CN113396169A - Photocurable silicone resin composition, silicone resin molded article obtained by curing the same, and method for producing the molded article - Google Patents
Photocurable silicone resin composition, silicone resin molded article obtained by curing the same, and method for producing the molded article Download PDFInfo
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- CN113396169A CN113396169A CN202080012462.9A CN202080012462A CN113396169A CN 113396169 A CN113396169 A CN 113396169A CN 202080012462 A CN202080012462 A CN 202080012462A CN 113396169 A CN113396169 A CN 113396169A
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- Prior art keywords
- silicone resin
- mass
- resin composition
- photopolymerization initiator
- unsaturated compound
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 113
- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003999 initiator Substances 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 238000002834 transmittance Methods 0.000 claims abstract description 37
- 230000003287 optical effect Effects 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003504 photosensitizing agent Substances 0.000 claims description 20
- -1 oxime ester Chemical class 0.000 claims description 14
- 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 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
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004040 coloring Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- 238000000016 photochemical curing Methods 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 description 20
- 239000005020 polyethylene terephthalate Substances 0.000 description 20
- 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
- 238000012360 testing method Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects 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
- 239000002904 solvent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000001035 drying Methods 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
- 239000011248 coating agent Substances 0.000 description 6
- 231100000241 scar Toxicity 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000000654 additive Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000001965 increasing effect Effects 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
- 230000035945 sensitivity Effects 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
- 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 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 208000032544 Cicatrix Diseases 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
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000037387 scars Effects 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 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
- 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
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 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
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 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
- 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
- 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- 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
- 238000010521 absorption reaction Methods 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
- 239000002585 base Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
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- 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
- 238000001914 filtration Methods 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
- 239000013022 formulation composition Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 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
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
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- 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
- PRBBFHSSJFGXJS-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O.C=CC(=O)OCC(C)(C)COC(=O)C=C PRBBFHSSJFGXJS-UHFFFAOYSA-N 0.000 description 1
- 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
- JJPJWPYRFJDRMH-UHFFFAOYSA-N 1,4-dipropoxynaphthalene Chemical compound C1=CC=C2C(OCCC)=CC=C(OCCC)C2=C1 JJPJWPYRFJDRMH-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
- NWWDDRUSXZNEDM-UHFFFAOYSA-N 2,6-di(propan-2-yloxy)naphthalene Chemical compound C1=C(OC(C)C)C=CC2=CC(OC(C)C)=CC=C21 NWWDDRUSXZNEDM-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
- UDQSUQGVJKUQSS-UHFFFAOYSA-N 2,6-dipropoxynaphthalene Chemical compound C(CC)OC1=CC2=CC=C(C=C2C=C1)OCCC UDQSUQGVJKUQSS-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
- 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
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-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
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-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
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [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
- ZZPGHNFYZUVXCF-UHFFFAOYSA-N C(C)(C)OC1=CC=C(C2=CC=CC=C12)OC(C)C Chemical compound C(C)(C)OC1=CC=C(C2=CC=CC=C12)OC(C)C ZZPGHNFYZUVXCF-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 238000005299 abrasion Methods 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
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000000903 blocking effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 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
- 238000013461 design Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002009 diols Chemical class 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
- 239000006185 dispersion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 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
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 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
- 239000003973 paint 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
- 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
Abstract
The invention provides a photo-curing silicone resin composition which reduces the influence of oxygen inhibition generated when a photo-curing silicone resin composition containing a silicone resin, an unsaturated compound and a photopolymerization initiator is cured, and can provide sufficient scratch resistance and less coloring even under low exposureA silicone resin molded body. One of which comprises: mixing a silicone resin (A1) with a resin composition containing at least one-R in the molecule3‑CR4＝CH2or-CR4＝CH2An unsaturated compound (a2) which is an unsaturated group represented by (a) and is radically copolymerizable with the silicone resin (a1) is represented by (1): 99-99: 1 (A) a silicone resin composition prepared in a mass ratio; and a photopolymerization initiator (D) having an optical path length of 1cm and a light transmittance of 360nm of less than 90% in a solution of 0.01% by mass, wherein 20% by mass or more of A2 is a hydroxyl group-containing unsaturated compound, and D is contained in an amount of 0.1% by mass or more and less than 20% by mass relative to the silicone resin composition (A).
Description
Technical Field
The present invention relates to a photocurable silicone resin composition that can provide a molded article having high scratch resistance and excellent transparency, and a silicone resin molded article that is a three-dimensional crosslinked article obtained by curing the photocurable silicone resin composition.
Background
In recent years, in all fields of displays, mobile devices, home electric appliances, automobile parts, and the like, demands for design, weight reduction, and thinning have been increasing, and as surface protective members for these, plastics, lightweight metals, and the like have been used instead of conventional glass or metals. However, plastics or a part of lightweight metals have a problem that they are easily damaged due to low surface hardness. Therefore, a method of providing a hard coat layer for protecting the surface can be used.
Acrylic compositions are mostly used for the hard coat layer. Acrylic compositions are generally used for paints, adhesives and the like because they can be cured in a short time and at a low temperature by forming a film and curing the film through a radical reaction by irradiation with active energy rays such as ultraviolet rays or electron beams, and the toughness can be maintained by the resin composition to be formulated.
As an example of the hard coat layer, the present inventors have made studies focusing on a silicone resin having a cage structure and a reactive functional group, and have found that a transparent silicone resin molded body having a high balance among surface hardness, heat resistance, mechanical properties, dimensional stability and the like can be provided by increasing the number of reactive functional groups in the silicone resin having a cage structure and blending an unsaturated compound copolymerizable therewith at a specific ratio, and have disclosed that the silicone resin molded body can be preferably used as an alternative to inorganic glass (patent documents 1 to 2). A method for producing the silicone resin having a cage structure is disclosed in patent document 3, in particular.
However, in the case where curing by radical polymerization is performed in the atmosphere, the silicone resin composition is affected by oxygen inhibition, and therefore, curing does not progress, and it is difficult to obtain sufficient scratch resistance. In order to improve the atmospheric curing property, a photopolymerization initiator is generally used as a highly sensitive material, and the amount of the photopolymerization initiator to be blended or the amount of exposure to light is increased.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4558643
Patent document 2: japanese patent No. 5698566
Patent document 3: japanese patent laid-open No. 2004-143449
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a photocurable silicone resin composition which, even when applied to general coating equipment or the like without requiring expensive equipment for blocking oxygen, reduces the effect of oxygen inhibition generated when a photocurable silicone resin composition containing a silicone resin, an unsaturated compound and a photopolymerization initiator is cured, and which can provide a silicone resin molded body having sufficient scratch resistance and little coloration even with a low exposure amount.
