KR20210124274A - A photocurable silicone resin composition, a silicone resin molded article obtained by curing the same, and a method for producing the molded article - Google Patents
A photocurable silicone resin composition, a silicone resin molded article obtained by curing the same, and a method for producing the molded article Download PDFInfo
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- KR20210124274A KR20210124274A KR1020217026301A KR20217026301A KR20210124274A KR 20210124274 A KR20210124274 A KR 20210124274A KR 1020217026301 A KR1020217026301 A KR 1020217026301A KR 20217026301 A KR20217026301 A KR 20217026301A KR 20210124274 A KR20210124274 A KR 20210124274A
- Authority
- KR
- South Korea
- Prior art keywords
- silicone resin
- mass
- resin composition
- group
- photocurable
- Prior art date
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 110
- 239000011342 resin composition Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 238000002834 transmittance Methods 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 230000003287 optical effect Effects 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 239000003504 photosensitizing agent Substances 0.000 claims description 20
- -1 oxime ester Chemical class 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 claims description 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 29
- 238000006460 hydrolysis reaction Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 18
- 239000005020 polyethylene terephthalate Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 239000012454 non-polar solvent Substances 0.000 description 11
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- LJSLYKNKVQMIJY-UHFFFAOYSA-N 1,4-diethoxynaphthalene Chemical compound C1=CC=C2C(OCC)=CC=C(OCC)C2=C1 LJSLYKNKVQMIJY-UHFFFAOYSA-N 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- JJPJWPYRFJDRMH-UHFFFAOYSA-N 1,4-dipropoxynaphthalene Chemical compound C1=CC=C2C(OCCC)=CC=C(OCCC)C2=C1 JJPJWPYRFJDRMH-UHFFFAOYSA-N 0.000 description 2
- UDQSUQGVJKUQSS-UHFFFAOYSA-N 2,6-dipropoxynaphthalene Chemical compound C(CC)OC1=CC2=CC=C(C=C2C=C1)OCCC UDQSUQGVJKUQSS-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- FWWRTYBQQDXLDD-UHFFFAOYSA-N 1,4-dimethoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=C(OC)C2=C1 FWWRTYBQQDXLDD-UHFFFAOYSA-N 0.000 description 1
- APQSQLNWAIULLK-UHFFFAOYSA-N 1,4-dimethoxynaphthalene Natural products C1=CC=C2C(C)=CC=C(C)C2=C1 APQSQLNWAIULLK-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SFMWCTLRFTWBQO-UHFFFAOYSA-N 2,6-diethoxynaphthalene Chemical compound C1=C(OCC)C=CC2=CC(OCC)=CC=C21 SFMWCTLRFTWBQO-UHFFFAOYSA-N 0.000 description 1
- AHKDVDYNDXGFPP-UHFFFAOYSA-N 2,6-dimethoxynaphthalene Chemical compound C1=C(OC)C=CC2=CC(OC)=CC=C21 AHKDVDYNDXGFPP-UHFFFAOYSA-N 0.000 description 1
- YWEJNVNVJGORIU-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-hydroxy-2-phenylacetate Chemical compound OCCOCCOC(=O)C(O)C1=CC=CC=C1 YWEJNVNVJGORIU-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- 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 1
- GJNKQJAJXSUJBO-UHFFFAOYSA-N 9,10-diethoxyanthracene Chemical compound C1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 GJNKQJAJXSUJBO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XZCITMHGTLMTKL-UHFFFAOYSA-N OC(C(C(=O)OCC(C)(CO)C)(C)C)O Chemical compound OC(C(C(=O)OCC(C)(CO)C)(C)C)O XZCITMHGTLMTKL-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
Abstract
실리콘 수지와 불포화 화합물과 광중합개시제를 포함하는 광경화성 실리콘 수지 조성물을 경화시킬 때에 발생하는 산소 저해의 영향을 감소시키고, 저노광량으로도 충분한 내찰상성과 착색이 적은 실리콘 수지 성형체를 부여하는 바와 같은 광경 화성 실리콘 수지 조성물을 제공한다. 실리콘 수지(A1)와 분자 중에 -R3-CR4= CH2 또는 -CR4=CH2로 나타내어지는 불포화기를 적어도 1개 포함함과 아울러, 상기 실리콘 수지(A1)와 라디칼 공중합이 가능한 불포화 화합물(A2)을 1:99~99:1의 질량 비율로 배합한 실리콘 수지 조성물(A)과 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광 투과율이 90% 미만인 광중합개시제(D)를 포함하고, 상기 A2는 20질량% 이상이 수산기를 포함하는 불포화 화합물이고, 상기 실리콘 수지 조성물(A)에 대하여 상기 D가 0.1질량% 이상 0.1% 이상 20질량% 미만으로 배합되는 광경화성 실리콘 수지 조성물 및 그 성형체이다.Reduces the effect of oxygen inhibition that occurs when curing a photocurable silicone resin composition comprising a silicone resin, an unsaturated compound, and a photopolymerization initiator, and provides a silicone resin molded article with sufficient scratch resistance and little coloration even at a low exposure dose. A chemical conversion silicone resin composition is provided. An unsaturated compound capable of radical copolymerization with the silicone resin (A1) while containing at least one unsaturated group represented by -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 in the molecule with the silicone resin (A1) A silicone resin composition (A) containing (A2) in a mass ratio of 1:99 to 99:1 and a photopolymerization initiator (D) having an optical path length of 1 cm and a wavelength of 360 nm of a 0.01 mass% solution and a light transmittance of less than 90% wherein A2 is an unsaturated compound containing 20% by mass or more of a hydroxyl group, and D is 0.1% by mass or more and 0.1% or more and less than 20% by mass relative to the silicone resin composition (A) A photocurable silicone resin composition and a molded product thereof.
Description
본 발명은, 높은 내찰상성 및 투명성 등이 우수한 성형체를 얻을 수 있는 광경화성 실리콘 수지 조성물, 및 이것을 경화시켜서 얻어진 3차원 가교체인 실리콘 수지 성형체에 관한 것이다.The present invention relates to a photocurable silicone resin composition capable of obtaining a molded article excellent in high scratch resistance and transparency, and the like, and a silicone resin molded article as a three-dimensional crosslinked body obtained by curing the same.
최근, 디스플레이나 모바일 기기, 가전 제품, 자동차 부품 등, 모든 분야에 있어서 의장성이나 경량화, 박형화의 니즈가 강해지고 있고, 그것들의 표면 보호 부재로서, 지금까지의 유리나 금속을 대신하여, 플라스틱이나 경량화 금속 등이 사용되고 있다. 그러나, 플라스틱이나 일부의 경량화 금속은 표면 경도가 낮아, 손상되기 쉽다는 과제가 있다. 그래서, 표면을 보호하는 하드 코트층을 형성하는 방법이 이용되고 있다.In recent years, in all fields, such as displays, mobile devices, home appliances, and automobile parts, the need for designability, weight reduction, and thickness reduction is increasing. metal is used. However, plastics and some lightweight metals have a low surface hardness and have a problem that they are easily damaged. Then, the method of forming the hard-coat layer which protects the surface is used.
이러한 하드 코트층에는 아크릴계 조성물이 많이 사용되고 있다. 아크릴계 조성물은, 일반적으로, 자외선이나 전자선 등의 활성 에너지선 조사에 의한 라디칼반응에 의해 성막·경화되기 때문에, 단시간 또한 저온으로 경화 가능하고, 배합되는 수지 조성에 의해 인성을 유지할 수 있기 때문에, 도료, 접착제 등에 널리 사용되고 있다.Many acrylic compositions are used for such a hard coat layer. Since acrylic compositions are generally formed and cured by radical reaction by irradiation with active energy rays such as ultraviolet rays or electron beams, they can be cured for a short time and at low temperatures, and toughness can be maintained by the resin composition to be blended. , adhesives, etc. are widely used.
이와 같은 하드 코트층의 일례로서, 본 발명자 등은, 바구니형 구조를 가짐과 아울러 반응성 관능기를 가지는 실리콘 수지에 착안해서 검토를 행해오고 있고, 이 바구니형 구조를 갖는 실리콘 수지에 있어서의 반응성 관능기 수를 증가시키고, 이것과 라디칼 공중합이 가능한 불포화 화합물을 특정 비율로 배합함으로써, 고표면 경도, 내열성, 기계적 특성 및 치수 안정성 등의 밸런스가 우수함과 아울러 투명한 실리콘 수지 성형체를 부여하는 것이 가능한 것을 찾아내고, 이것이 무기 유리의 대체 용도로서 적합하게 사용할 수 있는 것을 개시하고 있다(특허문헌1~2). 또한, 이와 같은 바구니형 구조를 갖는 실리콘 수지의 제조 방법에 대해서는, 특히, 특허문헌 3에서 개시하고 있다.As an example of such a hard coat layer, the inventors of the present invention have studied while paying attention to a silicone resin having a cage structure and a reactive functional group, and the number of reactive functional groups in the silicone resin having this cage structure By increasing and blending this and an unsaturated compound capable of radical copolymerization in a specific ratio, it is possible to provide a transparent silicone resin molded body with excellent balance of high surface hardness, heat resistance, mechanical properties and dimensional stability, etc., What can be used suitably as an alternative use of this inorganic glass is disclosed (patent documents 1-2). Moreover, about the manufacturing method of the silicone resin which has such a cage structure, patent document 3 is specifically disclosing.
그러나, 이러한 실리콘 수지 조성물에 대해서, 라디칼 중합 반응에 의한 경화를 대기 중에서 행했을 경우에는, 산소 저해의 영향을 받기 때문에, 경화가 진행되지 않는 점으로부터 충분한 내찰상성을 얻는 것은 곤란하다. 대기 경화성을 개선하기 위해서, 광중합개시제에 고감도 재료를 사용하고, 배합량을 증가시키는 것이나 노광량을 늘리는 것이 일반적이지만, 이들 방법에서는, 경화막에 광중합개시제의 착색이 남아 버리는 것이 과제이다.However, when hardening by radical polymerization reaction is performed in air|atmosphere with respect to such a silicone resin composition, since it receives the influence of oxygen inhibition, since hardening does not advance, it is difficult to acquire sufficient abrasion resistance. In order to improve atmospheric hardenability, it is common to use a highly sensitive material for a photoinitiator, and to increase a compounding quantity and to increase an exposure amount, but in these methods, it is a problem that coloring of a photoinitiator remains on a cured film.
산소를 차단하는 고가인 설비를 불필요로 해서 일반적인 도공 설비 등에도 적용할 시, 실리콘 수지와 불포화 화합물과 광중합개시제를 포함하는 광경화성 실리콘 수지 조성물을 경화시킬 때에 발생하는 산소 저해의 영향을 감소시키고, 저노광량으로도, 충분한 내찰상성과 착색이 적은 실리콘 수지 성형체를 부여하는 바와 같은 광경화성 실리콘 수지 조성물을 제공하는 것을 목적으로 한다.Reduces the effect of oxygen inhibition that occurs when curing a photocurable silicone resin composition containing a silicone resin, an unsaturated compound, and a photopolymerization initiator when applied to general coating equipment, etc. by eliminating the need for expensive equipment that blocks oxygen, It aims at providing the photocurable silicone resin composition which gives a silicone resin molded object with sufficient abrasion resistance and little coloring even at a low exposure dose.
본 발명자 등은, 이와 같은 광경화성 실리콘 수지 조성물에 대해서, 특히, 그 조성 중의 라디칼 중합 가능한 불포화 화합물과 광중합개시제의 조합에 대해서 예의 검토한 결과, 불포화 화합물로서 수산기를 포함하는 것을 소정량 배합하고, 또한, 특정의 광중합개시제와, 바람직하게는 특정의 광증감제를 소정량 사용함으로써, 상기 과제를 해결할 수 있는 것을 찾아내어 본 발명에 이르렀다.The present inventors, as a result of intensive studies on the combination of a radically polymerizable unsaturated compound and a photoinitiator in such a photocurable silicone resin composition, in particular, in the composition, blend a predetermined amount of an unsaturated compound containing a hydroxyl group, Moreover, by using a specific photoinitiator, Preferably, a specific photosensitizer in a predetermined amount, it discovered that the said subject could be solvable, and led to this invention.
