JP7455423B2 - Ink composition containing t-butylcyclohexyl (meth)acrylate - Google Patents
Ink composition containing t-butylcyclohexyl (meth)acrylate Download PDFInfo
- Publication number
- JP7455423B2 JP7455423B2 JP2022189213A JP2022189213A JP7455423B2 JP 7455423 B2 JP7455423 B2 JP 7455423B2 JP 2022189213 A JP2022189213 A JP 2022189213A JP 2022189213 A JP2022189213 A JP 2022189213A JP 7455423 B2 JP7455423 B2 JP 7455423B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- butylcyclohexyl
- ink composition
- acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 227
- -1 t-butylcyclohexyl Chemical group 0.000 title claims description 125
- 239000000203 mixture Substances 0.000 title claims description 85
- 239000000178 monomer Substances 0.000 claims description 77
- 239000011342 resin composition Substances 0.000 claims description 74
- 229920000642 polymer Polymers 0.000 claims description 64
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 21
- 230000003287 optical effect Effects 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000012719 thermal polymerization Methods 0.000 claims description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 3
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 3
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 claims description 2
- XUIXZBXRQFZHIT-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol Chemical compound COCC(O)COC(C)COC(C)CO XUIXZBXRQFZHIT-UHFFFAOYSA-N 0.000 claims description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 2
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 claims description 2
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 claims description 2
- SHJIJMBTDZCOFE-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol Chemical compound COC(O)COCCOCCOCCO SHJIJMBTDZCOFE-UHFFFAOYSA-N 0.000 claims description 2
- XXHDHAPOSIFMIG-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCC(O)OC1=CC=CC=C1 XXHDHAPOSIFMIG-UHFFFAOYSA-N 0.000 claims description 2
- OBFOSROPNNOGQF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 OBFOSROPNNOGQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000006226 butoxyethyl group Chemical group 0.000 claims description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 74
- 230000001070 adhesive effect Effects 0.000 description 74
- 239000010408 film Substances 0.000 description 60
- 238000012360 testing method Methods 0.000 description 51
- 238000000034 method Methods 0.000 description 43
- 239000000976 ink Substances 0.000 description 37
- 238000004383 yellowing Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 31
- 238000011156 evaluation Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 29
- 239000000758 substrate Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 239000000049 pigment Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000005034 decoration Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 230000001588 bifunctional effect Effects 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 206010040880 Skin irritation Diseases 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 230000036556 skin irritation Effects 0.000 description 12
- 231100000475 skin irritation Toxicity 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000008393 encapsulating agent Substances 0.000 description 10
- 239000002952 polymeric resin Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 229920003002 synthetic resin Polymers 0.000 description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000516 sunscreening agent Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000000475 sunscreen effect Effects 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 229910001507 metal halide Inorganic materials 0.000 description 7
- 150000005309 metal halides Chemical class 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 229920000298 Cellophane Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 3
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 2
- SDEXZERWEBDHSL-UHFFFAOYSA-N 2-ethenyl-4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=C)=N1 SDEXZERWEBDHSL-UHFFFAOYSA-N 0.000 description 2
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、高純度なｔ－ブチルシクロヘキシル（メタ）アクリレートをを含有するインク組成物に関する。 The present invention relates to an ink composition containing highly pure t-butylcyclohexyl (meth)acrylate.
ｔ－ブチルシクロヘキシル（メタ）アクリレートは分岐状のアルキル基と(メタ)アクリレート基で置換されたシクロヘキサンであり、ｃｉｓ型とｔｒａｎｓ型の立体異性体が存在し、またｏ－、ｍ－とｐ－の位置異性体も存在する。このような置換型シクロヘキサン中の特定異性体の含有量や異性体の混合比が化合物の臭気や耐熱性などの物理的、化学的性質に大きく影響を及ぼすことが知られている（特許文献１）。 t-Butylcyclohexyl (meth)acrylate is a cyclohexane substituted with a branched alkyl group and a (meth)acrylate group, and exists in cis and trans stereoisomers, as well as o-, m- and p- Positional isomers also exist. It is known that the content of specific isomers in such substituted cyclohexane and the mixing ratio of isomers greatly affect the physical and chemical properties such as odor and heat resistance of the compound (Patent Document 1) ).
ｔ－ブチルシクロヘキシル（メタ）アクリレートは単官能モノマーとして、インク、粘着剤、接着剤、コーティング剤、塗料、光造形用樹脂、封止材等に広く使用されている（特許文献２～４）。しかし、これらの用途に用いられる際に、ｔ－ブチルシクロヘキシル（メタ）アクリレートの異なる異性体含有量により、それを配合した樹脂組成物の着色や臭気、皮膚刺激性、各種基材への濡れ性や密着性など基本物性への影響について、未だに報告されていない。 T-butylcyclohexyl (meth)acrylate is widely used as a monofunctional monomer in inks, pressure-sensitive adhesives, adhesives, coating agents, paints, stereolithography resins, sealants, etc. (Patent Documents 2 to 4). However, when used in these applications, due to the different isomer contents of t-butylcyclohexyl (meth)acrylate, resin compositions containing it may suffer from coloration, odor, skin irritation, and wettability to various substrates. The effects on basic physical properties such as adhesion and adhesion have not yet been reported.
本発明の課題は、着色や臭気、皮膚刺激性が低く、各種基材への濡れ性や密着性に優れ、濡れ性向上剤や密着性向上剤として使用可能な重合性樹脂組成物、該組成物を重合して得られる重合物及び、該組成物と重合物からなる成型品を提供することである。 The object of the present invention is to provide a polymeric resin composition that has low coloring, odor, and skin irritation, has excellent wettability and adhesion to various substrates, and can be used as a wettability improver or an adhesion improver. It is an object of the present invention to provide a polymer obtained by polymerizing a product, and a molded product made of the composition and the polymer.
本発明者らは、かかる課題を解決すべく鋭意検討を行い、ｔｒａｎｓ型異性体を７０％以上含有するｔ－ブチルシクロヘキシル（メタ）アクリレートを１重量％以上配合させることにより、着色や臭気、皮膚刺激性が低く、各種基材への濡れ性や密着性に優れる重合性樹脂組成物、該組成物を重合して得られる重合物及び、該組成物と重合物からなる成型品が得られることを見出し、本発明に到達した。 The present inventors have conducted extensive studies to solve these problems, and have found that by incorporating 1% by weight or more of t-butylcyclohexyl (meth)acrylate containing 70% or more of the trans isomer, we can reduce the coloring, odor, and skin irritation. A polymerizable resin composition with low irritation and excellent wettability and adhesion to various substrates, a polymer obtained by polymerizing the composition, and a molded product made of the composition and the polymer can be obtained. They discovered this and arrived at the present invention.
すなわち本発明は、
（１）ｔ－ブチルシクロヘキシル（メタ）アクリレートを含有する重合性樹脂組成物であって、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体の含有量は７０％以上を有することを特徴とする重合性樹脂組成物、
（２）ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体の含有量とｐ－ｃｉｓ型異性体の含有量の合計は９０％以上を有することを特徴とする前記（１）に記載の重合性樹脂組成物、
（３）ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体とｐ－ｃｉｓ型異性体の含有量のモル比は２．３以上であることを特徴とする前記（１）又は前記（２）に記載の重合性樹脂組成物、
（４）前記（１）～（３）の何れか一項に記載の重合性樹脂組成物に、光重合開始剤及び／又は不飽和結合を有する化合物をさらに含有することを特徴とする活性エネルギー線硬化性樹脂組成物、
（５）前記（４）に記載の組成物を活性エネルギー線照射により重合して得られる重合物、
（６）前記（１）～（３）の何れか一項に記載の重合性樹脂組成物に、熱重合開始剤及び／又は不飽和結合を有する化合物をさらに含有することを特徴とする重合性樹脂組成物、
（７）前記（６）に記載の組成物を熱により重合して得られる重合物、
（８）前記（１）～（７）の組成物または重合物を含有することを特徴とする濡れ性向上剤、
（９）前記（１）～（７）の組成物または重合物を含有することを特徴とする密着性向上剤、
（１０）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする粘着剤組成物、
（１１）前記（１０）に記載の粘着剤組成物であって、かつ、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｍ－ｔｒａｎｓ型異性体の含有量は１．０％以下であることを特徴とする光学用粘着剤組成物、
（１２）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とするコーティング組成物、
（１３）前記（１２）に記載のコーティング組成物であって、かつ、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｍ－ｔｒａｎｓ型異性体の含有量は１．０％以下であることを特徴とする光学部材用コーティング組成物、
（１４）前記（１２）に記載のコーティング組成物であって、かつ、ｐ－ｔｒａｎｓ型異性体とｐ－ｃｉｓ型異性体の含有量のモル比は３．０以上であることを特徴とする、ポリオレフィン基材用コーティング組成物、
（１５）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とするインク組成物、
（１６）前記（１５）に記載のインク組成物であって、かつ、ｐ－ｔｒａｎｓ型異性体とｐ－ｃｉｓ型異性体の含有量のモル比は３．０以上であることを特徴とするインクジェット用インク組成物、
（１７）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする光学的立体造形用樹脂組成物、
（１８）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする接着剤組成物、
（１９）前記（１８）に記載の接着剤組成物であって、かつ、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｍ－ｔｒａｎｓ型異性体の含有量は１．０％以下であることを特徴とする光学用接着剤組成物、
（２０）前記（１８）に記載の接着剤組成物であって、かつ、ｐ－ｔｒａｎｓ型異性体とｐ－ｃｉｓ型異性体の含有量のモル比は３．０以上であることを特徴とする電子材料用接着剤組成物、
（２１）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする封止材組成物、
（２２）前記（２１）に記載の封止材組成物であって、かつ、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｍ－ｔｒａｎｓ型異性体の含有量は１．０％以下であることを特徴とする有機ＥＬ素子用封止材組成物、
（２３）前記（１１）、（１３）、（１６）、（１９）と（２２）に記載のいずれか一種以上組成物を用いて、光学用フィルム、シートの片面又は両面に塗布し、活性エネルギー線照射或いは熱による硬化又は積層硬化で得られた光学用成形品、
（２４）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする加飾フィルム用樹脂組成物、
（２５）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とするジェルネイル用樹脂組成物、
（２６）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする車両用コーティング組成物、
（２７）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする建築物用コーティング組成物、
（２８）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする界面活性剤、
（２９）前記（４）又は（６）に記載の組成物、及び／又は前記（５）又は（７）に記載の重合物を含有することを特徴とする分散剤、
を提供することである。
That is, the present invention
(1) A polymeric resin composition containing t-butylcyclohexyl (meth)acrylate, in which the content of p-trans type isomer in t-butylcyclohexyl (meth)acrylate is 70% or more. Characteristic polymerizable resin composition,
(2) In the above (1), the total content of p-trans type isomer and p-cis type isomer content in t-butylcyclohexyl (meth)acrylate is 90% or more. The polymerizable resin composition described above,
(3) The above (1) or the above, wherein the molar ratio of the content of the p-trans type isomer and the p-cis type isomer in t-butylcyclohexyl (meth)acrylate is 2.3 or more. The polymerizable resin composition according to (2),
(4) Active energy characterized in that the polymerizable resin composition according to any one of (1) to (3) above further contains a photopolymerization initiator and/or a compound having an unsaturated bond. Line curable resin composition,
(5) a polymer obtained by polymerizing the composition described in (4) above by irradiation with active energy rays,
(6) Polymerizable, characterized in that the polymerizable resin composition according to any one of (1) to (3) above further contains a thermal polymerization initiator and/or a compound having an unsaturated bond. resin composition,
(7) A polymer obtained by thermally polymerizing the composition described in (6) above,
(8) A wettability improver containing the composition or polymer of (1) to (7) above;
(9) An adhesion improver containing the composition or polymer of (1) to (7) above;
(10) A pressure-sensitive adhesive composition containing the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(11) The adhesive composition according to (10) above, characterized in that the content of m-trans isomer in t-butylcyclohexyl (meth)acrylate is 1.0% or less. an optical adhesive composition,
(12) A coating composition containing the composition described in (4) or (6) above and/or the polymer described in (5) or (7) above,
(13) The coating composition according to (12) above, characterized in that the content of m-trans isomer in t-butylcyclohexyl (meth)acrylate is 1.0% or less. Coating composition for optical members,
(14) The coating composition according to (12) above, characterized in that the molar ratio of the content of the p-trans isomer to the p-cis isomer is 3.0 or more. , coating composition for polyolefin substrates,
(15) An ink composition containing the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(16) The ink composition according to (15) above, characterized in that the molar ratio of the content of the p-trans isomer and the p-cis isomer is 3.0 or more. inkjet ink composition,
(17) A resin composition for optical three-dimensional modeling, characterized by containing the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(18) An adhesive composition comprising the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(19) The adhesive composition according to (18) above, characterized in that the content of m-trans isomer in t-butylcyclohexyl (meth)acrylate is 1.0% or less. an optical adhesive composition,
(20) The adhesive composition according to (18) above, wherein the molar ratio of the content of the p-trans isomer to the p-cis isomer is 3.0 or more. Adhesive composition for electronic materials,
(21) A sealing material composition containing the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(22) The encapsulant composition according to (21) above, wherein the content of m-trans isomer in t-butylcyclohexyl (meth)acrylate is 1.0% or less. Characteristic encapsulant composition for organic EL elements,
(23) Applying one or more of the compositions described in (11), (13), (16), (19) and (22) to one or both sides of an optical film or sheet to activate the Optical molded products obtained by energy ray irradiation, heat curing, or lamination curing,
(24) A resin composition for a decorative film, comprising the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(25) A resin composition for gel nails, comprising the composition described in (4) or (6) above, and/or the polymer described in (5) or (7) above,
(26) A coating composition for a vehicle, comprising the composition according to (4) or (6) above, and/or the polymer according to (5) or (7) above,
(27) A coating composition for buildings, comprising the composition according to (4) or (6) above, and/or the polymer according to (5) or (7) above,
(28) A surfactant containing the composition described in (4) or (6) above and/or the polymer described in (5) or (7) above,
(29) A dispersant containing the composition described in (4) or (6) above and/or the polymer described in (5) or (7) above,
The goal is to provide the following.
本発明のｐ－ｔｒａｎｓ型異性体の含有量７０％以上を有するｔ－ブチルシクロヘキシル（メタ）アクリレートを用いた重合性樹脂組成物は、臭気や皮膚刺激性が低いため、作業者が液体薬物やその揮発蒸気に接触することが想定される用途においても安全に使用することができる。また、着色が少なく、各種基材への濡れ性や密着性に優れるため、濡れ性向上剤、密着性向上剤として用いることができる。具体的な用途としては、インク(主にインクジェット、オフセット、スクリーン、フレキソ、水系)、粘着剤、接着剤、コーティング剤、塗料、光造形用樹脂、封止材、分散剤、界面活性剤、加飾コート剤、防曇塗料、電池用セパレータ、歯科材料等に好適に用いることができる。 The polymerizable resin composition of the present invention using t-butylcyclohexyl (meth)acrylate having a p-trans isomer content of 70% or more has low odor and skin irritation, so it is easy for workers to use liquid drugs. It can be used safely even in applications where contact with the volatile vapor is expected. In addition, since it has little coloring and has excellent wettability and adhesion to various substrates, it can be used as a wettability improver and an adhesion improver. Specific applications include ink (mainly inkjet, offset, screen, flexo, and water-based), pressure-sensitive adhesives, adhesives, coatings, paints, stereolithography resins, encapsulants, dispersants, surfactants, and additives. It can be suitably used for decorative coating agents, antifogging paints, battery separators, dental materials, etc.
以下、本発明を詳細に記載する。
本発明の重合性樹脂組成物の構成成分であるｔ－ブチルシクロヘキシル（メタ）アクリレートは、シクロヘキサン環にｔ－ブチル基と（メタ）アクリロイル基の２つの置換基が有するため、ｃｉｓ型、ｔｒａｎｓ型の異性体が発生する。また、２つの置換基の位置が、ｏ－位、ｍ－位、ｐ－位に結合することが可能であり、位置異性体も発生する。さらに、ａｘｉａｌとｅｑｕａｔｏｒｉａｌの立体配座も発生する。これらの異性体においては、立体構造の違いにより、分子内エネルギーや分子間相互作用に差異が発生し、各種物性に影響を及ぼす。
The present invention will be described in detail below.
Since t-butylcyclohexyl (meth)acrylate, which is a component of the polymerizable resin composition of the present invention, has two substituents, a t-butyl group and a (meth)acryloyl group, on the cyclohexane ring, it has a cis type and a trans type. isomers are generated. Further, the two substituents can be bonded to the o-position, m-position, or p-position, and positional isomers also occur. Furthermore, axial and equatorial conformations also occur. In these isomers, differences in steric structure cause differences in intramolecular energy and intermolecular interactions, which affect various physical properties.
本発明の重合性樹脂組成物に含まれるｔ－ブチルシクロヘキシル（メタ）アクリレートは、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であることが好ましい。本発明の効果を十分に奏する観点から、７５％以上であることがより好ましく、９０％以上であることがさらに好ましく、実質的に１００％であることが特に好ましい。ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であることによって、着色や臭気、皮膚刺激性、各種基材への濡れ性、密着性に優れたものとなる。 The t-butylcyclohexyl (meth)acrylate contained in the polymerizable resin composition of the present invention preferably has a p-trans isomer content of 70% or more. From the viewpoint of fully achieving the effects of the present invention, it is more preferably 75% or more, even more preferably 90% or more, and particularly preferably substantially 100%. When the content of the p-trans type isomer is 70% or more, it has excellent coloring, odor, skin irritation, and wettability and adhesion to various substrates.
本発明の重合性樹脂組成物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であることに加えて、ｐ－ｔｒａｎｓ型異性体の含有量とｐ－ｃｉｓ型異性体の含有量の合計が９０％以上の高純度なｔ－ブチルシクロヘキシル（メタ）アクリレートを用いることがより好ましく、本発明の効果をより有効に発揮させるためには９５％以上であることが特に好ましい。ｐ－ｔｒａｎｓ型異性体の含有量とｐ－ｃｉｓ型異性体の含有量の合計が９０％以上であることによって、着色や臭気、皮膚刺激性や、基材への濡れ性や密着性の低下要因となる他の不純物混入が抑制され、さらに本発明の各種用途へ好適に使用可能な組成物となるため好ましい。 The polymerizable resin composition of the present invention has a content of p-trans isomer of 70% or more, and also has a content of p-trans isomer and p-cis isomer. It is more preferable to use highly purified t-butylcyclohexyl (meth)acrylate with a total content of 90% or more, and particularly preferably 95% or more in order to more effectively exhibit the effects of the present invention. If the total content of p-trans type isomer and p-cis type isomer content is 90% or more, it may cause discoloration, odor, skin irritation, and decrease in wettability and adhesion to the substrate. This is preferable because the contamination of other impurities that may be a factor is suppressed, and the composition can be suitably used for various purposes of the present invention.
本発明の重合性樹脂組成物は、さらに、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体の含有量とｐ－ｃｉｓ型異性体の含有量のモル比が２．３以上であることが好ましい。２．３以上であると、重合性樹脂組成物中のｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体の含有量が多いため、着色や臭気、皮膚刺激性の低減効果や、基材への濡れ性や密着性向上効果をより発揮させることができるため特に好ましい。 The polymerizable resin composition of the present invention further has a molar ratio of the p-trans isomer content to the p-cis isomer content in t-butylcyclohexyl (meth)acrylate of 2.3 or more. It is preferable that there be. When it is 2.3 or more, the content of the p-trans type isomer in t-butylcyclohexyl (meth)acrylate in the polymerizable resin composition is high, so the effect of reducing coloring, odor, and skin irritation, It is particularly preferred because it can further exhibit the effect of improving wettability and adhesion to the base material.
ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるｔ－ブチルシクロヘキシル（メタ）アクリレートを高収率で取得する方法としては、出発原料中の異性体の含有量を調整する方法や、ｐ－ｃｉｓ型異性体とｐ－ｔｒａｎｓ型異性体を再結晶や蒸留精製などの分離方法で制御する方法などが挙げられる。例えば、エステル交換法によりｔ－ブチルシクロヘキシル（メタ）アクリレートを製造する場合、原料としてｔ－ブチルシクロヘサノールを使用するが、ｔ－ブチルシクロヘサノールの異性体構成をほぼそのままｔ－ブチルシクロヘキシル（メタ）アクリレートに反映することができる。また、ｔ－ブチルシクロヘサノールは通常ｔ－ブチルフェノールの水添反応で製造され、水添反応に使用される異なる触媒によってｃｉｓ型、ｔｒａｎｓ型など異性体の選択的合成が可能である。 Methods for obtaining t-butylcyclohexyl (meth)acrylate with a p-trans isomer content of 70% or more in high yield include a method of adjusting the isomer content in the starting material, and a method of adjusting the content of the isomer in the starting material. Examples include a method of controlling the -cis isomer and the p-trans isomer by separation methods such as recrystallization and distillation purification. For example, when producing t-butylcyclohexyl (meth)acrylate by a transesterification method, t-butylcyclohexyl (meth)acrylate is used as a raw material, but the isomer composition of t-butylcyclohexanol is almost unchanged from t-butylcyclohexyl ( This can be reflected in meta)acrylates. In addition, t-butylcyclohesanol is usually produced by hydrogenation reaction of t-butylphenol, and isomers such as cis type and trans type can be selectively synthesized by using different catalysts used in the hydrogenation reaction.
本発明の重合性樹脂組成物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるｔ－ブチルシクロヘキシル（メタ）アクリレートを１～１００重量％含有することができる。また、１～９０重量％含有することが好ましく、５～７０重量％含有することがさらに好ましい。本発明の重合性樹脂組成物は、各種基材に対する濡れ性や密着性が優れている。これは、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体の含有量は７０％以上であるためと発明者らは推測している。 The polymerizable resin composition of the present invention can contain 1 to 100% by weight of t-butylcyclohexyl (meth)acrylate having a p-trans isomer content of 70% or more. Further, the content is preferably 1 to 90% by weight, and more preferably 5 to 70% by weight. The polymerizable resin composition of the present invention has excellent wettability and adhesion to various substrates. The inventors speculate that this is because the content of p-trans type isomer in t-butylcyclohexyl (meth)acrylate is 70% or more.