Means for solving the problems
The present inventors have conducted intensive studies on the above-mentioned photocurable silicone resin composition, particularly on a combination of an unsaturated compound capable of undergoing radical polymerization and a photopolymerization initiator in the composition thereof, and as a result, have found that the above-mentioned problems can be solved by blending a predetermined amount of a hydroxyl group-containing compound as the unsaturated compound and using a predetermined amount of a specific photopolymerization initiator and preferably a specific photosensitizer, and have completed the present invention.
That is, the present invention is a photocurable silicone resin composition comprising:
mixing a silicone resin (A1) with a resin composition containing at least one-R in the molecule3-CR4＝CH2or-CR4＝CH2[ wherein, R3Represents alkylene, alkylidene or-O-C (═ O) -radical, R4An unsaturated compound (A2) which represents an unsaturated group represented by a hydrogen atom or an alkyl group and is radically copolymerizable with the silicone resin (A1) is represented by a general formula of 1: 99-99: 1 (A) a silicone resin composition prepared in a mass ratio; and
a photopolymerization initiator (D) having an optical path length of 1cm and a light transmittance at a wavelength of 360nm of less than 90% in a solution of 0.01% by mass,
at least 20% by mass or more of the unsaturated compound (A2) is a hydroxyl group-containing unsaturated compound,
the photopolymerization initiator (D) is contained in an amount of 0.1 mass% or more and less than 20 mass% based on the silicone resin composition (a).
10 to 100% by mass of the unsaturated compound (A2) may be a compound containing at least two-R in the molecule3-CR4＝CH2or-CR4＝CH2(wherein, R3Represents alkylene, alkylidene or-O-C (═ O) -radical, R4Represents a hydrogen atom or an alkyl group).
The silicone resin (A1) can be represented by the general formula (1)
[RSiO3/2]n(1)
Wherein R is an organic functional group having a (meth) acryloyl group, n is 8, 10 or 12, and the polyorganosilsesquioxane has a cage structure in the structural unit as a main component.
The photocurable silicone resin composition may further comprise a photopolymerization initiator (B) having an optical path length of 1cm and a light transmittance of 90% or more at a wavelength of 360nm in a solution of 0.01% by mass. Here, the photopolymerization initiator (B) may be a hydroxyphenyl ketone-based photopolymerization initiator.
The photo-curable silicone resin composition may further contain a photo sensitizer (C) having an optical path length of 1cm and a light transmittance of 360nm of 90% or more in a solution of 0.01% by mass. Here, the photosensitizer (C) may be a naphthalene-based photosensitizer.
The photopolymerization initiator (D) having an optical path length of 1cm and a light transmittance of 360nm of a wavelength of less than 90% in the 0.01 mass% solution may be at least one photopolymerization initiator selected from the group consisting of an α -aminophenylketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator.
The present invention also provides a silicone resin molded body obtained by radically copolymerizing the photocurable silicone resin composition and curing the resultant product.
Further, the present invention is a method for producing a silicone resin molded body, characterized in that the photo-curable silicone resin composition is irradiated with an active energy ray in the air and is subjected to radical copolymerization to form a silicone resin molded body.
ADVANTAGEOUS EFFECTS OF INVENTION
The photocurable silicone resin composition of the present invention can provide a molded article having high scratch resistance, high transparency, and high heat resistance, and can provide sufficient performance even in an atmospheric environment, and thus is suitable for surface protection members for various applications such as displays, housings of mobile devices, home electric appliances, automotive interior materials, and building members.
Detailed Description
The present invention will be further described below.
The photo-curable silicone resin composition of the present inventionComprising mixing a silicone resin (a1) (hereinafter, also referred to as "the present silicone resin") with an unsaturated compound (a2) (hereinafter, also simply referred to as "the unsaturated compound") in a 1: a2 ═ 1: 99-99: 1, the unsaturated compound (a2) containing at least one-R in the molecule3-CR4＝CH2or-CR4＝CH2And (b) an unsaturated group represented by (a) and being capable of radical copolymerization with the silicone resin (a1), wherein at least 20% by mass or more of the unsaturated compound (a2) is a hydroxyl group-containing unsaturated compound, and wherein a photopolymerization initiator (D) having an optical path length of 1cm of a 0.01% by mass solution and a light transmittance at a wavelength of 360nm of less than 90% is contained in an amount of 0.1% by mass or more and less than 20% by mass relative to the silicone resin composition (a) in addition to the silicone resin composition (a).
The present silicone resin (a1) used in the present invention may be a conventional silicone resin, and is preferably one containing, as a main component, a polyorganosilsesquioxane represented by the above general formula (1) and having a cage structure in a structural unit (also referred to as a cage polyorganosilsesquioxane).
In the general formula (1), R is an organic functional group having a (meth) acryloyl group, and n is 8, 10 or 12. Examples of the organic functional group having a (meth) acryloyl group include groups represented by the following general formula (4). In the general formula (4), m is an integer of 1-3, R1Is a hydrogen atom or a methyl group.
CH2＝CR1-COO-(CH2)m- (4)
The silicone resin contains an organic functional group having a (meth) acryloyl group on a silicon atom in the molecule. Specific examples of the cage polyorganosilsesquioxane of the general formula (1) wherein n is 8, 10 or 12 include cage structures represented by the following structural formulae (5), (6) and (7). In the following formula, R represents the same as R in the general formula (1).
[ solution 1]
Here, the silicone resin can be produced by the method described in patent document 3 and the like. For example, RSiX can be made3The silicon compound represented by the formula (I) is obtained by subjecting a silicon compound to hydrolysis reaction in the presence of a polar solvent and a basic catalyst and condensing a part of the silicon compound, and further subjecting the resultant hydrolysis product to recondensation in the presence of a nonpolar solvent and a basic catalyst. Here, R is an organic functional group having a (meth) acryloyl group, specifically a group represented by the general formula (4), and X represents a hydrolyzable group. Specific examples of preferable R include 3-methacryloxypropyl, methacryloxymethyl and 3-acryloxypropyl.
