JPS63260940A - Photoreactive surface treating agent and resin composition - Google Patents
Photoreactive surface treating agent and resin compositionInfo
- Publication number
- JPS63260940A JPS63260940A JP62095053A JP9505387A JPS63260940A JP S63260940 A JPS63260940 A JP S63260940A JP 62095053 A JP62095053 A JP 62095053A JP 9505387 A JP9505387 A JP 9505387A JP S63260940 A JPS63260940 A JP S63260940A
- Authority
- JP
- Japan
- Prior art keywords
- alkoxytitanium
- carboxylic acid
- component
- derivative
- unsaturated carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 32
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- -1 n- hexyl Chemical group 0.000 abstract description 24
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 abstract 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 239000012756 surface treatment agent Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 24
- 239000011159 matrix material Substances 0.000 description 18
- 239000000976 ink Substances 0.000 description 16
- 239000003973 paint Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000005304 optical glass Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WIKUXHHNKRKVGJ-UHFFFAOYSA-N (2-chlorophenyl)-(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1Cl WIKUXHHNKRKVGJ-UHFFFAOYSA-N 0.000 description 1
- QRWAIZJYJNLOPG-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) acetate Chemical compound C=1C=CC=CC=1C(OC(=O)C)C(=O)C1=CC=CC=C1 QRWAIZJYJNLOPG-UHFFFAOYSA-N 0.000 description 1
- URBLVRAVOIVZFJ-UHFFFAOYSA-N (3-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 URBLVRAVOIVZFJ-UHFFFAOYSA-N 0.000 description 1
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- DFYJCXSOGSYMAJ-UHFFFAOYSA-N (4-tert-butylphenyl)-phenylmethanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 DFYJCXSOGSYMAJ-UHFFFAOYSA-N 0.000 description 1
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- ZLWSWTKSTUPKDY-UHFFFAOYSA-K 16-methylheptadecanoate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)CCCCCCCCCCCCCCC([O-])=O.CC(C)CCCCCCCCCCCCCCC([O-])=O.CC(C)CCCCCCCCCCCCCCC([O-])=O ZLWSWTKSTUPKDY-UHFFFAOYSA-K 0.000 description 1
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- ICLGDYHCXUWIAA-UHFFFAOYSA-K 2-methylprop-2-enoate propan-2-olate titanium(4+) Chemical compound CC(C)O[Ti+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O ICLGDYHCXUWIAA-UHFFFAOYSA-K 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
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000168525 Croton tiglium Species 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JKQQZJHNUVDHKP-FQJIPJFPSA-N Flurogestone acetate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1CC[C@@](C(C)=O)(OC(=O)C)[C@@]1(C)C[C@@H]2O JKQQZJHNUVDHKP-FQJIPJFPSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- ZWPWLKXZYNXATK-UHFFFAOYSA-N bis(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=C(C)C=C1 ZWPWLKXZYNXATK-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001723 curing 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- RJUVPCYAOBNZAX-VOTSOKGWSA-N ethyl (e)-3-(dimethylamino)-2-methylprop-2-enoate Chemical compound CCOC(=O)C(\C)=C\N(C)C RJUVPCYAOBNZAX-VOTSOKGWSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、表面処理剤に係り、さらに詳しくは、テトラ
アルコギシチタンおよび/またはその加水分解縮合物の
置換基の一部を、不飽和カルボン酸残基で置換したアル
コキシチタンEft、 4体を主成分とする無機物質の
表面処理剤、ならびに、この表面処理剤を光重合性モノ
マーおよび/またはポリマーに添加配合した光硬化性樹
脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a surface treatment agent, and more specifically, some of the substituents of tetraalcogystitanium and/or its hydrolyzed condensate are unsaturated. An inorganic surface treatment agent mainly composed of alkoxy titanium Eft substituted with a carboxylic acid residue, and a photocurable resin composition containing this surface treatment agent added to a photopolymerizable monomer and/or polymer. Regarding.
本発明の表面処理剤は、光硬化性高分子マl−IJソッ
クス無機物質との複合系、たとえば、塗料、接着剤等に
使用することにより、光硬化性高分子マトリックスと無
機物質との親和性を改善することができる。The surface treatment agent of the present invention can be used in a composite system with a photocurable polymer MAI-IJ sock inorganic substance, such as a paint, an adhesive, etc., to improve the affinity between the photocurable polymer matrix and the inorganic substance. can improve sex.
また、本発明の光硬化性樹脂組成物は、塗料、レジスト
インキ、被覆剤、接着剤等として使用される。Moreover, the photocurable resin composition of the present invention is used as a paint, a resist ink, a coating agent, an adhesive, and the like.