本発明の重合性樹脂組成物中のｔ－ブチルシクロヘキシル（メタ）アクリレートの含有量が１重量％未満の場合、基材に対する濡れ性や密着性の改善効果が十分に得られない場合がある。 If the content of t-butylcyclohexyl (meth)acrylate in the polymerizable resin composition of the present invention is less than 1% by weight, the effect of improving wettability and adhesion to the substrate may not be sufficiently obtained.
本発明の樹脂組成物は、ｔ－ブチルシクロヘキシル（メタ）アクリレートにさらに光重合開始剤や不飽和結合を有する化合物を添加し、活性エネルギー線硬化性樹脂組成物として好適に用いることができる。また、樹脂組成物の液体粘度を調整するため、低粘度の不飽和結合１個を有する単官能モノマーを併用することができ、架橋密度を調整するため、不飽和結合２個以上を有する多官能モノマーを併用することができ、さらに柔軟性改善するため単官能又は多官能オリゴマー、非重合性ポリマー等を併用することができる。これらの併用成分は単独で加えてもよいし、２種類以上組み合わせることもできる。それぞれの配合量は、具体的な用途に応じて、適意に調整すれば良いが、樹脂組成物全量中では、単官能モノマーが１～７０重量％、多官能モノマーが１～５０重量％、オリゴマーは１～５０重量％、ポリマーは０．１～１０重量％であることが好ましい。 The resin composition of the present invention can be suitably used as an active energy ray-curable resin composition by further adding a photopolymerization initiator and a compound having an unsaturated bond to t-butylcyclohexyl (meth)acrylate. In addition, in order to adjust the liquid viscosity of the resin composition, a monofunctional monomer having one unsaturated bond with low viscosity can be used in combination, and in order to adjust the crosslinking density, a polyfunctional monomer having two or more unsaturated bonds can be used. Monomers can be used in combination, and monofunctional or polyfunctional oligomers, non-polymerizable polymers, etc. can also be used in combination to improve flexibility. These combined components may be added alone or in combination of two or more. The amount of each compounded may be adjusted appropriately depending on the specific use, but in the total amount of the resin composition, the monofunctional monomer is 1 to 70% by weight, the polyfunctional monomer is 1 to 50% by weight, and the oligomer is 1 to 70% by weight. is preferably 1 to 50% by weight, and the polymer is preferably 0.1 to 10% by weight.
本発明の樹脂組成物に用いられる多官能モノマー、オリゴマーとしては、不飽和結合２個以上を有する多官能（メタ）アクリレートや多官能（メタ）アクリルアミドが挙げられ、また、主鎖構造からウレタン系、エポキシ系とアクリル系等に分けられる。 Examples of the polyfunctional monomers and oligomers used in the resin composition of the present invention include polyfunctional (meth)acrylates and polyfunctional (meth)acrylamides having two or more unsaturated bonds; It is divided into epoxy type and acrylic type.
前記の多官能（メタ）アクリレートとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジテトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，７－ヘプタンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスルトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプパントリ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、アクリレートエステル（ジオキサングリコールジアクリレート）、アルコキシ化ヘキサンジオールジ（メタ）アクリレート、アルコキシ化シクロヘキサンジメタノールジ（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等のモノマーとオリゴマーが挙げられる。また、市販品で入手容易の観点から、多官能（メタ）アクリレートとしては、例えばＳＡＲＴＯＭＥＲ社製、商品名ＣＮ２２０３、ＣＮ２２７０、東亜合成社製、商品名Ｍ－６１００、Ｍ－８０６０、ウレタンアクリレートとしては、例えば日本合成化学社製、商品名ＵＶ－３２００Ｂ、ＵＶ－３０００Ｂ、ＵＶ―６６４０Ｂ、ＵＶ－３７００Ｂ、ＵＶ－３３１０Ｂ、ＵＶ－７０００Ｂや新中村化学工業社製、商品名Ｕ－４ＨＡ、Ｕ－２００ＰＡ、ダイセル・サイテック社製、商品名ＥＢＥＣＲＹＬ２４５、ＥＢＥＣＲＹＬ１２５９、ＥＢＥＣＲＹＬ８２１０、ＥＢＥＣＲＹＬ２８４、ＥＢＥＣＲＹＬ８４０２、ＳＡＲＴＯＭＥＲ社製、商品名ＣＮ９４４、ＣＮ９６９、ＣＮ９００２、ＣＮ９０２９、根上工業社製、商品名ＵＮ１２５５、ＵＮ－５５０７、共栄社化学社製、商品名ＡＨ－６００、ＵＡ－３０６Ｉ等を用いることができ、エポキシ（メタ）アクリレートとしては、ダイセル・サイテック社製、商品名ＥＢＥＣＲＹＬ１２５９、ＥＢＥＣＲＹＬ６０５、ＥＢＥＣＲＹＬ１６０６やＳＡＲＴＯＭＥＲ社製、商品名ＣＮ１１０、ＣＮ１２０、ＣＮ１５３等を使用できる。さらに、樹脂組成物の粘度や取扱いの容易さ等の観点から、ウレタンアクリレートＵＶ－６６４０ＢまたはＵ－２００ＰＡがより好ましい。
これらの多官能（メタ）アクリレートは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
Examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and ditetraethylene glycol di(meth)acrylate. (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate (meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified phosphoric acid di(meth)acrylate (meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Trimethylolethane tri(meth)acrylate, trimethylolepupane tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate Acrylate, cyclohexanedimethanol di(meth)acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy(meth)acrylate, urethane(meth)acrylate ) Examples include monomers and oligomers such as acrylates. In addition, from the viewpoint of easy availability of commercially available polyfunctional (meth)acrylates, for example, manufactured by SARTOMER, trade names CN2203 and CN2270, manufactured by Toagosei Co., Ltd., trade names M-6100 and M-8060, and urethane acrylates such as For example, manufactured by Nippon Gosei Kagaku Co., Ltd. under the trade names UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, UV-7000B, and manufactured by Shin-Nakamura Chemical Industry Co., Ltd. under the trade names U-4HA and U-200PA. , manufactured by Daicel Cytec, product name EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402, manufactured by SARTOMER, product name CN944, CN969, CN9002, CN9029, manufactured by Negami Kogyo Co., Ltd., product name UN1255, UN-5507, manufactured by Kyoeisha Chemical Co., Ltd. , product names AH-600, UA-306I, etc. can be used, and as epoxy (meth)acrylates, products manufactured by Daicel Cytec Corporation, product names EBECRYL1259, EBECRYL605, EBECRYL1606, and products manufactured by SARTOMER, product names CN110, CN120, CN153 can be used. etc. can be used. Further, from the viewpoint of the viscosity of the resin composition and ease of handling, urethane acrylate UV-6640B or U-200PA is more preferable.
These polyfunctional (meth)acrylates may be used alone or in combination of two or more.
前記の多官能（メタ）アクリルアミドとしては、メチレンビス（メタ）アクリルアミド、エチレンビス（メタ）アクリルアミド、ジアリル（メタ）アクリルアミド、ウレタンジ（メタ）アクリルアミド等が挙げられる。 Examples of the polyfunctional (meth)acrylamide include methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, diallyl(meth)acrylamide, urethane di(meth)acrylamide, and the like.
本発明の樹脂組成物に用いられる単官能モノマーは、単官能（メタ）アクリレート、単官能（メタ）アクリルアミドや不飽和ニトリルモノマー、スチレン、アミド基含有モノマー、メチロール基含有モノマー、アルコキシメチル基含有モノマー、ビニルエステル、オレフィン等分子鎖中に反応性二重結合を持つラジカル重合性化合物が挙げられる。 Monofunctional monomers used in the resin composition of the present invention include monofunctional (meth)acrylate, monofunctional (meth)acrylamide, unsaturated nitrile monomer, styrene, amide group-containing monomer, methylol group-containing monomer, and alkoxymethyl group-containing monomer. , vinyl esters, olefins, and other radically polymerizable compounds having reactive double bonds in their molecular chains.
前記単官能（メタ）アクリレートは、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ヒドロキシエチルアクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、トリデシル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、プロポキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、メトキシテトラエチレングリコール（メタ）アクリレート、２－（２－エトキシエトキシ）エチルアクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、フェノキシヘキサエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、メトキシトリプロピレングリコール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔｅｒｔ－ブチルシクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニ（メタ）アクリレート、テトラヒドロフルフリルアクリレート、２－メチル－２－アダマンチル（メタ）アクリレート、アリル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシヘキシル（メタ）アクリレート等が挙げられる。 The monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and hydroxyl. Ethyl acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, Methoxyethyl (meth)acrylate, Ethoxyethyl (meth)acrylate, Propoxyethyl (meth)acrylate, Butoxyethyl (meth)acrylate, Methoxydiethylene glycol (meth)acrylate, Methoxytriethylene glycol (meth)acrylate, Methoxytetraethylene glycol (meth)acrylate ) acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate , dicyclopentenyl (meth)acrylate, bornyl (meth)acrylate, isoborni (meth)acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl (meth)acrylate, allyl (meth)acrylate, hydroxyethyl (meth)acrylate , hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and the like.
前記単官能（メタ）アクリルアミドは、例えば、Ｎ－アルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ－アルコキシ（Ｃ１～Ｃ６、直鎖又は分岐鎖）アルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ－ヒドロキシアルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ、Ｎ－ジヒドロキシアルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ－ヒドロキシアルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）－Ｎ－アルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－（ジアルキル（Ｃ１～Ｃ６、直鎖又は分岐鎖）アミノ）アルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル（Ｃ１～Ｃ１８、直鎖又は分岐鎖）（メタ）アクリルアミド、Ｎ－アクリロイルモルフォリン、ダイアセトン(メタ)アクリルアミド等が挙げられる。特に、高純度の工業品で入手容易の観点から、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－イソプロピルアクリルアミド、Ｎ－アクリロイルモルフォリン、ダイアセトンアクリルアミド、Ｎ－（ジメチルアミノ）プロピル（メタ）アクリルアミド、Ｎ－ヒドロキシエチルアクリルアミドがより好ましい。
これらの単官能モノマーは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The monofunctional (meth)acrylamide is, for example, N-alkyl (C1 to C18, linear or branched) (meth)acrylamide, N-alkoxy (C1 to C6, linear or branched) alkyl (C1 to C18, Straight-chain or branched) (meth)acrylamide, N-hydroxyalkyl (C1-C18, straight-chain or branched) (meth)acrylamide, N,N-dihydroxyalkyl (C1-C18, straight-chain or branched) (meth) ) Acrylamide, N-hydroxyalkyl (C1 to C18, straight chain or branched chain) -N-alkyl (C1 to C18, straight chain or branched chain) (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N- (Dialkyl (C1-C6, straight-chain or branched) amino)alkyl (C1-C18, straight-chain or branched) (meth)acrylamide, N,N-dialkyl (C1-C18, straight-chain or branched) (meth) ) acrylamide, N-acryloylmorpholine, diacetone (meth)acrylamide and the like. In particular, from the viewpoint of high purity industrial products and easy availability, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-acryloylmorpholine, diacetone acrylamide, N-(dimethylamino)propyl (Meth)acrylamide and N-hydroxyethylacrylamide are more preferred.
These monofunctional monomers may be used alone or in combination of two or more.
本発明の樹脂組成物に用いられるオリゴマーやポリマーは、アクリル、エステル、エーテル、ウレタン、アミド等の骨格を有する直鎖状及び／又は分岐状のオリゴマー、ポリマーが挙げられ、具体的には、重量平均分子量が１０，０００未満の、前記の多官能（メタ）アクリレート及び／又は多官能（メタ）アクリルアミドからなるオリゴマー、及び／又は、重量平均分子量が１０，０００以上である反応性基を有する或いは有しないポリマーが挙げられる。 The oligomers and polymers used in the resin composition of the present invention include linear and/or branched oligomers and polymers having skeletons such as acrylic, ester, ether, urethane, and amide. An oligomer consisting of the above polyfunctional (meth)acrylate and/or polyfunctional (meth)acrylamide having an average molecular weight of less than 10,000, and/or having a reactive group having a weight average molecular weight of 10,000 or more, or Examples include polymers that do not have
前記の重量平均分子量が１０，０００以上の反応性基を有するポリマー（硬化性樹脂）としては、例えば、二官能ポリウレタン（メタ）アクリレート、多官能ポリウレタン（メタ）アクリレート、二官能ポリエステル（メタ）アクリレート、多官能ウレタン（メタ）アクリレート、二官能ポリエステル（メタ）アクリレート、多官能ポリエステル（メタ）アクリレート、二官能ポリエーテル（メタ）アクリレート、多官能ポリエーテル（メタ）アクリレート、二官能ポリアミド（メタ）アクリレート、多官能ポリアミド（メタ）アクリレート、二官能ポリ（メタ）アクリル酸エステル（メタ）アクリレート、多官能ポリ（メタ）アクリル酸エステル（メタ）アクリレート、二官能ポリ（メタ）アクリル酸エステル（メタ）アクリルアミド、多官能ポリ（メタ）アクリル酸エステル（メタ）アクリルアミド、二官能ポリ（メタ）アクリルアミド（メタ）アクリレート、多官能ポリ（メタ）アクリルアミド（メタ）アクリレート、二官能ポリスチレン（メタ）アクリレート、多官能ポリスチレン（メタ）アクリレート、二官能ポリアクリロニトリル（メタ）アクリレート、多官能ポリアクリロニトリル（メタ）アクリレート、二官能エポキシアクリレート（ビスフェノールＡ型）、多官能エポキシアクリレート（ビスフェノールＡ型）等が挙げられる。また、これらの硬化性樹は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the polymer (curable resin) having a reactive group having a weight average molecular weight of 10,000 or more include bifunctional polyurethane (meth)acrylate, polyfunctional polyurethane (meth)acrylate, and bifunctional polyester (meth)acrylate. , polyfunctional urethane (meth)acrylate, bifunctional polyester (meth)acrylate, polyfunctional polyester (meth)acrylate, bifunctional polyether (meth)acrylate, polyfunctional polyether (meth)acrylate, bifunctional polyamide (meth)acrylate , polyfunctional polyamide (meth)acrylate, bifunctional poly(meth)acrylic ester (meth)acrylate, polyfunctional poly(meth)acrylic ester (meth)acrylate, bifunctional poly(meth)acrylic ester (meth)acrylamide , polyfunctional poly(meth)acrylic acid ester (meth)acrylamide, bifunctional poly(meth)acrylamide (meth)acrylate, polyfunctional poly(meth)acrylamide (meth)acrylate, bifunctional polystyrene (meth)acrylate, polyfunctional polystyrene Examples include (meth)acrylate, bifunctional polyacrylonitrile (meth)acrylate, polyfunctional polyacrylonitrile (meth)acrylate, bifunctional epoxy acrylate (bisphenol A type), and polyfunctional epoxy acrylate (bisphenol A type). Further, these hardening trees may be used alone or in combination of two or more.
前記の重量平均分子量が１０，０００以上の反応性基を有しないポリマー（熱可塑性樹脂）としては、例えば、（メタ）アクリル系樹脂、環状ポリオレフィン系樹脂、セルロース系樹脂、ポリエステル系樹脂、ポリスルホン酸系樹脂、ポリメチルメタクリレートやアクリロニトリルとスチレンの共重合物等のポリアクリル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリイミド樹脂が挙げられる。これらの熱可塑性樹脂は単独で使用してもよいし、また２種類以上併用してもよい。 Examples of the polymer (thermoplastic resin) having a weight average molecular weight of 10,000 or more and having no reactive groups include (meth)acrylic resin, cyclic polyolefin resin, cellulose resin, polyester resin, and polysulfonic acid. Examples include polyacrylic resins such as polymethyl methacrylate and copolymers of acrylonitrile and styrene, polycarbonate resins, polyamide resins, and polyimide resins. These thermoplastic resins may be used alone or in combination of two or more.
本発明の活性エネルギー線硬化性樹脂組成物は、基材に塗布または成型した後、活性エネルギー線照射により硬化し、粘着シート、３次元成形方法で得られる立体造形物、ハードコーティング膜、防曇膜、及び粘着剤、接着剤、封止材などを有する成型品を製造することができる。 The active energy ray-curable resin composition of the present invention is applied to a substrate or molded, and then cured by active energy ray irradiation to produce an adhesive sheet, a three-dimensional object obtained by a three-dimensional molding method, a hard coating film, and an antifogging film. It is possible to produce a molded article having a film, a pressure-sensitive adhesive, an adhesive, a sealant, etc.
前記の活性エネルギー線とは、活性種を発生する化合物（光重合開始剤）を分解して活性種を発生させることのできるエネルギー線と定義される。このような活性エネルギー線としては、可視光、電子線、紫外線、赤外線、Ｘ線、α線、β線、γ線等の光エネルギー線が挙げられる。中でも、活性エネルギー線の発生装置、硬化速度及び安全性のバランスから紫外線を使用することが好ましい。又、紫外線源としては、キセノンランプ、低圧水銀ランプ、高圧水銀ランプ、メタルハライドランプ、紫外線ＬＥＤランプ、マイクロ波方式エキシマランプ等が挙げられる。 The active energy ray is defined as an energy ray that can decompose a compound (photopolymerization initiator) that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. Among these, it is preferable to use ultraviolet rays in view of the balance between the active energy ray generator, curing speed, and safety. Examples of the ultraviolet light source include xenon lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, ultraviolet LED lamps, and microwave excimer lamps.
活性エネルギー線照射は、窒素ガスや炭酸ガス等の不活性ガス雰囲気又は酸素濃度を低下させた雰囲気下で行うことが好ましいが、本発明の樹脂組成物にはＮ－置換（メタ）アクリルアミドを有するため、硬化性が良く、通常の空気雰囲気でも、薄膜も厚膜も、十分に硬化させることができる。活性エネルギー線の照射温度は、好ましくは１０～２００℃であり、照射時間は、好ましくは１秒～６０分である。 The active energy ray irradiation is preferably performed in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or in an atmosphere with a reduced oxygen concentration, but the resin composition of the present invention contains N-substituted (meth)acrylamide. Therefore, it has good curability, and both thin and thick films can be sufficiently cured even in a normal air atmosphere. The irradiation temperature of the active energy ray is preferably 10 to 200°C, and the irradiation time is preferably 1 second to 60 minutes.
本発明の活性エネルギー線硬化性樹脂組成物を硬化させる際には、必要に応じて光重合開始剤を添加しておくことができるが、電子線を用いる場合には特に必要はない。光重合開始剤はアセトフェノン系、ベンゾイン系、ベンゾフェノン系、チオキサントン系等の通常のものから適宜選択すればよい。市販品としてはＢＡＳＦ社製、商品名Ｄａｒｏｃｕｒ１１１６、Ｄａｒｏｃｕｒ １１７３、Ｉｒｇａｃｕｒｅ １８４、Ｉｒｇａｃｕｒｅ ３６９、Ｉｒｇａｃｕｒｅ ５００、Ｉｒｇａｃｕｒｅ ６５１、Ｉｒｇａｃｕｒｅ ７５４、Ｉｒｇａｃｕｒｅ ８１９、Ｉｒｇａｃｕｒｅ ９０７、Ｉｒｇａｃｕｒｅ １３００、Ｉｒｇａｃｕｒｅ １８００、Ｉｒｇａｃｕｒｅ １８７０、Ｉｒｇａｃｕｒｅ ２９５９、Ｄａｒｏｃｕｒ ４２６５、Ｄａｒｏｃｕｒ ＴＰＯ、ＵＣＢ社製、商品名ユベクリルＰ３６等を用いることができる。これらの光重合開始剤は１種又は２種以上を組み合わせて用いることができる。 When curing the active energy ray-curable resin composition of the present invention, a photopolymerization initiator can be added if necessary, but it is not particularly necessary when using an electron beam. The photopolymerization initiator may be appropriately selected from common ones such as acetophenone, benzoin, benzophenone, and thioxanthone. Commercially available products are manufactured by BASF and have trade names Darocur 1116, Darocur 1173, Irgacure 184, Irgacure 369, Irgacure 500, Irgacure 651, Irgacure 754, Irgacure 819, Irgacure. e 907, Irgacure 1300, Irgacure 1800, Irgacure 1870, Irgacure 2959, Darocur 4265 , Darocur TPO, manufactured by UCB, trade name Jubecryl P36, etc. can be used. These photopolymerization initiators can be used alone or in combination of two or more.
これらの光重合開始剤の使用量は特に制限されていないが、一般に活性エネルギー線硬化性樹脂組成物に対して、０．１～１０重量％、中でも１～５重量％が添加されることが好ましい。０．１重量％未満だと十分な硬化性が得られず、１０重量％を越えると硬化物の強度など性能が低下してしまう可能性がある。 The amount of these photopolymerization initiators to be used is not particularly limited, but it is generally added in an amount of 0.1 to 10% by weight, especially 1 to 5% by weight, based on the active energy ray-curable resin composition. preferable. If it is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 10% by weight, the strength and other performance of the cured product may deteriorate.
本発明の樹脂組成物は、ｔ－ブチルシクロヘキシル（メタ）アクリレートにさらに熱重合開始剤や不飽和結合を有する化合物を添加し、重合性樹脂組成物として好適に用いることができる。ここでいう不飽和結合を有する化合物は、前述の各種単官能、多官能のモノマー、オリゴマーのことであり、また、物性調整しやすい熱可塑性の重合物を得るため、不飽和結合１個を有する単官能モノマーが好ましく、さらに得られた重合物を粘着剤、接着剤として用いる場合、凝集力を高めるために架橋点を導入できるモノマーが特に好ましい。前述の単官能モノマーは単独で加えてもよいし、２種類以上組み合わせることもできる。これらの配合量は、具体的な用途に応じて、任意に調整すれば良いが、樹脂組成物全量中では、合計で１０～９９重量％であることが好ましい。 The resin composition of the present invention can be suitably used as a polymerizable resin composition by further adding a thermal polymerization initiator and a compound having an unsaturated bond to t-butylcyclohexyl (meth)acrylate. The compound having an unsaturated bond here refers to the various monofunctional and polyfunctional monomers and oligomers mentioned above, and in order to obtain a thermoplastic polymer whose physical properties can be easily adjusted, Monofunctional monomers are preferred, and when the resulting polymer is used as a pressure-sensitive adhesive or adhesive, monomers that can introduce crosslinking points to increase cohesive force are particularly preferred. The monofunctional monomers mentioned above may be added alone or in combination of two or more. The amount of these compounds may be adjusted as desired depending on the specific use, but it is preferably 10 to 99% by weight in total based on the total amount of the resin composition.