The hydrolyzable group X is not particularly limited as long as it is a group having hydrolyzability, and examples thereof include an alkoxy group, an acetoxy group, and the like, and an alkoxy group is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group. Methoxy is preferred because of its high reactivity.
If RSiX is shown3Among the silicon compounds represented, preferred compounds are: methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane. Among them, 3-methacryloxypropyltrimethoxysilane, which is easily available as a raw material, is preferably used.
Examples of the basic catalyst used in the hydrolysis reaction include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, and ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide can be preferably used in terms of high catalyst activity. Basic catalysts are usually used as aqueous solutions.
The hydrolysis reaction conditions are preferably 0 to 60 ℃ and more preferably 20 to 40 ℃. When the reaction temperature is lower than 0 ℃, the reaction rate becomes slow, and the hydrolyzable group remains in an unreacted state, resulting in a large reaction time. On the other hand, if the temperature is higher than 60 ℃, the reaction rate is too high, and therefore, a complicated condensation reaction proceeds, and as a result, the increase in molecular weight of the hydrolysis product is promoted. The reaction time is preferably 2 hours or more. If the reaction time is less than 2 hours, the hydrolysis reaction may not proceed sufficiently and the hydrolyzable group may remain unreacted.
The hydrolysis reaction requires the presence of water, which may also be supplied by an aqueous solution of the basic catalyst, or may be added in the form of additional water. The amount of water may be not less than the amount sufficient to hydrolyze the hydrolyzable group, and is preferably 1.0 to 1.5 times the theoretical amount. In addition, an organic polar solvent is required for the hydrolysis, and as the organic polar solvent, an alcohol such as methanol, ethanol, 2-propanol, or other organic polar solvent can be used. Preferably, a lower alcohol having 1 to 6 carbon atoms and having solubility in water is used, and more preferably, 2-propanol is used. When a nonpolar solvent is used, the reaction system becomes uneven, the hydrolysis reaction does not proceed sufficiently, and unreacted hydrolyzable groups remain, which is not preferable.
After the hydrolysis reaction is complete, the water or aqueous reaction medium is separated. The separation of water or the reaction solvent containing water can be carried out by means of evaporation under reduced pressure or the like. In order to sufficiently remove water and other impurities, a means such as adding a nonpolar solvent to dissolve the hydrolysis reaction product, washing the solution with saline solution or the like, and then drying with a drying agent such as anhydrous magnesium sulfate or the like may be employed. If the nonpolar solvent is separated by evaporation or the like, the hydrolysis reaction product can be recovered, and if the nonpolar solvent can be used as the nonpolar solvent used in the subsequent reaction, it is not necessary to separate it.
In the hydrolysis reaction, condensation reaction of the hydrolysate occurs together with the hydrolysis. The hydrolysate formed by the condensation reaction of the hydrolysate 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 depending on the reaction conditions, most, preferably almost all, of the hydrolyzable groups X are substituted with OH groups, and most, preferably 95% or more, of the OH groups are condensed. The hydrolysis product has a structure of various cage-type, ladder-type, and random-type silsesquioxanes, and even if a compound having a cage-type structure is used, the proportion of a complete cage-type structure is small, and the incomplete cage-type structure is mainly formed by opening a part of a cage. Therefore, the hydrolysis product obtained by the hydrolysis is further heated in an organic solvent in the presence of a basic catalyst to condense siloxane bonds (referred to as recondensation), thereby selectively producing a silsesquioxane having a cage structure.
Specifically, this is performed as follows. That is, as described above, after the hydrolysis reaction is completed, water or a water-containing reaction solvent is separated, and then the recondensation reaction is carried out in the presence of a nonpolar solvent and a basic catalyst. The reaction conditions for the recondensation reaction are preferably in the range of 100 to 200 ℃, and more preferably 110 to 140 ℃. If the reaction temperature is too low, a driving force sufficient for the recondensation reaction cannot be obtained and the reaction does not proceed. If the reaction temperature is too high, the (meth) acryloyl group may undergo a self-polymerization reaction, and therefore, it is necessary to suppress the reaction temperature, add a polymerization inhibitor, or the like. The reaction time is preferably 2 to 12 hours. The amount of the nonpolar solvent used may be an amount sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst used may be in the range of 0.1 to 10 mass% (wt%) relative to the hydrolysis reaction product.
The nonpolar solvent may be any solvent that is insoluble or hardly soluble in water, and is preferably a hydrocarbon solvent. The hydrocarbon solvent may be a nonpolar solvent having a low boiling point, such as toluene, benzene, or xylene. Among them, toluene is preferably used. The basic catalyst used in the hydrolysis reaction may be an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, or cesium hydroxide, or an ammonium hydroxide salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, or benzyltriethylammonium hydroxide, but is preferably a catalyst soluble in a nonpolar solvent such as tetraalkylammonium.
The hydrolysis product used for the recondensation is preferably a hydrolysis product obtained by washing with water, dehydrating, and concentrating, but may be used without washing with water or dehydrating. Water may be present during the reaction, but need not be actively added, and may be limited to the degree of moisture brought in by the basic catalyst solution. When the hydrolysis of the hydrolysis product is not sufficiently performed, a theoretical amount of water or more necessary for hydrolyzing the remaining hydrolyzable group is necessary, but the hydrolysis reaction is generally sufficiently performed. After the recondensation reaction, the catalyst was washed with water and concentrated to obtain a silsesquioxane mixture. The silsesquioxane mixture obtained preferably has the same number of silicon atoms as the number of (meth) acryloyl groups in the molecule.
The silsesquioxane mixture obtained in the above manner is different depending on the reaction conditions and the state of the hydrolysis product, and it is considered that the constituent components are 70% or more of the plurality of cage-type silsesquioxanes as a whole, and the remainder is a trapezoidal, randomly crosslinked silsesquioxane. Since these are difficult to separate and take a lot of time, in the present invention, when the cage-type silsesquioxane represented by the general formula (1) is used, it is preferable to use a silsesquioxane containing 70% or more of a plurality of cage-type silsesquioxanes. Further, if the content of the cage-type silsesquioxane is 70% or more, the obtained effects are not different. Among the constituents of the various cage-type silsesquioxanes, the T8 represented by the general formula (5) is 20 to 40%, the T10 represented by the general formula (6) is 40 to 50%, and the other constituent is T12 represented by the general formula (7). T8 was isolated as needle crystals by allowing the silsesquioxane mixture to stand below 20 ℃. The content ratio of the cage-type silsesquioxane can be confirmed by, for example, Gel Permeation Chromatography (GPC) or liquid Chromatography Mass Spectrometer (LC-MS).