近年、塗膜、インキ、被覆剤、接着剤等の樹脂薄膜分野
において、省エネルギー、無公害等の社会的要求から無
溶媒型の光硬化型の樹脂組成物が多用されるようになっ
てきた。たとえば、アクリラート、メタクリラート系オ
リゴマー等の光硬化性樹脂に光重合開始剤、ガラスピー
ズ等の無機充填剤および種々のシラン系カップリング剤
を配合した樹脂組成物が、民生用のプリント配線板に使
用される種々のレジストインキとして提案されている(
特開昭61−103968号公報、特開昭61−098
725号公報、特開昭60−195171号公報等参照
)。また、同様な組成の光フアイバー被覆剤が、工業材
料、 32. (8) 、 31 (1984)
に、塗料組成物、 が、特開昭48−028533号
公報に開示されている。In recent years, in the field of resin thin films such as coatings, inks, coatings, and adhesives, solvent-free photocurable resin compositions have come into widespread use due to social demands such as energy saving and non-pollution. For example, resin compositions made by blending photocurable resins such as acrylate and methacrylate oligomers with photopolymerization initiators, inorganic fillers such as glass beads, and various silane coupling agents are used in printed wiring boards for consumer use. Various resist inks have been proposed for use (
JP-A-61-103968, JP-A-61-098
725, JP-A-60-195171, etc.). In addition, optical fiber coating materials with similar compositions are used as industrial materials, 32. (8), 31 (1984)
A coating composition is disclosed in JP-A-48-028533.
また、エポキシ樹脂を主成分とする熱硬化性の樹脂組成
物に、酸化ケイ素等の無機充填剤、樹脂硬化剤およびシ
ラン系カップリング剤またはチタネート系カップリング
剤を配合した熱硬イヒ性のプリント配線板に使用する無
電解めっき用レジストインキが、特開昭60−0745
99号公報に開示されている。In addition, thermosetting prints are made by blending an inorganic filler such as silicon oxide, a resin curing agent, and a silane coupling agent or titanate coupling agent with a thermosetting resin composition whose main component is an epoxy resin. Resist ink for electroless plating used for wiring boards was published in Japanese Patent Application Laid-Open No. 60-0745.
It is disclosed in Publication No. 99.
現在、光硬化型のレジストインキが使用されているプリ
ント配線板の分野は、200μm以上の比較的に広い回
路間隔を有する民生用電子機器類の分野に限られ、コン
ピューターや制御機器等の高密度回路基板の要求される
産業用電子機器の分野には、未だ採用されていない。産
業用電子機器類のプリント配線板には、民生用電子機器
には要求されていない高電気絶縁性、加湿下におけるハ
ンダ耐熱性等が要求され、現在の民生用電子機器のプリ
ント配線板に使用されているレジストインキでは、その
性能を満足しないことがその理由となっている。Currently, the field of printed wiring boards in which photo-curable resist inks are used is limited to the field of consumer electronic devices with relatively wide circuit spacing of 200 μm or more, and high-density circuits such as computers and control equipment. It has not yet been adopted in the field of industrial electronic equipment that requires circuit boards. Printed wiring boards for industrial electronic equipment are required to have high electrical insulation properties and resistance to soldering heat under humidified conditions, which are not required for consumer electronic equipment. The reason for this is that the performance of the resist inks currently available is not satisfactory.
光学ガラスファイバー被覆剤においては、ガラスファイ
バーと被覆剤との間に空隙を生じると信号のロスおよび
ノイズとなるため、ガラスファイバーと被覆剤との密着
性が要求されるが、前記引用した組成物では、密着性が
不足する。また、このことは塗料塗膜においても同様で
ある。In optical glass fiber coatings, adhesion between the glass fibers and the coating is required because gaps between the glass fiber and the coating cause signal loss and noise. Then, adhesion is insufficient. This also applies to paint films.
また、熱硬化性の無電解めっき用レジストにおいては、
無機充填剤と熱硬化性樹脂との馴染みを改良する目的で
カップリング剤が使用されているが、これらのカップリ
ング剤を光硬化性の樹脂組成物に適用しても同様の特性
を持ったレジスト皮膜を得ることはできない。In addition, in thermosetting resist for electroless plating,
Coupling agents are used to improve the compatibility between inorganic fillers and thermosetting resins, but even when these coupling agents are applied to photocurable resin compositions, they do not have similar properties. It is not possible to obtain a resist film.