前記の架橋点を導入できるモノマーとしては、例えば、水酸基含有（メタ）アクリル系モノマー、カルボキシル基含有（メタ）アクリル系モノマー、アミノ基含有（メタ）アクリル系モノマー、アセトアセチル基含有（メタ）アクリル系モノマー、イソシアネート基含有（メタ）アクリル系モノマー、グリシジル基含有（メタ）アクリル系モノマー、オキサゾリン基含有（メタ）アクリル系モノマー、カルボニル基含有（メタ）アクリル系モノマーなどが挙げられる。 Examples of monomers capable of introducing the above-mentioned crosslinking points include hydroxyl group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, amino group-containing (meth)acrylic monomers, and acetoacetyl group-containing (meth)acrylic monomers. monomers, isocyanate group-containing (meth)acrylic monomers, glycidyl group-containing (meth)acrylic monomers, oxazoline group-containing (meth)acrylic monomers, carbonyl group-containing (meth)acrylic monomers, and the like.
前記の水酸基含有（メタ）アクリル系モノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレート類、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－ヒドロキシプロピル（メタ）アクリルアミドなどのヒドロキシアルキル（メタ）アクリルアミド類、その他、２－アクリロイルオキシエチル２－ヒドロキシエチルフタル酸、Ｎ－メチロール（メタ）アクリルアミドなどの１級水酸基含有（メタ）アクリル系モノマー、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ３－フェノキシプロピル（メタ）アクリレート、３－クロロ２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ３－フェノキシプロピル（メタ）アクリレートなどの２級水酸基含有（メタ）アクリル系モノマー、２，２－ジメチル２－ヒドロキシエチル（メタ）アクリレートなどの３級水酸基含有（メタ）アクリル系モノマーを挙げることができる。中でもヒドロキシアルキル（Ｃ１～Ｃ６、直鎖又は分岐鎖）（メタ）アクリレート類が好ましく用いられる。 Examples of the hydroxyl group-containing (meth)acrylic monomers include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. , hydroxyalkyl (meth)acrylates such as 8-hydroxyoctyl (meth)acrylate, hydroxyalkyl (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, others, 2- Acryloyloxyethyl 2-hydroxyethylphthalate, primary hydroxyl group-containing (meth)acrylic monomers such as N-methylol (meth)acrylamide, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2- Secondary hydroxyl group-containing (meth)acrylic monomers such as hydroxy 3-phenoxypropyl (meth)acrylate, 3-chloro 2-hydroxypropyl (meth)acrylate, 2-hydroxy 3-phenoxypropyl (meth)acrylate, 2,2- Examples include tertiary hydroxyl group-containing (meth)acrylic monomers such as dimethyl 2-hydroxyethyl (meth)acrylate. Among them, hydroxyalkyl (C1 to C6, linear or branched) (meth)acrylates are preferably used.
前記のカルボキシル基含有（メタ）アクリル系モノマーとしては、例えば、（メタ）アクリル酸、クロトン酸などのモノカルボン酸、マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、イタコン酸などのジカルボン酸、などが挙げられ、中でも（メタ）アクリル酸が好ましく用いられる。 Examples of the carboxyl group-containing (meth)acrylic monomers include monocarboxylic acids such as (meth)acrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid; Among them, (meth)acrylic acid is preferably used.
前記アミノ基含有（メタ）アクリル系モノマーとしては、例えば、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジ－ｔ－ブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレートなどのアミノアルキル（メタ）アクリレート類、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミドなどのアミノアルキル（Ｃ１～Ｃ６、直鎖又は分岐鎖）（メタ）アクリルアミド類が挙げられる。 Examples of the amino group-containing (meth)acrylic monomer include N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-di-t-butylaminoethyl. (meth)acrylate, aminoalkyl (meth)acrylates such as N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N, Examples include aminoalkyl (C1 to C6, linear or branched) (meth)acrylamides such as N-dimethylaminopropyl (meth)acrylamide.
前記アセトアセチル基含有（メタ）アクリル系モノマーとしては、例えば、２－（アセトアセトキシ）エチル（メタ）アクリレートなどが挙げられる。 Examples of the acetoacetyl group-containing (meth)acrylic monomer include 2-(acetoacetoxy)ethyl (meth)acrylate.
前記イソシアネート基含有（メタ）アクリル系モノマーとしては、２－アクリロイルオキシエチルイソシアネート、２－メタクリロイルオキシエチルイソシアネートやそれらのアルキレンオキサイド付加物などが挙げられる。 Examples of the isocyanate group-containing (meth)acrylic monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.
前記グリシジル基含有（メタ）アクリル系モノマーとしては、（メタ）アクリル酸グリシジル、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、Ｎ－２－ヒドロキシエチル（メタ）アクリルアミドグリシジルエーテル、Ｎ－メチル－Ｎ－２－ヒドロキシエチル（メタ）アクリルアミドグリシジルエーテルなどが挙げられる。 The glycidyl group-containing (meth)acrylic monomers include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, N-2-hydroxyethyl (meth)acrylamide glycidyl ether, N-methyl-N- Examples include 2-hydroxyethyl (meth)acrylamide glycidyl ether.
前記オキサゾリン基含有（メタ）アクリル系モノマーとしては、２－ビニル－２－オキサゾリン、４－メチル－２－ビニル－２－オキサゾリン、５－メチル－２－ビニル－２－オキサゾリン、４－エチル－２－ビニル－２－オキサゾリン、５－エチル－２－ビニル－２－オキサゾリン、４，４－ジメチル－２－ビニル－２－オキサゾリン、４，４－ジエチル－２－ビニル－２－オキサゾリン、４，５－ジメチル－２－ビニル－２－オキサゾリン、４，５－ジエチル－２－ビニル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン、４－メチル－２－イソプロペニル－２－オキサゾリン、５－メチル－２－イソプロペニル－２－オキサゾリン、４－エチル－２－イソプロペニル－２－オキサゾリン、５－エチル－２－イソプロペニル－２－オキサゾリン、４，４－ジメチル－２－イソプロペニル－２－オキサゾリン、４，４－ジエチル－２－イソプロペニル－２－オキサゾリン、４，５－ジメチル－２－イソプロペニル－２－オキサゾリン、４，５－ジエチル－２－イソプロペニル－２－オキサゾリンなど等が挙げられる。また、高反応性を有する２－ビニル－２－オキサゾリン、５－メチル－２－ビニル－２－オキサゾリン、４，４－ジメチル－２－ビニル－２－オキサゾリンが好ましく、さらに２－ビニル－２－オキサゾリンが最も好ましい。これら官能基含有（メタ）アクリル系モノマーは、１種類に限らず、複数の種類を組み合わせて使用してもよい。 The oxazoline group-containing (meth)acrylic monomers include 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2 -vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5 -dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl -2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline , 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline, etc. . In addition, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, and 4,4-dimethyl-2-vinyl-2-oxazoline, which have high reactivity, are preferable, and 2-vinyl-2-oxazoline is more preferable. Oxazolines are most preferred. These functional group-containing (meth)acrylic monomers are not limited to one type, and a plurality of types may be used in combination.
前記カルボニル基含有（メタ）アクリル系モノマーとしては、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミドなどが挙げられる。 Examples of the carbonyl group-containing (meth)acrylic monomer include diacetone acrylamide and diacetone methacrylamide.
熱重合性樹脂組成物の熱重合は、ラジカル重合開始剤存在下で公知の方法によって行うことができる。例えば、乳化重合、溶液重合、懸濁重合、塊状重合等の方法を用いられる。溶液重合は有機溶媒中の溶液重合法を採用する場合、重合して得られる重合物を溶解する溶媒であれば特に制限は無く、例えば、重合溶媒としては、ベンゼン、トルエン、エチルベンゼン、キシレンなどの芳香族炭化水素類、ヘキサン、ヘプタン、オクタン、デカン、シクロヘキサンなどの脂肪族炭化水素類、酢酸エチル、酢酸ブチル、酢酸２－ヒドロキシエチルなどのエステル類、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコールなどの脂肪族アルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、アセトニトリル、Ｎ，Ｎ-ジメチルホルムアミドなどが挙げられる。これらの有機溶媒はそれぞれ単独で、または２種以上を混合して用いることができる。特に、成形品を形成する際に除去しやすい点から低沸点の酢酸エチル、メチルエチルケトン、アセトンなどの使用が好ましい。 Thermal polymerization of the thermally polymerizable resin composition can be carried out by a known method in the presence of a radical polymerization initiator. For example, methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be used. When a solution polymerization method in an organic solvent is adopted, there is no particular restriction as long as the solvent dissolves the polymer obtained by polymerization. For example, the polymerization solvent may be benzene, toluene, ethylbenzene, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane, esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc. aliphatic alcohols, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, acetonitrile, and N,N-dimethylformamide. These organic solvents can be used alone or in combination of two or more. In particular, it is preferable to use ethyl acetate, methyl ethyl ketone, acetone, etc., which have a low boiling point, since they can be easily removed when forming a molded article.
また、熱ラジカル重合開始剤としては、アゾビスイソブチロニトリル、アゾビスバレロニトリル等のアゾ化合物系触媒や、ベンゾイルパーオキシド、過酸化水素等の過酸化物系触媒、過硫酸アンモニウム、過硫酸ナトリウムなどの過硫酸塩系触媒等を用いることができる。重合開始剤の使用量は、通常重合性単量体成分総量に対して０．００１～１０重量％程度である。さらに、連鎖移動剤による分子量の調整など通常のラジカル重合技術が適用される。 In addition, thermal radical polymerization initiators include azo compound catalysts such as azobisisobutyronitrile and azobisvaleronitrile, peroxide catalysts such as benzoyl peroxide and hydrogen peroxide, ammonium persulfate, and sodium persulfate. Persulfate-based catalysts such as the following can be used. The amount of the polymerization initiator used is usually about 0.001 to 10% by weight based on the total amount of polymerizable monomer components. Furthermore, ordinary radical polymerization techniques such as molecular weight adjustment using a chain transfer agent are applied.
本発明重合物の分子量は重量平均で１千～３００万であり、また５千～２５０万であることが好ましく、さらに１万～２００万であることが特に好ましい。重量平均分子量が１千～３００万の範囲内であれば、溶媒で溶解した場合の溶液粘度が高過ぎなく、低過ぎないため、好適に取り扱うことができ、塗膜やシート等の加工精度が高い。このような重合物が３０％になるように酢酸エチルで希釈した場合、通常、溶液粘度は１０～１０万Ｐａ・ｓ／２５℃であり、より好ましくは５００～１万ｍＰａ・ｓ／２５℃、特に好ましくは２０００～５０００ｍＰａ・ｓ／２５℃である。なお、粘度の測定は、ＪＩＳ Ｋ５６００－２－３（１９９９）のコーンプレート粘度計法に準じて行うことができる。 The weight average molecular weight of the polymer of the present invention is 1,000 to 3,000,000, preferably 5,000 to 2,500,000, and particularly preferably 10,000 to 2,000,000. If the weight average molecular weight is within the range of 1,000 to 3,000,000, the viscosity of the solution when dissolved in a solvent is neither too high nor too low, so it can be handled conveniently and the processing accuracy of coating films and sheets can be improved. expensive. When such a polymer is diluted with ethyl acetate to 30%, the solution viscosity is usually 100 to 100,000 Pa·s/25°C, more preferably 500 to 10,000 mPa·s/25°C. , particularly preferably 2000 to 5000 mPa·s/25°C. Note that the viscosity can be measured according to the cone-plate viscometer method of JIS K5600-2-3 (1999).
本発明の重合物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上を有するｔ－ブチルシクロヘキシル（メタ）アクリレートを構成成分として含有するため、十分な疎水性や親油性、各種基材に対する濡れ性、密着性を有する。このため、そのまま用いることができるが、さらに架橋剤により架橋されることで、より耐熱性、耐久性に優れたものを得ることができる。また、架橋する方法としては、（１）架橋剤を用いて架橋する方法、（２）不飽和基含有化合物及び重合開始剤を含有させ、活性エネルギー線及び／または熱による架橋する方法などが挙げられる。これらの架橋方法は一方を用いてもよいし、両方を併用してもよい。 Since the polymer of the present invention contains t-butylcyclohexyl (meth)acrylate having a p-trans isomer content of 70% or more as a constituent component, it has sufficient hydrophobicity and lipophilicity, and is compatible with various base materials. Has wettability and adhesion. Therefore, it can be used as is, but by further crosslinking with a crosslinking agent, it is possible to obtain a product with even better heat resistance and durability. Examples of crosslinking methods include (1) a method of crosslinking using a crosslinking agent, (2) a method of containing an unsaturated group-containing compound and a polymerization initiator, and crosslinking using active energy rays and/or heat. It will be done. One of these crosslinking methods may be used, or both may be used in combination.
前記（１）架橋剤を用いて架橋する方法としては、イソシアネート化合物、エポキシ化合物、アジリジン化合物、カルボキシル基化合物など、前記（メタ）アクリル系樹脂に含まれる官能基と反応し得る官能基を有する化合物を添加し反応させる方法が挙げられる。 (1) The method of crosslinking using a crosslinking agent includes a compound having a functional group that can react with a functional group contained in the (meth)acrylic resin, such as an isocyanate compound, an epoxy compound, an aziridine compound, or a carboxyl group compound. A method of adding and reacting is mentioned.
このうち、イソシアネート化合物としては、トリレンジイソシアネート、キシレンジイソシアネートなどの芳香族イソシアネート、イソホロンジイソシアネートなどの脂環族イソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族イソシアネートなどが挙げられる。より具体的には、イソシアネート化合物としては、例えば、ブチレンジイソシアネート、ヘキサメチレンジイソシアネートなどの低級脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネートなどの脂環族イソシアネート類、２，４－トリレンジイソシアネート、４，４'－ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ジイソシアネート類、トリメチロールプロパン／トリレンジイソシアネート３量体付加物（日本ポリウレタン工業社製、商品名：コロネートＬ）、トリメチロールプロパン／ヘキサメチレンジイソシアネート３量体付加物（日本ポリウレタン工業社製、商品名：コロネートＨＬ）、ヘキサメチレンジイソシアネートのイソシアヌレート体（日本ポリウレタン工業社製、商品名：コロネートＨＸ）などのイソシアネート付加物などが挙げられる。これらのイソシアネート化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 Among these, examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, as the isocyanate compound, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4 - Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Kogyo Co., Ltd., product name: Coronate L), Isocyanate adducts such as methylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Kogyo Co., Ltd., product name: Coronate HL), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Kogyo Co., Ltd., product name: Coronate HX) Examples include. These isocyanate compounds may be used alone or in combination of two or more.
エポキシ化合物としては、例えば、ポリエチレングリコールジグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、グリセリンジグリシジルエーテル、ジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラグリシジル－ｍ－キシレンジアミン（三菱瓦斯化学社製、商品名：ＴＥＴＲＡＤ－Ｘ）や１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製、商品名：ＴＥＴＲＡＤ－Ｃ）などが挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of the epoxy compound include polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N,N,N',N'-tetra Glycidyl-m-xylene diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-X) and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-C) ), etc. These compounds may be used alone or in combination of two or more.
アジリジン化合物としては、例えば、市販品としての商品名：ＨＤＵ、商品名：ＴＡＺＭ、商品名：ＴＡＺＯ（以上、相互薬工社製）などが挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 Examples of the aziridine compound include commercially available products such as HDU, TAZM, and TAZO (manufactured by Sogo Yakuko Co., Ltd.). These compounds may be used alone or in combination of two or more.
カルボキシル基化合物として、Ｌ－乳酸、Ｄ－乳酸、イソフタル酸、フタル酸、１，４－ナフタレンジカルボキシル基、２，６－ナフタレンジカルボキシル基、ジフェニルジカルボキシル基、ジフェノキシエタンジカルボキシル基、ジフェニルエーテルジカルボキシル基、ジフェニルスルホンジカルボキシル基などの芳香族ジカルボキシル基、１，３－シクロペンタンジカルボキシル基、１，３－シクロヘキサンジカルボキシル基、１，４－シクロヘキサンジカルボキシル基などの脂環式ジカルボキシル基、マロン酸、ジメチルマロン酸、コハク酸、３，３－ジエチルコハク酸、グルタル酸、２，２－ジメチルグルタル酸、アジピン酸、２－メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、アゼライン酸、セバシン酸、スベリン酸などの脂肪族ジカルボン酸、グリコール酸、３－ヒドロキシ酪酸、４－ヒドロキシ吉草酸、ヒドロキシプロピオン酸、ヒドロキシカプロン酸、ヒドロキシ安息香酸などのヒドロキシカルボキシル基、及びそれらのエステル形成性誘導体などから誘導されるジカルボキシル基を有する化合物が挙げられる。これらの化合物は単独で使用してもよく、また２種以上を混合して使用してもよい。 As carboxyl group compounds, L-lactic acid, D-lactic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxyl group, 2,6-naphthalene dicarboxyl group, diphenyldicarboxyl group, diphenoxyethanedicarboxyl group, diphenyl ether Aromatic dicarboxyl groups such as dicarboxyl group and diphenylsulfonedicarboxyl group; alicyclic dicarboxyl groups such as 1,3-cyclopentanedicarboxyl group, 1,3-cyclohexanedicarboxyl group, and 1,4-cyclohexanedicarboxyl group; Carboxyl group, malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid , aliphatic dicarboxylic acids such as sebacic acid and suberic acid, hydroxycarboxyl groups such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, and hydroxybenzoic acid, and their ester-forming properties. Examples include compounds having a dicarboxyl group derived from derivatives. These compounds may be used alone or in combination of two or more.
これらの架橋剤の使用量は、架橋すべき前記重合物中に含まれる官能基の量や分子量とのバランスにより、さらには、用途目的により適宜選択できるが、通常は、重合物１００重量％に対して、０．１～１５重量％含有されていることが好ましく、０．５～１０重量％含有されていることがより好ましい。含有量が０．１重量％よりも少ない場合、架橋剤による架橋形成が不十分となり、粘着剤等の成形品の凝集力が不足して十分な耐熱性が得られない場合があり、また、糊残りの原因となる傾向がある。一方、含有量が１５重量％を超える場合、架橋後の樹脂組成物の凝集力が大きく、柔軟性及び弾力が低下し、被着体へのなじみ性（濡れ性）が不十分となる傾向がある。 The amount of these crosslinking agents to be used can be selected depending on the amount of functional groups contained in the polymer to be crosslinked and the balance with the molecular weight, and also depending on the purpose of use, but usually it is On the other hand, the content is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. If the content is less than 0.1% by weight, the formation of crosslinks by the crosslinking agent will be insufficient, and the cohesive force of molded products such as adhesives may be insufficient and sufficient heat resistance may not be obtained. It tends to cause adhesive residue. On the other hand, if the content exceeds 15% by weight, the cohesive force of the crosslinked resin composition will be large, the flexibility and elasticity will decrease, and the conformability (wettability) to the adherend will tend to be insufficient. be.
さらに、前記架橋剤とともに、架橋を促進するために酸触媒、例えば、パラトルエンスルホン酸、リン酸、塩酸、塩化アンモニウムなどの架橋促進剤を併用することも可能であり、前記架橋促進剤の添加量は架橋剤に対して１０～５０重量％であることが好ましい。 Furthermore, in addition to the crosslinking agent, it is also possible to use an acid catalyst such as para-toluenesulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride, and the like in order to promote crosslinking, and the addition of the crosslinking promoter The amount is preferably from 10 to 50% by weight, based on the crosslinking agent.
前記（２）不飽和基含有化合物及び重合開始剤を含有させ、活性エネルギー線及び／または熱により架橋する方法としては、架橋剤として活性エネルギー線及び／または熱反応性不飽和結合を２個以上有する多官能モノマーと重合開始剤を添加し、活性エネルギー線及び／または熱で架橋させる方法が挙げられる。 (2) In the method of containing an unsaturated group-containing compound and a polymerization initiator and crosslinking with active energy rays and/or heat, two or more active energy rays and/or heat-reactive unsaturated bonds are used as the crosslinking agent. Examples include a method in which a polyfunctional monomer and a polymerization initiator are added and crosslinked with active energy rays and/or heat.
前記活性エネルギー線及び／または熱反応性不飽和結合を２個以上有する多官能モノマーとしてはビニル基、アクリロイル基、メタクリロイル基、ビニルベンジル基のような活性エネルギー線及び／または熱の照射で架橋処理（硬化）し得る１種または２種以上の活性エネルギー線及び／または熱反応性不飽和結合を２個以上有する多官能モノマー成分が用いられる。なお一般的には活性エネルギー線及び／または熱反応性不飽和結合が１０個以下のものが好適に用いられる。多官能モノマーは２種以上を併用することも可能である。 The polyfunctional monomer having two or more active energy ray and/or heat-reactive unsaturated bonds is a vinyl group, acryloyl group, methacryloyl group, or vinylbenzyl group, which can be crosslinked by active energy ray and/or heat irradiation. A polyfunctional monomer component having one or more types of active energy rays and/or two or more heat-reactive unsaturated bonds that can be cured is used. In general, those having 10 or less unsaturated bonds that are reactive to active energy rays and/or heat are preferably used. It is also possible to use two or more types of polyfunctional monomers in combination.
前記多官能モノマーは、２官能モノマー、３官能以上のモノマーを用いることができ、具体例としては、２官能モノマーとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールエチレンオキサイド変性ジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェートジエステルなどのモノマーが挙げられる。 As the polyfunctional monomer, a bifunctional monomer, a trifunctional or higher functional monomer can be used, and specific examples of the bifunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetrafunctional monomer. Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, Neo Pentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol Ethylene oxide modified di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester Examples include monomers such as di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.