즉, 본 발명은, 광경화성 실리콘 수지 조성물로서,That is, the present invention is a photocurable silicone resin composition,
실리콘 수지(A1)와, 분자 중에 -R3-CR4=CH2 또는 -CR4=CH2〔단, R3은 알킬렌기, 알킬리덴기 또는 -O-C(=O)-기를 나타내고, R4는 수소 원자 또는 알킬기를 나타낸다〕로 나타내어지는 불포화기를 적어도 1개 포함함과 아울러 상기 실리콘 수지(A1)와 라디칼 공중합이 가능한 불포화 화합물(A2)을, 1:99~99:1의 질량 비율로 배합한 실리콘 수지 조성물(A)과,Silicone resin (A1) and -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 in the molecule [provided that R 3 represents an alkylene group, an alkylidene group or a -OC(=O)- group, and R 4 represents a hydrogen atom or an alkyl group] containing at least one unsaturated group represented by A silicone resin composition (A), and
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제(D)를 포함하는 광경화성 실리콘 수지 조성물이며,It is a photocurable silicone resin composition comprising a photoinitiator (D) having an optical path length of 1 cm of a 0.01 mass% solution and a light transmittance of less than 90% at a wavelength of 360 nm,
상기 불포화 화합물(A2)은, 그 적어도 20질량% 이상이 수산기를 포함하는 불포화 화합물이며,The unsaturated compound (A2) is an unsaturated compound in which at least 20% by mass or more contains a hydroxyl group,
상기 실리콘 수지 조성물(A)에 대하여, 광중합개시제(D)가 0.1질량% 이상 20질량% 미만으로 배합되는 것을 특징으로 하는 광경화성 실리콘 수지 조성물이다.It is a photocurable silicone resin composition characterized by the above-mentioned with respect to the said silicone resin composition (A) mix|blended in 0.1 mass % or more and less than 20 mass % of a photoinitiator (D).
상기 불포화 화합물(A2)은, 그 10~100질량%가, 분자 중에 -R3-CR4=CH2 또는 -CR4=CH2(단, R3은 알킬렌기, 알킬리덴기 또는 -O-C(=O)-기를 나타내고, R4는 수소 원자 또는 알킬기를 나타낸다)로 나타내어지는 불포화기를 적어도 2개 포함하는 비실리콘형의 다관능 불포화 화합물인 것이 좋다.The said unsaturated compound (A2) is 10-100 mass % in a molecule|numerator -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 (provided that R 3 is an alkylene group, an alkylidene group or -OC( =O)-, and R 4 represents a hydrogen atom or an alkyl group), preferably a non-silicone-type polyfunctional unsaturated compound containing at least two unsaturated groups.
상기 실리콘 수지(A1)는, 일반식 (1)The silicone resin (A1) is the general formula (1)
[RSiO3/2]n (1)[RSiO 3/2 ] n (1)
〔단, R은 (메타)아크릴로일기를 갖는 유기 관능기이며, n은 8, 10 또는 12이다〕로 나타내어지고, 구조 단위 중에 바구니형 구조를 갖는 폴리오르가노실세스퀴옥산을 주된 성분으로 하는 것이 좋다.[provided that R is an organic functional group having a (meth)acryloyl group, and n is 8, 10 or 12], and having polyorganosilsesquioxane having a cage structure in the structural unit as a main component good.
상기 광경화성 실리콘 수지 조성물은, 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광중합개시제(B)를 더 포함하는 것이 좋다. 여기에서, 이와 같은 광중합개시제(B)가 히드록시페닐케톤계 광중합개시제인 것이 좋다.It is preferable that the said photocurable silicone resin composition further contains the photoinitiator (B) whose optical path length of 1 cm of 0.01 mass % solution, and the light transmittance of 360 nm of wavelength is 90% or more. Here, it is preferable that such a photoinitiator (B) is a hydroxyphenyl ketone type photoinitiator.
상기 광경화성 실리콘 수지 조성물은, 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광증감제(C)를 더 포함하는 것이 좋다. 여기에서, 이와 같은 광증감제(C)가 나프탈렌계 광증감제인 것이 좋다.It is preferable that the said photocurable silicone resin composition further contains the photosensitizer (C) whose optical path length of 0.01 mass % solution is 1 cm, and the light transmittance of 360 nm of wavelength is 90% or more. Here, it is preferable that such a photosensitizer (C) is a naphthalene type photosensitizer.
상기 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제(D)가, α-아미노알킬페논계 광중합개시제, 아실포스핀옥사이드계 광중합개시제 및 옥심에스테르계 광중합개시제로 이루어지는 군으로부터 선택되는 1종 이상의 광중합개시제인 것이 좋다.The optical path length of the 0.01% by mass solution of 1 cm and a light transmittance of 360 nm at a wavelength of less than 90% of the photopolymerization initiator (D) is an α-aminoalkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator. It is preferable that it is one or more types of photoinitiators selected from the group which consists of agents.
또한, 본 발명은 상기 광경화성 실리콘 수지 조성물을, 라디칼 공중합시켜 경화시켜서 얻어진 실리콘 수지 성형체이다.Moreover, this invention is a silicone resin molded object obtained by making radical copolymerize and hardening the said photocurable silicone resin composition.
또한 본 발명은, 상기 광경화성 실리콘 수지 조성물에, 대기 하에서 활성 에너지선을 조사하고 라디칼 공중합시켜서 실리콘 수지 성형체로 하는 것을 특징으로 하는 실리콘 수지 성형체의 제조 방법이다.Further, the present invention is a method for producing a silicone resin molded body characterized in that the photocurable silicone resin composition is irradiated with an active energy ray under the atmosphere and subjected to radical copolymerization to obtain a silicone resin molded body.
본 발명의 광경화성 실리콘 수지 조성물에 의하면, 높은 내찰상성을 갖고, 고투명성이며, 높은 내열성을 갖는 성형체를 얻을 수 있고, 대기 분위기 하에서도 충분한 성능이 얻어지기 때문에, 예를 들면, 디스플레이, 모바일 기기의 케이싱, 가전 제품이나 자동차 내장재, 건축 부재 등의 다양한 용도의 표면 보호 부재로서 적합하다.According to the photocurable silicone resin composition of the present invention, a molded article having high scratch resistance, high transparency, and high heat resistance can be obtained, and sufficient performance can be obtained even in an atmospheric environment. For example, displays and mobile devices. It is suitable as a surface protection member for various uses, such as casings, home appliances and automobile interior materials, and building members.
이하, 본 발명에 대해서 더욱 설명한다.Hereinafter, the present invention will be further described.
본 발명의 광경화성 실리콘 수지 조성물은, 실리콘 수지(A1)(이하, 「본 실리콘 수지」라고도 한다)와, 분자 중에 -R3-CR4=CH2 또는 -CR4=CH2로 나타내어지는 불포화기를 적어도 1개 포함하고, 상기 실리콘 수지(A1)와 라디칼 공중합이 가능한 불포화 화합물(A2)(이하, 단지, 「불포화 화합물」이라고도 한다)을, A1:A2=1:99~99:1의 질량 비율로 배합한 실리콘 수지 조성물(A)을 포함하고, 상기 불포화 화합물(A2)의 적어도 20질량% 이상이 수산기를 포함하는 불포화 화합물이며, 또한, 이 실리콘 수지 조성물(A)에 추가해서, 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제(D)를 실리콘 수지 조성물(A)에 대하여 0.1질량% 이상 20질량% 미만으로 포함한다.The photocurable silicone resin composition of the present invention comprises a silicone resin (A1) (hereinafter also referred to as “the present silicone resin”) and an unsaturated represented by -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 in a molecule. A mass of the unsaturated compound (A2) containing at least one group and capable of radical copolymerization with the silicone resin (A1) (hereinafter, simply referred to as “unsaturated compound”), A1:A2=1:99 to 99:1 by mass Including the silicone resin composition (A) blended in a proportion, at least 20% by mass or more of the unsaturated compound (A2) is an unsaturated compound containing a hydroxyl group, and in addition to this silicone resin composition (A), 0.01 mass % The optical path length of 1 cm and wavelength 360 nm light transmittance of less than 90% of the photoinitiator (D) containing 0.1 mass % or more and less than 20 mass % with respect to the silicone resin composition (A).
본 발명에 사용되는 본 실리콘 수지(A1)는, 공지의 실리콘계 수지를 사용할 수 있지만, 바람직한 형태로서는 상기 일반식 (1)로 나타내어지고, 구조 단위 중에 바구니형 구조를 갖는 폴리오르가노실세스퀴옥산(바구니형 폴리오르가노실세스퀴옥산이라고도 한다. 폴리오르가노실세스퀴옥산을 실세스퀴옥산이라고도 한다.)을 주성분으로 하는 것이다.As this silicone resin (A1) used in this invention, although a well-known silicone resin can be used, As a preferable form, it is represented by the said General formula (1), The polyorganosilsesquioxane which has a cage structure in a structural unit ( It is also called cage polyorganosilsesquioxane (polyorganosilsesquioxane is also called silsesquioxane) as the main component.
일반식 (1)에 있어서, R은 (메타)아크릴로일기를 갖는 유기 관능기이며, n은 8, 10 또는 12이다. (메타)아크릴로일기를 갖는 유기 관능기로서는, 하기 일반식 (4)로 나타내어지는 기를 들 수 있다. 일반식 (4) 중, m은 1~3의 정수이며, R1은 수소 원자 또는 메틸기이다.In General Formula (1), R is an organic functional group which has a (meth)acryloyl group, and n is 8, 10 or 12. As an organic functional group which has a (meth)acryloyl group, group represented by the following general formula (4) is mentioned. In general formula (4), m is an integer of 1-3, and R<1> is a hydrogen atom or a methyl group.
CH2=CR1-COO-(CH2)m- (4)CH 2 =CR 1 -COO-(CH 2 ) m - (4)
이와 같은 실리콘 수지는, 분자 중의 규소 원자 상에 (메타)아크릴로일기를 갖는 유기 관능기를 갖는다. 일반식 (1) 중의 n이 8, 10, 12인 바구니형 폴리오르가노실세스퀴옥산의 구체적인 구조로서는, 각각 하기 구조식 (5), (6) 및 (7)에 나타내는 바와 같은 바구니형 구조체를 들 수 있다. 또한, 하기 식 중의 R은 일반식 (1)에 있어서의 R과 동일한 것을 나타낸다.Such a silicone resin has an organic functional group which has a (meth)acryloyl group on the silicon atom in a molecule|numerator. Specific structures of cage polyorganosilsesquioxane in which n is 8, 10, and 12 in the general formula (1) include cage structures as shown in the following structural formulas (5), (6) and (7), respectively. can In addition, R in the following formula represents the same thing as R in General formula (1).
여기에서, 이와 같은 실리콘 수지는 상기 특허문헌 3 등에 기재된 방법으로 제조 가능하다. 예를 들면, RSiX3으로 나타내어지는 규소 화합물을 극성 용매 및 염기성 촉매 존재 하에서 가수분해 반응시킴과 아울러 일부 축합시키고, 얻어진 가수분해 생성물을 또한 비극성 용매 및 염기성 촉매 존재 하에서 재축합시켜서 얻을 수 있다. 여기에서, R은 (메타)아크릴로일기를 갖는 유기 관능기이며, 구체적으로는 상기 일반식 (4)로 나타내어지는 기이며, 또한, X는 가수분해성기를 나타낸다. 바람직한 R의 구체예를 나타내면, 3-메타크릴옥시프로필기, 메타크릴옥시메틸기, 3-아크릴옥시프로필기가 예시된다.Here, such a silicone resin can be manufactured by the method described in the said patent document 3 etc. For example, the silicon compound represented by RSiX 3 is hydrolyzed and partially condensed in the presence of a polar solvent and a basic catalyst, and the resulting hydrolysis product can be recondensed in the presence of a non-polar solvent and a basic catalyst. It can be obtained. Here, R is an organic functional group which has a (meth)acryloyl group, it is group specifically represented by the said General formula (4), and X represents a hydrolysable group. If the specific example of preferable R is shown, 3-methacryloxypropyl group, methacryloxymethyl group, 3-acryloxypropyl group will be illustrated.
가수분해성기 X는, 가수분해성을 갖는 기이면 특별히 한정되지 않고, 알콕실 기, 아세톡시기 등을 들 수 있지만, 알콕실기인 것이 바람직하다. 알콕실기로서는 메톡시기, 에톡시기, n- 또는 i-프로폭시기, 또는 n-, i- 또는 t-부톡시기 등을 들 수 있다. 메톡시기는 반응성이 높기 때문에 바람직하다.The hydrolyzable group X will not be specifically limited if it is group which has hydrolysability, Although an alkoxyl group, an acetoxy group, etc. are mentioned, It is preferable that it is an alkoxyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an n- or i-propoxy group, or an n-, i- or t-butoxy group. A methoxy group is preferable because of its high reactivity.
RSiX3으로 나타내어지는 규소 화합물 중에서 바람직한 화합물을 나타내면, 메타크릴옥시메틸트리에톡시실란, 메타크릴옥시메틸트리메톡시실란, 3-메타크릴옥시프로필트리클로로실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필트리클로로실란을 들 수 있다. 그 중에서도, 원료의 입수가 용이한 3-메타크릴옥시프로필트리메톡시실란을 사용하는 것이 바람직하다.Preferred compounds among the silicon compounds represented by RSiX 3 are methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, and 3-methacryloxypropyltrimethoxy silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltrichlorosilane are mentioned. Especially, it is preferable to use 3-methacryloxypropyl trimethoxysilane with an easy acquisition of a raw material.