The silicone resin may be a mixture of T8 to T12, or may be one obtained by separating or concentrating one or more of T8 and the like, but is not limited to the silicone resin obtained by the above method. The present silicone resin (a1) containing the silicone resin was prepared as described below in such a manner that the ratio of the unsaturated compound to the silicone resin (a 1: a2 ═ 1: 99-99: 1. preferably 3: 97-80: 20 in a mass ratio. The a1 is preferably blended so that the content thereof in the photocurable silicone resin composition is 2.5 to 75% by mass.
In the silicone resin composition (a), at least 20% by mass or more of the unsaturated compound (a2) copolymerizable with the silicone resin (a1) is a hydroxyl group-containing unsaturated compound, and at least one unsaturated group is contained.
The unsaturated group is represented by-R3-CR4＝CH2or-CR4＝CH2[ wherein, R3Represents alkylene, alkylidene or-O-C (═ O) -radical, R4Represents a hydrogen atom or an alkyl group. At R3When the carbon number is an alkylene group or an alkylidene group, the number of carbon atoms is preferably 1 to 6, and R is4In the case of an alkyl group, a methyl group is preferable.
The unsaturated compound (a2) is preferably a polyfunctional unsaturated compound containing 10 to 100% by mass of two or more or three or more unsaturated groups. By blending the polyfunctional unsaturated compound, a molded body having high surface hardness can be obtained. The polyfunctional unsaturated compound is preferably a non-silicone type compound containing no silicon atom.
Among the above-mentioned polyfunctional unsaturated compounds, examples of the unsaturated compound having a hydroxyl group include pentaerythritol triacrylate, glycerol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate and the like. Since these have hydroxyl groups in the molecule, the radicals generated by shortening the distance between the molecules by the interaction of the hydroxyl groups react with the double bond rapidly, thereby increasing the curing rate, and the radical polymerization proceeds before the reaction of oxygen with the radicals, thereby suppressing the inhibition of curing by oxygen. As described above, 20% by mass or more of the unsaturated compound (a2) blended in the silicone resin composition (a) must be a hydroxyl group-containing unsaturated compound, and preferably 30% by mass or more of a2 may be a hydroxyl group-containing unsaturated compound. If the amount is less than the above range, the effect of intermolecular interaction is reduced. The upper limit of the blending is not particularly limited, but if it exceeds 60 mass%, the effect of suppressing oxygen inhibition is hardly increased.
On the other hand, examples of the unsaturated compound having no hydroxyl group include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like. In addition to these, the following compounds and the like can be used: the terminal hydroxyl groups of the skeleton obtained by modifying a part or all of the hydroxyl groups of pentaerythritol or dipentaerythritol with a diol such as ethylene or isopropylene or γ -butyrolactone3-CR4＝CH2or-CR4＝CH2[ wherein, R3Represents alkylene, alkylidene or-O-C (═ O) -radical, R4A compound obtained by modifying an unsaturated group represented by a hydrogen atom or an alkyl group. Alternatively, urethane acrylate, acrylic copolymer acrylate, and the like can be exemplified. These polyfunctional unsaturated compounds and unsaturated compounds having no hydroxyl group may be used alone or in combination of two or more.
In addition, in the unsaturated compound (a2), a monofunctional or other difunctional monomer (unsaturated compound) having reactivity may be blended within a range not to lower the 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, and the like. Examples of the other difunctional monomer include tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, and the like.
The monofunctional monomer or the other difunctional monomer is preferably contained in the unsaturated compound (a2) in an amount of 20% by mass or less, more preferably 10% by mass or less. Blending at more than 20% by mass is not preferable because the surface hardness tends to decrease.
In the present specification, the silicone resin composition (a) containing the silicone resin (a1) and the unsaturated compound (a2) is referred to as a silicone resin composition (a), and the silicone resin composition (a) containing a photopolymerization initiator (B), a photosensitizer (C), and/or a photopolymerization initiator (D) (and other additives as needed) described below is referred to as a photocurable silicone resin composition of the present invention.
The silicone resin (a1) and the unsaturated compound (a2) may be prepared first, or the silicone resin (a1), the unsaturated compound (a2), the photopolymerization initiator (B) described later, and the photosensitizer (C) and/or the photopolymerization initiator (D) may be prepared simultaneously, and the order of preparation may be arbitrary. As described later, various additives may be contained in the photocurable silicone resin composition of the present invention, but the order of blending these additives is arbitrary.
The photopolymerization initiator (D) used in the photocurable silicone resin composition of the present invention is required to be a photopolymerization initiator which has an optical path length of 1cm in a 0.01 mass% solution, a light transmittance at a wavelength of 360nm of less than 90%, and has absorption in a long wavelength region. The photopolymerization initiator (D) is preferably at least one photopolymerization initiator selected from the group consisting of α -aminobenzone-based photopolymerization initiators, phosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators, and among these, α -aminobenzone-based photopolymerization initiators having high photocleavage efficiency are more preferably used. Specific examples of the α -aminophenylketone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one. The amount of the silicone resin composition (a) is 0.1% by mass or more and less than 20% by mass. From the viewpoint of photocurability and transparency (coloring property), the range of 0.1 to 10% by mass is preferable with respect to the silicone resin composition (a), and particularly from the viewpoint of transparency (coloring property), the range of 0.1 to less than 5% by mass is more preferable, and the range of 0.1 to 1% by mass is most preferable. If the amount is less than 0.1% by mass, the sensitivity of photocuring is low, and a cured product having sufficient hardness cannot be obtained. When the content is 20% by mass or more, the coloring tends to be strong. In addition, in order to adjust the photocurability or transparency, a phosphine oxide-based or oxime ester-based photopolymerization initiator may be used in combination, or may be used alone. Specific examples of the phosphine oxide-based photopolymerization initiator include bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and the like. Specific examples of the oxime ester photopolymerization initiator include ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyloxime), 1, 2-octanedione, 1- [4- (phenylthio) -,2- (0-benzoyloxime) ]. Further, when the photopolymerization initiator (D) is used in an amount of 0.1 to 1% by mass relative to the silicone resin composition (a), it is preferable to use a photosensitizer (C) described later in combination, particularly from the viewpoint of photocurability.