前記３官能以上のモノマーとしては、例えば、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（メタ）アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールペンタ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールテトラ（メタ）アクリレート、コハク酸変性ペンタエリスリトールトリ（メタ）アクリレートなどが挙げられる。 Examples of the trifunctional or higher functional monomer include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified tri( meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, Examples include succinic acid-modified pentaerythritol tri(meth)acrylate.
前記多官能モノマーの使用量は、架橋すべき重合物に対して０．０５～５０重量％で配合するのが好ましく、柔軟性、接着性（密着性）の点から、より好ましくは、０．１～３０重量％である。含有量が０．０５重量％よりも少ない場合、架橋剤による架橋形成が不十分となり、粘着剤や接着剤に用いた場合の凝集力が不足し、十分な耐熱性が得られない場合がある。一方、含有量が５０重量％を超える場合、例えば、ポリマーの凝集力が高くなりすぎ、柔軟性及び粘着力が低下し、被着体への濡れが不十分となって、剥離の原因となる傾向がある。 The amount of the polyfunctional monomer used is preferably 0.05 to 50% by weight based on the polymer to be crosslinked, and more preferably 0.05 to 50% by weight from the viewpoint of flexibility and adhesiveness. It is 1 to 30% by weight. If the content is less than 0.05% by weight, crosslinking by the crosslinking agent will be insufficient, resulting in insufficient cohesive force when used in pressure-sensitive adhesives or adhesives, and sufficient heat resistance may not be obtained. . On the other hand, if the content exceeds 50% by weight, for example, the cohesive force of the polymer becomes too high, the flexibility and adhesive strength decrease, and the wetting of the adherend becomes insufficient, causing peeling. Tend.
本発明の樹脂組成物及びそれから作製される成形品の特性を阻害しない範囲で、顔料、染料、界面活性剤、ブロッキング防止剤、レベリング剤、分散剤、消泡剤、酸化防止剤、紫外線増感剤、防腐剤等の他の任意成分を併用してもよい。また、本発明の樹脂組成物硬化（重合や架橋など）システムとして、ラジカル系単独でも、ラジカルとカチオンの混合系でも、ラジカルとアニオンの混合系でも、さらにＵＶ、ＥＢなど活性エネルギー線硬化と熱硬化の混合系でも、好適に使用することができる。 Pigments, dyes, surfactants, antiblocking agents, leveling agents, dispersants, antifoaming agents, antioxidants, ultraviolet sensitization, to the extent that they do not impair the properties of the resin composition of the present invention and molded articles made from it. Other optional ingredients such as agents and preservatives may be used in combination. In addition, the resin composition curing (polymerization, crosslinking, etc.) system of the present invention may be a radical system alone, a mixed system of radicals and cations, or a mixed system of radicals and anions. A mixed curing system can also be suitably used.
本発明の樹脂組成物を紙、布、不織布、ガラス、ポリエチレンテレフタレート、ジアセテートセルロース、トリアセテートセルロース、アクリル系ポリマー、ポリ塩化ビニル、セロハン、セルロイド、ポリカーボネート、ポリイミド等のプラスチック及び金属等の基材の表面や間に塗布、硬化させることにより、高性能のコーティング層やインク層、粘着剤層、封止材層又は接着剤層を得ることができる。特に、本発明の活性エネルギー線硬化性樹脂組成物は高透明性のウレタンオリゴマーを有するため、光学用粘着剤、光学用接着剤や封止材、光学用フィルムのコート材等光学用樹脂組成物として好適に用いることができる。又、これらの樹脂組成物を基材上に塗布する方法としては、スピンコート法、スプレーコート法、ディッピング法、グラビアロール法、ナイフコート法、リバースロール法、スクリーン印刷法、バーコーター法等通常の塗膜形成法が用いられることができる。又、基材間に塗布する方法としては、ラミネート法、ロールツーロール法等が挙げられる。 The resin composition of the present invention can be used for base materials such as paper, cloth, nonwoven fabric, glass, polyethylene terephthalate, diacetate cellulose, triacetate cellulose, acrylic polymers, polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide, and other plastics and metals. A high-performance coating layer, ink layer, pressure-sensitive adhesive layer, sealant layer, or adhesive layer can be obtained by applying and curing the coating layer on or between surfaces. In particular, since the active energy ray-curable resin composition of the present invention has a highly transparent urethane oligomer, it can be used as an optical adhesive, an optical adhesive, a sealing material, a coating material for an optical film, etc. It can be suitably used as In addition, methods for applying these resin compositions onto the base material include spin coating, spray coating, dipping, gravure roll, knife coating, reverse roll, screen printing, and bar coater methods. A coating film formation method can be used. Further, examples of the method for applying between base materials include a laminating method and a roll-to-roll method.
本発明の重合性樹脂組成物やこれを硬化した重合物を特に光学用材料、例えば、光学用粘着剤、コーティング材、接着剤、有機ＥＬ用封止材等に用いる場合は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるｔ－ブチルシクロヘキシル（メタ）アクリレート中のｍ－ｔｒａｎｓ型異性体の含有量は１．０％以下とすることが好ましい。ｍ－ｔｒａｎｓ型異性体の含有量を１．０％以下とすることで、ｍ－ｔｒａｎｓ型異性体由来の不純物（原料、副生成物など）の含有量も低減されるため、本発明の重合物が耐黄変性の向上などの光学特性に優れたものとなり、特に好適である。 When the polymerizable resin composition of the present invention or a cured polymer thereof is used for optical materials, such as optical adhesives, coating materials, adhesives, organic EL encapsulants, etc., p-trans type The content of m-trans type isomer in t-butylcyclohexyl (meth)acrylate having an isomer content of 70% or more is preferably 1.0% or less. By controlling the content of the m-trans isomer to 1.0% or less, the content of impurities (raw materials, by-products, etc.) derived from the m-trans isomer is also reduced. This is particularly suitable since the product has excellent optical properties such as improved yellowing resistance.
本発明の重合性樹脂組成物やこれを硬化した重合物を、特にポリオレフィン用コーティングやインクジェット用インク、電子材料用接着剤として用いる場合は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるｔ－ブチルシクロヘキシル（メタ）アクリレートのｐ－ｔｒａｎｓ型異性体とｐ－ｃｉｓ型異性体の含有量のモル比は３．０以上であることが特に好ましい。モル比を３．０以上とすることで嵩高いｔ－ブチルシクロヘキシル（メタ）アクリレートをより密に配列することができ、基材への濡れ性や密着性、接着性等の界面物性が優れたものとなるため、特に好適である。 When the polymerizable resin composition of the present invention or a cured polymer thereof is used particularly as a polyolefin coating, inkjet ink, or adhesive for electronic materials, the p-trans isomer content should be 70% or more. It is particularly preferable that the molar ratio of the content of the p-trans type isomer and the p-cis type isomer of a certain t-butylcyclohexyl (meth)acrylate is 3.0 or more. By setting the molar ratio to 3.0 or more, bulky t-butylcyclohexyl (meth)acrylate can be arranged more densely, resulting in excellent interfacial properties such as wettability, adhesion, and adhesion to the substrate. This is particularly suitable because the
以下に実施例と比較例を挙げて本発明を更に詳しく説明するが、本発明は以下の実施例に限定されるものではない。実施例及び比較例に記載する各構成成分の略称は以下の通りである。
ＴＢＣＨＡ：ｔ－ブチルシクロヘキシルアクリレート
ＢＡ：ブチルアクリレート
２－ＥＨＡ：２－エチルヘキシルアクリレート
ＨＥＡ：２－ヒドロキシエチルアクリレート
ＰＥＡ：フェノキシエチルアクリレート
ＳＴＡ：ステアリルアクリレート
ＮＶＣ：Ｎ－ビニルカプロラクタム
Ｍ－１０２：テトラエチレングリコールモノフェニルエーテルアクリレート（東亜合成株式会社製アロニックスＭ－１０２）
「ＤＭＡＡ」：Ｎ，Ｎ－ジメチルアクリルアミド（ＫＪケミカルズ（株）製、Ｋｏｈｓｈｙｌｍｅｒ(登録商標) ＤＭＡＡ（登録商標））
「ＤＥＡＡ」：Ｎ，Ｎ－ジエチルアクリルアミド（ＫＪケミカルズ（株）製、Ｋｏｈｓｈｙｌｍｅｒ(登録商標) ＤＥＡＡ（登録商標））
「ＨＥＡＡ」：Ｎ－ヒドロキシエチルアクリルアミド（ＫＪケミカルズ（株）製、Ｋｏｈｓｈｙｌｍｅｒ(登録商標) ＨＥＡＡ（登録商標））
「ＡＣＭＯ」：アクリロイルモルフォリン（ＫＪケミカルズ（株）製、Ｋｏｈｓｈｙｌｍｅｒ(登録商標) ＨＥＡＡ（登録商標））
「ＮＩＰＡＭ」：Ｎ－イソプロピルアクリルアミド（ＫＪケミカルズ（株）製、Ｋｏｈｓｈｙｌｍｅｒ(登録商標) ＮＩＰＡＭ（登録商標））
ＤＡＡＭ：ダイアセトンアクリルアミド（ＫＪケミカルズ（株）製、Ｋｏｈｓｈｙｌｍｅｒ(登録商標)）
ＧＡ：グリシジルアクリレート
ＡＡｃ：アクリル酸
ＵＶ－３０００Ｂ：ウレタンアクリレート（日本合成化学工業（株）製）
ＵＶ－６６４０Ｂ：ウレタンアクリレート（日本合成化学工業（株）製）
ＨＤＤＡ：１，６－ヘキサンジオールジアクリレート
ＴＭＰＴＡ：トリメチロールプロパントリアクリレート
Ｄａｒｏｃｕｒ１１７３：光重合開始剤（ＢＡＳＦジャパン（株）製）
Ｉｒｇａｃｕｒｅ１８４：光重合開始剤（ＢＡＳＦジャパン（株）製）
ＩｒｇａｃｕｒｅＴＰＯ：光重合開始剤（ＢＡＳＦジャパン（株）製）
ＡＩＢＮ：アゾビスイソブチロニトリル、熱重合開始剤
ＰＥ：ポリエチレン
ＰＰ：ポリプロピレン
ＰＥＴ：ポリエチレンテレフタレート（未処理品）
ＰＣ：ポリカーボネート
ＰＭＭＡ：ポリメチルメタクリレート
ＡＢＳ：アクリロニトリル－ブタジエン－スチレン樹脂
ＣＯＰ：シクロオレフィンポリマー
ＴＡＣ：トリアセチルセルロース
ＰＶＣ：ポリ塩化ビニル
ＬＣＰ：液晶ポリマー
ＰＥＥＫ：ポリエーテルエーテルケトン
ＳＰＣＣ：冷間圧延鋼板
ＳＵＳ：３０４ステンレス鋼
EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The abbreviations of each component described in Examples and Comparative Examples are as follows.
TBCHA: t-butylcyclohexyl acrylate BA: Butyl acrylate 2-EHA: 2-ethylhexyl acrylate HEA: 2-hydroxyethyl acrylate PEA: Phenoxyethyl acrylate STA: Stearyl acrylate NVC: N-vinylcaprolactam M-102: Tetraethylene glycol monophenyl Ether acrylate (Aronix M-102 manufactured by Toagosei Co., Ltd.)
"DMAA": N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd., Kohsylmer (registered trademark) DMAA (registered trademark))
"DEAA": N,N-diethylacrylamide (manufactured by KJ Chemicals Co., Ltd., Kohsylmer (registered trademark) DEAA (registered trademark))
"HEAA": N-hydroxyethylacrylamide (manufactured by KJ Chemicals Co., Ltd., Kohsylmer (registered trademark) HEAA (registered trademark))
"ACMO": Acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd., Kohsylmer (registered trademark) HEAA (registered trademark))
"NIPAM": N-isopropylacrylamide (manufactured by KJ Chemicals Co., Ltd., Kohsylmer (registered trademark) NIPAM (registered trademark))
DAAM: diacetone acrylamide (manufactured by KJ Chemicals Co., Ltd., Kohsylmer (registered trademark))
GA: Glycidyl acrylate AAc: Acrylic acid UV-3000B: Urethane acrylate (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.)
UV-6640B: Urethane acrylate (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.)
HDDA: 1,6-hexanediol diacrylate TMPTA: Trimethylolpropane triacrylate Darocur 1173: Photopolymerization initiator (manufactured by BASF Japan Co., Ltd.)
Irgacure 184: Photopolymerization initiator (manufactured by BASF Japan Co., Ltd.)
IrgacureTPO: Photopolymerization initiator (manufactured by BASF Japan Ltd.)
AIBN: Azobisisobutyronitrile, thermal polymerization initiator PE: Polyethylene PP: Polypropylene PET: Polyethylene terephthalate (untreated product)
PC: Polycarbonate PMMA: Polymethyl methacrylate ABS: Acrylonitrile-butadiene-styrene resin COP: Cycloolefin polymer TAC: Triacetyl cellulose PVC: Polyvinyl chloride LCP: Liquid crystal polymer PEEK: Polyether ether ketone SPCC: Cold rolled steel plate SUS: 304 stainless steel
実施例Ａ－１、２と比較例Ａ－３、４
ＴＢＣＨＡのｐ－ｔｒａｎｓ型異性体含有量と色相、臭気、皮膚刺激性、濡れ性、密着性との関係を表１に示す。各種評価は以下の測定方法により行った。
（色相）
透過色専用測定器（日本電色工業（株）社製 ＴＺ６０００）により、ＴＢＣＨＡモノマー原液の状態で、ＡＰＨＡを測定した。ＡＰＨＡは、数値が高いほど色が濃いことを示す。
（臭気）
ＴＢＣＨＡモノマー原液を用いて、作業員５名により臭いを嗅いで官能的に評価し、平均値を取った。
（皮膚刺激性）
ＧＬＰ適合設備にて、ＯＥＣＤガイドラインＮｏ．４０４に準じて評価した。
（濡れ性の評価）
ＴＢＣＨＡ １００重量部に光重合開始剤Ｄａｒｏｃｕｒ１１７３を５重量部加え、混合溶解させ、紫外線硬化可能な評価液を得た。得られた評価液を表１記載の各種基材にバーコーター（ＲＤＳ１２）で塗工し、塗工液のハジキ具合を目視にて観察した。
〇：ハジキ無し
×：ハジキあり
（密着性の評価）
紫外線照射装置（アイグラフィックス（株）社製 インバーター式コンベア装置ＥＣＳ－４０１１ＧＸ、メタルハライドランプＭ０４－Ｌ４１、７００ｍＷ／ｃｍ２、３０００ｍＪ／ｃｍ２）を使用し、上記の各種基材に塗工した評価液を完全に硬化させた。金属基材も特に脱脂等を行わずにそのまま塗工し、硬化させた。得られた硬化膜を碁盤目試験法により１ｍｍ角のます目を１００個作成し、セロハンテープを貼り付け、一気に剥がした時に基材側に硬化膜が残ったマス目の数を数えて評価した。残ったマス目数が多いほど密着性が高いことを示す。
◎：残ったマス目数１００
〇：残ったマス目数９０以上１００未満
△：残ったマス目数５０以上９０未満
×：残ったマス目数５０未満
Examples A-1, 2 and Comparative Examples A-3, 4
Table 1 shows the relationship between the p-trans isomer content of TBCHA and hue, odor, skin irritation, wettability, and adhesion. Various evaluations were performed using the following measurement methods.
(hue)
APHA was measured in the state of the TBCHA monomer stock solution using a transmitting color measuring instrument (TZ6000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). APHA indicates that the higher the value, the darker the color.
(Odor)
Using the TBCHA monomer stock solution, five workers sniffed and sensory-evaluated the odor, and the average value was taken.
(Skin irritation)
GLP compliant equipment, OECD guideline No. Evaluation was made according to 404.
(Evaluation of wettability)
5 parts by weight of a photopolymerization initiator Darocur 1173 was added to 100 parts by weight of TBCHA and mixed and dissolved to obtain an evaluation liquid capable of being cured by ultraviolet rays. The obtained evaluation liquids were applied to various substrates listed in Table 1 using a bar coater (RDS12), and the degree of repellency of the coating liquids was visually observed.
〇: No repellency ×: Repellency (evaluation of adhesion)
Evaluation using ultraviolet irradiation equipment (I-Graphics Co., Ltd. inverter type conveyor device ECS-4011GX, metal halide lamp M04-L41, 700mW/cm 2 , 3000mJ/cm 2 ) on the various substrates mentioned above. The liquid was completely cured. The metal base material was also coated as it was without any particular degreasing and was cured. The resulting cured film was evaluated by creating 100 squares of 1 mm square using the grid test method, pasting cellophane tape, and counting the number of squares where the cured film remained on the base material side when it was peeled off at once. . The larger the number of remaining squares, the higher the adhesion.
◎: Number of squares remaining 100
〇: Number of remaining squares 90 or more and less than 100 △: Number of remaining squares 50 or more and less than 90 ×: Number of remaining squares less than 50
表１に示すとおり、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満である場合、色相や臭気、皮膚刺激性が強く、多くの基材に対する濡れ性や密着性が不十分であった（比較例Ａ－５、Ａ－６）のに対し、本発明に用いられるＴＢＣＨＡは、７０％以上のｐ－ｔｒａｎｓ型異性体を含有するため、ＴＢＣＨＡ及びそれを含有する重合性樹脂組成物の色相、臭気、皮膚刺激性がともに低く、また各種汎用基材に対する濡れ性と密着性がともに良好であった（実施例Ａ－１～４）。特に密着性については、難密着基材であるＰＥ、ポリイミド、ＰＥＥＫに対して、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上有するＴＢＣＨＡも十分に満足できる密着性を示さなかったが、ｐ－ｔｒａｎｓ型異性体の含有量が９１％以上の実施例Ａ－２、Ａ－４において改善されることが認められた。従って、ｐ－ｔｒａｎｓ型異性体の含有量を７０％以上有するＴＢＣＨＡを含有する本発明の樹脂組成物は、各種汎用基材に対する濡れ性と密着性に優れるため、粘着剤、接着剤、コーティング剤、インク等に好適に用いることができる。特に、コーティング剤に関してはＳＵＳやＳＰＣＣなどの金属片や木材に対しても優れた密着性を示したことから、車両用コーティング剤、建築物用コーティング剤としても好適に用いることができる。 As shown in Table 1, when the content of the p-trans isomer was less than 70%, the color, odor, and skin irritation were strong, and the wettability and adhesion to many substrates were insufficient ( In contrast to Comparative Examples A-5 and A-6), TBCHA used in the present invention contains 70% or more of the p-trans isomer, so the hue of TBCHA and the polymeric resin composition containing it is , odor and skin irritation were low, and both wettability and adhesion to various general-purpose substrates were good (Examples A-1 to A-4). In particular, with regard to adhesion, TBCHA, which has a p-trans isomer content of 70% or more, did not show sufficiently satisfactory adhesion to PE, polyimide, and PEEK, which are difficult to adhere to base materials. It was observed that Examples A-2 and A-4, in which the content of the -trans isomer was 91% or more, were improved. Therefore, the resin composition of the present invention containing TBCHA having a p-trans isomer content of 70% or more has excellent wettability and adhesion to various general-purpose substrates, so it can be used as adhesives, adhesives, and coatings. , ink, etc. In particular, since the coating agent showed excellent adhesion to metal pieces such as SUS and SPCC and wood, it can also be suitably used as a coating agent for vehicles and a coating agent for buildings.
実施例Ａ－７～１０と比較例Ａ－１１～１３
紫外線硬化性モノマーとしてＡＣＭＯを用いて、ｐ－ｔｒａｎｓ型異性体含有量の異なるＴＢＣＨＡと混合し、実施例Ａ－１と同様に１００重量部の混合液に対して開始剤を５重量部加え、各種基材に対する濡れ性、密着性の評価を行った。各評価の結果を表２に示す。
Examples A-7 to 10 and Comparative Examples A-11 to 13
Using ACMO as an ultraviolet curable monomer, mix it with TBCHA having a different p-trans isomer content, add 5 parts by weight of an initiator to 100 parts by weight of the mixed solution as in Example A-1, Wettability and adhesion to various substrates were evaluated. Table 2 shows the results of each evaluation.
表２に示すとおり、ＡＣＭＯ単独の評価である比較例Ａ－１１では、多くの基材に濡れ性や密着性が低いのに対して、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを添加した実施例Ａ－７～１０では、濡れ性、密着性ともに改善された。一方、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満のＴＢＣＨＡをＡＣＭＯ中に添加しても、依然として多くの基材に対する濡れ性や密着性が不十分であった（比較例Ａ－１２、Ａ－１３）。従って、表２に示すデータから明らかなように、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるＴＢＣＨＡを含有する本発明の樹脂組成物が、汎用の紫外線硬化性モノマー等に対する濡れ性向上効果、密着性向上効果を有しており、濡れ性向上剤や密着性向上剤として好適に用いることができる。特に、コーティング剤に関しては、ＳＵＳやＳＰＣＣなどの金属片や木材に対しても優れた密着性を示したことから、車両用コーティング剤、建築物用コーティング剤としても好適に用いることができる。 As shown in Table 2, in Comparative Example A-11, which is an evaluation of ACMO alone, the wettability and adhesion to many substrates were low, but the content of p-trans isomer was 70% or more. In Examples A-7 to A-10 in which TBCHA was added, both wettability and adhesion were improved. On the other hand, even when TBCHA with a p-trans isomer content of less than 70% was added to ACMO, the wettability and adhesion to many substrates were still insufficient (Comparative Example A-12, A-13). Therefore, as is clear from the data shown in Table 2, the resin composition of the present invention containing TBCHA with a p-trans isomer content of 70% or more has a high wettability with general-purpose ultraviolet curable monomers, etc. It has an improving effect and an adhesion improving effect, and can be suitably used as a wettability improver or an adhesion improver. In particular, since the coating agent showed excellent adhesion to metal pieces such as SUS and SPCC and wood, it can also be suitably used as a coating agent for vehicles and a coating agent for buildings.
（重合性樹脂組成物Ｘ－１～Ｘ－６１の調製）
表３－１～表３－６に示す比例（重量部）で、ＴＢＣＨＡ、単官能モノマー、オリゴマー、多官能モノマー、重合開始剤を混合して溶解させ、重合性樹脂組成物を調製した。
(Preparation of polymerizable resin compositions X-1 to X-61)
A polymerizable resin composition was prepared by mixing and dissolving TBCHA, a monofunctional monomer, an oligomer, a polyfunctional monomer, and a polymerization initiator in the proportions (parts by weight) shown in Tables 3-1 to 3-6.