本発明は、無機充填剤や光学ファイバー等の無機物質表
面を改質し、これらと光硬化性樹脂との馴染みを改善す
る表面処理剤およびレジストインキや塗料組成物として
使用可能な光硬化性樹脂組成物を提供することを、その
目的とする。The present invention relates to a surface treatment agent that modifies the surface of inorganic substances such as inorganic fillers and optical fibers, and improves the compatibility of these with photocurable resins, and photocurable resins that can be used as resist inks and coating compositions. The object is to provide a composition.
本発明者等は、前記目的を達成すべく鋭意研究した結果
、置換基に不飽和結合を有するカルボン酸の残基を導入
したアルコキシチタン誘導体が、無機表面の改質効果が
大きく、かつ、光硬化性樹脂と共重合し、無機物質との
強固な複合系を形成し得ることを見出し、本発明を完成
した。As a result of intensive research to achieve the above object, the present inventors found that an alkoxytitanium derivative in which a carboxylic acid residue having an unsaturated bond was introduced as a substituent has a large effect of modifying the inorganic surface, and is photosensitive. The present invention was completed based on the discovery that it can be copolymerized with a curable resin to form a strong composite system with an inorganic substance.
本発明は、置換基の10〜65%がアルコキシ基j−O
R(ここに、Rは、炭素数1〜8の直鎖または分枝を有
するアルキル基を表す。)、残部が下記一般式で表され
る不飽和カルボン酸残基:1l−C=C−COO−
(ここに、「は、II 、 CI+3 、 CJa
、 CH:+Cll=C8−またはCJs Cl
l=Cll−を、R″は、11−またはC113−を表
す。)である平均縮合度が6以下のアルコキシチタン誘
導体を含有することを特徴とする表面処理剤(以下「第
1発明」と称す。)、ならびに成分A:光ラジカル重合
性モノマーおよび/またはポリマー、および成分B:前
記表面処理剤の主成分であるアルコキシチタン誘導体を
含有することを特徴とする光硬化性樹脂組成物である(
以下「第2発明」と称す。)。In the present invention, 10 to 65% of the substituents are alkoxy groups j-O
R (here, R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms), the remainder being an unsaturated carboxylic acid residue represented by the following general formula: 1l-C=C- COO- (Here, "II, CI+3, CJa
, CH:+Cll=C8- or CJs Cl
1 = Cll-, R'' represents 11- or C113-), and the average degree of condensation is 6 or less. Component A: a photo-radically polymerizable monomer and/or polymer, and Component B: an alkoxytitanium derivative which is the main component of the surface treatment agent. (
Hereinafter, this will be referred to as the "second invention." ).
本発明において、第1発明の表面処理剤の主成分であり
、かつ、第2発明の光硬化性樹脂組成物の成分Bである
アルコキシチタン誘導体は、下記一般式(11
%式%(11
で表され、式中のRが、炭素数1〜8の直鎖または分枝
を有するアルキル基、たとえば、メチル基。In the present invention, the alkoxy titanium derivative, which is the main component of the surface treatment agent of the first invention and component B of the photocurable resin composition of the second invention, has the following general formula (11 % formula % (11 where R is a linear or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group.
エチル基、プロピル基、イソプロピル基、ノルマルブチ
ル基、ペンチル基、ノルマルヘキシル基。Ethyl group, propyl group, isopropyl group, normal butyl group, pentyl group, normal hexyl group.
オクチル基、2−エチルヘキシル基等の1種または2種
以上であるテトラアルコキシチタンおよび/またはこれ
らのテトラアルコキシチタンを加水分解縮重合して得た
平均縮合度が6以下のアルコキシチタン・ポリマーの、
置1’J! IIs OR基の10〜65%を、下記
一般式(2)
%式%(2)
C11,−を表す、)で表される不飽和カルボン酸の残
基で110したアルコキシチタン誘導体である。Tetraalkoxytitanium containing one or more types of octyl group, 2-ethylhexyl group, etc. and/or an alkoxytitanium polymer having an average degree of condensation of 6 or less obtained by hydrolytic condensation of these tetraalkoxytitaniums,
Place 1'J! IIs is an alkoxytitanium derivative in which 10 to 65% of the OR group is replaced with a residue of an unsaturated carboxylic acid represented by the following general formula (2) (2) represents C11,-.
