JP2018145322A - Ultraviolet curable resin composition - Google Patents
Ultraviolet curable resin composition Download PDFInfo
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- JP2018145322A JP2018145322A JP2017042780A JP2017042780A JP2018145322A JP 2018145322 A JP2018145322 A JP 2018145322A JP 2017042780 A JP2017042780 A JP 2017042780A JP 2017042780 A JP2017042780 A JP 2017042780A JP 2018145322 A JP2018145322 A JP 2018145322A
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- resin composition
- curable resin
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- ultraviolet curable
- ultraviolet
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- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 12
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 description 22
- 238000001723 curing Methods 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 16
- -1 hexafluorophosphate Chemical compound 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012955 diaryliodonium Substances 0.000 description 2
- 125000005520 diaryliodonium group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CFXPUPHOOWUQRH-UHFFFAOYSA-N C(C1)C2OC2CC1C1CC2OC2CC1 Chemical compound C(C1)C2OC2CC1C1CC2OC2CC1 CFXPUPHOOWUQRH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N O=C(C1CC2OC2CC1)OCC1CC2OC2CC1 Chemical compound O=C(C1CC2OC2CC1)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N O=C(CCCCC(OCC1CC2OC2CC1)=O)OCC1CC2OC2CC1 Chemical compound O=C(CCCCC(OCC1CC2OC2CC1)=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- IHUNBGSDBOWDMA-AQFIFDHZSA-N all-trans-acitretin Chemical compound COC1=CC(C)=C(\C=C\C(\C)=C\C=C\C(\C)=C\C(O)=O)C(C)=C1C IHUNBGSDBOWDMA-AQFIFDHZSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-N 0.000 description 1
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、紫外線硬化性樹脂組成物に関する。 The present invention relates to an ultraviolet curable resin composition.
紫外線重合技術は、その速い重合速度、一般に無溶剤であることによる良好な作業性、極めて低いエネルギー必要量の省エネルギー化等の特性に加え、近年問題となっている環境汚染の低減が図れるという利点を有しているため、建装材料、包装材料、表示材料、電気電子部品材料、光学デバイス、ディスプレイなどの分野において、その利用は拡大傾向にある。 Ultraviolet polymerization technology has the advantage of reducing environmental pollution, which has become a problem in recent years, in addition to its high polymerization rate, good workability due to the absence of solvents, energy savings of extremely low energy requirements, etc. Therefore, their use is expanding in fields such as building materials, packaging materials, display materials, electric and electronic component materials, optical devices, and displays.
紫外線により重合して硬化する樹脂組成物としては、ラジカル重合性樹脂組成物とカチオン重合性樹脂組成物とが知られている。例えば、（メタ）アクリロイル基等を有する化合物を含むラジカル重合性樹脂組成物では、樹脂組成物の硬化が十分に進行する前にラジカル重合反応が停止する、ラジカル重合反応が進行するに従い硬化収縮を引き起こす場合があった。これに対して、シクロヘキセンオキシド基、オキセタン基等を含むカチオン重合性樹脂組成物は、接着強度の点で問題はあるが、ラジカルの停止反応又は失活を引き起こさず、硬化収縮の程度は小さいことから、基材のわずかな歪み等が問題になる偏光板等の光学部材に適用可能な材料として使用することが提案されている（例えば、特許文献１）。 As a resin composition that is polymerized and cured by ultraviolet rays, a radical polymerizable resin composition and a cationic polymerizable resin composition are known. For example, in a radical polymerizable resin composition containing a compound having a (meth) acryloyl group or the like, the radical polymerization reaction is stopped before the resin composition is sufficiently cured, and the curing shrinkage is caused as the radical polymerization reaction proceeds. There was a case. In contrast, the cationic polymerizable resin composition containing a cyclohexene oxide group, an oxetane group, or the like has a problem in terms of adhesive strength, but does not cause radical termination reaction or deactivation, and the degree of cure shrinkage is small. Therefore, it has been proposed to use it as a material applicable to an optical member such as a polarizing plate in which slight distortion of the substrate is a problem (for example, Patent Document 1).
特許文献１には、カチオン重合性化合物として脂環状エポキシ化合物、分子内に少なくとも２個の水酸基を有する化合物、及び光酸発生剤を含有する接着剤組成物が、短時間で硬化可能で、かつ接着強度等の性能に優れることが記載されている。 Patent Document 1 discloses that an adhesive composition containing an alicyclic epoxy compound as a cationic polymerizable compound, a compound having at least two hydroxyl groups in the molecule, and a photoacid generator can be cured in a short time, and It describes that it is excellent in performance such as adhesive strength.