実施例Ｂ－１～５と比較例Ｂ－６、７
粘着剤組成物として重合性樹脂組成物Ｘ－１～５とＸ－６～７を用い、下記方法にて、紫外線硬化型粘着シートの作製及び評価を行った。評価結果を表４に示す。
（紫外線硬化型粘着シートの作製方法）
厚さ１００μｍのＰＥＴフィルム表面に、膜厚が２５μｍになるように粘着剤組成物を塗布し、紫外線照射装置（アイグラフィックス（株）社製 インバーター式コンベア装置ＥＣＳ－４０１１ＧＸ、メタルハライドランプＭ０４－Ｌ４１、７００ｍＷ／ｃｍ２、２０００ｍＪ／ｃｍ２）を使用して硬化させた。その後、温度２３℃、相対湿度５０％の環境に１日置き、試験用の紫外線硬化型粘着シートを作製した。
（透明性）
ヘイズメーター（日本電色工業（株）社製 ＮＤＨ－２０００）により紫外線硬化型粘着シートの透過率を測定し、透明性を下記通り４段階に分けて評価した。
◎：透過率９０％以上
○：透過率８５％以上、９０％未満
△：透過率５０％以上、８５％未満
×：透過率５０％未満
（粘着力）
温度２３℃、相対湿度５０％の雰囲気下、作製した紫外線硬化型粘着シートを用いて被着体として表４に記載の各種基材の表面に貼り付け、手動式ローラー（４５ｍｍ幅、重量２Ｋｇ）で２往復圧着し、同雰囲気下で３０分間放置し、粘着力評価用の積層体を得た。得られた積層体を用いて、引っ張り試験機（ＯＲＩＥＮＴＥＣ社製 テンシロンＲＴＡ－１００）により、剥離速度３００ｍｍ／分にて１８０°剥離強度（Ｎ／２５ｍｍ）を測定し、粘着力（剥離強度）を下記通り４段階に分けて評価した。なお、本評価においては、測定バラツキの影響を少なくするため、測定を各５回実施し、最大値と最小値を除外した３回分の測定値を平均した値を粘着力として用いた。
◎：３０Ｎ／２５ｍｍ以上
○：１５Ｎ／２５ｍｍ以上、３０Ｎ／２５ｍｍ未満
△：８Ｎ／２５ｍｍ以上、１５Ｎ／２５ｍｍ未満
×：８Ｎ／２５ｍｍ未満
（耐汚染性）
上記の粘着力測定の試験と同様に紫外線硬化型粘着シートを被着体に加圧着させ、８０℃、２４時間放置した後、手動で紫外線硬化型粘着シートを剥がして、被着体表面の汚染状態（粘着剤の残り状態）を目視によって観察した。
◎：汚染なし
○：ごく僅かに汚染がある
△：僅かに汚染がある
×：糊（粘着剤）残りがある
（耐湿熱黄変性）
温度２３℃、相対湿度５０％の雰囲気下で２４時間静置した紫外線硬化型粘着シートを用いて、透過スペクトルを透過色測定専用機（日本電色工業(株)製 ＴＺ－６０００）により測定し、初期ｂ値とした。その後、紫外線硬化型粘着シートを８５℃、相対湿度８５％に設定した恒温恒湿機に５００時間を静置し、耐湿熱黄変性の加速試験を行った。試験後の粘着シートを同様に温度２３℃、相対湿度５０％の雰囲気下で２４時間静置し、透過色測定し、湿熱後ｂ値とした。また、湿熱後ｂ値と初期ｂ値の差は変化値Δｂとした（Δｂ＝湿熱後ｂ値－初期ｂ値）。耐湿熱黄変性は下記通り４段階分けて評価した。
◎：初期ｂ値、湿熱後ｂ値は共に０．２以下、かつ、Δｂは０．１以下である
○：初期ｂ値、湿熱後ｂ値は何れか一つまたは共に０．２を超えるが、共に０．５以下であり、かつ、Δｂは０．２以下である
△：初期ｂ値、湿熱後ｂ値は何れか一つまたは共に０．５を超えるが、共に１．０以下であり、かつ、Δｂは０．３以下である
×：初期ｂ値、湿熱後ｂ値は何れか一つまたは共に１．０を超え、或いは、Δｂは０．３を超える
（耐光黄変性）
上記の耐湿熱黄変性評価と同様に、耐光黄変性の加速試験を行い、試験前後のｂ値とそれらの差であるΔｂを測定、算出した。耐光黄変性の加速試験は紫外線フェードメーター（スガ試験機（株）社製 Ｕ４８）を用いて、ブラックパネル温度を６３℃に設定し、５００Ｗ／ｍ２の条件で１６８時間照射を行った。耐湿熱黄変性と同様に４段階に分けて評価した。
Examples B-1 to B-5 and Comparative Examples B-6 and 7
Using polymerizable resin compositions X-1 to X-5 and X-6 to X-7 as adhesive compositions, UV-curable adhesive sheets were produced and evaluated in the following manner. The evaluation results are shown in Table 4.
(Method for producing ultraviolet curable adhesive sheet)
An adhesive composition is applied to the surface of a PET film with a thickness of 100 μm so that the film thickness becomes 25 μm, and an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., inverter type conveyor device ECS-4011GX, metal halide lamp M04-L41) is applied. , 700 mW/cm 2 , 2000 mJ/cm 2 ). Thereafter, it was left in an environment with a temperature of 23° C. and a relative humidity of 50% for one day to produce an ultraviolet curable pressure-sensitive adhesive sheet for testing.
(transparency)
The transmittance of the ultraviolet curable pressure-sensitive adhesive sheet was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the transparency was evaluated in four stages as shown below.
◎: Transmittance 90% or more ○: Transmittance 85% or more, less than 90% △: Transmittance 50% or more, less than 85% ×: Transmittance less than 50% (adhesive strength)
In an atmosphere with a temperature of 23° C. and a relative humidity of 50%, the produced UV-curable adhesive sheet was applied to the surface of various substrates listed in Table 4 as adherends, and a manual roller (45 mm width, weight 2 kg) was applied. The laminate was pressed back and forth twice and left in the same atmosphere for 30 minutes to obtain a laminate for evaluation of adhesive strength. Using the obtained laminate, the 180° peel strength (N/25 mm) was measured using a tensile tester (Tensilon RTA-100 manufactured by ORIENTEC) at a peel rate of 300 mm/min, and the adhesive force (peel strength) was measured. The evaluation was divided into four stages as shown below. In this evaluation, in order to reduce the influence of measurement variations, each measurement was performed five times, and the average value of the three measurements excluding the maximum and minimum values was used as the adhesive force.
◎: 30N/25mm or more ○: 15N/25mm or more, less than 30N/25mm △: 8N/25mm or more, less than 15N/25mm ×: Less than 8N/25mm (stain resistance)
Similar to the above adhesion measurement test, the UV-curable adhesive sheet was pressure-bonded to the adherend, left at 80°C for 24 hours, and then manually peeled off to prevent contamination of the surface of the adherend. The state (remaining state of adhesive) was visually observed.
◎: No contamination ○: Very slight contamination △: Slight contamination ×: There is glue (adhesive) residue (moisture heat yellowing resistance)
Using an ultraviolet curable adhesive sheet that was allowed to stand for 24 hours in an atmosphere with a temperature of 23°C and a relative humidity of 50%, the transmission spectrum was measured using a dedicated transmission color measurement device (TZ-6000 manufactured by Nippon Denshoku Industries Co., Ltd.). , the initial b value. Thereafter, the ultraviolet curable pressure-sensitive adhesive sheet was left standing in a constant temperature and humidity machine set at 85° C. and 85% relative humidity for 500 hours to conduct an accelerated test for moisture and heat yellowing resistance. The pressure-sensitive adhesive sheet after the test was similarly allowed to stand for 24 hours in an atmosphere with a temperature of 23° C. and a relative humidity of 50%, the transmitted color was measured, and the b value was determined after moist heat. Further, the difference between the b value after moist heat and the initial b value was defined as a change value Δb (Δb=b value after moist heat−initial b value). Moisture heat yellowing resistance was evaluated in four stages as described below.
◎: The initial b value and the b value after moist heat are both 0.2 or less, and Δb is 0.1 or less. ○: The initial b value and the b value after moist heat are either one or both exceeding 0.2. , both are 0.5 or less, and Δb is 0.2 or less. △: Either or both of the initial b value and the b value after moist heat exceed 0.5, but both are 1.0 or less. , and Δb is 0.3 or less ×: Either or both of the initial b value and the b value after moist heat exceed 1.0, or Δb exceeds 0.3 (light yellowing resistance)
In the same way as in the moist heat yellowing resistance evaluation described above, an accelerated light yellowing resistance test was conducted, and the b values before and after the test and Δb, which is the difference between them, were measured and calculated. The accelerated light yellowing test was carried out using an ultraviolet fade meter (U48 manufactured by Suga Test Instruments Co., Ltd.), with the black panel temperature set at 63° C., and irradiation was performed at 500 W/m 2 for 168 hours. Similar to the moist heat yellowing resistance, the evaluation was divided into four stages.
表４に示すとおり、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性において、ｐ－ｔｒａｎｓ型異性体を７０％未満有するＴＢＣＨＡから得られた紫外線硬化型粘着シート（比較例Ｂ－６、７）と比較して、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡから得られた本発明の粘着シート（実施例Ｂ－１～５）の方が、いずれの評価試験も良好な結果を得た。また、実施例Ｂ－５に示すように、ｐ－ｔｒａｎｓ型異性体含有量が多いＴＢＣＨＡ中を用いると、基材への粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性がさらに優れたものとなる。従って、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡを含有する本発明の紫外線硬化型粘着剤組成物は粘着剤、感圧粘着剤、保護用粘着剤、再剥離用粘着剤、光学用粘着剤等に好適に用いることができる。また、粘着シートの性状からｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した重合性樹脂組成物は光学用成型品としても好適に用いることができる。 As shown in Table 4, the UV-curable adhesive sheet obtained from TBCHA having less than 70% p-trans isomer in terms of transparency, adhesive strength, stain resistance, resistance to moist heat yellowing, and resistance to light yellowing (comparative example) Compared to B-6 and B-7), the pressure-sensitive adhesive sheets of the present invention (Examples B-1 to B-5) obtained from TBCHA having 70% or more of p-trans isomer were better in all evaluation tests. Good results were obtained. Furthermore, as shown in Example B-5, when TBCHA containing a large amount of p-trans type isomer is used, the adhesion to the substrate, stain resistance, resistance to moist heat yellowing, and resistance to light yellowing are even better. It becomes something. Therefore, the ultraviolet curable adhesive composition of the present invention containing TBCHA having 70% or more of p-trans type isomer can be used as an adhesive, a pressure-sensitive adhesive, a protective adhesive, a removable adhesive, an optical adhesive, etc. It can be suitably used for agents, etc. Further, from the properties of the adhesive sheet, a polymerizable resin composition containing TBCHA having a p-trans isomer content of 70% or more can be suitably used as an optical molded product.
実施例Ｂ－８
温度計、撹拌機、還流冷却器及び窒素導入管を備えた反応装置内に、酢酸エチル２００重量部と前記重合性樹脂組成物Ｘ－８を１００重量部加え、さらにＡＩＢＮ ０．２重量部を加えて撹拌しながら窒素ガスを導入して装置内の空気を窒素に置換した。その後、還流温度まで昇温し、窒素を通しながら７時間反応させた。反応終了後、酢酸エチルを添加して、固形分３０％の重合物溶液（Ｂ－８）を得た。また、重合物溶液から３０重量部を取り出し、溶液中の揮発成分を完全に除去することにより重合物を取得した。その後、テトラヒドロフラン（ＴＨＦ）に溶解して、濃度０．５重量％の重合物溶液を調製し、一晩静置した。重合物のＴＨＦ溶液を０．４５μｍメンブレンフィルターでろ過し、ろ液を用いてゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定を行い（島津製作所製Ｐｒｏｍｉｎｅｎｃｅ ＧＰＣシステム、Ｓｈｏｄｅｘ ＫＦ－８０６Ｌカラム、溶離液ＴＨＦ）、ポリスチレン換算値により、重合物の重量平均分子量（Ｍｗ）が２９万であることを算出した。
Example B-8
Into a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 200 parts by weight of ethyl acetate and 100 parts by weight of the polymerizable resin composition In addition, nitrogen gas was introduced while stirring to replace the air in the apparatus with nitrogen. Thereafter, the temperature was raised to reflux temperature, and the mixture was reacted for 7 hours while passing nitrogen through the mixture. After the reaction was completed, ethyl acetate was added to obtain a polymer solution (B-8) with a solid content of 30%. Further, 30 parts by weight was taken out from the polymer solution and volatile components in the solution were completely removed to obtain a polymer. Thereafter, it was dissolved in tetrahydrofuran (THF) to prepare a polymer solution having a concentration of 0.5% by weight, and left overnight. The THF solution of the polymer was filtered through a 0.45 μm membrane filter, and the filtrate was subjected to gel permeation chromatography (GPC) measurement (Shimadzu Prominence GPC system, Shodex KF-806L column, eluent THF). Based on the converted value, it was calculated that the weight average molecular weight (Mw) of the polymer was 290,000.
実施例Ｂ－９～１１と比較例Ｂ－１２、１３
重合性樹脂組成物Ｘ－９～１３に変更した以外は、実施例Ｂ－８と同様に重合を行い、固形分３０％の重合物溶液（実施例Ｂ－９～１１と比較例Ｂ－１２、１３）を得た。得られた重合物の重量平均分子量（Ｍｗ）を測定し、結果を表５に纏めた。
得られたＢ－９～１１とＢ－１２、１３の重合物溶液を用いて、下記方法によりアクリル系粘着シートの作製及び評価を行った。
（アクリル系粘着剤の作製方法）
厚さ１００μｍのポリエチレンテレフタラート（ＰＥＴ）フィルム上に、乾燥後の厚みが２５μｍとなるよう重合物溶液Ｂ－８～１３をそれぞれ塗布し、８０℃で２分間乾燥させて、粘着剤層を形成した。次いで、温度２３℃、相対湿度５０％の環境に１日置き、試験用アクリル系粘着シートを得た。
上記と同様に、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性を評価し、結果を表５に纏めた。
Examples B-9 to 11 and Comparative Examples B-12 and 13
Polymerization was carried out in the same manner as in Example B-8, except that the polymerizable resin compositions were changed to X-9 to X-13. , 13) were obtained. The weight average molecular weight (Mw) of the obtained polymer was measured, and the results are summarized in Table 5.
Using the obtained polymer solutions of B-9 to B-11, B-12, and B-13, acrylic pressure-sensitive adhesive sheets were produced and evaluated by the following method.
(Method for producing acrylic adhesive)
Polymer solutions B-8 to B-13 were applied to a polyethylene terephthalate (PET) film with a thickness of 100 μm so that the thickness after drying would be 25 μm, and dried at 80°C for 2 minutes to form an adhesive layer. did. Next, it was left in an environment with a temperature of 23° C. and a relative humidity of 50% for one day to obtain an acrylic pressure-sensitive adhesive sheet for testing.
Transparency, adhesive strength, stain resistance, resistance to moist heat yellowing, and resistance to light yellowing were evaluated in the same manner as above, and the results are summarized in Table 5.
表５に示すとおり、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性において、ｐ－ｔｒａｎｓ型異性体を７０％未満有するＴＢＣＨＡから得られたアクリル系粘着シート（比較例Ｂ－１２、１３）と比較して、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡから得られた本発明の粘着シート（実施例Ｂ－８～１１）の方が、いずれの評価試験も良好な結果を得た。このように、上記した紫外線硬化型の粘着剤だけでなく、溶液中で重合させたアクリル重合物としても、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡを使用することにより密着性が改善され、耐汚染性や耐湿熱黄変性、耐光黄変性に優れた粘着剤が得られ、感圧粘着剤、保護用粘着剤、再剥離用粘着剤、光学用粘着剤等に好適に用いることができる。また、粘着シートの性状からｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した重合性樹脂組成物は光学用成型品としても好適に用いることができる。 As shown in Table 5, the acrylic adhesive sheet obtained from TBCHA having less than 70% p-trans isomer (Comparative Example B -12, 13), the adhesive sheets of the present invention (Examples B-8 to B-11) obtained from TBCHA having 70% or more of p-trans isomer were better in all evaluation tests. I got good results. In this way, adhesion can be improved by using TBCHA, which has 70% or more of the p-trans isomer, not only for the above-mentioned UV-curable adhesive but also for acrylic polymers polymerized in solution. , an adhesive with excellent stain resistance, resistance to moist heat yellowing, and resistance to light yellowing is obtained, and can be suitably used for pressure sensitive adhesives, protective adhesives, removable adhesives, optical adhesives, etc. . Further, from the properties of the adhesive sheet, a polymerizable resin composition containing TBCHA having a p-trans isomer content of 70% or more can be suitably used as an optical molded product.
実施例Ｂ－１４～１６と比較例Ｂ－１７、１８
重合性樹脂組成物Ｘ－１４～１８に変更した以外は、実施例Ｂ－８と同様に重合を行い、固形分３０％の重合物溶液（実施例Ｂ－１４～１６と比較例Ｂ－１７、１８）を得た。得られた重合物の重量平均分子量（Ｍｗ）を測定し、結果を表６に纏めた。
得られた各重合物溶液１００ｇを量り取って、ヘキサメチレンジイソシアネート（ＨＤＩ）の５０％酢酸エチルの溶液３ｇを添加し、均一に混合した後、乾燥後の厚みが２５μｍとなるようにＰＥＴフィルムに塗布し、８０℃で２分間乾燥させて、さらに４０℃の恒温槽で３日間エージングさせた後、温度２３℃、相対湿度５０％の環境に１日置き、試験用ウレタン系粘着シートを得た。
上記と同様に、ウレタン系粘着シートを用いて、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性を評価し、結果を表６に纏めた。
Examples B-14 to B-16 and Comparative Examples B-17 and 18
Polymerization was carried out in the same manner as in Example B-8, except that the polymerizable resin compositions were changed to X-14 to X-18. , 18) were obtained. The weight average molecular weight (Mw) of the obtained polymer was measured, and the results are summarized in Table 6.
Weigh out 100 g of each polymer solution obtained, add 3 g of a 50% solution of hexamethylene diisocyanate (HDI) in ethyl acetate, mix uniformly, and transfer to a PET film so that the thickness after drying is 25 μm. It was coated, dried at 80°C for 2 minutes, further aged in a constant temperature bath at 40°C for 3 days, and then placed in an environment at a temperature of 23°C and relative humidity of 50% for 1 day to obtain a urethane adhesive sheet for testing. .
In the same manner as above, the urethane adhesive sheet was used to evaluate transparency, adhesive strength, stain resistance, moist heat yellowing resistance, and light yellowing resistance, and the results are summarized in Table 6.
表６に示すとおり、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性において、ｐ－ｔｒａｎｓ型異性体を７０％未満有するＴＢＣＨＡから得られたウレタン系粘着シート（比較例Ｂ－１７、１８）と比較して、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡから得られた本発明の粘着シート（実施例Ｂ－１４～１６）の方が、いずれの評価試験も良好な結果を得た。このように、ウレタン系粘着シートにおいてもｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるＴＢＣＨＡを使用すると、粘着剤として優れた特性が得られることが示された。 As shown in Table 6, the urethane adhesive sheet obtained from TBCHA having less than 70% p-trans isomer (Comparative Example B -17, 18), the adhesive sheets of the present invention (Examples B-14 to B-16) obtained from TBCHA having 70% or more of the p-trans isomer were better in all evaluation tests. I got good results. Thus, it has been shown that excellent properties as an adhesive can be obtained when TBCHA having a p-trans isomer content of 70% or more is used in a urethane adhesive sheet.
実施例Ｂ－１９～２１と比較例Ｂ－２２、２３
重合性樹脂組成物Ｘ－１９～２３に変更した以外は、実施例Ｂ－８と同様に重合を行い、固形分３０％の重合物溶液（実施例Ｂ－１９～２１と比較例Ｂ－２２、２３）を得た。得られた重合物溶液の重合物の重量平均分子量（Ｍｗ）を測定した。結果を表７に示す。得られた各重合物溶液１００ｇを量り取って、１,２,３,６-テトラヒドロフタル酸無水物の５０％酢酸エチルの溶液３ｇを添加し、均一に混合した後、乾燥後の厚みが２５μｍとなるようにＰＥＴフィルムに塗布し、８０℃で２分間乾燥させて、さらに８０℃で３０分間加熱して架橋させた後、温度２３℃、相対湿度５０％の環境に１日置き、試験用エポキシ系粘着シートを得た。得られたエポキシ系粘着シートを用いて、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性を評価した。結果を表７に示す。
Examples B-19 to 21 and Comparative Examples B-22 and 23
Polymerization was carried out in the same manner as in Example B-8, except that the polymerizable resin compositions were changed to X-19 to X-23. , 23) were obtained. The weight average molecular weight (Mw) of the polymer in the obtained polymer solution was measured. The results are shown in Table 7. Weigh out 100 g of each polymer solution obtained, add 3 g of a 50% ethyl acetate solution of 1,2,3,6-tetrahydrophthalic anhydride, and mix uniformly. After drying, the thickness is 25 μm. It was applied to a PET film so that An epoxy adhesive sheet was obtained. Using the obtained epoxy pressure-sensitive adhesive sheet, transparency, adhesive strength, stain resistance, resistance to moist heat yellowing, and resistance to light yellowing were evaluated. The results are shown in Table 7.