さらに詳しくは、アルコキシチタン誘導体は、一般式(
11で表されるテトラアルコキシチタンのアルコキシ基
(−011基)の1〜2個を、前記一般式(2)で表さ
れる不飽和カルボン酸の残基で置換したアルコキシチタ
ン・モノマー誘導体、および一般式(1)で表されるテ
トラアルコキシチタンの縮合度が6以下アルコキシチタ
ン・ポリマーと、それらのしアルコキシ基数の0.10
〜0.65に相当するモル数の前記一般式(2)で表さ
れる不飽和カルボン酸の残基で′f1.taしたアルコ
キンチタン・ポリマー誘4体および前記七ツマー誘導体
とポリマー誘導体との混合物である。More specifically, alkoxytitanium derivatives have the general formula (
an alkoxytitanium monomer derivative in which 1 to 2 of the alkoxy groups (-011 groups) of tetraalkoxytitanium represented by 11 are substituted with residues of an unsaturated carboxylic acid represented by the general formula (2), and Alkoxytitanium polymers with a degree of condensation of tetraalkoxytitanium represented by general formula (1) of 6 or less and 0.10 of the number of alkoxy groups thereof
'f1. These are a mixture of a tanned alkoxytitanium polymer derivative and a heptamer derivative and a polymer derivative.
前記アルコキシチタン・ポリマーは、−C式(+1で表
されるテトラアルコキシチタンを、酸触媒またはアルカ
リ触媒の存在下に、当モル以下の水を用いて加水分解す
ることにより製造される。The alkoxytitanium polymer is produced by hydrolyzing tetraalkoxytitanium represented by the formula -C (+1) using an equimolar amount or less of water in the presence of an acid or alkali catalyst.
゛アルコ、トシチタン誘導体は、前記テトラアルコキシ
チタン、アルコキシチタン・ポリマーおよびそれらの混
合物と、それらの総アルコキシ基数の0.10〜0.6
5に相当するモル数の前記一般式(2)で表される不飽
和カルボン酸とを混合し、溶媒の存在下または不存在下
、40〜100℃の温度下に1.5〜5時間撹拌保持し
て反応させることにより、容易に合成され、ついで、反
応で副生ずるアルコールを、減圧下、30〜50℃の温
度で留去することにより目的とするアルコキシチタン誘
導体を製造することができる。゛Alkoxytitanium derivatives include the aforementioned tetraalkoxytitanium, alkoxytitanium polymer, and mixtures thereof, and 0.10 to 0.6 of the total number of alkoxy groups thereof.
and an unsaturated carboxylic acid represented by the general formula (2) in a mole number corresponding to 5, and stirred at a temperature of 40 to 100°C for 1.5 to 5 hours in the presence or absence of a solvent. By holding and reacting, the desired alkoxytitanium derivative can be easily synthesized, and then the desired alkoxytitanium derivative can be produced by distilling off the alcohol by-produced in the reaction at a temperature of 30 to 50° C. under reduced pressure.
これらの不飽和カルボン酸として、たとえば、C1l
! = CHCOOII、 C1l !IcII
= ClIC0OH。These unsaturated carboxylic acids include, for example, C1l
! = CHCOOII, C1l! IcII
= ClIC0OH.
CIh=C(CIli)COOII、 ’C112
CII=C(CI!3)COOHlCIl 1cIl
= CIl −C1l = ClIC0O11、CJs
Ctl−CIICOOIll
Cill 5clI = CI −Cll ” ClI
C0OH。CIh=C(CIli)COOII, 'C112
CII=C(CI!3) COOHlCIl 1cIl
= CIl −C1l = ClIC0O11, CJs
Ctl-CIICOOIll Cill 5clI = CI-Cll ” ClI
C0OH.
等が挙げられる。etc.
本発明の表面処理剤は、前記方法で得られたアルコキシ
チタン誘導体またはその有機溶媒溶液である。The surface treatment agent of the present invention is an alkoxytitanium derivative obtained by the above method or an organic solvent solution thereof.
有機溶媒としては、前記アルコキシチタン誘導体を溶解
し得るものであれば特に制限はないが、光重合性マトリ
ックスと無機物質との複合系に使用する場合には、光重
合性七ツマ−が好ましく使用される。光重合性七ツマ−
として、たとえば、アクリル酸、メタクリル酸、シクロ
へキシルアクリラート、フ゛チル了クリラード、ベンジ
ルアクリラート、2−エチルへキシルアクリラ−1・、
2−ヒドロキシエチル(メタ)アクリラート、2−ヒド
ロキシプロピル(メタ)アクリラート、グリシジルメタ
クリラート、スチレン、N−ビニルピロリドン等が挙げ
られる。The organic solvent is not particularly limited as long as it can dissolve the alkoxytitanium derivative, but when used in a composite system of a photopolymerizable matrix and an inorganic substance, a photopolymerizable nitrate is preferably used. be done. Photopolymerizable nanatsumer
Examples include acrylic acid, methacrylic acid, cyclohexyl acrylate, methylacrylate, benzyl acrylate, 2-ethylhexyl acrylate-1,
Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl methacrylate, styrene, and N-vinylpyrrolidone.