しかしながら、前記接着剤組成物を用いた偏光板では、基材の薄膜化が進むと湿熱試験、熱衝撃試験、及び高温保持試験で保護フィルムの剥離が起こるという問題があった。これは紫外線硬化時の収縮が大きいためであると考えられる。そこで、基材のさらなる薄膜化に伴い、紫外線硬化時の収縮がより小さい樹脂組成物が求められている。 However, in the polarizing plate using the adhesive composition, there is a problem that the protective film is peeled off in the wet heat test, the thermal shock test, and the high temperature holding test when the substrate is made thinner. This is presumably because the shrinkage during UV curing is large. Therefore, as the substrate becomes thinner, a resin composition having a smaller shrinkage at the time of ultraviolet curing is required.
本発明は、このような実状に鑑みてなされたものであり、紫外線硬化時の硬化収縮が小さく、且つ接着性に優れた紫外線硬化性樹脂組成物を提供することを目的とする。 The present invention has been made in view of such a situation, and an object of the present invention is to provide an ultraviolet curable resin composition having a small shrinkage during UV curing and excellent adhesiveness.
本発明者らは、紫外線硬化時の硬化収縮が小さく、且つ接着性に優れた紫外線硬化性樹脂組成物を開発すべく鋭意検討した結果、特定条件を満足する紫外線硬化性樹脂組成物により、上記課題を解決できることを見出した。本発明は、このような知見に基づき完成されたものである。 As a result of intensive studies to develop a UV curable resin composition having a small curing shrinkage during UV curing and excellent adhesiveness, the present inventors have found that the UV curable resin composition satisfying a specific condition has I found that the problem could be solved. The present invention has been completed based on such findings.
すなわち、本発明は、下記項１〜項３に示す紫外線硬化性樹脂組成物に係る。
項１． 分子内に２個以上のシクロヘキセンオキシド基を有する化合物（Ａ）、分子内に２個以上のメルカプト基を有する化合物（Ｂ）及び光酸発生剤（Ｃ）を含む、紫外線硬化性樹脂組成物。
項２． 前記メルカプト基が第二級メルカプト基である、上記項１記載の紫外線硬化性樹脂組成物。
項３． 前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の総質量に対して、（Ａ）成分を８０〜９９．４質量％、（Ｂ）成分を０．５〜２０質量％、及び（Ｃ）成分を０．１〜１０質量％の割合で含む、上記項１又は２に記載の紫外線硬化性樹脂組成物。
That is, this invention relates to the ultraviolet curable resin composition shown to the following items 1-3.
Item 1. An ultraviolet curable resin composition comprising a compound (A) having two or more cyclohexene oxide groups in the molecule, a compound (B) having two or more mercapto groups in the molecule, and a photoacid generator (C).
Item 2. Item 2. The ultraviolet curable resin composition according to Item 1, wherein the mercapto group is a secondary mercapto group.
Item 3. (A) component is 80-99.4 mass% with respect to the total mass of said (A) component, (B) component, and (C) component, (B) component is 0.5-20 mass%, and ( Item 3. The ultraviolet curable resin composition according to Item 1 or 2, comprising the component in a proportion of 0.1 to 10% by mass.
本発明によれば、紫外線硬化時の硬化収縮が小さく、且つ接着性に優れた紫外線硬化性樹脂組成物を提供することができる。また、本発明の紫外線硬化性樹脂組成物は、接着剤（偏光板等を含む液晶パネル、ＥＬパネル、ＰＤＰパネル、カラーフィルターまたは光ディスク基板などの用途）をはじめ、コーティング剤（導光板、偏光板、液晶パネル、ＥＬパネル、ＰＤＰパネル、ＯＨＰフィルム、光ファイバー、カラーフィルター、光ディスク基板、レンズ、液晶セル用プラスチック基板またはプリズムなどの用途）、封止剤（発光素子、受光素子、光電変換素子、または光伝送関連部品などの用途）などとして有用である。 According to the present invention, it is possible to provide an ultraviolet curable resin composition having a small curing shrinkage during ultraviolet curing and excellent adhesiveness. In addition, the ultraviolet curable resin composition of the present invention includes adhesives (uses for liquid crystal panels including polarizing plates, EL panels, PDP panels, color filters, optical disk substrates, etc.) and coating agents (light guide plates, polarizing plates). , Liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, liquid crystal cell plastic substrate or prism, etc.), sealant (light emitting element, light receiving element, photoelectric conversion element, or This is useful for applications such as optical transmission related parts).
