JPWO2012147710A1 - Curable composition and optical adhesive - Google Patents
Curable composition and optical adhesive Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000000853 adhesive Substances 0.000 title claims abstract description 19
- 230000003287 optical effect Effects 0.000 title claims abstract description 12
- 230000001070 adhesive effect Effects 0.000 title abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- -1 episulfide compound Chemical class 0.000 claims abstract description 42
- 229920006295 polythiol Polymers 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- MLGITEWCALEOOJ-UHFFFAOYSA-N 2-(thiiran-2-ylmethylsulfanylmethyl)thiirane Chemical compound C1SC1CSCC1CS1 MLGITEWCALEOOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 6
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 5
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 5
- 0 C*(C)C(C)(C)N*C1(NC1)O Chemical compound C*(C)C(C)(C)N*C1(NC1)O 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003553 thiiranes Chemical group 0.000 description 4
- COYTVZAYDAIHDK-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1CSC(CS)CS1 COYTVZAYDAIHDK-UHFFFAOYSA-N 0.000 description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- JSNABGZJVWSNOB-UHFFFAOYSA-N [3-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1 JSNABGZJVWSNOB-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000007514 bases Chemical group 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- QVQGTNFYPJQJNM-UHFFFAOYSA-N dicyclohexylmethanamine Chemical compound C1CCCCC1C(N)C1CCCCC1 QVQGTNFYPJQJNM-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical compound C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 description 1
- JFLJVRLBIZHFSU-UHFFFAOYSA-N 1,4-dithiane-2,5-dithiol Chemical compound SC1CSC(S)CS1 JFLJVRLBIZHFSU-UHFFFAOYSA-N 0.000 description 1
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- VSSFYDMUTATOHG-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)-3-[3-sulfanyl-2-(2-sulfanylethylsulfanyl)propyl]sulfanylpropane-1-thiol Chemical compound SCCSC(CS)CSCC(CS)SCCS VSSFYDMUTATOHG-UHFFFAOYSA-N 0.000 description 1
- NQLQMVQEQFIDQB-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)propane-1,3-dithiol Chemical compound SCCSC(CS)CS NQLQMVQEQFIDQB-UHFFFAOYSA-N 0.000 description 1
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- NXYWIOFCVGCOCB-UHFFFAOYSA-N 3-(2-sulfanylethylsulfanyl)-2-[3-sulfanyl-2-(2-sulfanylethylsulfanyl)propyl]sulfanylpropane-1-thiol Chemical compound SCCSCC(CS)SCC(CS)SCCS NXYWIOFCVGCOCB-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- LOZWAPSEEHRYPG-UHFFFAOYSA-N dithiane Natural products C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
高い屈折率を有し、且つ、作業に適した粘度、低収縮性、無色透明性といった光学用接着剤として求められる性能も兼ね備えた硬化性組成物を提供する。本発明によれば、エピスルフィド化合物とチオール化合物を反応させて得られるポリチオールオリゴマー（Ａ成分）と、エチレン性不飽和化合物（Ｂ成分）を含有する硬化性組成物を提供することができる。Provided is a curable composition having a high refractive index and having performances required as an optical adhesive such as viscosity, low shrinkage, and colorless transparency suitable for work. ADVANTAGE OF THE INVENTION According to this invention, the curable composition containing the polythiol oligomer (A component) obtained by making an episulfide compound and a thiol compound react, and an ethylenically unsaturated compound (B component) can be provided.
Description
本発明は、複合光学素子を作製する際に使用される光学用接着剤として好適な硬化性組成物に関するものである。 The present invention relates to a curable composition suitable as an optical adhesive used when producing a composite optical element.