本発明の表面処理剤は、無機物質表面にコーティングす
ることにより、その表面が改質され、無機物質と高分子
物質、特に光重合性マトリックスとの馴染みを向上させ
る。By coating the surface of an inorganic substance, the surface treatment agent of the present invention modifies the surface and improves the compatibility between the inorganic substance and a polymeric substance, particularly a photopolymerizable matrix.
表面処理の対象となる無機物質としては、炭酸カルシウ
ム、酸化チタン、炭酸マグネシウム、アルミナ、硫酸カ
ルシウム、硫酸バリウム、酸化鉄。Inorganic substances that can be surface treated include calcium carbonate, titanium oxide, magnesium carbonate, alumina, calcium sulfate, barium sulfate, and iron oxide.
チタン酸カリウム、タルク、カオリン、クレー。Potassium titanate, talc, kaolin, clay.
マイカ、ケイ酸カルシウム、シリカ、ゼオライト。Mica, calcium silicate, silica, zeolite.
ガラス粉末、カーボンブラ・ツク等の高分子マトリソク
スに添加される無機充填剤、真鍮粉、鉄粉。Glass powder, inorganic fillers added to polymer matrices such as carbon bra, brass powder, iron powder.
アルミ粉、銅粉、黄鉛、シンクロメート、モリブデート
・オレンジ、亜鉛華、酸化クロムグリーン。Aluminum powder, copper powder, yellow lead, synchromate, molybdate orange, zinc white, chromium oxide green.
カドミウムエロー、カドミウムレッド、硫酸鉛。Cadmium yellow, cadmium red, lead sulfate.
紺青2群青、コバルトバイオレット等の塗料に添加され
る無機顔料、グラスファイバー、光ファイバー等の無機
繊維、セラミック成形体、金属成形体等の無機成形体等
が挙げられる。Examples include inorganic pigments added to paints such as navy blue 2 ultramarine and cobalt violet, inorganic fibers such as glass fibers and optical fibers, and inorganic molded bodies such as ceramic molded bodies and metal molded bodies.
たとえば、高分子マトリックスに配合される無機充填剤
の場合、無機充填剤100重量部に対し、前記アルコキ
シチタン誘導体として0.1〜5重量部、好ましくは、
0.5〜2.5重量部をコーティングする。また、平面
状の無機物質の表面処理は、その表面にアルコキシチタ
ン誘導体の単層膜が形成される程度にコーティングする
ことで十分である。無機物質に対する表面処理剤の使用
量が過少な場合には、目的とする表面処理効果が発現せ
ず、また、過大に使用しても期待されるほどの効果の増
大は見込めない。For example, in the case of an inorganic filler blended into a polymer matrix, the alkoxy titanium derivative is preferably 0.1 to 5 parts by weight per 100 parts by weight of the inorganic filler.
Coat 0.5-2.5 parts by weight. Further, as for the surface treatment of a planar inorganic material, it is sufficient to coat the surface to such an extent that a monolayer film of an alkoxy titanium derivative is formed. If the amount of surface treatment agent used for the inorganic substance is too small, the intended surface treatment effect will not be achieved, and even if it is used in excess, the expected effect will not be increased.
無機物質の表面処理方法としては、無機物質表面に均一
に表面処理剤をコーティングできる方法であれば、とく
に制限はない。たとえば、表面処理剤に無機物質を浸漬
、乾燥する方法、表面処理剤を無機物質にスプレーコー
トする方法、表面処理剤を高分子マトリックスに予め添
加し、無機物質との複合系に適用する方法、高分子マト
リックスと無機充填剤との複合系に添加し混合する方法
等が採用される。There are no particular limitations on the method for surface treatment of inorganic substances as long as the method can uniformly coat the surface of the inorganic substance with a surface treatment agent. For example, a method of immersing an inorganic substance in a surface treatment agent and drying it, a method of spray coating the inorganic substance with a surface treatment agent, a method of adding the surface treatment agent to a polymer matrix in advance and applying it to a composite system with an inorganic substance, A method of adding and mixing a polymer matrix and an inorganic filler to a composite system is adopted.
本第2発明は、成分Aとして光ラジカル重合性モノマー
および/またはポリマー、および成分Bとして前記詳述
した表面処理剤の主成分であるアルコキシチタン誘導体
を含有する光硬化性樹脂組成物である。The second invention is a photocurable resin composition containing, as component A, a photoradically polymerizable monomer and/or polymer, and as component B, an alkoxytitanium derivative which is the main component of the surface treatment agent detailed above.