本発明の紫外線硬化性樹脂組成物は、分子内に２個以上のシクロヘキセンオキシド基を有する化合物（Ａ）（以下、「（Ａ）成分」という場合もある）、分子内に２個以上のメルカプト基を有する化合物（Ｂ）（以下、「（Ｂ）成分」という場合もある）及び光酸発生剤（Ｃ）（以下、「（Ｃ）成分」という場合もある）を含む。 The ultraviolet curable resin composition of the present invention comprises a compound (A) having two or more cyclohexene oxide groups in the molecule (hereinafter sometimes referred to as “component (A)”), and two or more mercapto in the molecule. And a compound (B) having a group (hereinafter also referred to as “component (B)”) and a photoacid generator (C) (hereinafter also referred to as “component (C)”).
前記（Ａ）成分は、分子内に２個以上のシクロヘキセンオキシド基を有する化合物である。シクロヘキセンオキシド基とは、脂肪族６員環を構成する２つの炭素原子と酸素原子とで構成されるエポキシ基を意味する。 The component (A) is a compound having two or more cyclohexene oxide groups in the molecule. The cyclohexene oxide group means an epoxy group composed of two carbon atoms and an oxygen atom constituting an aliphatic 6-membered ring.
前記（Ａ）成分の代表的な例としては、下記式（Ｉ−１）〜（Ｉ−４）で表される化合物が挙げられる。なお、下記式中のｎは、それぞれ１〜３０の整数を表す。
前記（Ａ）成分は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 As the component (A), one type can be used alone, or two or more types can be used in combination.
前記（Ａ）成分の含有量は、特に限定されない。前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の総質量に対して、好ましくは５０〜９９．４質量％、より好ましくは８０〜９９．４質量％、さらに好ましくは８５〜９９質量％である。前記（Ａ）成分の含有量を前記範囲とすることにより、紫外線硬化性に優れるとともに、紫外線硬化時の硬化収縮が小さい紫外線硬化性樹脂組成物を得ることができる。 The content of the component (A) is not particularly limited. Preferably it is 50-99.4 mass% with respect to the total mass of the said (A) component, (B) component, and (C) component, More preferably, it is 80-99.4 mass%, More preferably, it is 85-99 mass. %. By setting the content of the component (A) within the above range, it is possible to obtain an ultraviolet curable resin composition having excellent ultraviolet curability and small curing shrinkage during ultraviolet curing.
前記（Ｂ）成分は、分子内に２個以上のメルカプト基を有する化合物である。メルカプト基とは硫黄原子１つと水素原子１つとで構成される官能基（−ＳＨ）である。 The component (B) is a compound having two or more mercapto groups in the molecule. A mercapto group is a functional group (—SH) composed of one sulfur atom and one hydrogen atom.
前記（Ｂ）成分の代表的な例としては、下記式（II−１）〜（II−７）で表される化合物が挙げられる。
前記（Ｂ）成分は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。前記（Ｂ）成分として、前記メルカプト基が第二級メルカプト基である化合物、具体的には、上記式（II−４）、（II−５）、（II−６）、又は（II−７）の化合物が好ましい。前記（Ｂ）成分として第二級メルカプト基を有する化合物を用いると、紫外線硬化性に優れた組成物となる。 The component (B) can be used alone or in combination of two or more. As the component (B), a compound in which the mercapto group is a secondary mercapto group, specifically, the above formula (II-4), (II-5), (II-6), or (II-7) ) Is preferred. When a compound having a secondary mercapto group is used as the component (B), a composition having excellent ultraviolet curability is obtained.
前記（Ｂ）成分の含有量は、特に限定されない。前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の総質量に対して、好ましくは０．１〜５０質量％、より好ましくは０．５〜２０質量％である。前記（Ｂ）成分の含有量を前記範囲とすることにより、紫外線硬化性に優れるとともに、紫外線硬化時の硬化収縮が小さい紫外線硬化性樹脂組成物を得ることができる。 The content of the component (B) is not particularly limited. Preferably it is 0.1-50 mass% with respect to the total mass of the said (A) component, (B) component, and (C) component, More preferably, it is 0.5-20 mass%. By setting the content of the component (B) within the above range, it is possible to obtain an ultraviolet curable resin composition having excellent ultraviolet curability and small curing shrinkage during ultraviolet curing.
前記（Ｃ）成分は、光酸発生剤である。前記（Ｃ）成分として、紫外線照射により酸を発生するものであれば各種公知のものを格別限定なく使用できる。 The component (C) is a photoacid generator. As the component (C), various known compounds can be used without particular limitation as long as they generate an acid upon irradiation with ultraviolet rays.