가수분해 반응에 사용되는 염기성 촉매로서는, 수산화칼륨, 수산화나트륨, 수산화세슘 등의 알칼리 금속 수산화물, 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라부틸암모늄히드록시드, 벤질트리메틸암모늄히드록시드, 벤질트리에틸암모늄히드록시드 등의 수산화암모늄염이 예시된다. 이것들 중에서도, 촉매 활성이 높은 점으로부터 테트라메틸암모늄히드록시드가 바람직하게 사용된다. 염기성 촉매는 통상 수용액으로서 사용된다.Examples of the basic catalyst used in the hydrolysis reaction include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. and ammonium hydroxide salts such as oxide and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is preferably used from a point with high catalytic activity. A basic catalyst is usually used as an aqueous solution.
가수분해 반응 조건에 대해서는, 반응 온도는 0~60℃가 바람직하고, 20~40℃가 보다 바람직하다. 반응 온도가 0℃보다 낮으면, 반응 속도가 늦어지고 가수분해성기가 미반응의 상태에서 잔존해 버려 반응 시간을 많이 소비하는 결과가 된다. 한편, 60℃보다 높으면 반응 속도가 지나치게 빠르기 때문에 복잡한 축합 반응이 진행되어 결과적으로 가수분해 생성물의 고분자량화가 촉진된다. 또한, 반응 시간은 2시간 이상이 바람직하다. 반응 시간이 2시간에 충족되지 않으면, 가수분해 반응이 충분히 진행되지 않고 가수분해성기가 미반응의 상태에서 잔존해 버릴 우려가 있다.About hydrolysis reaction conditions, 0-60 degreeC is preferable and, as for reaction temperature, 20-40 degreeC is more preferable. When the reaction temperature is lower than 0°C, the reaction rate is slowed, the hydrolyzable group remains in an unreacted state, resulting in consumption of a large amount of reaction time. On the other hand, when the temperature is higher than 60° C., the reaction rate is too fast, so a complicated condensation reaction proceeds, and as a result, high molecular weight of the hydrolysis product is promoted. In addition, the reaction time is preferably 2 hours or more. If the reaction time is not satisfied in 2 hours, there is a possibility that the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group remains in an unreacted state.
가수분해 반응은 물의 존재가 필수이지만, 이것은 염기성 촉매의 수용액으로부터 공급할 수도 있고, 별도의 물로 해서 추가해도 좋다. 물의 양은 가수분해성기를 가수분해하기에 충분한 양 이상인 것이 좋고, 바람직하게는 이론량의 1.0~1.5배량이다. 또한, 가수분해시에는 유기 극성 용매를 사용하는 것이 필요하고, 유기 극성 용매로서는 메탄올, 에탄올, 2-프로판올 등의 알콜류, 또는 다른 유기 극성 용매를 사용할 수 있다. 바람직하게는, 물과 용해성이 있는 탄소수 1~6의 저급 알콜류이며, 2-프로판올을 사용하는 것이 보다 바람직하다. 비극성 용매를 사용하면, 반응계가 균일하게 되지 않고 가수분해 반응이 충분하게 진행되지 않아, 미반응의 가수분해성기가 잔존해 버려 바람직하지 못하다.Although the presence of water is essential for the hydrolysis reaction, it may be supplied from the aqueous solution of a basic catalyst, and may be added as separate water. The amount of water is preferably not less than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. In addition, it is necessary to use an organic polar solvent at the time of hydrolysis, and alcohols, such as methanol, ethanol, 2-propanol, or another organic polar solvent can be used as an organic polar solvent. Preferably, it is a C1-C6 lower alcohol which is soluble in water, and it is more preferable to use 2-propanol. When a nonpolar solvent is used, a reaction system does not become uniform, a hydrolysis reaction does not advance fully, unreacted hydrolysable group remains, and it is unpreferable.
가수분해 반응 종료 후는, 물 또는 물 함유 반응 용매를 분리한다. 물 또는 물 함유 반응 용매의 분리는, 감압 증발 등의 수단을 채용할 수 있다. 수분이나 그 밖의 불순물을 충분하게 제거하기 위해서는, 비극성 용매를 첨가해서 가수분해 반응 생성물을 용해시키고, 이 용액을 식염수 등으로 세정하고, 그 후 무수 황산 마그네슘 등의 건조제로 건조시키는 등의 수단을 채용할 수 있다. 비극성 용매를 증발 등의 수단으로 분리하면, 가수분해 반응 생성물을 회수할 수 있지만, 비극성 용매가 다음 반응에서 사용하는 비극성 용매로서 사용 가능하면, 이것을 분리할 필요는 없다.After completion of the hydrolysis reaction, water or a water-containing reaction solvent is separated. For the separation of water or the water-containing reaction solvent, a means such as evaporation under reduced pressure can be employed. In order to sufficiently remove moisture and other impurities, a method such as adding a non-polar solvent to dissolve the hydrolysis reaction product, washing the solution with saline or the like, and then drying with a desiccant such as anhydrous magnesium sulfate, etc. is employed. can do. If the non-polar solvent is separated by means such as evaporation, the hydrolysis reaction product can be recovered, but if the non-polar solvent can be used as a non-polar solvent used in the next reaction, it is not necessary to separate it.
가수분해 반응에서는 가수분해와 함께, 가수분해물의 축합 반응이 발생한다. 가수분해물의 축합 반응이 따르는 가수분해 생성물은, 통상, 수 평균 분자량이 1400~5000인 무색의 점성 액체로 된다. 가수분해 생성물은, 반응 조건에 따라 다르지만 수 평균 분자량이 1400~3000인 올리고머로 되고, 가수분해성기 X의 대부분, 바람직하게는 거의 전부가 OH기로 치환되고, 또한 그 OH기의 대부분, 바람직하게는 95% 이상이 축합되어 있다. 가수분해 생성물의 구조에 대해서는, 복수종의 바구니형, 사다리형, 랜덤형의 실세스퀴옥산이며, 바구니형 구조를 취하고 있는 화합물에 대해서도 완전한 바구니형 구조의 비율은 적고, 바구니의 일부가 열려 있는 불완전한 바구니형의 구조가 주로 되어 있다. 따라서, 이 가수분해로 얻어진 가수분해 생성물을, 또한, 염기성 촉매 존재 하, 유기 용매 중에서 가열함으로써 실록산 결합을 축합(재축합이라고 한다)시킴으로써 바구니형 구조의 실세스퀴옥산을 선택적으로 제조한다.In a hydrolysis reaction, a condensation reaction of a hydrolyzate generate|occur|produces with hydrolysis. The hydrolyzate, which is subjected to a condensation reaction of the hydrolyzate, is usually a colorless viscous liquid having a number average molecular weight of 1400 to 5000. The hydrolysis product is an oligomer having a number average molecular weight of 1400 to 3000, although depending on the reaction conditions, most, preferably almost all of the hydrolyzable groups X are substituted with OH groups, and most of the OH groups, preferably More than 95% is condensed. Regarding the structure of the hydrolysis product, there are multiple types of cage, ladder, and random silsesquioxanes, and even for compounds having cage structures, the ratio of the complete cage structure is small, and a part of the basket is open. It is mainly an incomplete basket-like structure. Therefore, the silsesquioxane having a cage structure is selectively produced by condensing the siloxane bonds (referred to as recondensation) by heating the hydrolysis product obtained by this hydrolysis in an organic solvent in the presence of a basic catalyst.
구체적으로는, 다음과 같이 행한다. 즉, 상기와 같이 가수분해 반응 종료 후에 있어서 물 또는 물 함유 반응 용매를 분리한 뒤, 비극성 용매 및 염기성 촉매의 존재 하에 재축합 반응을 행한다. 재축합 반응의 반응 조건에 대해서는, 반응 온도는 100~200℃의 범위가 바람직하고, 또한 110~140℃가 보다 바람직하다. 또한, 반응 온도가 지나치게 낮으면 재축합 반응을 시키기 위해서 충분한 드라이빙 포스가 얻어지지 않고 반응이 진행되지 않는다. 반응 온도가 지나치게 높으면 (메타)아크릴로일기가 자기 중합 반응을 일으킬 가능성이 있기 때문에, 반응 온도를 억제하거나, 중합금지제 등을 첨가할 필요가 있다. 반응 시간은 2~12시간이 바람직하다. 비극성 용매의 사용량은 가수분해 반응 생성물을 용해하기에 충분한 양인 것이 좋고, 염기성 촉매의 사용량은 가수분해 반응 생성물에 대하여 0.1~10질량%(wt%)의 범위인 것이 좋다.Specifically, it is carried out as follows. That is, after the completion of the hydrolysis reaction as described above, after separating water or a water-containing reaction solvent, the recondensation reaction is performed in the presence of a non-polar solvent and a basic catalyst. About the reaction conditions of a recondensation reaction, the range of 100-200 degreeC is preferable and, as for reaction temperature, 110-140 degreeC is more preferable. In addition, when the reaction temperature is too low, sufficient driving force is not obtained to cause the recondensation reaction, and the reaction does not proceed. If the reaction temperature is too high, since the (meth)acryloyl group may cause a self-polymerization reaction, it is necessary to suppress the reaction temperature or add a polymerization inhibitor or the like. The reaction time is preferably 2 to 12 hours. The amount of the non-polar solvent used is preferably an amount sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst used is preferably in the range of 0.1 to 10 mass % (wt%) based on the hydrolysis reaction product.
비극성 용매로서는, 물과 용해성이 없는 것이나 또는 거의 없는 것이면 좋지만, 탄화수소계 용매가 바람직하다. 이러한, 탄화수소계 용매로서는 톨루엔, 벤젠, 크실렌 등의 비점이 낮은 비극성 용매가 있다. 그 중에서도 톨루엔을 사용하는 것이 바람직하다. 또한, 염기성 촉매로서는, 상기 가수분해 반응에 사용되는 염기성 촉매를 사용할 수 있고, 수산화칼륨, 수산화나트륨, 수산화세슘 등의 알칼리 금속수산화물, 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라부틸암모늄히드록시드, 벤질트리메틸암모늄히드록시드, 벤질트리에틸암모늄히드록시드 등의 수산화암모늄염을 들 수 있지만, 테트라알킬암모늄 등의 비극성 용매에 가용성인 촉매가 바람직하다.The non-polar solvent may be one having little or no solubility in water, but a hydrocarbon-based solvent is preferable. Examples of such hydrocarbon-based solvents include non-polar solvents with low boiling points, such as toluene, benzene, and xylene. Among them, it is preferable to use toluene. As the basic catalyst, a basic catalyst used in the hydrolysis reaction can be used, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra Although ammonium hydroxide salts, such as butylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide, are mentioned, A catalyst soluble in nonpolar solvents, such as tetraalkylammonium, is preferable.
또한, 재축합에 사용하는 가수분해 생성물은 수세, 탈수하여 농축한 것을 사용하는 것이 바람직하지만, 수세, 탈수를 행하지 않아도 사용할 수 있다. 이 반응시, 물은 존재해도 좋지만, 적극적으로 추가할 필요는 없고, 염기성 촉매 용액으로부터 유입되는 수분 정도로 그치는 것이 좋다. 또한, 가수분해 생성물의 가수분해가 충분히 행해지고 있지 않은 경우에는, 잔존하는 가수분해성기를 가수분해하는 것에 필요한 이론량 이상의 수분이 필요하지만, 통상은 가수분해 반응이 충분히 행해진다. 재축합 반응 후는, 촉매를 수세하고 제거하고, 농축하여, 실세스퀴옥산 혼합물이 얻어진다. 얻어진 실세스퀴옥산 혼합물은, 바람직하게는, 분자 중의 규소 원자수와 (메타)아크릴로일기수가 동등한 것이다.In addition, it is preferable to use the hydrolyzed product used for recondensation, washing with water, dehydration, and using what was concentrated, but it can be used even if water washing and dehydration are not performed. In this reaction, although water may be present, it is not necessary to actively add it, and it is preferable to limit the amount of water flowing in from the basic catalyst solution. In addition, when the hydrolysis product is not sufficiently hydrolyzed, the amount of water more than the theoretical amount required to hydrolyze the remaining hydrolyzable groups is required, but usually the hydrolysis reaction is sufficiently performed. After the recondensation reaction, the catalyst is washed with water, removed, and concentrated to obtain a silsesquioxane mixture. The obtained silsesquioxane mixture, Preferably, the number of silicon atoms in a molecule|numerator and the number of (meth)acryloyl groups are equivalent.