成分Aの光ラジカル重合性モノマーおよび/またはポリ
マーは、光重合開始剤の存在下または不存在下に、可視
光、赤外線、紫外線、電子線、X線等の活性なエネルギ
ー線を照射することにより重合し、硬化する樹脂マトリ
ックスである。たとえば、光ラジカル重合性モノマーと
して、前記表面処理剤の溶媒として例示した化合物が、
また、光ラジカル重合性ポリマーとして、不飽和ポリエ
ステル樹脂、ポリオール(メタ)アクリレート。The photo-radically polymerizable monomer and/or polymer of component A is prepared by irradiating it with active energy rays such as visible light, infrared rays, ultraviolet rays, electron beams, and X-rays in the presence or absence of a photopolymerization initiator. It is a resin matrix that polymerizes and hardens. For example, as a photoradically polymerizable monomer, the compound exemplified as a solvent for the surface treatment agent,
In addition, unsaturated polyester resins and polyol (meth)acrylates are used as photo-radically polymerizable polymers.
ポリエステル(メタ)アクリレート、シリコン(メタ)
アクリレート、ポリブタジェン(メタ)アクリレート
メラミン(メタ)アクリレート、シクロペンタジェン(
メタ)アクリレートポリビニルアルコール(メタ)アク
リレート等の分子中にアクリロイル基および/またはメ
タクリロイル基を有する樹脂、電子線、X線等に感応す
るポリオレフィン樹脂等の熱可塑性樹脂などが挙げられ
る。Polyester (meth)acrylate, silicone (meth)
Acrylate, polybutadiene (meth)acrylate
Melamine (meth)acrylate, cyclopentadiene (
Examples include resins having an acryloyl group and/or methacryloyl group in the molecule, such as meth)acrylate polyvinyl alcohol (meth)acrylate, and thermoplastic resins such as polyolefin resins that are sensitive to electron beams, X-rays, etc.
光重合開始剤は、活性エネルギー線の照射により、ラジ
カルを発生するものであればよい。代表的な光重合開始
剤として、ベンゾイン、ベンゾインメチルエーテル、ベ
ンゾインエチルエーテル。The photopolymerization initiator may be one that generates radicals upon irradiation with active energy rays. Typical photopolymerization initiators include benzoin, benzoin methyl ether, and benzoin ethyl ether.
ベンゾインイソプロピルエーテル、ベンゾインイソブチ
ルエーテル、酢酸ベンゾイン、ベンゾフェノン、4−メ
トキシベンゾフェノン、4,4”−ジメチルベンゾフェ
ノン、4−ブロムベンゾフェノン。Benzoin isopropyl ether, benzoin isobutyl ether, benzoin acetate, benzophenone, 4-methoxybenzophenone, 4,4''-dimethylbenzophenone, 4-bromobenzophenone.
2.2’、4.4’−テトラクロルベンゾフェノン、2
−クロル−4゛−メチルベンゾフェノン、3−メチルベ
ンゾフェノン、4−t−ブチルベンゾフェノン。2.2',4.4'-tetrachlorobenzophenone, 2
-Chloro-4'-methylbenzophenone, 3-methylbenzophenone, 4-t-butylbenzophenone.
ベンジル、ベンジル酸、ジアセチル、メチレンブルー、
アセトフヱノン、 2.2’−ジェトキシアセトフェノ
ン、 9.10−フェナントレンキノン、2−メチルア
ントラキノン、2−エチルアントラキノン。Benzyl, benzylic acid, diacetyl, methylene blue,
Acetophenone, 2.2'-jethoxyacetophenone, 9.10-phenanthrenequinone, 2-methylanthraquinone, 2-ethylanthraquinone.
2−t−ブチルアントラキノン、1.4−ナフトキノン
、ジフェニルジスルフイッF、ジチオカーバメート、α
−クロロメチルナフタリン、アントラセン、塩化鉄等が
例示できる。2-t-butylanthraquinone, 1,4-naphthoquinone, diphenyl disulfide F, dithiocarbamate, α
-Chloromethylnaphthalene, anthracene, iron chloride, etc. can be exemplified.
特にベンジルジメチルケタール、2.2”−ジェトキシ
アセトフェノン、ベンゾインイソプロピルエーテル、ベ
ンゾインイソブチルエーテル、2−エチルアントラキノ
ン等が好ましく使用され、これらは1種の単独または2
種以上が併用される。In particular, benzyl dimethyl ketal, 2.2''-jethoxyacetophenone, benzoin isopropyl ether, benzoin isobutyl ether, 2-ethylanthraquinone, etc. are preferably used, and these may be used alone or in combination.