前記（Ｃ）成分の代表的な例としては、トリアリールスルホニウムヘキサフルオロホスフェート（例えば、ｐ−フェニルチオフェニルジフェニルスルホニウムヘキサフルオロホスフェート等）、トリアリールスルホニウムヘキサフルオロアンチモネート等のスルホニウム塩（特に、トリアリールスルホニウム塩）：ジアリールヨードニウムヘキサフルオロホスフェート、ジアリールヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ヨードニウム[４-（４-メチルフェニル-２-メチルプロピル）フェニル]ヘキサフルオロホスフェート等のヨードニウム塩が挙げられる。光酸発生剤は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 Representative examples of the component (C) include sulfonium salts such as triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) and triarylsulfonium hexafluoroantimonate (particularly triarylsulfonium hexafluoroantimonate). Reelsulfonium salt): diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodonium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexa Examples include iodonium salts such as fluorophosphate. A photo-acid generator can also be used individually by 1 type, and can also be used in combination of 2 or more type.
前記（Ｃ）成分の含有量は、特に限定されない。前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の総質量に対して、好ましくは０．１〜２０質量％、より好ましくは０．１〜１０質量％である。前記（Ｃ）成分の含有量を前記範囲とすることにより、紫外線硬化性に優れるとともに、接着性及び透明性に優れた紫外線硬化性樹脂組成物を得ることができる。 The content of the component (C) is not particularly limited. Preferably it is 0.1-20 mass% with respect to the total mass of the said (A) component, (B) component, and (C) component, More preferably, it is 0.1-10 mass%. By making content of the said (C) component into the said range, while being excellent in ultraviolet-curing property, the ultraviolet-curable resin composition excellent in adhesiveness and transparency can be obtained.
本発明の紫外線硬化性樹脂組成物は、必要に応じて、粘度を調整するための有機溶剤を、本発明の効果を損なわない範囲で含むことができる。前記有機溶剤としては、例えば、メチルエチルケトン、メチルイソブチルケトン、アセトン、酢酸エチル、酢酸ブチル、カルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトール、プロピレングリコールモノメチルエーテル、プロピレンカーボネート、トルエン、キシレン、イソプロパノール、ｎ−ブタノール等を挙げることができる。 The ultraviolet curable resin composition of this invention can contain the organic solvent for adjusting a viscosity as needed in the range which does not impair the effect of this invention. Examples of the organic solvent include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, carbitol acetate, propylene glycol monomethyl ether acetate, carbitol, propylene glycol monomethyl ether, propylene carbonate, toluene, xylene, isopropanol, n -Butanol etc. can be mentioned.
本発明の紫外線硬化性樹脂組成物が前記有機溶剤を含む場合、その配合量は、本発明の効果を損なわない範囲であれば、特に制限はない。前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の総質量に対して、通常０．０１〜１００倍質量、好ましくは１〜１０倍質量である。 When the ultraviolet curable resin composition of this invention contains the said organic solvent, there will be no restriction | limiting in particular if the compounding quantity is a range which does not impair the effect of this invention. It is 0.01-100 times mass normally with respect to the total mass of the said (A) component, (B) component, and (C) component, Preferably it is 1-10 times mass.
本発明の紫外線硬化性樹脂組成物には、必要に応じて、本発明の効果を損なわない範囲において、種々の添加剤を含有させることができる。前記添加剤として、例えば、可塑剤、表面調整剤、界面活性剤、紫外線吸収剤、酸化防止剤、無機フィラー、シランカップリング剤、コロイダルシリカ、消泡剤、湿潤剤、防錆剤、安定化剤等が挙げられる。 The ultraviolet curable resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. Examples of the additives include plasticizers, surface conditioners, surfactants, ultraviolet absorbers, antioxidants, inorganic fillers, silane coupling agents, colloidal silica, antifoaming agents, wetting agents, rust inhibitors, and stabilization. Agents and the like.
本発明の紫外線硬化性樹脂組成物が前記添加剤を含む場合、その配合量は、本発明の効果を損なわない範囲であれば、特に制限はない。前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の総質量に対して、通常０．０１〜１０００質量％、好ましくは０．０５〜１００質量％である。 When the ultraviolet curable resin composition of this invention contains the said additive, if the compounding quantity is a range which does not impair the effect of this invention, there will be no restriction | limiting in particular. It is 0.01-1000 mass% normally with respect to the total mass of the said (A) component, (B) component, and (C) component, Preferably it is 0.05-100 mass%.
本発明の紫外線硬化性樹脂組成物は、前記（Ａ）〜（Ｃ）成分、及び必要に応じて上記有機溶剤及び／又は添加剤を所望の割合で混合することによって製造することができる。各成分の混合方法および添加順序については、特段の限定はない。 The ultraviolet curable resin composition of this invention can be manufactured by mixing the said (A)-(C) component and the said organic solvent and / or additive in a desired ratio as needed. There are no particular limitations on the mixing method and order of addition of each component.