表７に示すとおり、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性において、ｐ－ｔｒａｎｓ型異性体を７０％未満有するＴＢＣＨＡから得られたエポキシ系粘着シート（比較例Ｂ－２２、２３）と比較して、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡから得られた本発明の粘着シート（実施例Ｂ－１９～２１）の方が、いずれの評価試験も良好な結果を得た。このようにエポキシ系粘着シートおいても、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるＴＢＣＨＡを使用すると、粘着剤として優れた特性が得られることが示された。 As shown in Table 7, the epoxy adhesive sheet obtained from TBCHA having less than 70% p-trans isomer (Comparative Example B -22, 23), the adhesive sheets of the present invention (Examples B-19 to B-21) obtained from TBCHA having 70% or more of the p-trans isomer were better in all evaluation tests. I got good results. As described above, it has been shown that even in epoxy adhesive sheets, when TBCHA having a p-trans isomer content of 70% or more is used, excellent properties as an adhesive can be obtained.
実施例Ｂ－２４
温度計、撹拌機、還流冷却器及び窒素導入管を備えた反応装置内に、水を１５０重量部と重合性樹脂組成物Ｘ－２２を１００重量部、ＡＩＢＮ ０．２重量部、ドデシルベンゼンスルホン酸ナトリウム１．０重量部を加えて撹拌しながら窒素ガスを導入して装置内の空気を窒素に置換した後、還流温度まで昇温し、窒素を通しながら８時間反応させた。反応終了後、水を添加して、固形分３０％の水系エマルジョン重合物溶液（実施例Ｂ－２２）を得た。
また、前記重合物溶液から３０重量部を取り出し、溶液中の揮発成分を完全に除去することにより重合物を取得した。その後、テトラヒドロフラン（ＴＨＦ）に溶解して、濃度０．５重量％の重合物溶液を調製し、一晩静置した。重合物のＴＨＦ溶液を０．４５μｍメンブレンフィルターでろ過し、ろ液を用いてゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定を行い（島津製作所製Ｐｒｏｍｉｎｅｎｃｅ ＧＰＣシステム、Ｓｈｏｄｅｘ ＫＦ－８０６Ｌカラム、溶離液ＴＨＦ）、ポリスチレン換算値により、重合物の重量平均分子量（Ｍｗ）が２０万であることを算出した。
Example B-24
In a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 150 parts by weight of water, 100 parts by weight of polymerizable resin composition X-22, 0.2 parts by weight of AIBN, and dodecylbenzenesulfone were placed. After adding 1.0 parts by weight of sodium chloride and introducing nitrogen gas while stirring to replace the air in the apparatus with nitrogen, the temperature was raised to reflux temperature, and reaction was carried out for 8 hours while passing nitrogen. After the reaction was completed, water was added to obtain an aqueous emulsion polymer solution (Example B-22) with a solid content of 30%.
Further, 30 parts by weight was taken out from the polymer solution and volatile components in the solution were completely removed to obtain a polymer. Thereafter, it was dissolved in tetrahydrofuran (THF) to prepare a polymer solution having a concentration of 0.5% by weight, and left overnight. The THF solution of the polymer was filtered through a 0.45 μm membrane filter, and the filtrate was subjected to gel permeation chromatography (GPC) measurement (Shimadzu Prominence GPC system, Shodex KF-806L column, eluent THF). Based on the converted value, it was calculated that the weight average molecular weight (Mw) of the polymer was 200,000.
実施例Ｂ－２５、２６と比較例Ｂ－２７、２８
重合性樹脂組成物Ｘ－２５～２８に変更した以外は、実施例Ｂ－２４と同様に重合を行い、固形分３０％の重合物溶液（実施例Ｂ－２５、２６と比較例Ｂ－２７、２８）を得た。得られた重合物の重量平均分子量（Ｍｗ）を測定し、結果を表８に纏めた。
得られた実施例Ｂ－２４～２６と比較例Ｂ－２７、２８の重合物溶液を用いて、下記方法によりエマルジョン型粘着シートの作製及び評価を行った。
（エマルジョン型粘着シートの作製方法）
厚さ１００μｍのポリエチレンテレフタラート（ＰＥＴ）フィルムに、乾燥後の厚みが２５μｍとなるように重合物溶液Ｂ－２４～２８をそれぞれ塗布し、９０℃で２分間乾燥させて、粘着剤層を形成した。次いで、温度２３℃、相対湿度５０％の環境に１日置き、試験用エマルジョン型粘着シートを得た。
上記同様に、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性を評価し、結果を表８に纏めた。
Examples B-25, 26 and Comparative Examples B-27, 28
Polymerization was carried out in the same manner as in Example B-24, except that the polymerizable resin compositions were changed to X-25 to X-28. , 28) were obtained. The weight average molecular weight (Mw) of the obtained polymer was measured, and the results are summarized in Table 8.
Using the obtained polymer solutions of Examples B-24 to B-26 and Comparative Examples B-27 and B-28, emulsion-type pressure-sensitive adhesive sheets were produced and evaluated by the following method.
(Method for producing emulsion type adhesive sheet)
Polymer solutions B-24 to B-28 were applied to a polyethylene terephthalate (PET) film with a thickness of 100 μm so that the thickness after drying was 25 μm, and dried at 90°C for 2 minutes to form an adhesive layer. did. Next, it was left in an environment with a temperature of 23° C. and a relative humidity of 50% for one day to obtain an emulsion-type pressure-sensitive adhesive sheet for testing.
In the same manner as above, transparency, adhesive strength, stain resistance, resistance to moist heat yellowing, and resistance to light yellowing were evaluated, and the results are summarized in Table 8.
表８に示すとおり、透明性、粘着力、耐汚染性、耐湿熱黄変性、耐光黄変性において、ｐ－ｔｒａｎｓ型異性体を７０％未満有するＴＢＣＨＡから得られたエマルジョン型粘着シート（比較例Ｂ－２７、２８）と比較して、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡから得られた本発明の粘着シート（実施例Ｂ－２４～２６）の方が、いずれの評価試験も良好な結果を得た。このようにエマルジョン型粘着シートおいても、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上であるＴＢＣＨＡを使用すると、粘着剤として優れた特性が得られることが示された。 As shown in Table 8, the emulsion-type adhesive sheet obtained from TBCHA having less than 70% p-trans isomer (Comparative Example B -27, 28), the adhesive sheets of the present invention (Examples B-24 to B-26) obtained from TBCHA having 70% or more of the p-trans isomer were better in all evaluation tests. I got good results. As described above, it has been shown that even in emulsion-type pressure-sensitive adhesive sheets, when TBCHA having a p-trans isomer content of 70% or more is used, excellent properties as a pressure-sensitive adhesive can be obtained.
実施例Ｂ－２９～３１と比較例Ｂ－３２、３３
重合性樹脂組成物Ｘ－２９～３３に変更した以外は、実施例Ｂ－２４と同様にして重合を行い、固形分３０％の重合物溶液（実施例Ｂ－２９～３１と比較例Ｂ－３２、３３）を得た。得られた重合物の重量平均分子量（Ｍｗ）を測定し、結果を表９に纏めた。
得られたＢ－２９～３３の重合物溶液を用いて下記方法により密着性の評価を行った。
（密着性の評価）
厚さ１００μｍのポリエチレンテレフタラート（ＰＥＴ）フィルムに、膜厚２５μｍになるように重合物溶液Ｂ－２９～３３をそれぞれ塗布し、９０℃で２分間乾燥させて、塗膜を形成した。得られた塗膜を碁盤目試験法により１ｍｍ角のます目を１００個作成し、セロハンテープを貼り付け、一気に剥がした時に基材側に硬化膜が残ったマス目の数を数えて評価した。
◎：残ったマス目数１００
〇：残ったマス目数９０以上１００未満
△：残ったマス目数５０以上９０未満
×：残ったマス目数５０未満
Examples B-29 to 31 and Comparative Examples B-32 and 33
Polymerization was carried out in the same manner as in Example B-24, except that the polymerizable resin compositions X-29 to 33 were used, and polymer solutions with a solid content of 30% (Examples B-29 to 31 and Comparative Example B- 32, 33) were obtained. The weight average molecular weight (Mw) of the obtained polymer was measured, and the results are summarized in Table 9.
Using the obtained polymer solutions of B-29 to B-33, adhesion was evaluated by the following method.
(Evaluation of adhesion)
Polymer solutions B-29 to B-33 were each applied to a 100 μm thick polyethylene terephthalate (PET) film to give a film thickness of 25 μm, and dried at 90° C. for 2 minutes to form a coating film. The obtained coating film was evaluated by creating 100 squares of 1 mm square using the grid test method, pasting cellophane tape, and counting the number of squares where the cured film remained on the base material side when it was peeled off at once. .
◎: Number of squares remaining 100
〇: Number of remaining squares 90 or more and less than 100 △: Number of remaining squares 50 or more and less than 90 ×: Number of remaining squares less than 50
表９に示すとおり、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した本発明の重合性樹脂組成物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満のＴＢＣＨＡを配合した重合性樹脂組成物と比較して、いずれの基材に対しても良好な密着性を示した（実施例Ｂ－２９～３１）。本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡは多様な基材への密着性に優れるため、インクやコーティング剤として好適に用いることができる。 As shown in Table 9, the polymerizable resin composition of the present invention containing TBCHA with a p-trans isomer content of 70% or more exhibited good adhesion to all substrates compared to the polymerizable resin composition containing TBCHA with a p-trans isomer content of less than 70% (Examples B-29 to 31). TBCHA of the present invention containing 70% or more p-trans isomer has excellent adhesion to a variety of substrates, and can therefore be suitably used as an ink or coating agent.
実施例Ｂ－３４－１、３４－２、Ｂ－３５－１、３５－２、３６と比較例Ｂ－３７－１、３７－２、Ｂ－３８－１、３８－２
重合性樹脂組成物Ｘ－３４～３８を用い、表１０に示す組成比に顔料と顔料分散剤を加えて攪拌し、インク組成物を調製した。また、調製したインク組成物を用いて、インクジェット印刷を行い、得られた印刷物の物性評価を行った。なお、クリアインク組成物においては顔料と顔料分散剤を配合せず、ブラックインク組成物は顔料ピグネントブラック７を６重量部、顔料分散剤アジスパーＰＢ８２１を４重量部配合したものと配合してないものそれぞれ評価を行った。評価の結果を表１０に纏めた。
（粘度）
インク組成物の粘度をＪＩＳ Ｋ５６００－２－３に準じて、コーンプレート型粘度計（東機産業（株）社製 ＲＥ５５０型粘度計）により測定した。インクジェット式印刷用のインク組成物として、粘度は下記通り４段階分けて評価した。
◎：５～１００ｍＰａ・ｓ未満
○：１００～５００ｍＰａ・ｓ未満
△：５００～２０００ｍＰａ・ ｓ未満
×：２０００ｍＰａ・ ｓ以上
（顔料分散性）
調製したインク組成物を用いて、調製直後及び２ヶ月静置後の顔料の凝集や沈殿状態を目視により観察し、顔料分散性は下記通り４段階分けて評価した。
◎：調製直後も２ヶ月静置後も、顔料の凝集や沈殿は全く認められなかった。
〇：調製直後には全く認められなかったが、２ヶ月静置後、僅かに顔料の沈殿が認められた。
△：調製直後には僅か、２ヶ月静置後には顔料の凝集や沈殿が明瞭に認められた。
×：調製直後にも顔料の凝集や沈殿が明瞭に認められた。
（紫外線照射による印刷物の作製）
得られたインク組成物を厚さ１００μｍのＰＥＴフィルムにバーコーター（ＲＤＳ１２）にて塗布し（乾燥後膜厚１０μｍ）、紫外線照射（アイグラフィックス（株）社製インバーター式コンベア装置ＥＣＳ－４０１１ＧＸ、メタハライドランプＭ０４－Ｌ４１）により硬化させ、印刷物を作製した。
（硬化性）
上記方法にて印刷物を作成する際、インク組成物が完全硬化（べたつかない状態）するまでの積算光量を測定し、硬化性を評価した。
◎：１０００ｍＪ／ｃｍ２で完全硬化
○：１０００～２０００ｍＪ／ｃｍ２で完全硬化
△：２０００～５０００ｍＪ／ｃｍ２で完全硬化
×：完全硬化までに５０００ｍＪ／ｃｍ２以上が必要
（表面乾燥性）
上記方法にて作製した印刷物を、室温２３℃、相対湿度５０％の環境に５分間静置し、印刷面に上質紙を重ね、荷重１ｋｇ／ｃｍ２の負荷を１分間かけ、紙へのインクの転写程度を評価した。
◎：インクが乾燥し、紙への転写が全くなかった
○：インクが乾燥し、紙への転写がわずかにあった
△：インクがほぼ乾燥し、紙への転写があった
×：インクが殆ど乾燥せず、紙への転写が多かった
（密着性の評価）
得られたインク組成物を各種基材に塗工し、紫外線照射装置（アイグラフィックス（株）社製インバーター式コンベア装置ＥＣＳ－４０１１ＧＸ、メタルハライドランプＭ０４－Ｌ４１、７００ｍＷ／ｃｍ２、３０００ｍＪ／ｃｍ２）を使用し、完全に硬化させた。得られた硬化膜を碁盤目試験法により１ｍｍ角のます目を１００個作成しセロハンテープを貼り付け、一気に剥がした時に基材側に硬化膜が残ったマス目の数を数えて評価した。
◎：残ったマス目数１００
〇：残ったマス目数９０以上１００未満
△：残ったマス目数５０以上９０未満
×：残ったマス目数５０未満
（インクジェット印刷と印刷適性評価）
上記で作製したインク組成物を市販インクジェットプリンター（富士フイルム（株）社製 ＬｕｘｅｌＪｅｔ Ｕ Ｖ３５０ＧＴＷ）に充填し、コート紙を用いて、ベタ画像を印刷し、インクの印刷適正を以下の方法にて評価した。
（吐出安定性）
得られた印刷物の印刷状態を目視により評価した。
◎：ノズル抜けなく、良好に印刷されている
〇：わずかにノズル抜けあり
△：広い範囲にてノズル抜けがあり
×：不吐出がある
（鮮明度）
顔料を配合したインク組成物から得られた印刷物の画像鮮明度を目視で観察した。
◎：インクにじみが全く見られなく、画像が鮮明であった
○：インクにじみが殆どなく、画像が良好であった
△：インクにじみが若干見られた
×：インクにじみが著しくみられた
（耐熱黄変性）
得られたクリアインク組成物を用いて、サブストレート基板（＃１２５－Ｅ２０）に膜厚１０μｍとなるようにバーコーター（ＲＤＳ１２）で塗布し、上記と同様にメタルハライドランプで硬化させた。得られた塗膜の色相をＳｐｃｅｔｒｏｌｉｎｏ（ＧｒｅｔａｇＭａｃｂｅｔｈ社製）により測定し、６０℃に保持した恒温槽に１週間放置した。その後、塗膜の色相を再度測定し、加熱前後の色相値変化（ΔＥ＝加熱後色相－加熱前色相）により耐黄変性を評価した。
◎：０＜＝ΔＥ＜＝０．２
〇：０．２＜ΔＥ＜＝０．５
△：０．５＜ΔＥ＜＝１．０
×：１．０＜ΔＥ
Examples B-34-1, 34-2, B-35-1, 35-2, 36 and Comparative Examples B-37-1, 37-2, B-38-1, 38-2
Using polymerizable resin compositions X-34 to X-38, pigments and pigment dispersants were added to the composition ratios shown in Table 10 and stirred to prepare ink compositions. Furthermore, inkjet printing was performed using the prepared ink composition, and the physical properties of the resulting printed matter were evaluated. In addition, the clear ink composition does not contain a pigment and a pigment dispersant, and the black ink composition contains 6 parts by weight of the pigment Pignent Black 7 and 4 parts by weight of the pigment dispersant Ajisper PB821. Each item was evaluated. The evaluation results are summarized in Table 10.
(viscosity)
The viscosity of the ink composition was measured according to JIS K5600-2-3 using a cone-plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.). As an ink composition for inkjet printing, the viscosity was evaluated in four stages as described below.
◎: 5 to less than 100 mPa・s ○: 100 to less than 500 mPa・s △: 500 to less than 2000 mPa・s ×: 2000 mPa・s or more (pigment dispersibility)
Using the prepared ink composition, the state of aggregation and precipitation of the pigment was visually observed immediately after preparation and after standing for 2 months, and the pigment dispersibility was evaluated in four stages as described below.
◎: No aggregation or precipitation of the pigment was observed either immediately after preparation or after standing for 2 months.
○: Not observed at all immediately after preparation, but slight precipitation of pigment was observed after standing for 2 months.
Δ: Pigment aggregation and precipitation were clearly observed immediately after preparation, but after being left standing for 2 months.
×: Pigment aggregation and precipitation were clearly observed even immediately after preparation.
(Preparation of printed matter by ultraviolet irradiation)
The obtained ink composition was applied to a PET film with a thickness of 100 μm using a bar coater (RDS12) (film thickness after drying: 10 μm), and irradiated with ultraviolet light (inverter type conveyor device ECS-4011GX manufactured by I-Graphics Co., Ltd.). It was cured using a metahalide lamp M04-L41) to produce printed matter.
(curability)
When creating a printed matter using the above method, the cumulative amount of light until the ink composition was completely cured (no sticky state) was measured to evaluate the curability.
◎: Completely cured at 1000mJ/ cm2 ○: Completely cured at 1000-2000mJ/ cm2 △: Completely cured at 2000-5000mJ/cm2 ×: Requires 5000mJ/ cm2 or more for complete curing (surface drying)
The printed matter produced by the above method was left to stand for 5 minutes at a room temperature of 23°C and a relative humidity of 50%, then high-quality paper was placed on the printed surface, and a load of 1 kg/cm 2 was applied for 1 minute to ink on the paper. The degree of transcription was evaluated.
◎: The ink was dry and there was no transfer to the paper. ○: The ink was dry and there was a slight transfer to the paper. △: The ink was almost dry and there was some transfer to the paper. ×: The ink was There was almost no drying, and there was a lot of transfer to paper (adhesion evaluation)
The obtained ink composition was applied to various base materials, and an ultraviolet irradiation device (inverter type conveyor device ECS-4011GX manufactured by Eye Graphics Co., Ltd., metal halide lamp M04-L41, 700 mW/cm 2 , 3000 mJ/cm 2 ) was used and completely cured. The resulting cured film was evaluated by making 100 1 mm square squares using the grid test method, pasting cellophane tape on it, and counting the number of squares where the cured film remained on the base material side when it was peeled off all at once.
◎: Number of squares remaining 100
〇: Number of remaining squares 90 or more and less than 100 △: Number of remaining squares 50 or more and less than 90 ×: Number of remaining squares less than 50 (inkjet printing and printing suitability evaluation)
The ink composition prepared above was filled into a commercially available inkjet printer (LuxelJet U V350GTW manufactured by Fujifilm Corporation), a solid image was printed using coated paper, and the printing suitability of the ink was evaluated by the following method. did.
(Discharge stability)
The printing condition of the obtained printed matter was visually evaluated.
◎: Good printing with no nozzle missing 〇: Slight nozzle missing △: Nozzle missing in a wide range ×: Ejection failure (clarity)
The image clarity of the printed matter obtained from the ink composition containing the pigment was visually observed.
◎: There was no ink bleeding at all and the image was clear. ○: There was almost no ink bleeding and the image was good. △: Some ink bleeding was observed. ×: There was significant ink bleeding (heat resistant). yellowing)
The resulting clear ink composition was applied to a substrate (#125-E20) with a bar coater (RDS12) to a film thickness of 10 μm, and cured using a metal halide lamp in the same manner as above. The hue of the resulting coating film was measured using Spcetrolino (manufactured by Gretag Macbeth), and the film was left in a constant temperature bath kept at 60° C. for one week. Thereafter, the hue of the coating film was measured again, and the yellowing resistance was evaluated based on the change in hue value before and after heating (ΔE = hue after heating - hue before heating).
◎: 0<=ΔE<=0.2
〇: 0.2<ΔE<=0.5
△: 0.5<ΔE<=1.0
×: 1.0<ΔE
表１０に示すとおり、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＨＣＨＡから得られた本発明のインク組成物は、いずれも、インクジェットインクとして良好な粘度を有し、顔料分散性、硬化性、各種基材に対する密着性、耐熱黄変性に優れ、また、得られた印刷物は優れた吐出安定性や表面乾燥性、鮮明度を示した。特に、硬化性や表面乾燥性について、ｐ－ｔｒａｎｓ型異性体含有量の上昇につれて更なる向上が確認され、ＴＢＣＨＡのｐ－ｔｒａｎｓ型異性体の含有量が多い程優れる傾向が確認された（実施例Ｂ－３５－１）。また、インク組成物の顔料分散性は、分散剤を添加しない場合（実施例Ｂ－３６）においても、添加した場合（実施例Ｂ－３４－２、３５－２）と同様に良好であった。このことから、ｐ－ｔｒａｎｓ型異性体を７０％以上有するＴＢＣＨＡは顔料に対する分散性向上の効果を有し、分散性向上剤としての効果も有することが示された。 As shown in Table 10, the ink compositions of the present invention obtained from TBHCHA having 70% or more of p-trans type isomers all have good viscosity as inkjet inks, pigment dispersibility, curability, It had excellent adhesion to various substrates and heat yellowing resistance, and the resulting printed matter showed excellent ejection stability, surface drying properties, and sharpness. In particular, it was confirmed that curing properties and surface drying properties were further improved as the p-trans isomer content increased, and it was confirmed that the higher the content of the p-trans isomer of TBCHA, the better it was (implemented). Example B-35-1). Furthermore, the pigment dispersibility of the ink composition was as good even when no dispersant was added (Example B-36) as when it was added (Examples B-34-2 and 35-2). . This indicates that TBCHA having 70% or more of the p-trans type isomer has the effect of improving the dispersibility of pigments and also has the effect as a dispersibility improver.