In the photocurable silicone resin composition of the present invention, the following photopolymerization initiator (B) and photosensitizer (C) may be used.
The photopolymerization initiator (B) used in the photocurable silicone resin composition of the present invention is preferably a highly transparent photopolymerization initiator having an optical path length of 1cm in a 0.01 mass% solution, a light transmittance of 360nm wavelength of 90% or more, and no absorption in the visible light region. The photopolymerization initiator (B) is preferably a hydroxyphenyl ketone photopolymerization initiator, and specific examples of the compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) -benzyl ] phenyl } -2-methylpropan-1-one. The amount of the silicone resin composition (a) to be blended is in the range of 1 to 10% by mass, preferably 3 to 10% by mass, from the viewpoint of photocurability and transparency. If the amount is less than 1% by mass, the effect of improving the sensitivity of photocuring is low, and the desired effect of improving hardness cannot be obtained. When the amount exceeds 10% by mass, coloration tends to be strong, and an unreacted photopolymerization initiator may bleed out, and therefore, the amount is preferably within the above range. In addition, in order to adjust the photocurability or transparency, a plurality of hydroxyphenyl ketone photopolymerization initiators may be combined.
The photosensitizer (C) used in the photocurable silicone resin composition of the present invention is preferably a high-transparency photosensitizer which has an optical path length of 1cm and a light transmittance of 360nm wavelength of 90% or more and does not absorb in the visible light region, and which is a 0.01 mass% solution. The photosensitizer (C) is preferably a naphthalene-based photosensitizer, and specific examples of the compound include 1, 4-dimethoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-di (n-propoxy) naphthalene, 1, 4-di (isopropoxy) naphthalene, 2, 6-dimethoxynaphthalene, 2, 6-diethoxynaphthalene, 2, 6-di (n-propoxy) naphthalene, 2, 6-di (isopropoxy) naphthalene, and the like. The amount of the silicone resin composition (a) to be blended is in the range of 0.1 to 3% by mass, preferably 0.5 to 3% by mass, from the viewpoint of photocurability and transparency. If the amount is less than 0.5% by mass, the effect of enhancing the sensitizer is not exhibited, and the desired effect of enhancing the hardness cannot be obtained. When the content exceeds 3% by mass, the coloring tends to be strong, and therefore, the content is preferably within the above range. In order to adjust the photocurability or transparency, a plurality of naphthalene-based photosensitizers may be combined.
In an actual production process for mass production, since the hard coat layer is desirably formed in an atmosphere other than a nitrogen atmosphere in terms of productivity and safety, an initiator having high photocleavage efficiency such as the photopolymerization initiator (D) is used. These are generally colored or easily discolored under a weather test, and thus cannot be used in large amounts. On the other hand, a non-coloring initiator represented by the photopolymerization initiator (B) tends to have insufficient sensitivity, and the hard coat layer surface is insufficiently cured due to oxygen inhibition. Therefore, as described above, it is necessary to use a specific amount of the photopolymerization initiator (D), but when the amount of the photopolymerization initiator (D) used is reduced, in particular, from the viewpoint of photocurability, the shortage of sensitivity is compensated by the use of the photosensitizer (C) in combination, and curing can be performed with a low exposure amount, and by using the photopolymerization initiator (D) having a high sensitivity in a range of less coloring, the effect of oxygen inhibition on the surface of the hard coat layer can be improved and the scratch resistance can be improved.
Various additives may be added to the photocurable silicone resin composition of the present invention within the range not departing from the object of the present invention. Examples of the various additives include organic/inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, fluorescent brighteners, crosslinking agents, dispersion aids, and resin components.
The photocurable silicone resin molded body of the present invention can be produced by curing the photocurable silicone resin composition by irradiation with active energy rays such as visible light rays or ultraviolet rays or electron beams, and preferably, a cured molded body can be obtained by irradiation with ultraviolet rays having a wavelength of 10nm to 400nm or visible light rays having a wavelength of 400nm to 700 nm. The wavelength of the light to be used is not particularly limited, and near ultraviolet rays having a wavelength of 200nm to 400nm can be preferably used. Examples of lamps that can be used as the ultraviolet light generating source include low-pressure mercury lamps (output: 0.4W/cm to 4W/cm), high-pressure mercury lamps (40W/cm to 160W/cm), ultrahigh-pressure mercury lamps (173W/cm to 435W/cm), metal halide lamps (80W/cm to 160W/cm), and the like.
The method of obtaining a molded article (silicone resin copolymer or cured product) by irradiation with an active energy ray such as light irradiation may be either an oxygen-blocking environment or an atmospheric environment, but the composition of the present invention is preferably a polymerization-cured product in an atmospheric environment because a good molded article can be obtained, and thus the polymerization-cured product can be preferably performed in an atmospheric environment. For example, the following methods can be exemplified: a method for producing a molded article having a desired shape 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 cure the composition by polymerization, and releasing the cured composition from the mold; or a method of producing a sheet-like molded article by applying the photocurable silicone resin composition of the present invention to a moving steel belt using a blade or a roll coater without using a die, and polymerizing and curing the composition by an ultraviolet lamp.
The shape of the molded article is arbitrary, and may be a film, a coating film or the like. The molded article can be obtained by radical copolymerization of the photocurable silicone resin composition of the present invention. The molded article or cured product of the present invention is a three-dimensionally crosslinked polymer, and in such a case, the same molding and curing method as that for the thermosetting resin can be used.
Further, the following method can be exemplified: a method of forming a molded article as a hard coat film on the surface of a substrate by coating the photocurable silicone resin composition of the present invention on various substrates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate (PET), metal plate, glass, and the like, or by coating the substrate after dilution with various solvents. Specifically, there may be mentioned a casting method, a roll coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method and a dipping method. The coating film thickness was adjusted in accordance with the solid content concentration, taking into account the film thickness formed after drying and curing by an ultraviolet lamp. When a solvent is used for adjusting the solid content concentration, the solvent is preferably removed by drying or the like after coating. The drying temperature is set to a condition that the base material used is not deformed, and the drying time is preferably 1 hour or less from the viewpoint of productivity. The thickness of the hard coat film is 0.5 to 100 μm, preferably 1 to 60 μm, from the viewpoint of abrasion resistance and adhesion.