こうして得られた紫外線硬化性樹脂組成物を用いて所望の硬化物を調製するためには、該組成物を所定の基材にコーティングしまたは所定の型枠に充填し、該組成物が有機溶剤を含む場合は該有機溶剤を揮発させた後、紫外線を照射すればよい。有機溶剤の揮発方法は、有機溶剤の種類、量、膜厚等に応じて適宜決定すればよく、例えば、常圧または減圧下で、通常４０〜１５０℃程度、好ましくは６０〜１００℃に加熱する方法が挙げられる。加熱時間は、通常５秒間〜２時間程度である。 In order to prepare a desired cured product using the ultraviolet curable resin composition thus obtained, the composition is coated on a predetermined substrate or filled in a predetermined mold, and the composition is an organic solvent. When the organic solvent is contained, the organic solvent is volatilized and then irradiated with ultraviolet rays. The method for volatilizing the organic solvent may be appropriately determined according to the type, amount, film thickness, etc. of the organic solvent. For example, it is usually heated to about 40 to 150 ° C., preferably 60 to 100 ° C. under normal pressure or reduced pressure. The method of doing is mentioned. The heating time is usually about 5 seconds to 2 hours.
紫外線照射は、硬化層の耐久性及び接着性を安定して確保するため、５０〜５００ｍＷ／ｃｍ２程度の照射強度で行うことが好ましく、１００〜２００ｍＷ／ｃｍ２程度がより好ましい。また、積算光量は、５０〜１００００ｍＪ／ｃｍ２であることが好ましく、１００〜５０００ｍＪ／ｃｍ２であることがより好ましい。 UV irradiation, in order to stably ensure the durability and adhesion of the cured layer, preferably performed at an irradiation intensity of about 50 to 500 mW / cm 2, about 100~200mW / cm 2 is more preferable. Moreover, it is preferable that it is 50-10000 mJ / cm < 2 >, and, as for integrated light quantity, it is more preferable that it is 100-5000 mJ / cm < 2 >.
上記紫外線硬化性樹脂組成物の硬化に使用する紫外線の光源としては、フュージョンＨランプ、キセノンランプ、高圧水銀灯、メタルハライドランプを有する紫外線照射装置等が挙げられる。 Examples of the ultraviolet light source used for curing the ultraviolet curable resin composition include an ultraviolet irradiation device having a fusion H lamp, a xenon lamp, a high pressure mercury lamp, and a metal halide lamp.
また、紫外線照射して得られた硬化物を、さらに加熱することで、高硬度、強度、耐久性等の硬化物の物性を一層向上させることができる。加熱の方法は適宜決定すればよい。加熱温度は、４０〜３００℃程度、好ましくは１００〜２５０℃であり、加熱時間は通常１分間〜６時間程度である。 Moreover, the physical property of hardened | cured material, such as high hardness, intensity | strength, durability, can further be improved by further heating the hardened | cured material obtained by ultraviolet irradiation. What is necessary is just to determine the method of a heating suitably. The heating temperature is about 40 to 300 ° C., preferably 100 to 250 ° C., and the heating time is usually about 1 minute to 6 hours.
（接着剤への適用）
本発明の紫外線硬化性樹脂組成物は、接着剤として使用することができる。具体的には、所定の基材間に本発明の紫外線硬化性樹脂組成物を介在させ、ついで該組成物を紫外線硬化させることで接着層を得ることができる。前記基材としては、ガラス、鉄、アルミ、銅、ＩＴＯ等の無機基材；ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニルフィルム、アイオノマー樹脂フィルム、エチレン・（メタ）アクリル酸共重合体フィルム、エチレン・（メタ）アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルム等の有機基材；さらにはこれらの架橋フィルム、積層フィルム等、各種公知のものを適宜に選択して使用することができる。ただし、紫外線硬化性樹脂組成物を紫外線硬化させるためには、少なくとも片面が紫外線を透過する必要がある。また、紫外線硬化性樹脂組成物が有機溶剤等の揮発成分を含む場合、接着剤の発泡を防ぐために紫外線硬化性樹脂組成物中の揮発成分を１０質量％未満、好ましくは５質量％未満にするか、貼り合わせ時に揮発成分を除去しておくことが好ましい。上述のような紫外線硬化性樹脂組成物で接着することで、接着層が透明な接着物が得られるため、偏光板等含む液晶パネル、ＥＬパネル、ＰＤＰパネル、カラーフィルター、光ディスク基板等を作成するのに好適である。
(Application to adhesive)
The ultraviolet curable resin composition of the present invention can be used as an adhesive. Specifically, the adhesive layer can be obtained by interposing the ultraviolet curable resin composition of the present invention between predetermined substrates and then curing the composition with ultraviolet rays. Examples of the substrate include inorganic substrates such as glass, iron, aluminum, copper and ITO; polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, Polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film Organic substrates such as polystyrene film, polycarbonate film, polyimide film, and fluororesin film; It can be appropriately selected and used as the. However, in order to cure the ultraviolet curable resin composition with ultraviolet rays, at least one surface needs to transmit ultraviolet rays. When the ultraviolet curable resin composition contains a volatile component such as an organic solvent, the volatile component in the ultraviolet curable resin composition is less than 10% by mass, preferably less than 5% by mass in order to prevent foaming of the adhesive. Or it is preferable to remove a volatile component at the time of bonding. By adhering with the ultraviolet curable resin composition as described above, an adhesive with a transparent adhesive layer can be obtained, so that a liquid crystal panel including a polarizing plate, an EL panel, a PDP panel, a color filter, an optical disk substrate, etc. are prepared. It is suitable for.