実施例Ｂ－３９～４１と比較例Ｂ－４２、４３
重合性樹脂組成物Ｘ－３９～４３を用い、下記方法にて、光造形物の試験片作製を行い、硬度、強度および伸度を測定した。評価結果を表１１に示す。
（試験片の作製）
水平に設置したガラス板上に厚さ７５μｍの重剥離ＰＥＴフィルム（東洋紡株式会社製ポリエステルフィルムＥ７００１） を密着させ、厚さ１ｍｍ、内部が６０ ｍｍ×１００ｍｍのスペーサーを設置し、スペーサーの内側に得られた重合性樹脂組成物（Ｘ－３９～４１、Ｘ－４２、４３）を充填した後、更にその上に厚さ５０μｍの軽剥離ＰＥＴフィルム（東洋紡株式会社製、ポリエステルフィルムＥ７００２）を重ね、紫外線を照射（装置：アイグラフィックス製、インバーター式コンベア装置ＥＣＳ－４０１１Ｇ Ｘ、メタルハライドランプ：アイグラフィックス製Ｍ０４－Ｌ４１、紫外線照度２００ ｍＷ／ｃｍ２ 、積算光量１０００ｍＪ／ｃｍ２） し、樹脂組成物を硬化させた。その後、両側の剥離ＰＥＴフィルムを取り除いて、実施例Ｂ－３９～４１及び比較例Ｂ－４２、４３の試験片を得た。
Examples B-39 to 41 and Comparative Examples B-42 and 43
Using polymerizable resin compositions X-39 to 43, test pieces of optically modeled objects were prepared by the following method, and hardness, strength, and elongation were measured. The evaluation results are shown in Table 11.
(Preparation of test piece)
A 75 μm thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) was placed on a horizontally placed glass plate, and a 1 mm thick spacer with an internal size of 60 mm x 100 mm was placed on the inside of the spacer. After filling the polymeric resin compositions (X-39 to 41, Irradiated with ultraviolet light (equipment: I - Graphics, inverter conveyor device ECS-4011G Hardened things. Thereafter, the peelable PET films on both sides were removed to obtain test pieces of Examples B-39 to B-41 and Comparative Examples B-42 and B-43.
（ゴム硬度測定）
作製した実施例用の試験片（Ｂ－３９～４１）及び比較例用の試験片（Ｂ－４２、４３）を用いて、各６枚重ねにし、ＪＩＳＫ６２５３「ゴムの硬さ試験方法」によりショアＡ硬度を測定した。また、ショアＡ硬度が９０より大きい場合はショアＤ硬度を測定した。
（破断伸度）
作製した実施例用の試験片（Ｂ－３９～４１）及び比較例用の試験片（Ｂ－４２、４３）を用いて、ＪＩＳ Ｋ６２５１に準拠した３号ダンベル型に打ち抜いて、ダンベル型試験片を作製した後、ＪＩＳ Ｋ７１６１に従って、卓上形精密万能試験機（株式会社島津製作所製 オートグラフＡＧＳ－Ｘ）を用い、２５℃の温度環境下にて、引張速度１００ｍｍ／分、チャック間距離５０ｍｍの条件で破断伸度を測定した。
(Rubber hardness measurement)
Using the prepared test pieces for Examples (B-39 to 41) and test pieces for Comparative Examples (B-42, 43), stacked 6 sheets each, and shore-tested them according to JIS K6253 "Rubber Hardness Test Method". A hardness was measured. Moreover, when the Shore A hardness was greater than 90, the Shore D hardness was measured.
(Elongation at break)
Using the prepared test pieces for Examples (B-39 to 41) and test pieces for Comparative Examples (B-42, 43), punch them into a No. 3 dumbbell shape in accordance with JIS K6251 to obtain dumbbell-shaped test pieces. After manufacturing, in accordance with JIS K7161, using a tabletop precision universal testing machine (Autograph AGS-X, manufactured by Shimadzu Corporation), it was tested at a tensile speed of 100 mm/min and a distance between chucks of 50 mm in a temperature environment of 25°C. The elongation at break was measured under the following conditions.
表１１に示すとおり、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上を有するＴＢＣＨＡから得られた本発明の樹脂組成物を硬化して得られた共重合物（実施例Ｂ－３９～４１）はいずれもショアＤ 硬度７０以上を示す硬質樹脂であり、またそれらは１５％以上の破断伸度と１５ＭＰａ以上の引張強度を有し、硬質樹脂として良好な強靭性を示した。特にｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを５０重量部含有した試験片（実施例Ｂ－４０）では２０％以上の破断伸度と２０ＭＰａ以上の引張強度が確認され、優れた強靭性を有するため、ＳＬＡ方式やＤＬＰ方式の光造形法による３Ｄプリンターの硬質なモデル材やＳＬＡ方式のサポート材用の活性エネルギー線硬化性樹脂組成物としても好適である。 As shown in Table 11, copolymers obtained by curing the resin composition of the present invention obtained from TBCHA having a p-trans isomer content of 70% or more (Examples B-39 to 41) ) are all hard resins exhibiting Shore D hardness of 70 or more, and they also have elongation at break of 15% or more and tensile strength of 15 MPa or more, showing good toughness as a hard resin. In particular, the test piece containing 50 parts by weight of TBCHA with a p-trans isomer content of 70% or more (Example B-40) had an elongation at break of 20% or more and a tensile strength of 20 MPa or more, which was excellent. Because of its strong toughness, it is also suitable as an active energy ray-curable resin composition for hard model materials for 3D printers using stereolithography methods such as SLA and DLP methods, and support materials for SLA methods.
実施例Ｂ－４４～４６と比較例Ｂ－４７、４８
重合性樹脂組成物Ｘ－４４～４８を用い、下記方法にて爪装飾用コート剤の作製及び評価を行った。評価結果を表１２に示す。
Examples B-44 to 46 and Comparative Examples B-47 and 48
Using polymerizable resin compositions X-44 to X-48, nail decoration coating agents were prepared and evaluated in the following manner. The evaluation results are shown in Table 12.
（爪装飾コートの作製方法）
重合性樹脂組成物を爪上にフラットブラシを用いて均一に塗布し、ジェルネイル専用ＵＶ照射装置（３６Ｗ）を用いて６０秒照射することで、爪上に爪装飾を形成した。
(Method for producing nail decoration coat)
The polymeric resin composition was uniformly applied onto the nails using a flat brush, and irradiated for 60 seconds using a UV irradiation device (36W) exclusively for gel nails to form nail decorations on the nails.
（硬化性）
上記方法にて得られた爪装飾の表面を指で触り、べたつき具合を評価した。
◎：べたつきが全くない。
○：若干のべたつきがあるが、表面に指の跡が残らない。
△：べとつきがあり、表面に指の跡が残る。
×：べとつきがひどく、表面に指が貼りつく。
（平滑性）
上記方法にて得られた爪装飾の表面を目視にて確認した。
◎：表面が平滑であり、塗布面全てにおいて凹凸がみられない。
○：全体的に平滑であるが、一部凹凸がみられる。
△：塗布後に一部、フラットブラシによる刷毛跡が残る。
×：塗布後にフラットブラシによる刷毛跡が残る。
（光沢性）
上記方法にて得られた爪装飾の表面を目視にて観察した。
◎：表面光沢がある。
○：光の反射は確認できるが、うっすらと曇りがみられる。
△：表面が全体的に若干曇る。
×：表面が曇る。
（密着性）
上記方法にて得られた爪装飾を他の爪で引っ掻いた後の外観変化を目視にて確認した。
◎：外観に変化なし。
○：爪装飾の一部に浮き上がりがあり、白化が確認された。
△：爪装飾の一部に剥離を確認した。
×：爪装飾の顕著な剥離を確認した。
（除去性）
上記方法にて得られた爪装飾を覆うようにして、アセトンを含んだコットンを載せた。次にアルミホイルで爪全体を覆い、サニメント手袋をした後１０分間温水につけて放置した。その後、アルミホイルとコットンを取り除き、布を用いて軽く擦った。
◎：布を用いずとも、容易に爪装飾を剥離することができた。
○：布を用いて軽く擦ると、容易に爪装飾を剥離することができた。
△：布を用いて１分ほど擦り続けると、爪装飾を剥離することができた。
×：アセトンを膨潤しておらず、布で擦っても剥離できない。
(curability)
The surface of the nail decoration obtained by the above method was touched with a finger to evaluate the degree of stickiness.
◎: No stickiness at all.
○: There is some stickiness, but no finger marks remain on the surface.
△: It is sticky and leaves finger marks on the surface.
×: So sticky that your fingers stick to the surface.
(Smoothness)
The surface of the nail decoration obtained by the above method was visually confirmed.
◎: The surface is smooth and no unevenness is observed on the entire coated surface.
○: Overall smooth, but some unevenness is observed.
△: Some brush marks left by the flat brush remain after application.
×: Brush marks left by a flat brush remain after application.
(Glossiness)
The surface of the nail decoration obtained by the above method was visually observed.
◎: Surface glossy.
○: Light reflection can be confirmed, but slight cloudiness is observed.
Δ: The entire surface is slightly cloudy.
×: The surface becomes cloudy.
(Adhesion)
After the nail decoration obtained by the above method was scratched with another nail, changes in appearance were visually confirmed.
◎: No change in appearance.
○: Part of the nail decoration was raised and whitening was confirmed.
△: Peeling was observed in a part of the nail decoration.
×: Significant peeling of the nail decoration was observed.
(removability)
Cotton containing acetone was placed so as to cover the nail decoration obtained by the above method. Next, I covered the entire nail with aluminum foil, put on sanitary gloves, and soaked it in warm water for 10 minutes. Thereafter, the aluminum foil and cotton were removed, and the surface was lightly rubbed with a cloth.
◎: The nail decoration could be easily peeled off without using cloth.
○: The nail decoration could be easily peeled off by rubbing lightly with a cloth.
Δ: The nail decoration could be peeled off by continuing to rub with a cloth for about 1 minute.
×: Not swollen with acetone and cannot be removed even if rubbed with cloth.
表１２に示すとおり、本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した重合性樹脂組成物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満のＴＢＣＨＡを配合した重合性樹脂組成物と比較して、硬化性、平滑性、光沢性、密着性、除去性のすべての評価において良好であった（実施例Ｂ－４４～４６）。本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡは硬化性に優れるため、汎用の他の紫外線硬化性モノマーと混合した場合においても、表面タック性や硬度を低下させることなく、爪装飾用コート剤として好適に使用することができる。 As shown in Table 12, the polymeric resin composition of the present invention containing TBCHA with a p-trans isomer content of 70% or more can contain TBCHA with a p-trans isomer content of less than 70%. Compared to the blended polymeric resin composition, the results were good in all evaluations of curability, smoothness, gloss, adhesion, and removability (Examples B-44 to B-46). Since the TBCHA of the present invention with a p-trans isomer content of 70% or more has excellent curability, it can be mixed with other general-purpose ultraviolet curable monomers without reducing surface tackiness or hardness. , can be suitably used as a coating agent for nail decoration.
実施例Ｂ－４９～５１と比較例Ｂ－５２、５３
重合性樹脂組成物Ｘ－４９～５３を用い、下記方法にてプレキュアタイプの加飾コート剤用樹脂組成物の評価を行った。
Examples B-49 to 51 and Comparative Examples B-52 and 53
Using polymerizable resin compositions X-49 to 53, precure type resin compositions for decorative coating agents were evaluated in the following manner.
重合性樹脂組成物を厚さ１８０μｍのＰＣフィルム（「パンライトＰＣ－２１５１」帝人社製）上にバーコーター（ＲＤＳ ６）を用い、乾燥後膜厚が５μｍとなるように塗布した後、８０℃にて３分間乾燥し、未硬化の塗膜を得た後、紫外線照射（高圧水銀ランプ ３００ｍＷ／ｃｍ２、１０００ｍＪ／ｃｍ２）して塗膜を硬化させ、ハードコート層を有する積層体を得た。得られた積層体を切り取り、ハードコート層の耐表面タック性、伸び率、鉛筆硬度、耐傷性、耐折り曲げ性と耐日焼け止め剤性を下記方法により評価を行った。結果を表１３に示す。 The polymeric resin composition was coated onto a 180 μm thick PC film (“Panlite PC-2151” manufactured by Teijin) using a bar coater (RDS 6) so that the film thickness after drying was 5 μm, and then After drying at ℃ for 3 minutes to obtain an uncured coating film, the coating film was cured by UV irradiation (high pressure mercury lamp 300mW/cm 2 , 1000mJ/cm 2 ) to form a laminate having a hard coat layer. Obtained. The obtained laminate was cut out, and the surface tack resistance, elongation rate, pencil hardness, scratch resistance, bending resistance, and sunscreen resistance of the hard coat layer were evaluated by the following methods. The results are shown in Table 13.
（１）耐表面タック性
得られた積層体を用いて、膜の表面を指で触り、べたつき具合を評価した。
◎：べたつきが全くない。
〇：若干のべたつきがあるが、表面に指の跡が残らない。
△：べたつきがあり、表面に指の跡が残る。
×：べたつきがひどく、表面に指が貼りつく。
(1) Surface tack resistance Using the obtained laminate, the surface of the film was touched with a finger to evaluate the degree of stickiness.
◎: No stickiness at all.
○: Slightly sticky, but no finger marks remain on the surface.
△: It is sticky and leaves finger marks on the surface.
×: So sticky that your fingers stick to the surface.
（２）伸び率
得られた積層体を長さ５０ｍｍ、幅１５ｍｍにカットし、テンシロン万能試験機ＲＴＡ－１００（オリエンテック社製）にチャック間距離２５ｍｍにて固定し、温度１５０℃に設定したオーブン中にて２５０ｍｍ／ｍｉｎの速度にて、外観を目視観察しながら一方向に引張り、塗工層に割れ又は白化を生じたときの試験片の長さ（ｍｍ）を測定した。伸び率は下記方法により算出し、評価を行った。
伸び率（％）＝（試験後試料片長さ／２５）×１００％
◎：伸び率が２００％以上
〇：伸び率が１５０以上２００％未満
△：伸び率が１１０％以上１５０％未満
×：伸び率が１１０％未満
(2) Elongation rate The obtained laminate was cut to a length of 50 mm and a width of 15 mm, and was fixed in a Tensilon universal testing machine RTA-100 (manufactured by Orientech Co., Ltd.) with a distance between chucks of 25 mm, and the temperature was set at 150°C. The test piece was pulled in one direction at a speed of 250 mm/min in an oven while visually observing the appearance, and the length (mm) of the test piece was measured when cracking or whitening occurred in the coating layer. The elongation rate was calculated and evaluated by the following method.
Elongation rate (%) = (specimen length after test/25) x 100%
◎: Elongation rate is 200% or more ○: Elongation rate is 150 or more and less than 200% △: Elongation rate is 110% or more and less than 150% ×: Elongation rate is less than 110%
（３）鉛筆硬度
試験片をＪＩＳ Ｋ ５６００に準拠して、鉛筆を４５°の角度で１０ｍｍ程度引っ掻いた後、硬化膜表面に傷の付かない最も硬い鉛筆を鉛筆硬度とした。
◎：鉛筆硬度が２Ｈ以上
○：鉛筆硬度がＨＢ～Ｈ
△：鉛筆硬度が３Ｂ～Ｂ
×：鉛筆硬度が４Ｂ以下
(3) Pencil hardness The test piece was scratched with a pencil at an angle of 45° to a depth of about 10 mm in accordance with JIS K 5600, and the hardest pencil that did not leave any scratches on the surface of the cured film was defined as the pencil hardness.
◎: Pencil hardness is 2H or more ○: Pencil hardness is HB-H
△: Pencil hardness is 3B to B
×: Pencil hardness is 4B or less
（４）耐傷性
試験片を＃００００のスチールウールを加重２５０ｇにて１０往復し、硬化膜表面に目視にて観察した。
◎：膜の剥離や傷の発生は認められない。
○：膜の一部にわずかな細い傷が認められる。
△：膜全体に筋上の傷が認められる。
×：膜の剥離が生じる。
（５）耐折り曲げ性
試験片を塗膜面が外側になるように１８０°に折り曲げ、１ｋｇの重しを載せて１０分間放置し、硬化膜表面の割れの有無を目視にて観察した。
◎：まったく割れが見られなかった。
○：折り曲げ部が一部白化した。
△：折り曲げ部において一部割れが見られた。
×：折り曲げ部において割れが見られた。
（６）耐日焼け止め剤性
試験片の表面に日焼け止め剤であるＵｌｔｒａＳｈｅｅｒ ＤＲＹ－ＴＯＵＣＨ ＳＵＮＳＣＲＥＥＮ ＳＰＦ１００＋（ニュートロジーナ社製）を直径１ｃｍ程度となるように塗布し、８０℃にて６時間加熱し、放冷後、中性洗剤にて洗い流し、表面の状態を観察した。
◎：日焼け止め剤の跡がまったく見られなかった。
○：日焼け止め剤を塗布した部分に透明な後がわずかに見られる。
△：日焼け止め剤を塗布した部分に白く跡が残り、表面が膨れている。
×：日焼け止め剤を塗布した部分がべたつき、表面が剥がれている。
(4) Scratch Resistance The test piece was subjected to 10 reciprocations of #0000 steel wool under a load of 250 g, and the surface of the cured film was visually observed.
◎: No peeling of the film or occurrence of scratches is observed.
○: A few thin scratches are observed in a part of the film.
△: Linear scratches are observed throughout the membrane.
×: Peeling of the film occurs.
(5) Bending resistance The test piece was bent at 180° so that the coating surface faced outward, a 1 kg weight was placed on it, and the test piece was left for 10 minutes, and the presence or absence of cracks on the surface of the cured film was visually observed.
◎: No cracks were observed.
○: Part of the folded portion turned white.
Δ: Partial cracking was observed at the bent portion.
×: Cracks were observed at the bent portion.
(6) Sunscreen resistance A sunscreen agent, UltraSheer DRY-TOUCH SUNSCREEN SPF100+ (manufactured by Neutrogena), was applied to the surface of the test piece to a diameter of about 1 cm, heated at 80°C for 6 hours, and left to stand. After cooling, it was washed with a neutral detergent and the surface condition was observed.
◎: No traces of sunscreen were observed.
○: A slight transparent residue is seen in the area where the sunscreen was applied.
△: White marks remain on the area where the sunscreen was applied, and the surface is swollen.
×: The area where the sunscreen was applied was sticky and the surface was peeled off.
表１３に示すとおり、本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した重合性樹脂組成物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満のＴＢＣＨＡを配合した重合性樹脂組成物と比較して、耐表面タック性、伸び率、鉛筆硬度、耐傷性、耐折り曲げ性、耐日焼け止め剤性のすべての評価において良好であった（実施例Ｂ－４９～５１）。本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡは硬度、伸び性や耐久性に優れるため、加飾コート剤として汎用の他の紫外線硬化性モノマーと混合した場合においても、表面タック性や硬度を低下させることなく、加飾コート剤として好適に使用することができる。 As shown in Table 13, the polymeric resin composition of the present invention containing TBCHA with a p-trans isomer content of 70% or more can contain TBCHA with a p-trans isomer content of less than 70%. Compared to the blended polymeric resin composition, it was good in all evaluations of surface tack resistance, elongation, pencil hardness, scratch resistance, bending resistance, and sunscreen resistance (Example B-49 ~51). The TBCHA of the present invention with a p-trans isomer content of 70% or more has excellent hardness, elongation, and durability, so even when mixed with other general-purpose ultraviolet curable monomers as a decorative coating agent, It can be suitably used as a decorative coating agent without reducing surface tackiness or hardness.
実施例Ｂ－５４～５７と比較例Ｂ－５８、５９
重合性樹脂組成物Ｘ－５４～５９を用い、紫外線硬化性接着剤を調製し、下記方法にて偏光板作製及び偏光板の物性評価を行った。結果を表１４に示す。
（紫外線照射による偏光板の作製）
卓上型ロール式ラミネーター機（Ｒｏｙａｌ Ｓｏｖｅｒｅｉｇｎ製 ＲＳＬ－３８２Ｓ）を用いて、２枚の透明フィルムの間にポリビニルアルコール系偏光フィルムを挟み、透明フィルムと偏光フィルムの間に、実施例又は比較例の接着剤を、厚さ１０μｍになるように貼り合わせた。貼り合わせた透明フィルムの上面から紫外線を照射（装置：アイグラフィックス製 インバーター式コンベア装置ＥＣＳ－４０１１ＧＸ、メタルハライドランプ：アイグラフィックス製 Ｍ０４－Ｌ４１、紫外線照度：７００ｍＷ／ｃｍ２、積算光量：１０００ｍＪ／ｃｍ２）し、偏光フィルムの両側に透明フィルムを有する偏光板を作製した。なお、透明フィルムとして、アクリル系保護フィルム（カネカ社製のサンデュレンＳＤ－０１４）を使用した。
Examples B-54 to 57 and Comparative Examples B-58 and 59
An ultraviolet curable adhesive was prepared using polymerizable resin compositions X-54 to 59, and a polarizing plate was prepared and the physical properties of the polarizing plate were evaluated using the following method. The results are shown in Table 14.
(Preparation of polarizing plate by ultraviolet irradiation)
Using a tabletop roll laminator machine (RSL-382S manufactured by Royal Sovereign), a polyvinyl alcohol-based polarizing film was sandwiched between two transparent films, and the adhesive of Examples or Comparative Examples was placed between the transparent film and the polarizing film. The materials were bonded together to a thickness of 10 μm. Irradiate ultraviolet rays from the top surface of the bonded transparent film (equipment: I-Graphics inverter conveyor device ECS-4011GX, metal halide lamp: I-Graphics M04-L41, UV illuminance: 700 mW/cm 2 , cumulative light intensity: 1000 mJ/ cm 2 ), and a polarizing plate having transparent films on both sides of the polarizing film was prepared. Note that an acrylic protective film (Sunduren SD-014 manufactured by Kaneka Corporation) was used as the transparent film.