More than one species is used in combination.
本発明の光硬化性樹脂組成物には、その使用態様、たと
えば、インキ、塗料、接着剤、被覆剤等に適合させるた
めに、前記フィラーまたは顔料としての無機物質を始め
、反応性希釈剤、光重合促進剤、安定剤、接着性賦与剤
、レベリング剤、光沢賦与剤、かび防止剤、泡消し剤、
皮張り防止剤などを添加配合することができる。The photocurable resin composition of the present invention may contain inorganic substances as fillers or pigments, reactive diluents, Photopolymerization accelerator, stabilizer, adhesion agent, leveling agent, gloss agent, mold inhibitor, defoaming agent,
Anti-skinning agents and the like can be added.
本発明の光硬化性樹脂組成物は、成分Aの光ラジカル重
合性モノマーおよび/またはポリマーからなる高分子マ
トリックス100重量部に対し、成分Bのアルコキシチ
タン誘導体0.0001〜10重量部、成分Cの光重合
開始剤0.05〜10重量部、好ましくは0.1〜5重
景重量配合した組成物である。The photocurable resin composition of the present invention is composed of 0.0001 to 10 parts by weight of an alkoxytitanium derivative as component B, and 0.0001 to 10 parts by weight of an alkoxytitanium derivative as component C, based on 100 parts by weight of a polymer matrix consisting of a photoradically polymerizable monomer and/or polymer as component A. The composition contains 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, of a photopolymerization initiator.
成分Bのアルコキシチタン誘導体の配合量は、組成物の
使用態様により大きく異なり、たとえば、フィラーや顔
料の配合されたインキ、塗料等の場合には、r+i前記
したように無機物質100重量部に対し0.1〜5重量
部、好ましくは0.5〜2.5重量部配合される。また
、無機成形体等にクリアー塗膜を形成する被覆剤、塗料
、接着剤等の場合には、成分Bのアルコキシチタン誘導
体の配合量は、前記高分子マトリ・アク2100重量部
に対し、o、0001〜0.1重量部、好ましくは0.
001−0.05重量部である。The amount of the alkoxy titanium derivative as component B varies greatly depending on the usage of the composition. For example, in the case of ink, paint, etc. containing fillers and pigments, the amount of the alkoxy titanium derivative as component B varies based on 100 parts by weight of the inorganic substance as described above. It is blended in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2.5 parts by weight. In addition, in the case of coating agents, paints, adhesives, etc. that form clear coatings on inorganic molded objects, etc., the amount of the alkoxy titanium derivative as component B is o ,0001 to 0.1 parts by weight, preferably 0.0001 to 0.1 parts by weight.
001-0.05 parts by weight.
本発明の光硬化性樹脂組成物は、無機物質の被覆剤、塗
料、接着剤等に、また、フィラーや顔料を配合してレジ
スト・インキ、塗料等に好適に使用される。The photocurable resin composition of the present invention is suitably used in inorganic coatings, paints, adhesives, etc., and in combination with fillers and pigments, resist inks, paints, etc.
本発明は、置換基に不飽和カルボン酸残基を有するアル
コキシチタン誘導体を主成分とするごとを特徴とする無
機物質の表面処理剤、および、このアルコキシチタン誘
導体を光ラジカル重合性の高分子マトリックスに配合し
たことを特徴とする光硬化性樹脂組成物である。The present invention relates to a surface treatment agent for an inorganic substance characterized in that the main component is an alkoxy titanium derivative having an unsaturated carboxylic acid residue as a substituent, and a photo-radically polymerizable polymer matrix containing this alkoxy titanium derivative. This is a photocurable resin composition characterized in that it is blended with.
アルコキシチタン誘導体において、アルコキシ基(−O
R基)は、加水分解性の反応性置換基であり、無機物質
の表面に存在する一011基と反応して無機物質とチタ
ノキサン誘導体とが有機的に結合すると共に、無機物質
の表面に存在する付着水分により重合して、チタノキサ
ン構造を有する皮膜を形成する。In alkoxy titanium derivatives, an alkoxy group (-O
R group) is a hydrolyzable reactive substituent that reacts with the 1011 group present on the surface of the inorganic substance to organically bond the inorganic substance and the titanoxane derivative, and also The adhering moisture causes polymerization to form a film having a titanoxane structure.