（コーティング剤への適用）
本発明の紫外線硬化性樹脂組成物は、コーティング剤として使用することができる。具体的には、本発明の紫外線硬化性樹脂組成物を所望の基材にコーティングし、紫外線硬化させることでコーティング層を得ることができる。前記基材としては、前記の接着層の形成に用いたものと同様のものを使用することができる。また、本発明の紫外線硬化性樹脂組成物を有機溶剤で希釈することで、コーティング性を向上させることもできる。上述のような紫外線硬化性樹脂組成物をコーティングし、紫外線硬化させることで、導光板、偏光板、液晶パネル、ＥＬパネル、ＯＨＰフィルム、光ファイバー、カラーフィルター、光ディスク基板、レンズ、液晶セル用プラスチック基板、プリズム等にコーティング層を形成させることができる。
(Application to coating agent)
The ultraviolet curable resin composition of the present invention can be used as a coating agent. Specifically, a coating layer can be obtained by coating the ultraviolet curable resin composition of the present invention on a desired substrate and curing it with ultraviolet rays. As the substrate, those similar to those used for forming the adhesive layer can be used. Moreover, coating property can also be improved by diluting the ultraviolet curable resin composition of this invention with an organic solvent. A light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, an OHP film, an optical fiber, a color filter, an optical disk substrate, a lens, and a plastic substrate for a liquid crystal cell by coating and curing the ultraviolet curable resin composition as described above. A coating layer can be formed on the prism or the like.
（封止剤への適用）
本発明の紫外線硬化性樹脂組成物は、封止剤として使用することができる。具体的には、本発明の紫外線硬化性樹脂組成物を、例えば１００μｍ以上の厚みになるように塗布し、または所定の型枠に流し込んだ後、紫外線硬化させることで、透明な硬化物で封止された成形材料を得ることができる。このような材料は、発光素子、受光素子、光電変換素子、光伝送関連部品等の光学部品用途に、特に好適である。当該成形硬化物を作成する際には、前記接着剤の場合と同様に、該組成物中の揮発成分を１０質量％未満、好ましくは５質量％未満にすることが好ましい。
(Application to sealant)
The ultraviolet curable resin composition of the present invention can be used as a sealant. Specifically, the ultraviolet curable resin composition of the present invention is applied so as to have a thickness of, for example, 100 μm or more, or poured into a predetermined mold, and then cured by ultraviolet curing, thereby sealing with a transparent cured product. A stopped molding material can be obtained. Such a material is particularly suitable for use in optical parts such as a light emitting element, a light receiving element, a photoelectric conversion element, and an optical transmission related part. When producing the molded cured product, as in the case of the adhesive, the volatile component in the composition is preferably less than 10% by mass, preferably less than 5% by mass.
上記紫外線硬化性樹脂組成物を塗布する方法としては、例えばバーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等を利用することができる。
以上より、本発明の紫外線硬化性樹脂組成物は、接着剤（偏光板等を含む液晶パネル、ＥＬパネル、ＰＤＰパネル、カラーフィルターまたは光ディスク基板などの用途）をはじめ、コーティング剤（導光板、偏光板、液晶パネル、ＥＬパネル、ＰＤＰパネル、ＯＨＰフィルム、光ファイバー、カラーフィルター、光ディスク基板、レンズ、液晶セル用プラスチック基板またはプリズムなどの用途）、封止剤（発光素子、受光素子、光電変換素子、または光伝送関連部品などの用途）などとして有用である。
As a method for applying the ultraviolet curable resin composition, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
From the above, the ultraviolet curable resin composition of the present invention includes a coating agent (light guide plate, polarized light) including an adhesive (a liquid crystal panel including a polarizing plate, an EL panel, a PDP panel, a color filter, or an optical disk substrate). Plate, liquid crystal panel, EL panel, PDP panel, OHP film, optical fiber, color filter, optical disk substrate, lens, plastic substrate for liquid crystal cell or prism), sealing agent (light emitting element, light receiving element, photoelectric conversion element, It is also useful for applications such as optical transmission related parts).