이와 같이 해서 얻어지는 실세스퀴옥산 혼합물은, 반응 조건이나 가수분해 생성물의 상태에 따라 다르지만, 구성 성분은, 복수종 바구니형 실세스퀴옥산이 전체의 70% 이상이며, 나머지는 래더형, 랜덤 가교형의 실세스퀴옥산으로 생각된다. 이것들은 분리가 곤란하고 다대한 수고가 들기 때문에, 본 발명에 있어서는, 일반식 (1)로 나타내어지는 바구니형 실세스퀴옥산을 사용할 경우에는, 복수종 바구니형 실세스퀴옥산이 70% 이상 함유하는 실세스퀴옥산을 사용하는 것이 바람직하다. 또한, 바구니형 실세스퀴옥산 함유량이 70% 이상이면 얻어지는 효과에 차이는 없다. 복수종의 바구니형 실세스퀴옥산의 구성 성분은 일반식 (5)로 나타내어지는 T8이 20~40%, 일반식 (6)으로 나타내어지는 T10이 40~50%이며, 그 밖의 성분은 일반식 (7)로 나타내어지는 T12이다. T8은 실세스퀴옥산 혼합물을 20℃ 이하에서 방치함으로써 바늘 형상의 결정으로 해서 석출시켜 분리할 수 있다. 또한, 바구니형 실세스퀴옥산의 함유 비율에 대해서는, 예를 들면, GPC나 LC-MS 등을 사용하여 확인할 수 있다.Although the silsesquioxane mixture obtained in this way changes with reaction conditions and the state of a hydrolysis product, as for a structural component, multiple types of cage silsesquioxane is 70% or more of the whole, and the remainder is ladder type and random bridge|crosslinking. It is thought to be a type of silsesquioxane. Since these are difficult to separate and require a great deal of effort, in the present invention, when cage silsesquioxane represented by the general formula (1) is used, 70% or more of cage silsesquioxane is contained. It is preferable to use silsesquioxane. Moreover, there is no difference in the effect obtained as cage silsesquioxane content is 70 % or more. As for the structural component of multiple types of cage silsesquioxane, T8 represented by General formula (5) is 20-40%, T10 represented by General formula (6) is 40-50%, Other components are General formula T12 represented by (7). T8 can be separated by precipitating the silsesquioxane mixture as needle-shaped crystals by leaving the mixture at 20°C or lower. In addition, about the content rate of cage silsesquioxane, it can confirm using GPC, LC-MS, etc., for example.
이와 같은 실리콘 수지는, T8~T12의 혼합물이라도 좋고, 이것으로부터 T8 등의 1 또는 2를 분리 또는 농축한 것이라도 좋지만, 상기 제법으로 얻어진 실리콘 수지에 한정되는 것은 아니다. 이와 같은 실리콘 수지를 포함하는 본 실리콘 수지(A1)에 대해서는, 후기하는 바와 같이 불포화 화합물과, A1:A2=1:99~99:1, 바람직하게는 3:97~80:20의 질량 비율로 되도록 배합된다. 이 A1은, 바람직하게는, 광경화성 실리콘 수지 조성물 중에 2.5~75질량%로 되도록 배합되는 것이 좋다.A mixture of T8 to T12 may be sufficient as such a silicone resin, and what isolate|separated or concentrated 1 or 2, such as T8, may be sufficient as it, However, It is not limited to the silicone resin obtained by the said manufacturing method. About this silicone resin (A1) containing such a silicone resin, as below-mentioned, it is a mass ratio of A1:A2=1:99-99:1, Preferably 3:97-80:20 with an unsaturated compound. combined as much as possible. It is good to mix|blend this A1 so that it may become like this, Preferably it may become 2.5-75 mass % in a photocurable silicone resin composition.
실리콘 수지 조성물(A)에 있어서, 본 실리콘 수지(A1)와 공중합 가능한 불포화 화합물(A2)에 대해서는, 적어도 그 20질량% 이상이 수산기를 포함하는 불포화 화합물이며, 또한, 불포화기를 적어도 1개 이상 포함하는 것이다.In the silicone resin composition (A), with respect to the unsaturated compound (A2) copolymerizable with the present silicone resin (A1), at least 20% by mass or more thereof is an unsaturated compound containing a hydroxyl group, and containing at least one unsaturated group will do
상기 불포화기는, -R3-CR4=CH2 또는 -CR4=CH2〔단, R3은 알킬렌기, 알킬리덴기 또는 -O-C(=O)-기를 나타내고, R4는 수소 원자 또는 알킬기를 나타낸다〕로 나타내어진다. R3이 알킬렌기, 알킬리덴기일 경우에는, 그것들의 탄소수는 1~6인 것이 바람직하고, R4가 알킬기일 경우에는 메틸기가 바람직하다.The unsaturated group is -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 [provided that R 3 represents an alkylene group, an alkylidene group or a -OC(=O)- group, and R 4 is a hydrogen atom or an alkyl group represents]. When R<3> is an alkylene group or an alkylidene group, it is preferable that those carbon number is 1-6, and when R<4> is an alkyl group, a methyl group is preferable.
불포화 화합물(A2)은, 바람직하게는, 상기 불포화기를 2개 이상 또는 3개 이상 갖는 다관능 불포화 화합물을 10~100질량% 포함한다. 이러한 다관능 불포화 화합물을 배합함으로써 고표면 경도의 성형체를 얻을 수 있다. 다관능 불포화 화합물은 규소 원자를 갖지 않는 비실리콘형의 화합물인 것이 바람직하다.The unsaturated compound (A2), Preferably, 10-100 mass % of the polyfunctional unsaturated compound which has 2 or more or 3 or more of the said unsaturated groups is included. By mix|blending such a polyfunctional unsaturated compound, the molded object of high surface hardness can be obtained. It is preferable that a polyfunctional unsaturated compound is a non-silicon type compound which does not have a silicon atom.
상기 다관능 불포화 화합물 중 수산기를 포함하는 불포화 화합물로서는, 펜타에리스리톨트리아크릴레이트, 글리세린디메타크릴레이트, 디펜타에리스리톨펜타 아크릴레이트, 디펜타에리스리톨테트라아크릴레이트 등을 예시할 수 있다. 이것들은 분자 중에 수산기를 갖기 위해서 수산기의 상호 작용에 의해 분자간의 거리가 줄어듦으로써 발생한 라디칼이 신속히 이중결합과 반응함으로써 경화 속도가 향상하고, 산소와 라디칼의 반응보다 먼저 라디칼 중합이 진행됨으로써, 산소에 의한 경화 저해를 억제하는 것이 가능하게 된다. 상기와 같이, 실리콘 수지 조성물(A)에 배합되는 불포화 화합물(A2)의 20질량% 이상이 수산기를 포함하는 불포화 화합물일 필요가 있고, 바람직하게는, A2의 중의 30질량% 이상이 수산기를 포함하는 불포화 화합물인 것이 좋다. 이 범위를 밑돌면 분자간의 상호 작용의 효과가 희미해진다. 배합의 상한은 특별히 없지만, 60 질량%를 초과하면 산소 저해 억제 효과의 상승은 거의 없어진다.As an unsaturated compound containing a hydroxyl group among the said polyfunctional unsaturated compounds, pentaerythritol triacrylate, glycerol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, etc. can be illustrated. In order to have hydroxyl groups in the molecule, the radicals generated by reducing the distance between molecules by the interaction of hydroxyl groups rapidly react with double bonds, thereby improving the curing rate, and radical polymerization proceeds before the reaction between oxygen and radicals. It becomes possible to suppress the hardening inhibition by this. As described above, 20% by mass or more of the unsaturated compound (A2) to be blended into the silicone resin composition (A) needs to be an unsaturated compound containing a hydroxyl group, and preferably, 30% by mass or more of A2 contains a hydroxyl group. It is preferable that it is an unsaturated compound. Below this range, the effect of intermolecular interactions becomes dim. Although there is no upper limit in particular of mixing|blending, when it exceeds 60 mass %, the raise of the oxygen inhibition inhibitory effect almost disappears.
한편으로, 수산기를 포함하지 않는 불포화 화합물로서는, 트리메티롤프로판트리아크릴레이트, 펜타에리스리톨테트라아크릴레이트, 디펜타에리스리톨헥사아크릴레이트 등을 예시할 수 있다. 또한, 이것들 이외에도 펜타에리스리톨, 디펜타에리스리톨의 일부 또는 전부의 히드록시기를 에틸렌, 이소프로필렌 등의 글리콜이나 γ-부틸올락톤 등으로 변성해서 얻어지는 골격의 말단 히드록시기의 전부를, 또한 -R3-CR4=CH2 또는 -CR4=CH2〔단, R3은 알킬렌기, 알킬리덴기 또는 -O-C(=O)-기를 나타내고, R4는 수소 원자 또는 알킬기를 나타낸다〕로 나타내어지는 불포화기로 변성한 화합물 등도 사용할 수 있다. 또는, 우레탄아크릴레이트, 아크릴 공중합체 아크릴레이트 등을 예시할 수 있다. 또한, 이것들의 다관능 불포화 화합물이나 수산기를 포함하지 않는 불포화 화합물 등은, 각각 단독으로 사용해도, 2종류 이상을 혼합해서 사용해도 좋다.On the other hand, as an unsaturated compound which does not contain a hydroxyl group, trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. can be illustrated. In addition to these, all of the terminal hydroxyl groups of the skeleton obtained by modifying a part or all of the hydroxyl groups of pentaerythritol and dipentaerythritol with glycols such as ethylene or isopropylene, γ-butylolactone, etc., further -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 [provided that R 3 represents an alkylene group, an alkylidene group or a -OC(=O)- group, R 4 represents a hydrogen atom or an alkyl group] A compound etc. can also be used. Or urethane acrylate, acrylic copolymer acrylate, etc. can be illustrated. In addition, these polyfunctional unsaturated compounds, the unsaturated compound which do not contain a hydroxyl group, etc. may be used individually, respectively, or may mix and use 2 or more types.
또한, 상기 불포화 화합물(A2)에는, 표면 경도를 저하시키지 않는 범위에서 반응성의 단관능 또는 다른 2관능 모노머(불포화 화합물)를 배합해도 좋다. 단관능 모노머로서는, 스티렌, 아세트산 비닐, N-비닐피롤리돈, 부틸아크릴레이트, 2-에틸헥실아크릴레이트, n-헥실아크릴레이트, 시클로헥실아크릴레이트, n-데실아크릴레이트, 이소보닐아크릴레이트, 디시클로펜테닐옥시에틸아크릴레이트, 페녹시에틸아크릴레이트, 트리플루오로에틸메타크릴레이트 등을 예시할 수 있다. 다른 2관능 모노머로서는, 트리프로필렌글리콜디아크릴레이트, 1,6-헥산디올디아크릴레이트, 비스페놀A디글리시딜에테르디아크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 히드록시피바린산 네오펜틸글리콜디아크릴레이트 등을 예시할 수 있다.Moreover, you may mix|blend with the said unsaturated compound (A2) a reactive monofunctional or other bifunctional monomer (unsaturated compound) in the range which does not reduce surface hardness. Examples of the monofunctional monomer include styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, Dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, etc. can be illustrated. Examples of other bifunctional monomers include tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, and neopentyl glycol dihydroxypivalate. acrylates and the like can be exemplified.
단관능 모노머나 다른 2관능 모노머는, 상기 불포화 화합물(A2) 중에 20질량% 이하로 포함되는 것이 바람직하고, 보다 바람직하게는 10질량% 이하이다. 20질량%보다 많게 배합하면 표면 경도가 저하되는 경향이 있으므로 바람직하지 않다.It is preferable that a monofunctional monomer and another bifunctional monomer are contained in the said unsaturated compound (A2) in 20 mass % or less, More preferably, it is 10 mass % or less. When it mix|blends more than 20 mass %, since surface hardness tends to fall, it is unpreferable.
또한, 본 명세서에 있어서는, 상기 실리콘 수지(A1)와, 상기 불포화 화합물(A2)을 배합한 것을 실리콘 수지 조성물(A)이라 하고, 이 실리콘 수지 조성물(A)에, 후기하는 광중합개시제(B), 광증감제(C) 및/또는 광중합개시제(D)(및, 필요에 따라 기타의 첨가제 등)를 배합한 것을, 본 발명의 광경화성 실리콘 수지 조성물이라고 하는 것으로 한다.In addition, in this specification, what mix|blended the said silicone resin (A1) and the said unsaturated compound (A2) is called a silicone resin composition (A), In this silicone resin composition (A), the below-mentioned photoinitiator (B) , the photosensitizer (C) and/or the photopolymerization initiator (D) (and, if necessary, other additives, etc.) blended shall be referred to as the photocurable silicone resin composition of the present invention.
배합의 방법에 대해서는, 실리콘 수지(A1)와, 불포화 화합물(A2)을 먼저 배합해도 좋고, 또는, 실리콘 수지(A1)와, 불포화 화합물(A2)과, 후기하는 광중합개시제(B), 광증감제(C) 및/또는 광중합개시제(D)를 동시에 배합해도 좋고, 배합의 순서는 임의이다. 또한, 후기하는 바와 같이, 본 발명의 광경화성 실리콘 수지 조성물에는, 각종 첨가제를 포함할 수 있지만, 이들 배합의 순서도 임의이다.About the method of mixing|blending, you may mix|blend a silicone resin (A1) and an unsaturated compound (A2) first, or a silicone resin (A1), an unsaturated compound (A2), a photoinitiator (B) mentioned later, photosensitization The agent (C) and/or the photoinitiator (D) may be blended simultaneously, and the order of blending is arbitrary. In addition, although various additives can be included in the photocurable silicone resin composition of this invention so that it may mention later, the order of these mixing|blending is also arbitrary.