The silicone resin molded body of the present invention obtained in the above manner has a pencil hardness (according to Japanese Industrial Standards (JIS) K5600) of 2H or more, preferably 3H or more, and preferably the scratch resistance is not damaged under a load of at least 500g in a steel wool test. The transparent and colorless liquid is preferable, and the value of the Yellowness Index (YI) is less than 2, more preferably less than 1, and still more preferably less than 0.8.
Examples
Hereinafter, embodiments of the present invention are shown. The silicone resins used in the following examples were obtained by the methods shown in the following synthetic examples.
[ Synthesis example 1]
In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 40ml of 2-propanol (IPA) as a solvent and a 5% aqueous tetramethylammonium hydroxide solution (tmah (tetramethylammonium hydroxide) as an alkaline catalyst were charged. To the addition funnel were added IPA15ml and 3-methacryloxypropyltrimethoxysilane (MTMS: SZ-6300 manufactured by Toray Dow Corning, Silicone Co., Ltd.) 12.69g, and the IPA solution of MTMS was added dropwise at room temperature over 30 minutes while stirring the reaction vessel. After the addition of MTMS was completed, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 50ml of toluene. The reaction solution was washed with saturated saline water until neutral, and then dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration and concentrated, whereby 25.8g of a hydrolysis product (silsesquioxane) was obtained. The silsesquioxanes are colorless viscous liquids that are soluble in various organic solvents.
Then, 20.65g of the obtained silsesquioxane, 82ml of toluene, and 3.0g of a 10% aqueous solution of TMAH were put into a reaction vessel equipped with a stirrer, Dean-Stark, and a cooling tube, and slowly heated to remove water by evaporation. Further heating to 130 ℃ allowed toluene to recondensate at reflux temperature. The temperature of the reaction solution at this time was 108 ℃. After stirring for 2 hours after toluene reflux, the reaction was terminated. The reaction solution was washed with saturated saline water until neutral, and then dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration and concentrated, whereby 18.77g of the intended polyhedral oligomeric silsesquioxane (mixture) was obtained. The resulting cage silsesquioxane (S1) was a colorless viscous liquid soluble in various organic solvents.
Mass spectrometry analysis of the reaction product after the recondensation reaction by liquid chromatography confirmed that the molecular structures of the structural formulae (5), (6) and (7) had a composition ratio of T8 to the molecular ion having an ammonium ion in which R is a methacryloyl group: t10: t12: others are about 2: 4: 1: 3, a silicone resin having a cage structure as a main component was confirmed. T8, T10 and T12 correspond to those in which R is methacryloyl group in the formulae (5), (6) and (7), respectively.
[ measurement of light transmittance ]
The light transmittance of a 0.01 mass% solution of the photopolymerization initiator and the photosensitizer was measured using a spectrophotometer (UV 3600 manufactured by Shimadzu corporation) and a borosilicate glass unit having an optical path length of 1 cm. The light transmittance at a wavelength of 360nm was measured using propylene glycol monomethyl ether as a solvent and a reference. Hereinafter, the description of the light transmittance indicates a value measured by the method.
[ example 1]
The cage-type silicone resin having methacryloyl groups on all silicon atoms obtained in synthesis example 1 (S1): 25 parts by mass of dipentaerythritol pentaacrylate as a hydroxyl group-containing acrylate [ OH1, 35% by mass contained in KYARAD (KYARAD) DPHA manufactured by japan chemicals (japan): 26.25 parts by mass of dipentaerythritol hexaacrylate containing no hydroxyl group [ a1, 65% by mass in KYARAD (KYARAD) DPHA manufactured by japan chemicals (japan): 48.75 parts by mass of 1-hydroxy-cyclohexylphenylketone (B1, luminous transmittance 96.3%, Omnirad 184 manufactured by IGM Co.) as a photopolymerization initiator (B): 7.5 parts by mass of 1, 4-diethoxynaphthalene (transmittance 98.6%, ANTHRACURE UVS-2171 industrially produced kawasaki chemical modification) as a photosensitizer (C): 0.5 part by mass of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (D1, luminous transmittance 87.4%, Omnirad (Omnirad)907) manufactured by IGM Co., Ltd.) as a photopolymerization initiator (D): 0.75 part by mass to obtain a transparent photo-curable silicone resin composition.
Next, the obtained photo-curable silicone resin composition: 50 parts by mass of propylene glycol monomethyl ether: 50 parts by mass of a fluorine-based surface conditioner: 1 part by mass, and the mixture was cast (cast) into a PET substrate (thickness 250 μm) in an atmosphere so as to become 20 μm in thickness using a bar coater. Drying at 60 deg.C for 10 min, and using 30W/cm high pressure mercury lamp at 1000mJ/cm2Cumulative exposure ofThe resulting mixture was cured to obtain a PET laminate test piece in which a silicone resin molded body layer having a thickness of 10 μm was formed on the surface of a PET substrate.
Evaluation of various properties was carried out by the following methods. The evaluation results are shown in table 1.
[ scratch resistance ]
Using #0000 steel wool under the load of 500g/cm2The PET laminate test piece was subjected to a 10-time reciprocating test under the load of (1), and the number of scratches was visually evaluated. Further, the load was also evaluated at 1000g/cm2Under a load of 1000g/cm, the number of flaws in a 1000-time reciprocating test2The results of 1000 reciprocating tests are shown in parentheses in tables 1 to 2.
Good: no scar
Δ: less than 10 scars
X: there are more than 10 scars
[ Pencil hardness ]
The PET laminate test piece was scratched using mitsubishi pencil UNI according to JIS K5600 under a load of 750g at an angle of 45 degrees, and visually evaluated for a hardness without damage.
Good: 2H or more
X: less than 2H
[ coloring Property ]
The PET laminate test piece was subjected to YI measurement using a spectrophotometer (UV 3600 manufactured by shimadzu corporation) with a PET substrate as a blank, and was determined.
Very good: YI less than 0.8
Good: YI of 0.8 or more and less than 1.0
Δ: y1 is 1.0 or more and less than 2.0
X: YI of 2.0 or more
[ appearance ]
The appearance of the PET laminate test piece was visually judged.