アクリレート化合物等を主成分とする光硬化性組成物は、光学素子を作製する際の接着剤として幅広く使用されている。接着剤にとって、接着性、硬化性、機械的強度、耐久性、および光学特性は基本性能であるが、近年では光学素子の高機能化に伴って、屈折率が重要な性能になっている。特に接着剤の高屈折率化は光学設計の自由度が広がるので要望が高い。高い屈折率を有する接着剤が使用される用途例としては、２枚のレンズの張り合わせで構成される色消しレンズ（アクロマートレンズ）、ガラスと樹脂の複合で構成されるハイブリッド型非球面レンズ、ダイクロイックプリズムなどの複雑形状をしたプリズム等が挙げられる。これらの用途に使用される接着剤には、高い屈折率だけでなく、密着性、光硬化性、無色透明性、作業に適した粘度といった性能も当然要求される。 A photocurable composition mainly composed of an acrylate compound or the like is widely used as an adhesive for producing an optical element. For adhesives, adhesiveness, curability, mechanical strength, durability, and optical properties are basic performances, but in recent years, the refractive index has become an important performance as the functionality of optical elements increases. In particular, increasing the refractive index of the adhesive is highly desired because the degree of freedom in optical design is expanded. Examples of applications in which an adhesive having a high refractive index is used include an achromatic lens (achromatic lens) composed of two lenses bonded together, a hybrid aspherical lens composed of a composite of glass and resin, and dichroic Examples include prisms having complicated shapes such as prisms. Adhesives used for these applications naturally require not only a high refractive index but also performance such as adhesion, photocurability, colorless transparency, and viscosity suitable for work.
高い屈折率を有する多官能（メタ）アクリレート化合物としては、９，９−ビス（４−（２−アクリロキシエトキシ）フェニル）フルオレン（以下、Ａ−ＢＰＥＦと呼ぶ）（硬化物の屈折率１．６２）や４，４’−ビス（メタクリロイルチオ）ジフェニルスルフィド（以下、ＭＰＳＭＡと呼ぶ）（硬化物の屈折率１．６９）等が知られている。しかしながら、これらの化合物は常温で固体であるため、単独での使用は難しい。
また、一般的に多官能（メタ）アクリレート化合物は硬化に伴う収縮が大きく、接着剤として使用した場合に密着性低下の原因となる。一方、（メタ）アクリレート化合物等のエチレン性不飽和化合物とチオール化合物を組み合わせたエン・チオール組成物は、硬化に伴う収縮が小さいことが知られている。As a polyfunctional (meth) acrylate compound having a high refractive index, 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene (hereinafter referred to as A-BPEF) (refractive index of cured product 1. 62), 4,4′-bis (methacryloylthio) diphenyl sulfide (hereinafter referred to as MPSMA) (refractive index of cured product 1.69) and the like are known. However, since these compounds are solid at room temperature, it is difficult to use them alone.
In general, a polyfunctional (meth) acrylate compound has a large shrinkage due to curing, and causes a decrease in adhesion when used as an adhesive. On the other hand, it is known that an ene / thiol composition obtained by combining an ethylenically unsaturated compound such as a (meth) acrylate compound and a thiol compound has a small shrinkage due to curing.
特許文献１には、Ａ−ＢＰＥＦ、エチレン性不飽和化合物、およびチオール化合物から構成されるエン・チオール組成物が記載されている。実施例によると、硬化物の屈折率は高々１．５８〜１．６１の範囲である。
特許文献２には、ＭＰＳＭＡ、ビニル系モノマー、およびポリチオールから構成されるエン・チオール組成物が記載されている。実施例によると、硬化物の屈折率は最高で１.６４９である。しかしながら、ＭＰＳＭＡは黄着色しやすく、また固体であるため組成物への溶解量に限界があった。
また、特許文献３には、フルオレン環を有する樹脂成分と、ＭＰＳＭＡ等のジフェニルスルフィド骨格を有する硫黄含有化合物とで構成される樹脂組成物が記載されており、屈折率１．７２４を有する樹脂が例示されている。しかしながら、該発明における樹脂組成物とは、実質的にはフルオレン環を有するポリエステルと硫黄含有化合物を混練した熱可塑性樹脂であって硬化性組成物ではなく、当然ながら光硬化性は付与できない。Patent Document 1 describes an ene-thiol composition composed of A-BPEF, an ethylenically unsaturated compound, and a thiol compound. According to the examples, the refractive index of the cured product is at most in the range of 1.58 to 1.61.
Patent Document 2 describes an ene-thiol composition composed of MPSMA, a vinyl monomer, and polythiol. According to the example, the refractive index of the cured product is 1.649 at the maximum. However, MPSMA is easily yellow-colored and has a limit in the amount of dissolution in the composition because it is solid.
Patent Document 3 describes a resin composition composed of a resin component having a fluorene ring and a sulfur-containing compound having a diphenyl sulfide skeleton such as MPSMA, and a resin having a refractive index of 1.724. Illustrated. However, the resin composition in the present invention is substantially a thermoplastic resin obtained by kneading a polyester having a fluorene ring and a sulfur-containing compound and is not a curable composition, and of course, photocurability cannot be imparted.