본 발명의 광경화성 실리콘 수지 조성물에 사용되는 광중합개시제(D)는, 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만이며, 장파장역에 흡수를 가지는 광중합개시제를 사용하는 것이 필요하다. 이와 같은 광중합개시제(D)로서는, 바람직하게는 α-아미노알킬페논계 광중합개시제, 포스핀옥사이드계 광중합개시제 및 옥심에스테르계 광중합개시제로 이루어지는 군으로부터 선택되는 1종 이상의 광중합개시제를 들 수 있고, 그 중, 광개열 효율이 높은 α-아미노알킬페논계 광중합개시제를 사용하는 것이 보다 바람직하다. α-아미노알킬페논계 광중합개시제의 구체적인 화합물로서는, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부타논-1, 2-디메틸아미노-2-(4-메틸-벤질)-1-(4-모리폴린-4-일-페닐)-부탄-1-온 등을 예시할 수 있다. 배합량으로서는, 실리콘 수지 조성물(A)에 대하여 0.1질량% 이상 20질량% 미만으로 한다. 광경화성과 투명성(착색성)의 관점으로부터, 실리콘 수지 조성물(A)에 대하여 0.1~10질량%의 범위가 바람직하고, 특히 투명성(착색성)의 관점에서는 0.1질량% 이상 5질량% 미만이 보다 바람직하고, 0.1~1질량%가 가장 바람직한 범위이다. 0.1질량% 미만이면 광경화성의 감도가 낮고, 충분한 경도의 경화물이 얻어지지 않는다. 또한, 20질량% 이상이면 착색이 강해지는 경향이 있다. 또한, 광경화성이나 투명성을 조정하기 위해서, 포스핀옥사이드계 및 옥심에스테르계 광중합개시제를 조합시켜도 좋고, 단독으로 사용해도 좋다. 포스핀옥사이드계 광중합개시제의 구체적인 화합물로서는, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드 등을 예시할 수 있다. 또한, 옥심에스테르계 광중합개시제의 구체적인 화합물로서는, 에탄온,1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-,1-(0-아세틸옥심), 1,2-옥탄디온,1-[4-(페닐티오)-,2-(O-벤조일옥심)] 등을 예시할 수 있다. 또한, 이 광중합개시제(D)를 실리콘 수지 조성물(A)에 대하여 0.1~1질량%로 비교적 적게 사용할 경우에는, 특히 광경화성의 관점으로부터 후술하는 광증감제(C)를 병용하는 것이 바람직하다.The photopolymerization initiator (D) used in the photocurable silicone resin composition of the present invention has an optical path length of 1 cm of a 0.01 mass% solution, a light transmittance of 360 nm at a wavelength of less than 90%, and a photopolymerization initiator having absorption in a long wavelength region. it is necessary to do As such a photoinitiator (D), Preferably, at least one type of photoinitiator selected from the group consisting of α-aminoalkylphenone-based photoinitiators, phosphine oxide-based photoinitiators and oxime ester-based photoinitiators can be mentioned, and Among them, it is more preferable to use an α-aminoalkylphenone-based photopolymerization initiator with high photocleavage efficiency. Specific examples of the α-aminoalkylphenone-based photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one etc. can be exemplified. As a compounding quantity, you shall be 0.1 mass % or more and less than 20 mass % with respect to a silicone resin composition (A). From the viewpoint of photocurability and transparency (colorability), the range is preferably 0.1 to 10% by mass relative to the silicone resin composition (A), and in particular, from the viewpoint of transparency (colorability), 0.1% by mass or more and less than 5% by mass is more preferable. , 0.1 to 1 mass % is the most preferable range. If it is less than 0.1 mass %, the sensitivity of photocuring property is low, and hardened|cured material of sufficient hardness cannot be obtained. Moreover, there exists a tendency for coloring to become strong in it being 20 mass % or more. Moreover, in order to adjust photocurability and transparency, a phosphine oxide type|system|group and an oxime ester type|system|group photoinitiator may be combined and you may use independently. Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, etc. can be illustrated as a specific compound of a phosphine oxide type photoinitiator. In addition, as a specific compound of an oxime ester type photoinitiator, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyl oxime) , 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)] and the like can be exemplified. Moreover, when using this photoinitiator (D) in 0.1-1 mass % relatively little with respect to a silicone resin composition (A), it is preferable to use together the photosensitizer (C) mentioned later especially from a photocurability viewpoint.
또한, 본 발명의 광경화성 실리콘 수지 조성물에는, 다음과 같은 광중합개시제(B)와 광증감제(C)를 사용해도 좋다.Moreover, you may use the following photoinitiator (B) and photosensitizer (C) for the photocurable silicone resin composition of this invention.
여기에서, 본 발명의 광경화성 실리콘 수지 조성물에 사용되는 광중합개시제(B)로서는, 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상이며, 가시광 영역에 흡수가 없는 투명성이 높은 광중합개시제를 사용하는 것이 바람직하다. 이와 같은 광중합개시제(B)로서는, 바람직하게는 히드록시페닐케톤계 광중합개시제를 들 수 있고, 구체적인 화합물로서는, 1-히드록시시클로헥실페닐-케톤, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-[4-(2-히드록시에톡시)-페닐]-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-1-{4-[4-(2-히드록시-2-메틸프로피오닐)-벤질]페닐}-2-메틸프로판-1-온 등을 예시할 수 있다. 배합량으로서는, 광경화성과 투명성의 관점으로부터, 실리콘 수지 조성물(A)에 대하여 1~10질량%의 범위, 바람직하게는 3~10질량%의 범위이다. 1질량% 미만이면 광경화성의 감도의 향상 효과가 낮고, 기대하는 경도 향상 효과가 얻어지지 않는다. 또한 10질량%를 초과하면 착색이 강해지는 경향이 있고, 미반응의 광중합개시제가 블리드아웃해 오는 경우가 있기 때문에, 상기 범위에서 사용하는 것이 바람직하다. 또한, 광경화성이나 투명성을 조정하기 위해 복수의 히드록시페닐케톤계 광중합개시제를 조합시켜도 좋다.Here, as the photopolymerization initiator (B) used in the photocurable silicone resin composition of the present invention, the 0.01 mass % solution has an optical path length of 1 cm and a light transmittance of 360 nm at a wavelength of 90% or more, and transparency without absorption in the visible region It is preferable to use this high photopolymerization initiator. As such a photoinitiator (B), Preferably, a hydroxyphenyl ketone type photoinitiator is mentioned, As a specific compound, 1-hydroxycyclohexylphenyl- ketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4- [4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one and the like can be exemplified. As a compounding quantity, it is the range of 1-10 mass % with respect to a silicone resin composition (A) from a viewpoint of photocurability and transparency, Preferably it is the range of 3-10 mass %. If it is less than 1 mass %, the effect of improving the sensitivity of the photocurability is low, and the effect of improving the hardness to be expected is not obtained. Moreover, when it exceeds 10 mass %, since coloring tends to become strong and an unreacted photoinitiator may bleed out, it is preferable to use within the said range. Moreover, in order to adjust photocurability and transparency, you may combine several hydroxyphenyl ketone type photoinitiators.
또한, 본 발명의 광경화성 실리콘 수지 조성물에 사용되는 광증감제(C)로서는, 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상이며, 가시광 영역에 흡수가 없는 투명성이 높은 광증감제를 사용하는 것이 바람직하다. 이와 같은 광증감제(C)로서는, 바람직하게는 나프탈렌계 광증감제를 바람직하게 들 수 있고, 구체적인 화합물로서는, 1,4-디메톡시나프탈렌, 1,4-디에톡시나프탈렌, 1,4-디(n-프로폭시)나프탈렌 또는 1,4-디(i-프로폭시)나프탈렌, 2,6-디메톡시나프탈렌, 2,6-디에톡시나프탈렌, 2,6-디(n-프로폭시)나프탈렌 또는 2,6-디(i-프로폭시)나프탈렌 등을 예시할 수 있다. 배합량으로서는, 광경화성과 투명성의 관점으로부터, 실리콘 수지 조성물(A)에 대하여 0.1~3질량%의 범위, 바람직하게는 0.5~3질량%의 범위이다. 0.5 질량% 미만이면 증감제의 향상 효과가 발휘되지 않고, 기대하는 경도 향상 효과가 얻어지지 않는다. 또한 3질량%를 초과하면 착색이 강해지는 경향이 있기 때문에, 상기 범위에서 사용하는 것이 바람직하다. 광경화성이나 투명성을 조정하기 위해 복수의 나프탈렌계 광증감제를 조합시켜도 좋다.In addition, as the photosensitizer (C) used in the photocurable silicone resin composition of the present invention, the 0.01 mass% solution has an optical path length of 1 cm and a light transmittance of 360 nm at a wavelength of 90% or more, and there is no absorption in the visible region. It is preferable to use this high photosensitizer. As such a photosensitizer (C), Preferably, a naphthalene type photosensitizer is mentioned preferably, As a specific compound, 1, 4- dimethoxy naphthalene, 1, 4- diethoxy naphthalene, 1, 4- di (n-propoxy)naphthalene or 1,4-di(i-propoxy)naphthalene, 2,6-dimethoxynaphthalene, 2,6-diethoxynaphthalene, 2,6-di(n-propoxy)naphthalene or 2,6-di(i-propoxy)naphthalene etc. can be illustrated. As a compounding quantity, it is the range of 0.1-3 mass % with respect to a silicone resin composition (A) from a viewpoint of photocurability and transparency, Preferably it is the range of 0.5-3 mass %. If it is less than 0.5 mass %, the improvement effect of a sensitizer will not be exhibited but the expected hardness improvement effect will not be acquired. Moreover, since there exists a tendency for coloring to become strong when it exceeds 3 mass %, it is preferable to use in the said range. In order to adjust photocurability and transparency, you may combine several naphthalene type photosensitizer.
양산을 목적으로 한 실제의 제조 공정에 있어서 하드 코트층은 생산성, 안전성의 면으로부터 질소 분위기 하가 아니라, 대기 분위기 하에서 형성하는 것이 바람직하지만, 그러기 위해서는 광중합개시제(D)와 같은 광개열 효율이 높은 개시제를 사용하게 된다. 이것들은 대개 원래 착색되어 있거나, 내후 시험 하에 있어서 변색되기 쉬운 성질을 갖고 있기 때문에 대량으로 사용할 수 없다. 한편, 광중합개시제(B)로 대표되는 착색이 없는 개시제는 감도가 부족하기 쉬운 경향이 있어, 하드 코트층 표면이 산소 저해에 의한 경화 부족으로 된다. 그 때문에, 상기와 같이, 광중합개시제(D)를 특정량 사용하는 것이 필요하게 되지만, 광중합개시제(D)의 사용량을 적게 할 경우에는, 광경화성의 관점으로부터 특히 광증감제(C)를 병용함으로써 감도 부족을 보충함과 아울러, 저노광량으로의 경화를 가능하게 하고, 고감도인 광중합개시제(D)를 착색이 적은 범위에서 사용함으로써 하드 코트층 표면의 산소 저해의 영향을 개선해 내찰상성을 향상시킬 수 있다.In the actual manufacturing process for the purpose of mass production, it is preferable to form the hard coat layer under an atmospheric atmosphere rather than a nitrogen atmosphere from the viewpoint of productivity and safety. initiator will be used. These cannot be used in large quantities because they are usually originally colored or have the property of being prone to discoloration under weathering tests. On the other hand, an initiator without coloring represented by the photopolymerization initiator (B) tends to lack sensitivity, and the hard coat layer surface becomes insufficient in curing due to oxygen inhibition. Therefore, as described above, it is necessary to use a specific amount of the photoinitiator (D), but when reducing the amount of the photoinitiator (D) to be used, from the viewpoint of photocurability, especially by using the photosensitizer (C) together. In addition to compensating for the lack of sensitivity, curing at a low exposure dose is possible, and by using the highly sensitive photopolymerization initiator (D) in a range with little coloration, the effect of oxygen inhibition on the surface of the hard coat layer can be improved, and the scratch resistance can be improved. have.
본 발명의 광경화성 실리콘 수지 조성물에는, 본 발명의 목적으로부터 제외되지 않는 범위에서 각종 첨가제를 첨가할 수 있다. 각종 첨가제로서 유기/무기 필러, 가소제, 난연제, 열안정제, 산화방지제, 광안정제, 자외선흡수제, 활제, 대전방지제, 이형제, 발포제, 핵제, 착색제, 형광증백제, 가교제, 분산조제, 수지 성분등을 예시할 수 있다.Various additives can be added to the photocurable silicone resin composition of this invention in the range which is not excluded from the objective of this invention. As various additives, organic/inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, optical brighteners, crosslinking agents, dispersing agents, resin components, etc. can be exemplified.