Good: no abnormality
X: foreign matter and surface defects were observed
Examples 2 to 11 and comparative examples 1 to 2
PET laminate test pieces having a resin molded body layer formed on the surface thereof were obtained in the same manner as in example 1, except that the formulation compositions were set to the weight ratios shown in tables 1 and 2. Then, evaluation was performed in the same manner as in example 1.
[ example 12]
The cage-type silicone resin having methacryloyl groups on all silicon atoms obtained in synthesis example 1 (S1): 25 parts by mass of dipentaerythritol pentaacrylate as a hydroxyl group-containing acrylate [ OH1, 35% by mass contained in KYARAD (KYARAD) DPHA manufactured by japan chemicals (japan): 26.25 parts by mass of dipentaerythritol hexaacrylate containing no hydroxyl group [ a1, 65% by mass in KYARAD (KYARAD) DPHA manufactured by japan chemicals (japan): 48.75 parts by mass of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (D1, luminous transmittance 87.4%, Omnirad (Omnirad)907) manufactured by IGM Co., Ltd.) as a photopolymerization initiator (D): 8 parts by mass to obtain a transparent photo-curable silicone resin composition.
Next, the obtained photo-curable silicone resin composition: 50 parts by mass of propylene glycol monomethyl ether: 50 parts by mass of a fluorine-based surface conditioner: 1 part by mass, and the mixture was cast (cast) into a PET substrate (thickness 250 μm) in an atmosphere so as to become 20 μm in thickness using a bar coater. Drying at 60 deg.C for 10 min, and using 30W/cm high pressure mercury lamp at 1000mJ/cm2The resultant was cured by the cumulative exposure to light, and a PET laminate test piece was obtained in which a silicone resin molded body layer having a thickness of 10 μm was formed on the surface of a PET base material.
Evaluation of various properties was carried out by the following methods. The evaluation results are shown in table 3.
[ scratch resistance ]
Using #0000 steel wool under the load of 500g/cm2The PET laminate test piece was subjected to a 10-time reciprocating test under the load of (1), and the number of scratches was visually evaluated.
Good: no scar
Δ: less than 10 scars
X: there are more than 10 scars
[ Pencil hardness ]
The PET laminate test piece was scratched using mitsubishi pencil UNI according to JIS K5600 under a load of 750g at an angle of 45 degrees, and visually evaluated for a hardness without damage.
Good: 2H or more
X: less than 2H
[ coloring Property ]
The PET laminate test piece was subjected to YI measurement using a spectrophotometer (UV 3600 manufactured by shimadzu corporation) with a PET substrate as a blank, and was determined.
Very good: YI less than 0.8
Good: YI of 0.8 or more and less than 1.0
Δ: y1 is 1.0 or more and less than 2.0
X: YI of 2.0 or more
[ appearance ]
The appearance of the PET laminate test piece was visually judged.
Good: no abnormality
X: foreign matter and surface defects were observed
Examples 13 to 19 and comparative examples 3 to 7
PET laminate test pieces having a resin molded body layer formed on the surface thereof were obtained in the same manner as in example 12, except that the formulation compositions were set to the weight ratios shown in table 3 and table 4.
Abbreviations in the tables are as follows.
S1: synthesis of the Silicone resin obtained in example 1
OH 1: dipentaerythritol pentaacrylate [ 35% by mass of KAYARAD DPHA manufactured by KAYARAD (KAYARAD)
a 1: dipentaerythritol hexaacrylate [ 65% by mass of Kayarad (KAYARAD) DPHA manufactured by Kayaku Kabushiki Kaisha ]
OH 2: pentaerythritol triacrylate [ Light Acrylate PE-3A (manufactured by Kyoeisha chemical Co., Ltd.) ] 60% by mass
a 2: pentaerythritol tetraacrylate [ Light Acrylate PE-3A manufactured by Kyoeisha chemical Co., Ltd. ]40% by mass ]
a 3: trimethylolpropane triacrylate (A-TMPT made by Ningzhongcun chemical Co., Ltd.)
a 4: dimethylol tricyclodecane diacrylate [ Light Acrylate DCP-A manufactured by KyoeishｃA chemical Co., Ltd ]
U1: urethane acrylate oligomer [ UA-122P manufactured by Mizhongcun chemical (Strand) ]
B1: photopolymerization initiator 1-hydroxy-cyclohexylphenyl ketone having an optical path length of 0.01% by mass solution of 1cm and a light transmittance at a wavelength of 360nm of 90% or more (light transmittance 96.3%, Omnirad 184 manufactured by IGM Co., Ltd.)
B2: a photopolymerization initiator 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) -benzyl ] phenyl } -2-methylpropane-1-one (luminous transmittance: 96.0%, Omnirad 127 manufactured by IGM Co., Ltd.) having an optical path length of 0.01 mass% solution of 1cm and a luminous transmittance at a wavelength of 360nm of 90% or more
C: 0.01% by mass of a solution, 1, 4-diethoxynaphthalene (transmittance of 98.6%, Anthracure UVS-2171) having an optical path length of 1cm and a light transmittance of 90% or more at a wavelength of 360nm
D1: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (optical transmittance: 87.4%, Omnirad 907, manufactured by IGM Co.) as a photopolymerization initiator having an optical path length of 1cm and a light transmittance at a wavelength of 360nm of less than 90% in a 0.01 mass% solution
D2: 0.01% by mass of a solution, a photopolymerization initiator bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide having an optical path length of 1cm and a light transmittance at a wavelength of 360nm of less than 90% (light transmittance 66.5%, Omnirad 819 manufactured by IGM Co., Ltd.)
D3: 0.01% by mass of a photopolymerization initiator ethanone having an optical path length of 1cm and a light transmittance at a wavelength of 360nm of less than 90%, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyloxime) (light transmittance 1.5%, Irgacure (OXE) 02 manufactured by BASF corporation)
P: mixture of oxy-phenyl-acetic acid 2- [ 2-oxo-2-phenyl-acetoxy-ethoxy ] -ethyl ester and oxy-phenyl-acetic acid 2- [ 2-hydroxy-ethoxy ] -ethyl ester [ Omirade (Omnirad)754, manufactured by IGM (Strand) ]
E: 0.01% by mass of a solution, a photosensitizer 9, 10-diethoxyanthracene (having a light transmittance of 2.0%, Kawasaki chemical conversion, Anthrakura (Anthracure) UVS-1101) having an optical path length of 1cm and a light transmittance of 360nm of less than 90%
Q1: halogen-based flame retardant (Proroguard SR-720N manufactured by first Industrial pharmaceutical Co., Ltd.)