従って、本発明の目的は、高い屈折率を有し、且つ、作業に適した粘度、低収縮性、無色透明性といった光学用接着剤として求められる性能も兼ね備えた硬化性組成物を提供することにある。 Accordingly, an object of the present invention is to provide a curable composition having a high refractive index and also having performances required as an optical adhesive such as viscosity, low shrinkage, and colorless transparency suitable for work. It is in.
本発明者らは、上記課題を解決するために鋭意検討した結果、エピスルフィド化合物とチオール化合物を反応させて得られるポリチオールオリゴマー（Ａ成分）と、エチレン性不飽和化合物（Ｂ成分）を含有した硬化性組成物が、接着剤として作業性に適した粘度を有し、且つ硬化に伴う収縮が小さいことから、光学用接着剤として好適であることを見出した。以上の知見に基づき、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have cured a polythiol oligomer (A component) obtained by reacting an episulfide compound and a thiol compound and an ethylenically unsaturated compound (B component). It has been found that the adhesive composition is suitable as an optical adhesive because it has a viscosity suitable for workability as an adhesive and has a small shrinkage due to curing. Based on the above findings, the present invention has been achieved.
本発明によれば、高い屈折率を有し、且つ、作業に適した粘度、低収縮性、無色透明性といった光学用接着剤としての性能も兼ね備えた硬化性組成物を提供することができる。 According to the present invention, it is possible to provide a curable composition having a high refractive index and also having performance as an optical adhesive such as viscosity, low shrinkage, and colorless transparency suitable for work.
本発明の硬化性組成物は、エピスルフィド化合物とチオール化合物を反応させて得られるポリチオールオリゴマー（Ａ成分）と、エチレン性不飽和化合物（Ｂ成分）を含有して構成される。 The curable composition of the present invention comprises a polythiol oligomer (A component) obtained by reacting an episulfide compound and a thiol compound, and an ethylenically unsaturated compound (B component).
まず、ポリチオールオリゴマー（Ａ成分）の製造方法について説明する。
ポリチオールオリゴマーの原料となるエピスルフィド化合物とは、１分子中に１個以上のエピスルフィド基を有する化合物である。特に、硬化性組成物の高屈折率化と架橋性を追求した場合、下記一般式（１）
で表わされる化合物が好ましい。一般式（１）で表わされる化合物の例としては、ビス（２，３−エピチオプロピル）スルフィド等が挙げられる。First, the manufacturing method of a polythiol oligomer (A component) is demonstrated.
The episulfide compound used as a raw material for the polythiol oligomer is a compound having one or more episulfide groups in one molecule. In particular, when pursuing higher refractive index and crosslinkability of the curable composition, the following general formula (1)
The compound represented by these is preferable. Examples of the compound represented by the general formula (1) include bis (2,3-epithiopropyl) sulfide.
ポリチオールオリゴマーの原料となるチオール化合物とは、１分子中に１個以上のチオール基を有する化合物であり、直鎖状、分岐鎖状、環状のいずれであってもよく、１分子中に２個以上のチオール基を有するポリチオール化合物であることが好ましい。
特に、硬化性組成物の高屈折率化と作業性に適した粘度を追求した場合、下記一般式（２）から（４）で表わされるポリチオール化合物が好ましい。
In particular, when pursuing a viscosity suitable for increasing the refractive index and workability of the curable composition, polythiol compounds represented by the following general formulas (2) to (4) are preferable.