（表面形状観察）
得られた偏光板表面を目視によって観察し、下記基準で評価した。
◎：偏光板の表面に微小なスジも凹凸ムラも確認できない
○：偏光板の表面に部分的に微小なスジが確認できる
△：偏光板の表面に微小なスジや凹凸ムラが確認できる
×：偏光板の表面に明らかなスジや凹凸ムラが確認できる
（剥離強度）
温度２３℃、相対湿度５０％の条件下、２０ｍｍ×１５０ｍｍに裁断した偏光板（試験片）を、引っ張り試験機（島津製作所製 オートグラフＡＧＸＳ－Ｘ ５００Ｎ）に取り付けた試験板に両面接着テープを用いて貼り付けた。両面接着テープを貼付していない方の透明保護フィルムと偏光フィルムの一片を、２０～３０ｍｍ程度あらかじめ剥がしておき、上部つかみ具にチャックし、剥離速度３００ｍｍ／ｍｉｎにて９０°剥離強度（Ｎ／２０ｍｍ）を測定した。
◎：３．０（Ｎ／２０ｍｍ）以上
○：１．５（Ｎ／２０ｍｍ）以上、３．０（Ｎ／２０ｍｍ）未満
△：１．０（Ｎ／２０ｍｍ）以上、１．５（Ｎ／２０ｍｍ）未満
×：１．０（Ｎ／２０ｍｍ）未満
（耐水性）
得られた偏光板を２０×８０ｍｍに切断し、６０℃の温水に４８時間浸漬した後、偏光子と保護フィルム、位相差フィルム、光学補償フィルムとの界面における剥離の有無を確認した。判定は下記の基準で行った。
◎：偏光子と保護フィルムとの界面で剥離なし（１ｍｍ未満）
○：偏光子と保護フィルムとの界面の一部に剥離あり（１ｍｍ以上、３ｍｍ未満）
△：偏光子と保護フィルムとの界面の一部に剥離あり（３ｍｍ以上、５ｍｍ未満）
×：偏光子と保護フィルムとの界面で剥離あり（５ｍｍ以上）
（耐久性）
得られた偏光板を１５０ｍｍ×１５０ｍｍに裁断し、冷熱衝撃装置（エスペック社製ＴＳＡ－１０１Ｌ－Ａ）に入れ、－４０℃～８０℃のヒートショックを各３０分間、１００回行い、下記基準で評価した。
◎：クラックの発生なし
○：端部にのみ５ｍｍ以下の短いクラックの発生あり
△：端部以外の場所にクラックが短い線状に発生している。しかし、その線により偏光板が２つ以上の部分に分離してはいない
×：端部以外の場所にクラックの発生あり、その線により、偏光板が２つ以上の部分に分離している
（耐熱黄変性）
得られた偏光板を３０ｍｍ×３０ｍｍに裁断し、透過色相のａ値及びｂ値を測定し（（株）島津製作所製の紫外可視分光光度計ＵＶ－２４５０にて、波長３８０～７８０ｎｍの平行透過色相ａ値及び直交透過色相ｂ値を測定し、透過色相のａｂ値（ａｂ＝（ａ２＋ｂ２）１／２）を算出した。その後、偏光板を９０℃の恒温槽に４８時間保持し、耐熱黄変性試験を行った。試験後のａｂ値を同様に算出し、Δａｂ（Δａｂ＝試験後のａｂ値－試験前のａｂ値）の値が黄変の指標とした。Δａｂ＝０の場合は、黄変せず、Δａｂが大きくなるほど黄変が大きいことを意味する。
◎：０＜＝Δａｂ＜＝２
○：２＜Δａｂ＜＝６
△：６＜Δａｂ＜＝１０
×：１０＜Δａｂ
(Surface shape observation)
The surface of the obtained polarizing plate was visually observed and evaluated according to the following criteria.
◎: No microscopic streaks or uneven unevenness can be observed on the surface of the polarizing plate. ○: Microscopic streaks can be observed partially on the surface of the polarizing plate. △: Microscopic streaks or uneven unevenness can be observed on the surface of the polarizing plate. ×: Clear streaks and irregularities can be seen on the surface of the polarizing plate (peel strength)
At a temperature of 23°C and a relative humidity of 50%, a polarizing plate (test piece) cut into 20 mm x 150 mm was attached to a test plate attached to a tensile tester (Autograph AGXS-X 500N, manufactured by Shimadzu Corporation), and double-sided adhesive tape was attached to it. Pasted using. A piece of the transparent protective film and the polarizing film on which the double-sided adhesive tape is not attached is peeled off in advance by about 20 to 30 mm, chucked in the upper grip, and measured at a peeling speed of 300 mm/min at 90° peel strength (N/ 20 mm) was measured.
◎: 3.0 (N/20mm) or more ○: 1.5 (N/20mm) or more, less than 3.0 (N/20mm) △: 1.0 (N/20mm) or more, 1.5 (N/20mm) ×: Less than 1.0 (N/20mm) (water resistance)
The obtained polarizing plate was cut into a size of 20×80 mm and immersed in warm water at 60° C. for 48 hours, and then the presence or absence of peeling at the interface between the polarizer and the protective film, retardation film, and optical compensation film was confirmed. Judgment was made based on the following criteria.
◎: No peeling at the interface between polarizer and protective film (less than 1 mm)
○: Peeling at part of the interface between the polarizer and the protective film (1 mm or more, less than 3 mm)
△: Peeling at part of the interface between the polarizer and the protective film (3 mm or more, less than 5 mm)
×: Peeling at the interface between the polarizer and the protective film (5 mm or more)
(durability)
The obtained polarizing plate was cut to 150 mm x 150 mm, placed in a thermal shock device (TSA-101L-A manufactured by Espec), and subjected to heat shock of -40°C to 80°C 100 times for 30 minutes each. evaluated.
◎: No cracks occurred. ○: Short cracks of 5 mm or less occurred only at the edges. △: Short linear cracks occurred at locations other than the edges. However, the line does not separate the polarizing plate into two or more parts. ×: Cracks occur at locations other than the edges, and the line separates the polarizing plate into two or more parts ( heat-resistant yellowing)
The obtained polarizing plate was cut to 30 mm x 30 mm, and the a value and b value of the transmitted hue were measured (parallel transmission at wavelengths of 380 to 780 nm using a UV-visible spectrophotometer UV-2450 manufactured by Shimadzu Corporation). The hue a value and orthogonal transmission hue b value were measured, and the ab value of the transmission hue (ab = (a2 + b2) 1/2) was calculated.Then, the polarizing plate was kept in a thermostat at 90°C for 48 hours, and the heat-resistant yellow A denaturation test was conducted. The ab value after the test was calculated in the same way, and the value of Δab (Δab = ab value after the test - ab value before the test) was taken as an index of yellowing. If Δab = 0, No yellowing occurs, and the larger Δab, the greater the yellowing.
◎:0<=Δab<=2
○:2<Δab<=6
△: 6<Δab<=10
×: 10<Δab
表１４に示すとおり、本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した偏光板は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満のＴＢＣＨＡを配合した偏光板と比較して、偏光板表面にスジやムラがなく、剥離強度、耐水性、耐久性、耐熱黄変性のすべての評価において良好であった（実施例Ｂ－５４～５９）。本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡは保護フィルムであるアクリル系フィルムに対するぬれ性と密着性に優れるため、偏光板として使用するに十分な接着力を有し、また、接着剤として汎用の他の紫外線硬化性モノマーと混合した場合においても、接着力や耐水性、耐久性を低下させることなく、偏光板用接着剤として好適に使用することができる。 As shown in Table 14, the polarizing plate containing TBCHA containing 70% or more of the p-trans isomer of the present invention is the polarizing plate containing TBCHA containing less than 70% of the p-trans isomer. Compared to the plate, there were no streaks or unevenness on the surface of the polarizing plate, and it was good in all evaluations of peel strength, water resistance, durability, and heat yellowing resistance (Examples B-54 to B-59). The TBCHA of the present invention with a p-trans isomer content of 70% or more has excellent wettability and adhesion to an acrylic film that is a protective film, so it has sufficient adhesive strength to be used as a polarizing plate. Furthermore, even when mixed with other general-purpose ultraviolet curable monomers as an adhesive, it can be suitably used as an adhesive for polarizing plates without reducing adhesive strength, water resistance, or durability.
実施例Ｂ－６０～Ｂ－６３と比較例Ｂ－６４、６５
重合性樹脂組成物Ｘ－６０～６５を用い、紫外線硬化性封止材を調製した。その後、得られた封止材を用い、下記方法にて、紫外線硬化による封止材樹脂硬化物の作製及び物性評価を行った。
（紫外線硬化型封止材樹脂硬化物の作製方法）
ガラス板（縦５０ｍｍ×横５０ｍｍ×厚さ５ｍｍ）上にシリコン製のスペーサー（縦３０ｍｍ×横１５ｍｍ×厚さ３ｍｍ）をセットし、スペーサーの内部に銅箔（縦５ｍｍ×横５０ｍ×厚み８０μｍ）を入れ、上記にて調製した紫外線硬化型封止材を注入した。十分に脱気した後、紫外線を照射（装置：アイグラフィックス製インバーター式コンベア装置ＥＣＳ－４０１１ＧＸ、メタルハライドランプ：アイグラフィックス製 Ｍ０４－Ｌ４１、紫外線照度：７００ｍＷ／ｃｍ２、積算光量：１０００ｍＪ／ｃｍ２）し、封止材樹脂硬化物を作製した。得られた硬化物の特性を下記方法で評価した。結果を表１５に示す。
Examples B-60 to B-63 and Comparative Examples B-64 and 65
Ultraviolet curable encapsulants were prepared using polymerizable resin compositions X-60 to X-65. Thereafter, using the obtained sealant, a cured sealant resin was prepared by ultraviolet curing and the physical properties were evaluated in the following manner.
(Method for producing cured ultraviolet curable encapsulant resin)
A silicon spacer (30 mm long x 15 mm wide x 3 mm thick) is set on a glass plate (50 mm long x 50 mm wide x 5 mm thick), and a copper foil (5 mm long x 50 m wide x 80 μm thick) is placed inside the spacer. was added, and the ultraviolet curable encapsulant prepared above was injected. After sufficient degassing, irradiate with ultraviolet light (equipment: ECS-4011GX inverter conveyor manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW/cm 2 , cumulative light intensity: 1000 mJ/cm 2 ) A cured sealing material resin was prepared. The properties of the obtained cured product were evaluated by the following method. The results are shown in Table 15.
（透明性）
作製した硬化物を温度２３℃、相対湿度５０％の雰囲気下で、２４時間を静止した。それ後、前記と同様にヘイズメーターにより透過率を測定し、透明性を評価した。
（耐湿熱黄変性）
得られた初期の硬化物を用いて、温度２３℃、相対湿度５０％の雰囲気下で、２４時間を静止した。それ後、硬化物の透過スペクトルを透過色測定専用機（ＴＺ－６０００、日本電色工業(株)製）により測定し、初期ｂ値とした。硬化膜を用いて、８５℃、相対湿度８５％に設定した恒温恒湿機に５００時間を静置し、耐湿熱黄変性の加速試験を行った。試験後の硬化膜を同様に温度２３℃、相対湿度５０％の雰囲気下で２４時間を静止し、透過色測定し、湿熱後ｂ値とした。また、湿熱後ｂ値と初期ｂ値の差は変化値Δｂとした（Δｂ＝湿熱後ｂ値－初期ｂ値）。耐湿熱黄変性は下記通り４段階分けて評価した。
◎：初期ｂ値、湿熱後ｂ値は共に０．２以下、かつ、Δｂは０．１以下である
○：初期ｂ値、湿熱後ｂ値は何れか一つまたは共に０．２を超えるが、共に０．５以下であり、かつ、Δｂは０．２以下である
△：初期ｂ値、湿熱後ｂ値は何れか一つまたは共に０．５を超えるが、共に１．０以下であり、かつ、Δｂは０．３以下である
×：初期ｂ値、湿熱後ｂ値は何れか一つまたは共に１．０を超え、或いは、Δｂは０．３を超える。
（吸水率試験）
得られた硬化物から１ｇを切り取って、試験片として温度８５℃×相対湿度９５％の恒温恒湿機にセットし、４８時間静置後、再び試験片の重量を測定し、吸水率を下記式により算出した。
吸水率(％)＝（吸湿後重量―吸湿前重量）/吸湿前重量×１００
◎：吸水率は１．０％未満
○：吸水率は１．０％以上、かつ２．０％未満
△：吸水率は２．０％以上、かつ３．０％未満
×：吸水率は３．０％以上
（アウトガス試験）
得られた硬化物から１ｇを切り取って、試験片として温度１００℃に設定した恒温槽に静置し、乾燥窒素気流を２４時間流して、その後再び試験片の重量を測定し、下記式によりアウトガスの発生率を算出した。
アウトガス発生率(％)＝（恒温後の重量―恒温前の重量）/恒温前の重量×１００
◎：発生率は０．１％未満
○：発生率は０．１％以上、かつ０．３％未満
△：発生率は０．３％以上、かつ１．０％未満
×：発生率は１．０％以上
（耐ヒートリサイクル性）
得られた硬化物を－４０℃で３０分間、次に１００℃で３０分間放置を１サイクルとして１００回繰り返し、硬化物の状態を目視によって観察した。
◎：全く変化が見られない
〇：わずかに気泡の発生が見られるが、クラックの発生が見られない。透明である。
△：多少の気泡或いはクラックの発生が見られ、わずかな曇である。
×：気泡又はクラックが全面的に発生し、半透明状態である。
（耐腐食性）
耐湿熱黄変性試験後、銅箔の表面を目視で観察し、銅板から硬化膜をゆっくり剥がして、銅箔（厚み８０μｍ）に貼りあわせた試験片（Ｃｕ耐腐食性評価用）を用いて、温度６０℃、相対湿度９５％に設定した恒温恒湿機に１６８時間を静置した。その後、硬化膜をアルミ基板又は銅箔から剥がして、目視でアルミ基板と銅箔の表面を観察し、硬化膜の耐腐食性を評価した。
◎：腐食なし
○：僅かに腐食
△：少し腐食
×：著しい腐食
(transparency)
The produced cured product was left still for 24 hours in an atmosphere with a temperature of 23° C. and a relative humidity of 50%. Thereafter, transmittance was measured using a haze meter in the same manner as above to evaluate transparency.
(Moist heat yellowing resistance)
The obtained initial cured product was left at rest for 24 hours in an atmosphere with a temperature of 23° C. and a relative humidity of 50%. Thereafter, the transmission spectrum of the cured product was measured using a dedicated transmission color measurement device (TZ-6000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and was determined as the initial b value. The cured film was left standing in a constant temperature and humidity machine set at 85° C. and 85% relative humidity for 500 hours to perform an accelerated test for resistance to moist heat yellowing. The cured film after the test was similarly kept at rest for 24 hours in an atmosphere with a temperature of 23° C. and a relative humidity of 50%, the transmitted color was measured, and the b value was determined after moist heat. Further, the difference between the b value after moist heat and the initial b value was defined as a change value Δb (Δb=b value after moist heat−initial b value). Moisture heat yellowing resistance was evaluated in four stages as described below.
◎: The initial b value and the b value after moist heat are both 0.2 or less, and Δb is 0.1 or less. ○: The initial b value and the b value after moist heat are either one or both exceeding 0.2. , both are 0.5 or less, and Δb is 0.2 or less. △: Either or both of the initial b value and the b value after moist heat exceed 0.5, but both are 1.0 or less. , and Δb is 0.3 or less ×: Either or both of the initial b value and the b value after moist heat exceed 1.0, or Δb exceeds 0.3.
(Water absorption test)
Cut out 1 g from the obtained cured product, set it as a test piece in a constant temperature and humidity machine at a temperature of 85 ° C and relative humidity of 95%, leave it for 48 hours, then measure the weight of the test piece again, and calculate the water absorption rate as shown below. Calculated using the formula.
Water absorption rate (%) = (weight after moisture absorption - weight before moisture absorption) / weight before moisture absorption x 100
◎: Water absorption rate is less than 1.0% ○: Water absorption rate is 1.0% or more and less than 2.0% △: Water absorption rate is 2.0% or more and less than 3.0% ×: Water absorption rate is 3 .0% or more (outgas test)
Cut out 1 g from the obtained cured product and leave it as a test piece in a constant temperature bath set at a temperature of 100°C. A stream of dry nitrogen was passed through it for 24 hours, and then the weight of the test piece was measured again. The incidence rate was calculated.
Outgas generation rate (%) = (Weight after constant temperature - Weight before constant temperature) / Weight before constant temperature x 100
◎: Incidence rate is less than 0.1% ○: Incidence rate is 0.1% or more and less than 0.3% △: Incidence rate is 0.3% or more and less than 1.0% ×: Incidence rate is 1 .0% or more (heat recycling resistance)
The resulting cured product was left at -40°C for 30 minutes and then at 100°C for 30 minutes, which was repeated 100 times, and the condition of the cured product was visually observed.
◎: No change is observed. ○: Slight generation of bubbles is observed, but no cracks are observed. It is transparent.
Δ: Some bubbles or cracks are observed, and there is slight cloudiness.
×: Bubbles or cracks are generated over the entire surface, and the sample is in a translucent state.
(Corrosion resistance)
After the moist heat yellowing test, the surface of the copper foil was visually observed, the cured film was slowly peeled off from the copper plate, and a test piece (for evaluating Cu corrosion resistance) was pasted on the copper foil (thickness 80 μm). It was left standing for 168 hours in a constant temperature and humidity machine set at a temperature of 60° C. and a relative humidity of 95%. Thereafter, the cured film was peeled off from the aluminum substrate or copper foil, and the surfaces of the aluminum substrate and copper foil were visually observed to evaluate the corrosion resistance of the cured film.
◎: No corrosion ○: Slight corrosion △: Slight corrosion ×: Significant corrosion
表１５に示すとおり、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを配合した本発明の封止材樹脂硬化物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満のＴＢＣＨＡを配合した封止材樹脂硬化物と比較して、透明性、吸水率、アウトガス発生率、体ヒートリサイクル性、耐湿熱黄変性、耐腐食性のすべての評価において良好であった（実施例Ｂ－６０～６３）。本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡは封止材として汎用の他の紫外線硬化性モノマーと混合した場合においても、透明性や吸水性を低下させることなく、封止材用樹脂として好適に使用することができる。 As shown in Table 15, the cured encapsulant resin of the present invention containing TBCHA with a p-trans isomer content of 70% or more is TBCHA with a p-trans isomer content of less than 70%. Compared to the cured encapsulant resin containing B, it was better in all evaluations of transparency, water absorption rate, outgassing rate, body heat recyclability, moist heat yellowing resistance, and corrosion resistance (Example B -60 to 63). The TBCHA of the present invention having a p-trans isomer content of 70% or more can be used as a sealing material without reducing transparency or water absorption even when mixed with other general-purpose ultraviolet curable monomers. It can be suitably used as a resin for a retaining material.
以上のように、実施例と比較例の評価結果に示すとおり、本発明のｐ－ｔｒａｎｓ型異性体の含有量が７０％以上のＴＢＣＨＡを含有する重合性樹脂組成物は、色目や、硬化性、各種基材への密着性、接着性等、各用途で求められる各種物性が良好であることが示された。一方、同じＴＢＣＨＡであっても、ｐ－ｔｒａｎｓ型異性体の含有量が７０％未満であれば、上記用途で求められる各種物性や性能が達成できないことが認められた。 As described above, as shown in the evaluation results of Examples and Comparative Examples, the polymerizable resin composition containing TBCHA with a content of p-trans type isomer of 70% or more of the present invention has poor color and curable properties. It was shown that various physical properties required for each application, such as adhesion and adhesion to various substrates, were good. On the other hand, it has been found that even if the same TBCHA is used, if the p-trans isomer content is less than 70%, various physical properties and performances required for the above-mentioned uses cannot be achieved.
以上説明してきたように、本発明の重合性樹脂組成物は、ｐ－ｔｒａｎｓ型異性体の含有量が７０％以上を有するｔ－ブチルシクロヘキシル（メタ）アクリレートを配合することによって、着色も臭気も低く、皮膚刺激性が低く、各種基材への濡れ性や密着性が良好であるため、濡れ性向上剤、密着性向上剤として用いることができる。また、インク(主にインクジェット、オフセット、スクリーン、フレキソ、水系、光造形のモデル材とサポート材)、粘着剤、接着剤、コーティング剤、塗料、光造形用樹脂、封止材、分散剤、界面活性剤、加飾コート剤、防曇塗料、電池用セパレータ、歯科材料等に広く使用することができる。
As explained above, the polymerizable resin composition of the present invention is free from coloration and odor by incorporating t-butylcyclohexyl (meth)acrylate having a p-trans isomer content of 70% or more. It has low skin irritation and good wettability and adhesion to various substrates, so it can be used as a wettability improver and an adhesion improver. In addition, ink (mainly inkjet, offset, screen, flexo, water-based, stereolithography model materials and support materials), adhesives, adhesives, coatings, paints, stereolithography resins, encapsulants, dispersants, interfaces. It can be widely used in activators, decorative coating agents, anti-fog paints, battery separators, dental materials, etc.
Claims (11)
重合性組成物中のｔ－ブチルシクロヘキシル（メタ）アクリレートの含有量は５～９０重量％であり、ｔ－ブチルシクロヘキシル（メタ）アクリレート中のｐ－ｔｒａｎｓ型異性体の含有量は７０％以上であり、
不飽和結合を有する化合物は不飽和結合１個を有する単官能モノマー、不飽和結合２個以上を有する多官能モノマー、不飽和結合２個以上を有する多官能オリゴマーのいずれか1種以上を有するインク組成物。 Contains a polymerizable resin composition containing t-butylcyclohexyl (meth)acrylate and a compound having an unsaturated bond (excluding t-butylcyclohexyl (meth)acrylate) and/or a polymer of the polymerizable resin composition An ink composition comprising:
The content of t-butylcyclohexyl (meth)acrylate in the polymerizable composition is 5 to 90% by weight, and the content of p-trans type isomer in t-butylcyclohexyl (meth)acrylate is 70% or more. can be,
The compound having an unsaturated bond is an ink containing one or more of the following: a monofunctional monomer having one unsaturated bond, a polyfunctional monomer having two or more unsaturated bonds, and a polyfunctional oligomer having two or more unsaturated bonds. Composition.
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| Publication number | Publication date |
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| JP7251724B2 (en) | 2023-04-04 |
| JP7433615B2 (en) | 2024-02-20 |
| JP2023029905A (en) | 2023-03-07 |
| JP2023053945A (en) | 2023-04-13 |
| JP7470947B2 (en) | 2024-04-19 |
| JP2023024478A (en) | 2023-02-16 |
| JP7417230B2 (en) | 2024-01-18 |
| JP7430889B2 (en) | 2024-02-14 |
| JP7430888B2 (en) | 2024-02-14 |
| JP2020033532A (en) | 2020-03-05 |
| JP2023016900A (en) | 2023-02-02 |
| JP2023027132A (en) | 2023-03-01 |
| JP2023016899A (en) | 2023-02-02 |
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