="Currently amended] In the method for producing an acrylic ester compound according to claim 1 or 2, the following general formula (2):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent; A is a divalent organic group; X is a sulfur atom) Or an oxygen atom, provided that when X is an oxygen atom, R ₁ is an aromatic moiety which may have a substituent to esterify the sulfur-containing compound to form an acrylic ester. Way.
[7" claim-type="Currently amended] A compound according to claim 6, wherein in formula (2), R ₁ is an aromatic moiety which may have a substituent, A is-(CH ₂ ) _m- (m is an integer of 1 to 3), and X is a sulfur atom. Method for producing an acrylic acid ester compound, characterized in that.
[8" claim-type="Currently amended] The esterification for forming an acrylic acid ester according to claim 6 or 7, wherein the compound represented by the general formula (2) is reacted with a halopropionic acid or an acid halide thereof to form a halopropionic acid compound. A process for producing an acrylic ester compound, characterized in that it is carried out by dehalogenation of a propionic acid compound.
[9" claim-type="Currently amended] General formula (2) below:

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent; A is a divalent organic group; X is a sulfur atom) Or an oxygen atom, provided that when X is an oxygen atom, R ₁ is an aromatic moiety which may have a substituent.
[10" claim-type="Currently amended] 10. The compound of claim 9, wherein R ₁ in the general formula (2) is an aromatic residue which may have a substituent, A is-(CH ₂ ) _m- (m is an integer of 1 to 3), and X is a sulfur atom. A sulfur containing compound characterized by the above-mentioned.

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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:
2000-09-22|Priority to JP2000288320

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2000-09-22|Priority to JPJP-P-2000-00288320

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2001-09-22|Application filed by 사토 아키오, 미쯔이카가쿠 가부시기가이샤

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2002-03-29|Publication of KR20020023673A

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2004-10-20|Application granted

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2004-10-20|Publication of KR100453344B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2000288320|2000-09-22|

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JPJP-P-2000-00288320|2000-09-22|