一般式（２）で表わされる化合物の例としては、１，５−ジメルカプト−３−チアペンタン、２−メルカプトメチル−１，５−ジメルカプト−３−チアペンタン、２，４−ビス（メルカプトメチル）−１，５−ジメルカプト−３−チアペンタン、４−メルカプトメチル−１，８−ジメルカプト−３，６−ジチアオクタン、４，８−ビス（メルカプトメチル）−１，１１−ジメルカプト−３，６，９−トリチアウンデカン、４，７−ビス（メルカプトメチル）−１，１１−ジメルカプト−３，６，９−トリチアウンデカン、５，７−ビス（メルカプトメチル）−１，１１−ジメルカプト−３，６，９−トリチアウンデカン等が挙げられ、一般式（３）で表わされる化合物の例としては、２，５−ジメルカプト−１，４−ジチアン、２，５−ジメルカプトメチル−１，４−ジチアン、２，５−ジメルカプトエチル−１，４−ジチアン等が挙げられ、一般式（４）で表わされる化合物の例としては、キシリレンジチオール等が挙げられる。一般式（２）から（４）で表わされる化合物以外のポリチオール化合物としては、エチレングリコールビス（３−メルカプトプロピオネート）、トリメチオールプロパントリス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、ベンゼンジチオール、トリレンジチオール等が挙げられる。 Examples of the compound represented by the general formula (2) include 1,5-dimercapto-3-thiapentane, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, and 2,4-bis (mercaptomethyl) -1. , 5-dimercapto-3-thiapentane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithia Undecane, 4,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 5,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9- Examples of the compound represented by the general formula (3) include 2,5-dimercapto-1,4-dithiane and 2,5-dimene. Kaputomechiru dithiane, 2,5-mercaptoethyl-1,4-dithiane, and examples of the compound represented by formula (4), xylylenedithiol and the like. Examples of polythiol compounds other than the compounds represented by the general formulas (2) to (4) include ethylene glycol bis (3-mercaptopropionate), trimethiolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), benzenedithiol, tolylenedithiol and the like.
エピスルフィド化合物とチオール化合物の反応は、例えば生成物が２量体の場合、下記の反応式
に従って進行する。エピスルフィド基とチオール基が反応して２級のチオール基が生成する。エピスルフィド化合物とチオール化合物の混合比は、エピスルフィド基１モルに対してチオール基が１．０〜２．０モルの範囲が好ましい。１．０モル未満では、未反応のエピスルフィド基が残存して好ましくないし、２．０モルを超えると得られるポリチオールオリゴマーの粘度が低下して好ましくない。The reaction between the episulfide compound and the thiol compound is, for example, when the product is a dimer,
Proceed according to. The episulfide group and the thiol group react to produce a secondary thiol group. The mixing ratio of the episulfide compound and the thiol compound is preferably in the range of 1.0 to 2.0 mol of thiol group per mol of episulfide group. If it is less than 1.0 mol, an unreacted episulfide group remains unpreferable, and if it exceeds 2.0 mol, the viscosity of the polythiol oligomer obtained is lowered, which is not preferable.
エピスルフィド化合物とチオール化合物の反応は、触媒の存在下あるいは非存在下で加熱することで進行するが、触媒を使用する方法が好ましい。触媒としては塩基性化合物が好ましく、アミン、アンモニウム塩、ホスフィン、ホスホニウム塩等が挙げられる。触媒の使用量は、エピスルフィド化合物とチオール化合物の合計量１００重量部に対して、０．００５〜５重量部の範囲が好ましく、０．０５〜０．５重量部の範囲がより好ましい。 The reaction between the episulfide compound and the thiol compound proceeds by heating in the presence or absence of a catalyst, but a method using a catalyst is preferred. The catalyst is preferably a basic compound, and examples thereof include amines, ammonium salts, phosphines, and phosphonium salts. The amount of the catalyst used is preferably in the range of 0.005 to 5 parts by weight and more preferably in the range of 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of the episulfide compound and the thiol compound.
エピスルフィド化合物とチオール化合物の反応は、エチレン性不飽和化合物（Ｂ成分）の存在下で行っても構わない。また、必要に応じて溶媒を使用してもよい。溶媒を使用する場合には溶媒を留去する後工程が必要となる。反応温度は特に限定されないが、０〜１００℃の範囲が好ましく、反応の進行具合を見ながら徐々に温度を上げていってもよい。反応時間は、原料の種類、エピスルフィド化合物とチオール化合物の混合比、反応温度などの様々な条件に依るので一概には規定できないが、３０分間〜２４時間の範囲が好ましい。 The reaction between the episulfide compound and the thiol compound may be performed in the presence of an ethylenically unsaturated compound (component B). Moreover, you may use a solvent as needed. When using a solvent, a post-process for distilling off the solvent is required. Although reaction temperature is not specifically limited, The range of 0-100 degreeC is preferable, and you may raise temperature gradually, seeing the progress of reaction. The reaction time depends on various conditions such as the type of raw material, the mixing ratio of the episulfide compound and the thiol compound, and the reaction temperature, but cannot be defined unconditionally, but a range of 30 minutes to 24 hours is preferable.