以下に本発明を実施例により更に具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。また実施例中、「％」は特に断りのない限り「質量％」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” means “% by mass” unless otherwise specified.
＜紫外線硬化性樹脂組成物の調製＞
実施例１〜９および比較例１〜３
各成分を表１に示したとおりに配合し、紫外線硬化性樹脂組成物を調製した。なお、（Ｃ）成分は、有効成分が表１に記載の使用量となるように配合した。
<Preparation of UV curable resin composition>
Examples 1-9 and Comparative Examples 1-3
Each component was blended as shown in Table 1 to prepare an ultraviolet curable resin composition. In addition, (C) component was mix | blended so that an active ingredient might be the usage-amount of Table 1.
表１において、使用する各成分は以下のとおりである。
（Ａ−１）：３，４，３’，４’−ジエポキシビシクロヘキシル、
（Ａ−２）：３’，４’−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート（（株）ダイセル製、商品名「セロキサイド２０２１Ｐ」）、
（Ｂ−１）：トリメチロールプロパントリス（３−メルカプトプロピオネート）（ＳＣ有機化学工業（株）製、商品名「ＴＭＭＰ」）、
（Ｂ−２）：ジペンタエリスリトールヘキサキス（３−メルカプトプロピオネート）（ＳＣ有機化学工業（株）製、商品名「ＤＰＭＰ」）、
（Ｂ−３）：ペンタエリスリトールテトラキス（３−メルカプトブチレート）（昭和電工（株）製、商品名「カレンズＭＴ ＰＥ１」）、
（Ｂ−４）：１，４−ビス（３−メルカプトブチリルオキシ）ブタン（昭和電工（株）製、商品名「カレンズＭＴ ＢＤ１」）、
（Ｂ−５）：１，３，５−トリス（３−メルカプトブチリルオキシエチル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオンブタン（昭和電工（株）製、商品名「カレンズＭＴ ＮＲ１」）、
（Ｃ−１）：４−（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロアンチモネート（有効成分５０％、希釈剤プロピレンカーボネート、サンアプロ（株）製、商品名「ＣＰＩ−１０１Ａ」）、
（Ｄ−１）：ポリカプロラクトントリオール（（株）ダイセル製、商品名「プラクセル３０３」）。
In Table 1, each component used is as follows.
(A-1): 3,4,3 ′, 4′-diepoxybicyclohexyl,
(A-2): 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name “Celoxide 2021P”),
(B-1): Trimethylolpropane tris (3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd., trade name “TMMP”),
(B-2): Dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd., trade name “DPMP”),
(B-3): Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK, trade name “Karenz MT PE1”),
(B-4): 1,4-bis (3-mercaptobutyryloxy) butane (product name “Karenz MT BD1” manufactured by Showa Denko KK),
(B-5): 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trionebutane (Showa Denko ( Product name "Karenz MT NR1"),
(C-1): 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate (active ingredient 50%, diluent propylene carbonate, manufactured by San Apro Co., Ltd., trade name “CPI-101A”),
(D-1): Polycaprolactone triol (manufactured by Daicel Corporation, trade name “Placcel 303”).
（紫外線硬化性樹脂組成物の硬化性）
実施例１〜９および比較例１〜３の紫外線硬化性樹脂組成物を膜厚５０μｍＰＥＴフィルム（東洋紡（株）製、商品名「コスモシャインＡ４１００」）の上に膜厚１０μｍになるようにバーコーターでコーティングし、紫外線照射装置を用い、３６５ｎｍの紫外線検出器で積算照度７５０ｍＷｍＪ／ｃｍ２及び積算光量が３００ｍＪ／ｃｍ２となるように紫外線を照射した。硬化性は、得られた硬化物の指触でのタック感により評価した。
(Curability of UV curable resin composition)
A bar coater was prepared by coating the ultraviolet curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 on a 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4100”). Using an ultraviolet irradiation device, ultraviolet rays were irradiated with a 365 nm ultraviolet detector so that the integrated illuminance was 750 mWmJ / cm 2 and the integrated light amount was 300 mJ / cm 2 . The curability was evaluated based on the tackiness of the obtained cured product with the touch of a finger.