Q2: fluorescent whitening agent (Tinopal OB manufactured by BASF)
Unsaturated compound total: total amount of unsaturated Compounds (parts by mass)
OH total: total amount (parts by mass) of unsaturated compound having hydroxyl group
OH proportion: proportion (mass%) of hydroxyl group-containing unsaturated Compound in unsaturated Compound
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
Claims (10)
1. A photo-curable silicone resin composition characterized by comprising:
silicon is mixedThe ketone resin (A1) is a mixture of a resin containing at least one-R in the molecule3-CR4＝CH2or-CR4＝CH2[ wherein, R3Represents alkylene, alkylidene or-O-C (═ O) -radical, R4An unsaturated compound (A2) which represents an unsaturated group represented by a hydrogen atom or an alkyl group and which is capable of radical copolymerization with the silicone resin (A1), wherein the molar ratio of the unsaturated compound (A2) to the unsaturated compound (A2) is 1: 99-99: 1 (A) a silicone resin composition prepared in a mass ratio; and
a photopolymerization initiator (D) having an optical path length of 1cm and a light transmittance at a wavelength of 360nm of less than 90% in a solution of 0.01% by mass,
at least 20% by mass or more of the unsaturated compound (A2) is a hydroxyl group-containing unsaturated compound,
the photopolymerization initiator (D) is contained in an amount of 0.1 mass% or more and less than 20 mass% based on the silicone resin composition (a).
2. The photocurable silicone resin composition according to claim 1, wherein 10 to 100% by mass of the unsaturated compound (A2) is at least two-R groups in a molecule3-CR4＝CH2or-CR4＝CH2[ wherein, R3Represents alkylene, alkylidene or-O-C (═ O) -radical, R4A non-silicone type polyfunctional unsaturated compound which represents an unsaturated group represented by a hydrogen atom or an alkyl group.
3. The photocurable silicone resin composition according to claim 1 or 2, wherein the silicone resin (A1) is represented by general formula (1)
[RSiO3/2]n (1)
Wherein R is an organic functional group having a (meth) acryloyl group, n is 8, 10 or 12, and the polyorganosilsesquioxane has a cage structure in the structural unit as a main component.
4. The photocurable silicone resin composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator (B) having an optical path length of 1cm in a 0.01 mass% solution and a light transmittance of 90% or more at a wavelength of 360 nm.
5. The photocurable silicone resin composition according to claim 4, wherein the photopolymerization initiator (B) having an optical path length of 1cm in a 0.01 mass% solution and a light transmittance of 90% or more at a wavelength of 360nm is a hydroxyphenyl ketone-based photopolymerization initiator.
6. The photocurable silicone resin composition according to any one of claims 1 to 5, further comprising a photosensitizer (C) which is 0.01 mass% solution and has an optical path length of 1cm and a light transmittance at a wavelength of 360nm of 90% or more.
7. The photocurable silicone resin composition according to claim 6, wherein the photosensitizer (C) having an optical path length of 1cm in a 0.01 mass% solution and a light transmittance of 90% or more at a wavelength of 360nm is a naphthalene-based photosensitizer.
8. The photocurable silicone resin composition according to any one of claims 1 to 7, wherein the photopolymerization initiator (D) having an optical path length of 1cm in a 0.01 mass% solution and a light transmittance at a wavelength of 360nm of less than 90% is at least one photopolymerization initiator selected from the group consisting of α -aminophenylketone photopolymerization initiators, phosphine oxide photopolymerization initiators, and oxime ester photopolymerization initiators.
9. A silicone resin molded body obtained by radically copolymerizing the photocurable silicone resin composition according to any one of claims 1-8 and curing the resultant.
10. A method for producing a silicone resin molded body, characterized in that a silicone resin molded body is formed by irradiating the photo-curable silicone resin composition according to any one of claims 1 to 8 with an active energy ray under the atmospheric air and performing radical copolymerization.
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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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|---|---|---|---|---|
| CN101027330A (en) * | 2004-09-27 | 2007-08-29 | 新日铁化学株式会社 | Silica-containing silicone resin composition and its molded product |
| JP2008201818A (en) * | 2007-02-16 | 2008-09-04 | Jsr Corp | Curable composition, cured film and laminate thereof |
| JP2016216623A (en) * | 2015-05-21 | 2016-12-22 | 荒川化学工業株式会社 | Ultraviolet curable coating agent composition and cured film thereof |
| JP2018141104A (en) * | 2017-02-28 | 2018-09-13 | 中国塗料株式会社 | Active energy ray-curable resin composition for floor material, coated floor material, method for producing coated floor material and floor material contamination prevention method |
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| JPH0656948A (en) * | 1992-08-13 | 1994-03-01 | Showa Denko Kk | Transparent solid resin having functional organic molecule incorporated therein and its production |
| JP4256756B2 (en) | 2002-09-30 | 2009-04-22 | 新日鐵化学株式会社 | Method for producing cage-type silsesquioxane resin having functional group |
| DE602004031510D1 (en) | 2003-03-27 | 2011-04-07 | Nippon Steel Chemical Co | SILICONE RESIN COMPOSITION AND FORM 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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- 2020-02-07 JP JP2020571305A patent/JPWO2020162615A1/ja active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027330A (en) * | 2004-09-27 | 2007-08-29 | 新日铁化学株式会社 | Silica-containing silicone resin composition and its molded product |
| JP2008201818A (en) * | 2007-02-16 | 2008-09-04 | Jsr Corp | Curable composition, cured film and laminate thereof |
| JP2016216623A (en) * | 2015-05-21 | 2016-12-22 | 荒川化学工業株式会社 | Ultraviolet curable coating agent composition and cured film thereof |
| JP2018141104A (en) * | 2017-02-28 | 2018-09-13 | 中国塗料株式会社 | Active energy ray-curable resin composition for floor material, coated floor material, method for producing coated floor material and floor material contamination prevention method |
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