次に、本発明の硬化性組成物について説明する。
本発明の硬化性組成物とは、前述したポリチオールオリゴマー（Ａ成分）と、エチレン性不飽和化合物（Ｂ成分）を含有して構成される。Next, the curable composition of this invention is demonstrated.
The curable composition of the present invention comprises the polythiol oligomer (A component) described above and an ethylenically unsaturated compound (B component).
エチレン性不飽和化合物（Ｂ成分）とは、１分子中に２個以上のエチレン性不飽和結合を有する化合物であり、エチレン性不飽和結合基としてはアクリロイル基、メタクリロイル基、ビニル基、アリル基等が挙げられる。特に、硬化性組成物の高屈折率化を追求した場合、分子内に芳香環や複素環を有する化合物が好ましく、このような化合物の例としては、イソシアヌル酸トリアリル、シアヌル酸トリアリル、フタル酸ジアリル、イソフタル酸ジアリル、テレフタル酸ジアリル、トリメリット酸トリアリル、ピロメリット酸テトラアリル、一般式（５）で表わされる化合物、一般式（６）で表わされる化合物等が挙げられる。
一般式（５）で表わされる化合物の例としては、４，４’−ビス（メタクリロイルチオ）ジフェニルスルフィド、４，４’−ビス（メタクリロイルチオ）ジフェニルスルホン等が挙げられ、一般式（６）で表わされる化合物としては、９，９−ビス（４−（２−アクリロキシエトキシ）フェニル）フルオレン等が挙げられる。 Examples of the compound represented by the general formula (5) include 4,4′-bis (methacryloylthio) diphenyl sulfide, 4,4′-bis (methacryloylthio) diphenyl sulfone, and the like. Examples of the compound represented include 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene.
Ａ成分とＢ成分の配合比は、Ｂ成分中のエチレン性不飽和結合基１モルに対して、Ａ成分中のチオール基が０．５〜１.５モルの範囲が好ましく、０．８〜１．２モルの範囲が好ましい。０．５モル未満ではＡ成分の効果が少なくて実用的でなく、１.５モルを超えると硬化時に未反応のチオール基が残存しやすくて好ましくない。尚、前記したエピスルフィド化合物とチオール化合物の反応式から分かるように、Ａ成分中のチオール基の総量は、ポリチオールオリゴマーの原料として用いたチオール化合物に含まれるチオール基の総量と同じになる。 The blending ratio of the A component and the B component is preferably in the range of 0.5 to 1.5 mol of the thiol group in the A component with respect to 1 mol of the ethylenically unsaturated bond group in the B component, 0.8 to A range of 1.2 moles is preferred. If the amount is less than 0.5 mol, the effect of the component A is small and is not practical. If the amount exceeds 1.5 mol, an unreacted thiol group tends to remain at the time of curing, which is not preferable. As can be seen from the reaction formula of the episulfide compound and the thiol compound, the total amount of thiol groups in the component A is the same as the total amount of thiol groups contained in the thiol compound used as a raw material for the polythiol oligomer.
本発明の硬化性組成物は、硬化触媒の存在下あるいは非存在下で、加熱重合させることで硬化される。好ましい方法は硬化触媒を使用する方法で、硬化触媒としては有機過酸化物やアゾ化合物などの遊離ラジカルを発生させる化合物や、アミンやホスフィンなどの塩基性化合物が挙げられる。硬化触媒の添加量は、硬化性組成物１００重量部に対して、０．００１〜５重量部の範囲が好ましく、０．０１〜１重量部の範囲がより好ましい。重合温度は０〜１５０℃の範囲が好ましく、２０〜１２０℃の範囲がより好ましく、徐々に温度を上げていっても構わない。重合時間は、ポリチオール化合物とエン化合物の配合比、硬化触媒の種類や添加量、硬化性組成物の重量、重合温度などの様々な条件に依るので一概には規定できないが、１０分間〜５０時間の範囲が好ましく、３０分間〜２４時間の範囲がより好ましい。 The curable composition of the present invention is cured by heat polymerization in the presence or absence of a curing catalyst. A preferred method is a method using a curing catalyst, and examples of the curing catalyst include compounds that generate free radicals such as organic peroxides and azo compounds, and basic compounds such as amines and phosphines. The addition amount of the curing catalyst is preferably in the range of 0.001 to 5 parts by weight and more preferably in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the curable composition. The polymerization temperature is preferably in the range of 0 to 150 ° C, more preferably in the range of 20 to 120 ° C, and the temperature may be gradually increased. Although the polymerization time depends on various conditions such as the blending ratio of the polythiol compound and the ene compound, the type and addition amount of the curing catalyst, the weight of the curable composition, the polymerization temperature, etc., it cannot be defined unconditionally, but 10 minutes to 50 hours The range of 30 minutes to 24 hours is more preferable.