（紫外線硬化性樹脂組成物の接着性）
実施例１〜９および比較例１〜３の紫外線硬化性樹脂組成物を膜厚５０μｍＰＥＴフィルム（東洋紡（株）製、商品名「コスモシャインＡ４１００」）の上に膜厚１０μｍになるようにバーコーターでコーティングし、紫外線照射装置を用い、３６５ｎｍの紫外線検出器で積算照度７５０ｍＷｍＪ／ｃｍ２及び積算光量が３００ｍＪ／ｃｍ２となるように紫外線を照射した。接着性は、得られた硬化物サンプルを碁盤目剥離試験治具を用い１ｍｍ２クロスカットを１００個作成し、セロテープ（登録商標、ニチバン（株）製）をその上に貼り付け、へらを用いて均一に押し付け後、９０度方向に剥離し、硬化層の残存個数を評価した。
(Adhesiveness of UV curable resin composition)
A bar coater was prepared by coating the ultraviolet curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 on a 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4100”). Using an ultraviolet irradiation device, ultraviolet rays were irradiated with a 365 nm ultraviolet detector so that the integrated illuminance was 750 mWmJ / cm 2 and the integrated light amount was 300 mJ / cm 2 . Adhesiveness is obtained by making 100 pieces of 1 mm 2 crosscuts using a cross-cut peel test jig for the obtained cured product sample, attaching cello tape (registered trademark, manufactured by Nichiban Co., Ltd.) on it, and using a spatula After pressing uniformly, it peeled in the direction of 90 degrees, and the number of remaining cured layers was evaluated.
（紫外線硬化性樹脂組成物の硬化収縮）
実施例１〜９および比較例１〜３の紫外線硬化性樹脂組成物を膜厚５０μｍＰＥＴフィルム（東洋紡（株）製、商品名「コスモシャインＡ４１００」）の上に膜厚１０μｍになるようにバーコーターでコーティングし、紫外線照射装置を用い、３６５ｎｍの紫外線検出器で積算照度７５０ｍＷｍＪ／ｃｍ２及び積算光量が３００ｍＪ／ｃｍ２となるように紫外線を照射した。硬化収縮は、得られた硬化物／ＰＥＴフィルムのそりの程度で評価した。得られた硬化物／ＰＥＴフィルムを１０ｃｍ四方に切り抜き、浮きあがった四隅高さの合計の平均として数値化した。
(Cure shrinkage of UV curable resin composition)
A bar coater was prepared by coating the ultraviolet curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 on a 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4100”). Using an ultraviolet irradiation device, ultraviolet rays were irradiated with a 365 nm ultraviolet detector so that the integrated illuminance was 750 mWmJ / cm 2 and the integrated light amount was 300 mJ / cm 2 . Curing shrinkage was evaluated by the degree of warpage of the obtained cured product / PET film. The obtained cured product / PET film was cut out in a 10 cm square and quantified as an average of the total height of the four corners that floated.
表２から、比較例１〜３の樹脂組成物に対し、実施例、特に実施例４、５、７および８の樹脂組成物は、高い硬化性、高い接着性及び低い硬化収縮（低いそり）を実現していることがわかった。よって、実施例１〜９の樹脂組成物は、偏光板等含む液晶パネル、ＥＬパネル、ＰＤＰパネル、カラーフィルター、光ディスク基板等を作成する接着剤として好適である。また、導光板、偏光板、液晶パネル、ＥＬパネル、ＯＨＰフィルム、光ファイバー、カラーフィルター、光ディスク基板、レンズ、液晶セル用プラスチック基板、プリズム等でのコーティング剤として好適である。さらに、このような材料は、発光素子、受光素子、光電変換素子、光伝送関連部品等の光学部品用途に、特に好適である。 From Table 2, with respect to the resin compositions of Comparative Examples 1 to 3, the resin compositions of Examples, particularly Examples 4, 5, 7 and 8, have high curability, high adhesiveness and low cure shrinkage (low warpage). It turns out that has been realized. Therefore, the resin compositions of Examples 1 to 9 are suitable as an adhesive for forming a liquid crystal panel including a polarizing plate, an EL panel, a PDP panel, a color filter, an optical disk substrate, and the like. Moreover, it is suitable as a coating agent for a light guide plate, a polarizing plate, a liquid crystal panel, an EL panel, an OHP film, an optical fiber, a color filter, an optical disk substrate, a lens, a plastic substrate for a liquid crystal cell, a prism and the like. Furthermore, such a material is particularly suitable for use in optical parts such as a light emitting element, a light receiving element, a photoelectric conversion element, and an optical transmission related part.
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| JP2022065475A (en) * | 2020-10-15 | 2022-04-27 | 協立化学産業株式会社 | Cationic polymerizable resin composition |
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