본 발명의 광경화성 실리콘 수지 성형체는, 상기 광경화성 실리콘 수지 조성물에 가시광선이나 자외선이나 전자선 등의 활성 에너지선의 조사에 의해 경화시킴으로써 제조할 수 있고, 바람직하게는, 파장 10~400㎚의 자외선이나 파장 400~700㎚의 가시광선을 조사함으로써 경화한 성형체를 얻을 수 있다. 사용하는 광의 파장은 특별히 제한되는 것은 아니지만, 특히 파장 200~400㎚의 근자외선이 적합하게 사용된다. 자외선 발생원으로서 사용되는 램프로서는, 저압 수은 램프(출력: 0.4~4W/㎝), 고압 수은 램프(40~160W/㎝), 초고압 수은 램프(173~435W/㎝), 메탈할라이드 램프(80~160W/㎝) 등을 예시할 수 있다.The photocurable silicone resin molded article of the present invention can be produced by curing the photocurable silicone resin composition by irradiation with active energy rays such as visible rays, ultraviolet rays, or electron beams, preferably ultraviolet rays with a wavelength of 10 to 400 nm or A cured molded article can be obtained by irradiating the visible light with a wavelength of 400 to 700 nm. Although the wavelength in particular of the light to be used is not restrict|limited, In particular, near-ultraviolet rays with a wavelength of 200-400 nm are used suitably. Examples of the lamp used as the ultraviolet ray generator include a low-pressure mercury lamp (output: 0.4 to 4 W/cm), a high-pressure mercury lamp (40 to 160 W/cm), an ultra-high pressure mercury lamp (173 to 435 W/cm), and a metal halide lamp (80 to 160 W). /cm) and the like.
광조사 등의 활성 에너지선의 조사에 의해 성형체(실리콘 수지 공중합체 또는 경화물)를 얻는 방법으로서는, 산소 차단 분위기 하 또는 대기 분위기 하의 어느 쪽이라도 좋지만, 본 발명의 조성물은 대기 분위기 하에서의 중합 경화라도 양호한 성형체를 부여하는 점으로부터, 바람직하게는 대기 분위기 하에서 행하는 것이 좋다. 예를 들면, 임의의 캐비티 형상을 갖고, 석영 유리 등의 투명 소재로 구성된 금형 내에, 본 발명의 광경화성 실리콘 수지 조성물을 주입하고, 자외선 램프로 자외선을 조사해서 중합 경화를 행하고, 금형으로부터 탈형시킴으로써 소망의 형상의 성형체를 제조하는 방법이나, 금형을 사용하지 않을 경우에는, 예를 들면, 이동하는 스틸 벨트 상에 닥터 블레이드나 롤 형상의 코터를 사용하여 본 발명의 광경화성 실리콘 수지 조성물을 도포하고, 자외선 램프로 중합 경화시킴으로써 시트 형상의 성형체를 제조하는 방법 등을 예시할 수 있다.As a method of obtaining a molded article (silicone resin copolymer or cured product) by irradiation with active energy rays such as light irradiation, either under an oxygen barrier atmosphere or an atmospheric atmosphere may be used, but the composition of the present invention may be cured by polymerization under an atmospheric atmosphere. From the point of providing a molded object, Preferably, it is good to carry out in an atmospheric condition. For example, by injecting the photocurable silicone resin composition of the present invention into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, irradiating ultraviolet rays with an ultraviolet lamp to perform polymerization curing, and demolding from the mold A method for manufacturing a molded article having a desired shape, or when a mold is not used, for example, a doctor blade or a roll-shaped coater is used on a moving steel belt to apply the photocurable silicone resin composition of the present invention, , a method of producing a sheet-shaped molded article by polymerization and curing with an ultraviolet lamp, and the like can be exemplified.
성형체의 형상은 임의이고, 필름이나 도막 등이라도 좋다. 이 성형체는, 본 발명의 광경화성 실리콘 수지 조성물을 라디칼 공중합시켜서 얻어진다. 본 발명의 성형체 또는 경화물은 3차원 가교 중합체이며, 이 경우, 열경화성 수지와 마찬가지의 성형 경화법을 채용할 수 있다.The shape of the molded object is arbitrary, and a film, a coating film, etc. may be sufficient. This molded article is obtained by radical copolymerizing the photocurable silicone resin composition of the present invention. The molded article or cured product of the present invention is a three-dimensional crosslinked polymer, and in this case, the same molding and curing method as that of the thermosetting resin can be employed.
또한, 폴리카보네이트나 폴리메타크릴산 메틸, 폴리에틸렌테레프탈레이트(PET), 금속판, 유리 등의 각종 기재에, 본 발명의 광경화성 실리콘 수지 조성물을 도포, 또는 각종 용제로 희석해서 도포함으로써, 하드 코트 피막으로서의 성형체를 기재 표면에 형성하는 방법을 예시할 수 있다. 구체적으로는, 유연법, 롤러 코팅법, 바 코팅법, 분무 코팅법, 에어나이프 코팅법, 스핀 코팅법, 플로우 코팅법, 커튼 코팅법 및 딥핑법을 들 수 있다. 또한, 도공막 두께는, 건조, 자외선 램프에 의한 경화 후의 형성막 두께를 고려하여, 고형분 농도에 의해 조정한다. 고형분 농도의 조정에 용제를 사용했을 경우에는, 도포 후는 용제를 건조 등에 의해 제거하는 것이 바람직하다. 건조 온도는, 사용하는 기재가 변형되지 않는 조건으로 하고, 건조 시간은, 생산성의 관점으로부터 1시간 이하가 바람직하다. 또한, 내찰상성 및 부착성의 관점으로부터, 하드 코팅 피막의 두께는 0.5~100㎛, 바람직하게는 1~60㎛이다.In addition, by applying the photocurable silicone resin composition of the present invention to various substrates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate (PET), metal plate, glass, or diluting it with various solvents and applying it, a hard coat film The method of forming the molded object as a base material on the surface can be illustrated. Specifically, the casting method, the roller coating method, the bar coating method, the spray coating method, the air knife coating method, the spin coating method, the flow coating method, the curtain coating method, and the dipping method are mentioned. In addition, a coating film thickness considers drying and the formed film thickness after hardening by an ultraviolet lamp, and adjusts it with solid content concentration. When a solvent is used for adjustment of solid content concentration, it is preferable to remove a solvent by drying etc. after application|coating. The drying temperature is set as a condition in which the base material to be used is not deformed, and the drying time is preferably 1 hour or less from the viewpoint of productivity. Moreover, from a viewpoint of abrasion resistance and adhesiveness, the thickness of a hard-coat film is 0.5-100 micrometers, Preferably it is 1-60 micrometers.
이와 같이 하여 얻어지는 본 발명의 실리콘 수지 성형체는, 연필 경도(JISK5600에 준거)가 2H 이상, 바람직하게는 3H 이상이며, 내찰상성이 스틸 울 시험에서 적어도 500g 하중으로 손상되지 않는 것이 바람직하다. 또한, 무색 투명인 것이 바람직하고, 황색도(YI)의 값이 2 미만, 보다 바람직하게는 1 미만, 더 바람직하게는 0.8 미만이다.The silicone resin molded article of the present invention obtained in this way preferably has a pencil hardness (according to JISK5600) of 2H or more, preferably 3H or more, and that scratch resistance is not impaired by a load of at least 500 g in the steel wool test. Moreover, it is preferable that it is colorless and transparent, and the value of yellowness (YI) is less than 2, More preferably, it is less than 1, More preferably, it is less than 0.8.
(실시예)(Example)
이하, 본 발명의 실시예를 나타낸다. 또한, 하기 실시예에 사용한 실리콘 수지는, 하기의 합성예에 나타낸 방법으로 얻은 것이다.Hereinafter, the Example of this invention is shown. In addition, the silicone resin used in the following example was obtained by the method shown in the following synthesis example.
[합성예 1][Synthesis Example 1]
교반기, 적하 로트, 온도계를 구비한 반응 용기에, 용매로서 2-프로판올(IPA) 40ml와, 염기성 촉매로서 5% 테트라메틸암모늄히드록시드 수용액(TMAH 수용액)을 장입했다. 적하 로트에 IPA 15ml와 3-메타크릴옥시프로필트리메톡시실란(MTMS: 토레이·다우코닝·실리콘 가부시키가이샤제 SZ-6300) 12.69g을 넣고, 반응 용기를 교반하면서, 실온에서 MTMS의 IPA 용액을 30분 걸쳐 적하했다. MTMS 적하 종료 후, 가열하지 않고 2시간 교반했다. 2시간 교반 후, 감압 하에서 용매를 제거하고, 톨루엔 50ml에서 용해했다. 반응 용액을 포화 식염수에서 중성으로 될 때까지 수세한 후, 무수 황산 마그네슘으로 탈수했다. 무수 황산 마그네슘을 여과 선별하고, 농축함으로써 가수분해 생성물(실세스퀴옥산)을 25.8g 얻었다. 이 실세스퀴옥산은 여러가지 유기 용제에 가용인 무색의 점성 액체였다. 40 ml of 2-propanol (IPA) as a solvent and 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) were charged into the reaction vessel provided with a stirrer, a dripping funnel, and a thermometer as a basic catalyst. 15 ml of IPA and 12.69 g of 3-methacryloxypropyltrimethoxysilane (MTMS: Toray Dow Corning Silicon Co., Ltd. SZ-6300) were put into the dropping funnel, and the IPA solution of MTMS was stirred at room temperature while stirring the reaction vessel. was added dropwise over 30 minutes. After completion of MTMS dripping, it stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral, and then dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 25.8 g of a hydrolysis product (silsesquioxane). This silsesquioxane was a colorless, viscous liquid soluble in various organic solvents.
이어서, 교반기, 딘스타크, 냉각관을 구비한 반응 용기에 상기에서 얻어진 실세스퀴옥산 20.65g과 톨루엔 82ml와 10% TMAH 수용액 3.0g을 넣고, 서서히 가열해 물을 증류 제거했다. 또한 130℃까지 가열해 톨루엔을 환류 온도에서 재축합 반응을 행했다. 이 때의 반응 용액의 온도는 108℃였다. 톨루엔 환류 후 2시간 교반한 후, 반응을 종료로 했다. 반응 용액을 포화 식염수로 중성으로 될 때까지 수세한 후, 무수 황산 마그네슘으로 탈수했다. 무수 황산 마그네슘을 여과 선별하고, 농축함으로써 목적물인 바구니형 실세스퀴옥산(혼합물)을 18.77g 얻었다. 얻어진 바구니형 실세스퀴옥산(S1)은 여러가지 유기 용제에 가용인 무색의 점성 액체였다.Next, 20.65 g of silsesquioxane obtained above, 82 ml of toluene, and 3.0 g of a 10% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, Dean-Stark and a cooling tube, and the water was distilled off gradually by heating. Furthermore, it heated to 130 degreeC, and toluene was recondensed at reflux temperature. The temperature of the reaction solution at this time was 108 degreeC. After refluxing toluene and stirring for 2 hours, the reaction was terminated. The reaction solution was washed with saturated brine until neutral, and then dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered and concentrated to obtain 18.77 g of cage silsesquioxane (mixture) as the target product. The obtained cage silsesquioxane (S1) was a colorless viscous liquid soluble in various organic solvents.
재축합 반응 후의 반응물의 액체 크로마토그래피 분리 후의 질량 분석을 행한 바, 상기 구조식 (5), (6) 및 (7)의 분자 구조에 있어서 R을 메타크릴로일기로 한 것에 대하여 암모늄 이온이 붙은 분자 이온이 확인되고, 구성 비율은 T8:T10:T12:기타가 약 2:4:1:3이며, 바구니형 구조를 주된 성분으로 하는 실리콘 수지인 것을 확인할 수 있다. 또한, T8, T10, 및 T12는, 각각 식 (5), (6) 및 (7)에 있어서 R을 메타크릴로일기로 한 것에 대응한다.As a result of mass spectrometry after liquid chromatography separation of the reactant after the recondensation reaction, in the molecular structures of the above structural formulas (5), (6) and (7), R is a methacryloyl group, and an ammonium ion is attached to the molecule. Ions are confirmed, and the composition ratio is T8:T10:T12:others about 2:4:1:3, and it can be confirmed that the silicone resin has a cage-like structure as a main component. In addition, T8, T10, and T12 correspond to what made R a methacryloyl group in Formula (5), (6), and (7), respectively.
[광투과율 측정][Measurement of light transmittance]
광중합개시제와 광증감제의 0.01질량% 용액의 광투과율은, 분광 광도계(시마즈 세이사쿠쇼제 UV3600), 광로 길이 1㎝의 붕규산 유리제 셀을 사용하여 측정했다. 용매 및 레퍼런스에는, 프로필렌글리콜모노메틸에테르를 사용하여 파장 360㎚의 광투과율을 측정했다. 이후, 광투과율의 기재는 본 법에 의해 측정한 값을 나타낸다.The light transmittance of the 0.01 mass % solution of a photoinitiator and a photosensitizer was measured using the spectrophotometer (Shimadzu Corporation UV3600), and the cell made from borosilicate glass with an optical path length of 1 cm. As a solvent and a reference, the light transmittance of wavelength 360nm was measured using propylene glycol monomethyl ether. Hereinafter, the description of the light transmittance indicates the value measured by this method.