また、本発明の硬化性組成物は、ラジカル系光重合開始剤の存在下で、紫外光や可視光などの活性光線を照射することで硬化させることも可能である。ラジカル系光重合開始剤とは、光分解によって活性な遊離ラジカルを生成させるものであれば特に限定されない。このような化合物の具体例としては、２，２−メトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド等が挙げられる。ラジカル系光重合開始剤は単独でも２種類以上を混合して使用しても構わない。その含有量は特に限定されないが、硬化性組成物１００重量部に対して、０．１〜１０重量部の範囲が好ましく、０．５〜５重量部の範囲がより好ましい。 In addition, the curable composition of the present invention can be cured by irradiation with an actinic ray such as ultraviolet light or visible light in the presence of a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it generates an active free radical by photolysis. Specific examples of such compounds include 2,2-methoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Examples thereof include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like. The radical photopolymerization initiators may be used alone or in combination of two or more. Although the content is not specifically limited, The range of 0.1-10 weight part is preferable with respect to 100 weight part of curable compositions, The range of 0.5-5 weight part is more preferable.
本発明の硬化性組成物には必要に応じて、重合禁止剤、酸化防止剤、光安定剤（ＨＡＬＳ）、紫外線吸収剤、シランカップリング剤、離型剤、顔料、染料等を添加することが可能である。 If necessary, a polymerization inhibitor, an antioxidant, a light stabilizer (HALS), an ultraviolet absorber, a silane coupling agent, a release agent, a pigment, a dye, and the like may be added to the curable composition of the present invention. Is possible.
硬化性組成物の粘度に関して、接着剤としての使用を想定した場合、粘度が低すぎると、接着剤が垂れたり流れたり、張り合わせの際に被着体がずれたりして好ましくない。また、粘度が高すぎると、接着剤の吐出や塗布が困難になったり、張り合わせの際に気泡を噛んだりして好ましくない。本発明で言う作業性に適した粘度とは、塗布方法や張り合わせ方法といった接着剤の使用形態にも依るので一概には規定できないが、好ましくは５００〜１０，０００ｍＰａ・ｓの範囲である。 Assuming that the viscosity of the curable composition is used as an adhesive, if the viscosity is too low, the adhesive may sag or flow, or the adherend may be displaced during lamination, which is not preferable. On the other hand, if the viscosity is too high, it is not preferable because it becomes difficult to discharge or apply the adhesive, or the air bubbles are bitten at the time of pasting. The viscosity suitable for workability in the present invention depends on the use form of the adhesive such as a coating method and a bonding method, and thus cannot be defined unconditionally, but is preferably in the range of 500 to 10,000 mPa · s.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例中における硬化収縮率は、下記の計算式に従い、硬化前後における屈折率から計算した。
Ｘ＝（１−ｄ１／ｄ２）×１００［％］
Ｒ＝（ｎ２−１）／（ｎ２＋２）×Ｍ／ｄ
硬化前後でＲ／Ｍは一定なので、上の２式より、
Ｘ＝［１−｛（ｎ１２−１）/（ｎ１２＋２）｝／｛（ｎ２２−１）/（ｎ２２＋２）｝］×１００［％］
（式中、Ｘは硬化収縮率、ｄは比重、ｄ１は硬化前の比重、ｄ２は硬化後の比重、Ｒは分子屈折、ｎは屈折率、ｎ１は硬化前の屈折率、ｎ２は硬化後の屈折率、Ｍは分子量を表す。）
また、硬化性組成物の粘度は、コーン／プレート型粘度計ＤＶ−II＋（ブルックフィールド社製）を用いて、温度２５℃にて測定した。硬化性組成物および硬化膜の屈折率は、アッベ屈折計ＮＡＲ−３Ｔ（アタゴ社製）を用いて測定した。硬化膜の透過率は、分光光度計Ｕ−３５００（日立ハイテク社製）を用いて、硬化膜の厚み０．２５ｍｍ、測定波長４００ｎｍにて測定した。EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the cure shrinkage rate in an Example was computed from the refractive index before and behind hardening according to the following formula.
X = (1−d1 / d2) × 100 [%]
R = (n 2 −1) / (n 2 +2) × M / d
Since R / M is constant before and after curing,
X = [1-{(n1 2 -1) / (n1 2 +2)} / {(n2 2 -1) / (n2 2 +2)}] × 100 [%]
(Where X is the curing shrinkage ratio, d is the specific gravity, d1 is the specific gravity before curing, d2 is the specific gravity after curing, R is the molecular refraction, n is the refractive index, n1 is the refractive index before curing, and n2 is the after curing. The refractive index of M and M represents the molecular weight.)
The viscosity of the curable composition was measured at a temperature of 25 ° C. using a cone / plate viscometer DV-II + (manufactured by Brookfield). The refractive indexes of the curable composition and the cured film were measured using an Abbe refractometer NAR-3T (manufactured by Atago Co., Ltd.). The transmittance of the cured film was measured using a spectrophotometer U-3500 (manufactured by Hitachi High-Tech) at a thickness of 0.25 mm and a measurement wavelength of 400 nm.
実施例１
３００ｍｌフラスコに、ビス（２，３−エピチオプロピル）スルフィド２８ｇ、１，５−ジメルカプト−３−チアペンタン３５ｇ、およびジシクロヘキシルメチルアミン０．５ｇをとり、６０℃にて２４時間撹拌を続けた。以上の手順でポリチオールオリゴマーを作製した。
これにイソシアヌル酸トリアリル３７ｇを加えて、均一になるまで撹拌した。以上の手順で硬化性組成物を作製した。
硬化性組成物１００重量部に対して、１−ヒドロキシ−シクロヘキシルフェニルケトン３重量部を加えて、均一になるまで撹拌して、減圧脱泡した。これを離型処理された２枚のガラス板で挟み、メタルハライドランプ（１２０Ｗ／ｃｍ）からの光を３０ｃｍの距離から３分間照射した後、硬化した膜をガラス板から剥がした。以上の手順で厚み０．２５ｍｍの硬化膜を作製した。
硬化性組成物および硬化膜の物性は表１に示す通りであった。Example 1
A 300 ml flask was charged with 28 g of bis (2,3-epithiopropyl) sulfide, 35 g of 1,5-dimercapto-3-thiapentane, and 0.5 g of dicyclohexylmethylamine, and stirring was continued at 60 ° C. for 24 hours. The polythiol oligomer was produced by the above procedure.
To this, 37 g of triallyl isocyanurate was added and stirred until uniform. The curable composition was produced in the above procedure.
To 100 parts by weight of the curable composition, 3 parts by weight of 1-hydroxy-cyclohexyl phenyl ketone was added, stirred until uniform, and degassed under reduced pressure. This was sandwiched between two release-treated glass plates, irradiated with light from a metal halide lamp (120 W / cm) for 3 minutes from a distance of 30 cm, and then the cured film was peeled off from the glass plate. A cured film having a thickness of 0.25 mm was produced by the above procedure.
The physical properties of the curable composition and the cured film were as shown in Table 1.
実施例２
３００ｍｌフラスコに、ビス（２，３−エピチオプロピル）スルフィド３３ｇ、１，５−ジメルカプト−３−チアペンタン３３ｇ、イソシアヌル酸トリアリル３４ｇ、およびジシクロヘキシルメチルアミン０．５ｇをとり、６０℃にて２４時間撹拌を続けた。以上の手順で硬化性組成物を作製した。
硬化膜の作製を実施例１と同様にして行った。硬化性組成物および硬化膜の物性は表１に示す通りであった。Example 2
In a 300 ml flask, take 33 g of bis (2,3-epithiopropyl) sulfide, 33 g of 1,5-dimercapto-3-thiapentane, 34 g of triallyl isocyanurate, and 0.5 g of dicyclohexylmethylamine, and stir at 60 ° C. for 24 hours. Continued. The curable composition was produced in the above procedure.
A cured film was produced in the same manner as in Example 1. The physical properties of the curable composition and the cured film were as shown in Table 1.