[실시예 1][Example 1]
합성예 1에서 얻은 바와 같은 메타크릴로일기를 모든 규소 원자 상에 가진 바구니형 실리콘 수지(S1): 25질량부, 수산기를 포함하는 아크릴레이트로서 디펜타에리스리톨펜타아크릴레이트〔OH 1, 니폰 가야쿠(주)제 KYARAD DPHA에 35질량% 포함된다〕: 26.25질량부, 수산기를 포함하지 않는 디펜타에리스리톨헥사아크릴레이트〔a1, 니폰 가야쿠(주)제 KYARAD DPHA에 65질량% 포함된다〕: 48.75질량부, 광중합개시제(B)로서 1-히드록시-시클로헥실페닐케톤(B1, 광투과율 96.3%, IGM사제 Omnirad184): 7.5질량부, 광증감제(C)로서 1,4-디에톡시나프탈렌(광투과율 98.6%, 가와사키 카세이 고교제 안트라큐어 UVS-2171): 0.5질량부, 광중합개시제(D)로서 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온(D1, 광투과율 87.4%, IGM사제 Omnirad907): 0.75질량부를 혼합하고, 투명한 광경화성 실리콘 수지 조성물을 얻었다.A cage silicone resin having methacryloyl groups on all silicon atoms as obtained in Synthesis Example 1 (S1): 25 parts by mass, dipentaerythritol pentaacrylate as an acrylate containing a hydroxyl group [OH 1, Nippon Kayaku KYARAD DPHA manufactured by KYARAD Co., Ltd. contains 35 mass %]: 26.25 parts by mass, dipentaerythritol hexaacrylate not containing a hydroxyl group [a1, KYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. contains 65 mass %]: 48.75 Parts by mass, 1-hydroxy-cyclohexylphenyl ketone (B1, light transmittance 96.3%, Omnirad184 manufactured by IGM) as a photoinitiator (B): 7.5 parts by mass, 1,4-diethoxynaphthalene as a photosensitizer (C) (C) Light transmittance 98.6%, Kawasaki Kasei Kogyo Anthracure UVS-2171): 0.5 mass part, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 as a photoinitiator (D) -On (D1, light transmittance 87.4%, IGM company Omnirad907): 0.75 mass parts was mixed, and the transparent photocurable silicone resin composition was obtained.
이어서, 얻어진 광경화성 실리콘 수지 조성물: 50질량부, 프로필렌글리콜모노메틸에테르: 50질량부, 불소계 표면조정제: 1질량부를 혼합하고, 이 혼합물을 대기 중에 있어서, PET 기재(두께 250㎛)에 바 코터를 사용하여 두께 20㎛로 되도록 캐스팅(유연)했다. 이것을 60℃에서 10분간 건조한 후, 30W/㎝의 고압 수은 램프를 사용하여, 1000mJ/㎠의 적산 노광량으로 경화시키고, PET 기재 표면에 두께 10㎛의 실리콘 수지 성형체의 층을 형성해서 이루어지는 PET 적층체 시험편을 얻었다.Next, the obtained photocurable silicone resin composition: 50 parts by mass, propylene glycol monomethyl ether: 50 parts by mass, and a fluorine-based surface conditioner: 1 part by mass were mixed, and the mixture was mixed in the air to a PET substrate (thickness of 250 µm) with a bar coater. was cast (flexible) to a thickness of 20 µm using After drying this at 60° C. for 10 minutes, using a high-pressure mercury lamp of 30 W/cm, curing it at an accumulated exposure dose of 1000 mJ/cm 2 , and forming a layer of a silicone resin molded body having a thickness of 10 μm on the surface of the PET substrate. A test piece was obtained.
각종 특성의 평가는 이하의 방법으로 측정했다. 평가 결과를 표 1에 나타낸다.Evaluation of various characteristics was measured with the following method. An evaluation result is shown in Table 1.
[내찰상성][Scratch resistance]
PET 적층체 시험편을, #0000 스틸 울을 사용하여 하중 500g/㎠의 하중 하에서 10왕복 시험을 행하고, 육안으로 흠집의 개수를 평가했다. 또한, 하중 1000g/㎠의 하중 하에서 1000왕복 시험했을 때의 흠집의 개수도 평가하고, 이 하중 1000g/㎠·1000왕복 시험의 경우의 결과는 표 1~2 중에 괄호쓰기로 나타냈다.The PET laminated body test piece was subjected to 10 reciprocating tests using #0000 steel wool under a load of 500 g/cm 2 , and visually evaluated the number of scratches. In addition, the number of scratches when the 1000 reciprocal test was performed under a load of 1000 g/cm 2 was evaluated, and the results of the 1000 g/cm 2 · 1000 reciprocal test under this load were shown in parentheses in Tables 1 and 2.
○: 흠집 없음○: No scratches
△: 10개 미만의 흠집 있음△: less than 10 scratches
×: 10개 이상의 흠집 있음×: 10 or more scratches
[연필 경도][Pencil hardness]
PET 적층체 시험편에 대해서, JIS K 5600에 준거하고, 미쓰비시 연필 유니 를 사용하여 750g 하중, 45도의 각도로 세게 긁어, 흠집이 나지 않는 경도를 육안으로 판정했다.About the PET laminated body test piece, based on JISK5600, using the Mitsubishi pencil uni, the 750 g load, scraping hard at the angle of 45 degrees, and the hardness which does not damage|wound were judged visually.
○: 2H 이상○: 2H or more
×: 2H 미만×: less than 2H
[착색성][Colorability]
PET 적층체 시험편에 대해서, 분광 광도계(시마즈 세이사쿠쇼제 UV3600)를 사용하여, PET 기재를 블랭크로 해서 YI 측정을 행해 판정했다.About the PET laminated body test piece, using the spectrophotometer (Shimadzu Corporation UV3600), the PET base material was used as a blank, and YI measurement was performed and it determined.
◎: YI가 0.8 미만(double-circle): YI is less than 0.8
○: YI가 0.8 이상, 1.0 미만○: YI is 0.8 or more and less than 1.0
△: Y1이 1.0 이상, 2.0 미만△: Y1 is 1.0 or more and less than 2.0
×: YI가 2.0 이상×: YI is 2.0 or more
[외관][Exterior]
PET 적층체 시험편에 대해서, 육안으로 외관을 판정했다.About the PET laminated body test piece, the external appearance was judged visually.
○: 이상 없음○: No abnormality
×: 이물, 표면 성상 불량이 확인된 것×: A foreign substance and a defect in surface properties were confirmed
[실시예 2~11, 및 비교예 1~2][Examples 2-11, and Comparative Examples 1-2]
배합 조성을 표 1 및 표 2에 나타내는 중량 비율로 한 것 외는, 실시예 1과 마찬가지로 해서, 표면에 수지 성형체의 층을 형성해서 이루어지는 PET 적층체 시험편을 얻었다. 그 후, 실시예 1과 마찬가지로 평가를 행했다.Except having made the compounding composition into the weight ratio shown in Table 1 and Table 2, it carried out similarly to Example 1, and obtained the PET laminated body test piece which forms the layer of the resin molded object on the surface. Then, it evaluated similarly to Example 1.
[실시예 12][Example 12]
합성예 1에서 얻은 바와 같은 메타크릴로일기를 모든 규소 원자 상에 가진 바구니형 실리콘 수지(S1): 25질량부, 수산기를 포함하는 아크릴레이트로서 디펜타에리스리톨펜타아크릴레이트〔OH1, 니폰 가야쿠(주)제 KYARAD DPHA에 35질량% 포함된다〕: 26.25질량부, 수산기를 포함하지 않는 디펜타에리스리톨헥사아크릴레이트〔a1, 니폰 가야쿠(주)제 KYARAD DPHA에 65질량% 포함된다〕: 48.75질량부, 광중합개시제(D)로서 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온(D1, 광투과율 87.4%, IGM사제 Omnirad907): 8질량부를 혼합하고, 투명한 광경화성 실리콘 수지 조성물을 얻었다.A cage silicone resin having methacryloyl groups on all silicon atoms as obtained in Synthesis Example 1 (S1): 25 parts by mass, dipentaerythritol pentaacrylate [OH1, Nippon Kayaku ( KYARAD DPHA manufactured by KYARAD Co., Ltd. contains 35 mass %]: 26.25 parts by mass, dipentaerythritol hexaacrylate not containing a hydroxyl group [a1, KYARAD DPHA manufactured by Nippon Kayaku Co., Ltd. contains 65 mass %]: 48.75 mass Part, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (D1, light transmittance 87.4%, Omnirad907 manufactured by IGM) as a photoinitiator (D): 8 parts by mass was mixed to obtain a transparent photocurable silicone resin composition.
이어서, 얻어진 광경화성 실리콘 수지 조성물: 50질량부, 프로필렌글리콜모노메틸에테르: 50질량부, 불소계 표면조정제: 1질량부를 혼합하고, 이 혼합물을 대기 중에 있어서, PET 기재(두께 250㎛)에 바 코터를 사용하여 두께 20㎛로 되도록 캐스팅(유연)했다. 이것을 60℃에서 10분간 건조한 후, 30W/㎝의 고압 수은 램프를 사용하여, 1000mJ/㎠의 적산 노광량으로 경화시키고, PET 기재 표면에 두께 10㎛의 실리콘 수지 성형체의 층을 형성해서 이루어지는 PET 적층체 시험편을 얻었다.Next, the obtained photocurable silicone resin composition: 50 parts by mass, propylene glycol monomethyl ether: 50 parts by mass, and a fluorine-based surface conditioner: 1 part by mass were mixed, and the mixture was mixed in the air to a PET substrate (thickness of 250 µm) with a bar coater. was cast (flexible) to a thickness of 20 µm using After drying this at 60° C. for 10 minutes, using a high-pressure mercury lamp of 30 W/cm, curing it at an accumulated exposure dose of 1000 mJ/cm 2 , and forming a layer of a silicone resin molded body having a thickness of 10 μm on the surface of the PET substrate. A test piece was obtained.
각종 특성의 평가는 이하의 방법으로 측정했다. 평가 결과를 표 3에 나타낸다.Evaluation of various characteristics was measured with the following method. Table 3 shows the evaluation results.
[내찰상성][Scratch resistance]
PET 적층체 시험편을, #0000 스틸 울을 사용하여 하중 500g/㎠의 하중 하에서 10왕복 시험을 행하고, 육안으로 흠집의 개수를 평가했다.The PET laminated body test piece was subjected to 10 reciprocating tests using #0000 steel wool under a load of 500 g/cm 2 , and visually evaluated the number of scratches.
○: 흠집 없음○: No scratches
△: 10개 미만의 흠집 있음△: less than 10 scratches
×: 10개 이상의 흠집 있음×: 10 or more scratches
[연필 경도][Pencil hardness]
PET 적층체 시험편에 대해서, JIS K 5600에 준거하고, 미쓰비시 연필 유니 를 사용하여 750g 하중, 45도의 각도로 세게 긁어, 흠집이 나지 않는 경도를 육안으로 판정했다.About the PET laminated body test piece, based on JISK5600, using the Mitsubishi pencil uni, the 750 g load, scraping hard at the angle of 45 degrees, and the hardness which does not damage|wound were judged visually.
○: 2H 이상○: 2H or more
×: 2H 미만×: less than 2H
[착색성][Colorability]
PET 적층체 시험편에 대해서, 분광 광도계(시마즈 세이사쿠쇼제 UV3600)를 사용하여, PET 기재를 블랭크로 해서 YI 측정을 행해 판정했다.About the PET laminated body test piece, using the spectrophotometer (Shimadzu Corporation UV3600), the PET base material was used as a blank, and YI measurement was performed and it determined.
◎: YI가 0.8 미만(double-circle): YI is less than 0.8
○: YI가 0.8 이상, 1.0 미만○: YI is 0.8 or more and less than 1.0
△: Y1이 1.0 이상, 2.0 미만△: Y1 is 1.0 or more and less than 2.0
×: YI가 2.0 이상×: YI is 2.0 or more
[외관][Exterior]
PET 적층체 시험편에 대해서, 육안으로 외관을 판정했다.About the PET laminated body test piece, the external appearance was judged visually.
○: 이상 없음○: No abnormality
×: 이물, 표면 성상 불량이 확인된 것×: A foreign substance and a defect in surface properties were confirmed
[실시예 13~19, 및 비교예 3~7][Examples 13-19, and Comparative Examples 3-7]
배합 조성을 표 3 및 표 4에 나타내는 중량 비율로 한 것 외는, 실시예 12와 마찬가지로 해서, 표면에 수지 성형체의 층을 형성해서 이루어지는 PET 적층체 시험편을 얻었다.Except having made the compounding composition into the weight ratio shown in Table 3 and Table 4, it carried out similarly to Example 12, and obtained the PET laminated body test piece which forms the layer of the resin molded object on the surface.
표 중의 약호는 다음과 같다.The abbreviations in the table are as follows.
S1: 합성예 1에서 얻어진 실리콘 수지S1: Silicone resin obtained in Synthesis Example 1
OH1: 디펜타에리스리톨펜타아크릴레이트〔니폰 가야쿠(주)제 KAYARAD DPHA에 35질량% 포함된다〕OH1: dipentaerythritol pentaacrylate [35% by mass is contained in KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.]
a1: 디펜타에리스리톨헥사아크릴레이트〔니폰 가야쿠(주)제 KAYARAD DPHA에 65질량% 포함된다〕a1: dipentaerythritol hexaacrylate [65 mass % contained in KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.]
OH2: 펜타에리스리톨트리아크릴레이트〔교에이샤 카가쿠(주)제 라이트아크릴레이트PE-3A에 60질량% 포함된다〕OH2: pentaerythritol triacrylate [60 mass % contained in Kyoeisha Chemical Co., Ltd. light acrylate PE-3A]
a2: 펜타에리스리톨테트라아크릴레이트〔교에이샤 카가쿠(주)제 라이트아크릴레이트PE-3A에 40질량% 포함된다〕a2: pentaerythritol tetraacrylate [40 mass % contained in Kyoeisha Chemical Co., Ltd. light acrylate PE-3A]
a3: 트리메티롤프로판트리아크릴레이트〔신나카무라 카가쿠(주)제 A-TMPT〕a3: Trimethylolpropane triacrylate [A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.]
a4: 디메티롤트리시클로데칸디아크릴레이트〔교에이샤 카가쿠(주)제 라이트아크릴레이트DCP-A〕a4: Dimethylol tricyclodecane diacrylate [light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.]
U1: 우레탄아크릴레이트 올리고머〔신나카무라 카가쿠(주)제 UA-122P〕U1: Urethane acrylate oligomer [UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd.]
B1: 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광중합개시제 1-히드록시-시클로헥실페닐케톤(광투과율 96.3%, IGM사제 Omnirad184)B1: Photoinitiator 1-hydroxy-cyclohexylphenyl ketone (light transmittance 96.3%, Omnirad184 manufactured by IGM) having a light transmittance of 90% or more at an optical path length of 1 cm and a wavelength of 360 nm of a 0.01% by mass solution
B2: 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광중합개시제 2-히드록시-1-{4-[4-(2-히드록시-2-메틸프로피오닐)-벤질]페닐}-2-메틸 프로판-1-온(광투과율 96.0%, IGM사제 Omnirad127)B2: Photopolymerization initiator 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-, having an optical path length of 1 cm and a light transmittance of 90% or more at a wavelength of 360 nm of a 0.01% by mass solution Benzyl]phenyl}-2-methyl propan-1-one (light transmittance 96.0%, Omnirad127 manufactured by IGM)
C: 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광증감제 1,4-디에톡시나프탈렌(광투과율 98.6%, 가와사키 카세이 고교제 안트라큐어 UVS-2171)C: 1 cm of optical path length of 0.01 mass % solution, and 1,4-diethoxynaphthalene, a photosensitizer having a light transmittance of 90% or more at a wavelength of 360 nm (light transmittance 98.6%, Anthracure UVS-2171 manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
D1: 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온(광투과율 87.4%, IGM사제 Omnirad907)D1: Photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one having an optical path length of 1 cm and a light transmittance of less than 90% at a wavelength of 360 nm of a 0.01% by mass solution (Light transmittance 87.4%, Omnirad907 manufactured by IGM)
D2: 0.01질량% 용액의 광로 길이 1㎝, 파장360㎚의 광투과율이 90% 미만인 광중합개시제 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥산드(광투과율 66.5%, IGM사제Omnirad819)D2: Photoinitiator bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (light transmittance 66.5%, Omnirad819 manufactured by IGM) having an optical path length of 1 cm of 0.01 mass% solution and a light transmittance of 360 nm at a wavelength of less than 90% )
D3: 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제 에탄온,1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-,1-(O-아세틸 옥심)(광투과율 1.5%, BASF사제 Irgacure OXE02)D3: Photoinitiator ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- having a light transmittance of less than 90% at an optical path length of 1 cm and a wavelength of 360 nm of a 0.01% by mass solution General]-,1-(O-acetyl oxime) (light transmittance 1.5%, Irgacure OXE02 manufactured by BASF)
P: oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethylester와, oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethylester의 혼합물〔IGM(주)제 Omnirad754〕P: A mixture of oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethylester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethylester [IGM (main ) made Omnirad754]
E: 0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광증감제 9,10-디에톡시안트라센(광투과율 2.0%, 가와사키 카세이 고교제 안트라큐어 UVS-1101)E: Photosensitizer 9,10-diethoxyanthracene (light transmittance 2.0%, Anthracure UVS-1101 manufactured by Kawasaki Kasei Kogyo Co., Ltd.) having an optical path length of 1 cm and a wavelength of 360 nm of less than 90% E: 0.01 mass% solution
Q1: 할로겐계 난연제(다이이치 고교 세이야쿠제 피로가드 SR-720N)Q1: Halogen-based flame retardant (Pyroguard SR-720N manufactured by Daiichi Kogyo Seiyaku)
Q2: 형광증백제(BASF제 TinopalOB)Q2: Fluorescent brightener (TinopalOB made by BASF)
불포화 화합물 합계: 불포화 화합물의 합계량(질량부)Sum of unsaturated compounds: Total amount of unsaturated compounds (parts by mass)
OH 합계: 수산기를 포함하는 불포화 화합물의 합계량(질량부)Total OH: Total amount of unsaturated compounds containing hydroxyl groups (parts by mass)
OH 비율: 불포화 화합물 중 수산기를 포함하는 불포화 화합물의 비율(질량%)OH ratio: ratio of unsaturated compounds containing a hydroxyl group among unsaturated compounds (mass %)
Claims (10)
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제(D)를 포함하는 광경화성 실리콘 수지 조성물이며,
상기 불포화 화합물(A2)은, 그 적어도 20질량% 이상이 수산기를 포함하는 불포화 화합물이며,
상기 실리콘 수지 조성물(A)에 대하여, 광중합개시제(D)가 0.1질량% 이상 20질량% 미만으로 배합되는 것을 특징으로 하는 광경화성 실리콘 수지 조성물.Silicone resin (A1) and -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 in the molecule [provided that R 3 represents an alkylene group, an alkylidene group or a -OC(=O)- group, and R 4 represents a hydrogen atom or an alkyl group] containing at least one unsaturated group represented by A silicone resin composition (A), and
It is a photocurable silicone resin composition comprising a photoinitiator (D) having an optical path length of 1 cm of a 0.01 mass% solution and a light transmittance of less than 90% at a wavelength of 360 nm,
The unsaturated compound (A2) is an unsaturated compound in which at least 20% by mass or more contains a hydroxyl group,
A photocurable silicone resin composition, characterized in that, with respect to the silicone resin composition (A), a photoinitiator (D) is blended in an amount of 0.1% by mass or more and less than 20% by mass.
상기 불포화 화합물(A2)은, 그 10~100질량%가, 분자 중에 -R3-CR4=CH2 또는 -CR4=CH2〔단, R3은 알킬렌기, 알킬리덴기 또는 -O-C(=O)-기를 나타내고, R4는 수소 원자 또는 알킬기를 나타낸다〕로 나타내어지는 불포화기를 적어도 2개 포함하는 비실리콘형의 다관능 불포화 화합물인 것을 특징으로 하는 광경화성 실리콘 수지 조성물.The method of claim 1,
The said unsaturated compound (A2), 10-100 mass % of the molecule|numerator is -R 3 -CR 4 =CH 2 or -CR 4 =CH 2 [provided that R 3 is an alkylene group, an alkylidene group, or -OC( = O) - group, and R 4 represents a hydrogen atom or an alkyl group].
상기 실리콘 수지(A1)가 일반식 (1)
[RSiO3/2]n (1)
〔단, R은 (메타)아크릴로일기를 갖는 유기 관능기이며, n은 8, 10 또는 12이다〕로 나타내어지고, 구조 단위 중에 바구니형 구조를 갖는 폴리오르가노실세스퀴옥산을 주된 성분으로 하는 것을 특징으로 하는 광경화성 실리콘 수지 조성물.3. The method according to claim 1 or 2,
The silicone resin (A1) is the general formula (1)
[RSiO 3/2 ] n (1)
[provided that R is an organic functional group having a (meth)acryloyl group, and n is 8, 10 or 12], and having a polyorganosilsesquioxane having a cage structure in the structural unit as a main component A photocurable silicone resin composition, characterized in that.
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광중합개시제(B)를 더 포함하는 것을 특징으로 하는 광경화성 실리콘 수지 조성물.4. The method according to any one of claims 1 to 3,
The photocurable silicone resin composition further comprising a photoinitiator (B) having an optical path length of 1 cm and a light transmittance of 90% or more at a wavelength of 360 nm of a 0.01% by mass solution.
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광중합개시제(B)가, 히드록시페닐케톤계 광중합개시제인 것을 특징으로 하는 광경화성 실리콘 수지 조성물.5. The method of claim 4,
The photopolymerization initiator (B) having an optical path length of 1 cm and a wavelength of 360 nm and a light transmittance of 90% or more of a 0.01% by mass solution is a hydroxyphenyl ketone-based photopolymerization initiator. A photocurable silicone resin composition.
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광증감제(C)를 더 포함하는 것을 특징으로 하는 광경화성 실리콘 수지 조성물.6. The method according to any one of claims 1 to 5,
A photocurable silicone resin composition comprising a photosensitizer (C) having an optical path length of 1 cm and a light transmittance of at least 90% at a wavelength of 360 nm of a 0.01% by mass solution.
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 이상인 광증감제(C)가, 나프탈렌계 광증감제인 것을 특징으로 하는 광경화성 실리콘 수지 조성물.7. The method of claim 6,
The photosensitizer (C) having an optical path length of 1 cm and a light transmittance of 90% or more at a wavelength of 360 nm of a 0.01% by mass solution is a naphthalene-based photosensitizer, a photocurable silicone resin composition.
0.01질량% 용액의 광로 길이 1㎝, 파장 360㎚의 광투과율이 90% 미만인 광중합개시제(D)가, α-아미노알킬페논계 광중합개시제, 포스핀옥사이드계 광중합개시제 및 옥심에스테르계 광중합개시제로 이루어지는 군으로부터 선택되는 1종 이상의 광중합개시제인 것을 특징으로 하는 광경화성 실리콘 수지 조성물.8. The method according to any one of claims 1 to 7,
The photopolymerization initiator (D) having an optical path length of 1 cm and a wavelength of 360 nm of a 0.01 mass% solution having a light transmittance of less than 90% is composed of an α-aminoalkylphenone-based photopolymerization initiator, a phosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator. A photocurable silicone resin composition, characterized in that it is at least one photoinitiator selected from the group.
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| JP2019180136 | 2019-09-30 | ||
| PCT/JP2020/004911 WO2020162615A1 (en) | 2019-02-08 | 2020-02-07 | Photocurable silicone resin composition, silicone resin molded body obtained by curing same and method for manufacturing said molded body |
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| JP2004143449A (en) | 2002-09-30 | 2004-05-20 | Nippon Steel Chem Co Ltd | Cage-type silsesquioxan resin with functional group and method for producing the same |
| JP4558643B2 (en) | 2003-03-27 | 2010-10-06 | 新日鐵化学株式会社 | Silicone resin composition and molded body thereof |
| JP5698566B2 (en) | 2011-03-08 | 2015-04-08 | 新日鉄住金化学株式会社 | Silicone resin composition and molded body thereof |
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| JP5000303B2 (en) * | 2004-09-27 | 2012-08-15 | 新日鐵化学株式会社 | Silica-containing silicone resin composition and molded article thereof |
| JP5092440B2 (en) * | 2007-02-16 | 2012-12-05 | Ｊｓｒ株式会社 | Curable composition, cured film thereof and laminate |
| JP6519946B2 (en) * | 2015-05-21 | 2019-05-29 | 荒川化学工業株式会社 | UV curable coating composition and cured film thereof |
| JP6837869B2 (en) * | 2017-02-28 | 2021-03-03 | 中国塗料株式会社 | Active energy ray-curable resin composition for flooring materials, coated flooring materials, manufacturing methods for coated flooring materials, and methods for preventing contamination of flooring materials. |
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| JP2004143449A (en) | 2002-09-30 | 2004-05-20 | Nippon Steel Chem Co Ltd | Cage-type silsesquioxan resin with functional group and method for producing the same |
| JP4558643B2 (en) | 2003-03-27 | 2010-10-06 | 新日鐵化学株式会社 | Silicone resin composition and molded body thereof |
| JP5698566B2 (en) | 2011-03-08 | 2015-04-08 | 新日鉄住金化学株式会社 | Silicone resin composition and molded body thereof |
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