実施例３〜８
エピスルフィド化合物、ポリチオール化合物、およびエチレン性不飽和化合物の種類と仕込み量を表１に示す内容に変える以外は実施例２と同様にして硬化性組成物および硬化膜の作製を行った。硬化性組成物および硬化膜の物性は表１に示す通りであった。Examples 3-8
A curable composition and a cured film were prepared in the same manner as in Example 2 except that the types and amounts of the episulfide compound, polythiol compound, and ethylenically unsaturated compound were changed to those shown in Table 1. The physical properties of the curable composition and the cured film were as shown in Table 1.
比較例１
３００ｍｌフラスコに、２，５−ジメルカプトメチル−１，４−ジチアン５５ｇ、およびイソシアヌル酸トリアリル４５ｇをとり、均一になるまで撹拌した。以上の手順で硬化性組成物を作製した。
硬化膜の作製を実施例１と同様にして行った。硬化性組成物および硬化膜の物性は表２に示す通りであった。なお、実施例と比較して性能が劣る値には下線を引いた。Comparative Example 1
In a 300 ml flask, 55 g of 2,5-dimercaptomethyl-1,4-dithiane and 45 g of triallyl isocyanurate were taken and stirred until uniform. The curable composition was produced in the above procedure.
A cured film was produced in the same manner as in Example 1. The physical properties of the curable composition and the cured film were as shown in Table 2. In addition, the value which performance is inferior compared with an Example was underlined.
比較例２〜４
チオール化合物、エチレン性不飽和化合物の種類と仕込み量を表２に示す内容に変える以外は比較例１と同様にして硬化性組成物および硬化膜の作製を行った。硬化性組成物および硬化膜の物性は表２に示す通りであった。なお、実施例と比較して性能が劣る値には下線を引いた。Comparative Examples 2-4
A curable composition and a cured film were prepared in the same manner as in Comparative Example 1 except that the types and amounts of the thiol compound and ethylenically unsaturated compound were changed to those shown in Table 2. The physical properties of the curable composition and the cured film were as shown in Table 2. In addition, the value which performance is inferior compared with an Example was underlined.
表中略語の説明
（ａ−１）ビス（２，３−エピチオプロピル）スルフィド
（ｂ−１）１，５−ジメルカプト−３−チアペンタン
（ｂ−２）２，５−ジメルカプトメチル−１，４−ジチアン
（ｂ−３）ｍ−キシリレンジチオール
（ｃ−１）イソシアヌル酸トリアリル
（ｃ−２）トリメリット酸トリアリル
（ｃ−３）フタル酸ジアリル
（ｃ−４）４，４’−ビス（メタクリロイルチオ）ジフェニルスルフィド
（ｃ−５）２，２−ビス（４−（アクリロキシジエトキシ）フェニル）プロパン
Explanation of Abbreviations in Table (a-1) Bis (2,3-epithiopropyl) sulfide (b-1) 1,5-dimercapto-3-thiapentane (b-2) 2,5-dimercaptomethyl-1, 4-dithiane (b-3) m-xylylene dithiol (c-1) triallyl isocyanurate (c-2) triallyl trimellitic acid (c-3) diallyl phthalate (c-4) 4,4′-bis ( Methacryloylthio) diphenyl sulfide (c-5) 2,2-bis (4- (acryloxydiethoxy) phenyl) propane
Claims (7)
で表わされる化合物である請求項１に記載の硬化性組成物。The episulfide compound is represented by the following general formula (1)
The curable composition of Claim 1 which is a compound represented by these.
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| JP7056314B2 (en) * | 2018-03-29 | 2022-04-19 | 日産化学株式会社 | Thioepoxy resins, curable resin compositions, cured products thereof, and electronic devices |
| KR102512563B1 (en) * | 2019-05-24 | 2023-03-20 | 주식회사 엘지화학 | Curable composition and optical material comprising the cured product thereof |
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| US5270439A (en) * | 1988-10-20 | 1993-12-14 | Sumitomo Seika Chemicals Co., Ltd. | Method of producing a curable composition containing 4,4'-bis(methacryloylthio)diphenylsulfide |
| JP4506929B2 (en) * | 2002-11-27 | 2010-07-21 | 三菱瓦斯化学株式会社 | Cyclic polythiol compound |
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| JP5732749B2 (en) * | 2010-06-02 | 2015-06-10 | 三菱瓦斯化学株式会社 | Method for producing (poly) episulfide compound for optical material |
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