一方、不飽和カルボン酸残基は、非加分解性の有機(樹
脂)7トリソクスと親和性を有する、かつ、構造中に光
反応性の不飽和二重結合を有する置換基である。したが
って、光硬化前の高分子7トリソクス中においては、フ
ィラーや顔料等の無機物質の樹脂への分散性を、また、
無機成形体に適用した場合には、その濡れ性を向上させ
る。また、光硬化後は、高分子マトリックスと共に硬化
し、樹脂マトリックスと充填剤、顔料、無機表面との密
着性、接着性を向上させる。On the other hand, the unsaturated carboxylic acid residue is a substituent that has an affinity for non-hydrolyzable organic (resin) 7-trisox and has a photoreactive unsaturated double bond in its structure. Therefore, in the polymer 7 trisox before photocuring, the dispersibility of inorganic substances such as fillers and pigments in the resin is
When applied to an inorganic molded body, it improves its wettability. Furthermore, after photocuring, it is cured together with the polymer matrix, improving the adhesion and adhesion between the resin matrix and fillers, pigments, and inorganic surfaces.
アルコキシチタン誘導体中のアルコキシ基(−OR基)
が過少な場合、すなわち、不飽和カルボン酸残基で過剰
に置換されたアルコキシチタン誘導体の場合、掻めて不
安定で容易にゲル化するばかりでなく、無機物質と反応
性の一0ff基が不足するため無機物質との結合および
チタノキサン構造皮膜の形成が不十分とな乙。一方、不
飽和カルボン酸残基が過少な場合には、高分子マトリッ
クスとの親和性および反応性が不足し、無機物質と高分
子マトリックスとの結合力が低下する。したがって、ア
ルコキシチタン誘導体中のアルコキシ基(−OR基)は
、35〜90%の範囲であることが好ましい。Alkoxy group (-OR group) in alkoxy titanium derivative
If there is too little of the alkoxy titanium derivative, that is, if the alkoxy titanium derivative is excessively substituted with unsaturated carboxylic acid residues, it will not only be unstable and easily gel, but also have 10ff groups that are reactive with inorganic substances. Due to the lack of titanoxane, bonding with inorganic substances and formation of a titanoxane structural film are insufficient. On the other hand, if there are too few unsaturated carboxylic acid residues, the affinity and reactivity with the polymer matrix will be insufficient, and the bonding strength between the inorganic substance and the polymer matrix will decrease. Therefore, the alkoxy group (-OR group) in the alkoxy titanium derivative preferably ranges from 35 to 90%.
本発明を、実施例および比較例により、さらに詳細に説
明する。The present invention will be explained in more detail with reference to Examples and Comparative Examples.
ただし、本発明の範囲は、以下の実施例により何等限定
されるものではない。However, the scope of the present invention is not limited in any way by the following examples.
なお、以下の例中において、1部」および「%」は、断
りのない限り重量基串である。In addition, in the following examples, "1 part" and "%" are based on weight unless otherwise specified.
実施例1 アルコキシチタン誘導体の合成(3)試料(
T−1)
撹拌機、温度計、空冷冷却器および加熱装置を(It!
tえた反応フラスコに、テトライソプロポキシチタン(
TPT)284部を仕込み、クロトン酸80部(対TP
Tモル比−1)を徐々に添加し、60゛Cに加温して3
時間攪拌保持した後、減圧して副生じたイソプロパツー
ルを留去し、淡黄色透明な、25℃における粘度が2.
4ボイズの液状物(T−1)を得た。Example 1 Synthesis of alkoxytitanium derivative (3) Sample (
T-1) Add a stirrer, thermometer, air-cooled condenser, and heating device (It!
Add tetraisopropoxy titanium (
284 parts of TPT) and 80 parts of crotonic acid (to TP
T molar ratio -1) was gradually added and heated to 60°C.
After stirring and maintaining for an hour, the pressure was reduced to distill off the by-produced isopropanol, leaving it as a pale yellow and transparent product with a viscosity of 2.5°C at 25°C.
A liquid material (T-1) with 4 voids was obtained.
得られた試料(T−1)の赤外線吸収スベクトル(IR
)分析の結果、不飽和二重結合に基づく吸収が認められ
た。また、強熱残分(TiOJ法による分析の結果、T
i含有量は15.5%であった。Infrared absorption vector (IR) of the obtained sample (T-1)
) As a result of analysis, absorption based on unsaturated double bonds was observed. In addition, the ignition residue (as a result of analysis by TiOJ method, T
The i content was 15.5%.
以上の分析結果から、試料(T−1)は、TPTのイソ
プロポキシ基の1個が、クロトン酸残基で置換されたア
ルコキシチタン誘導体を主成分とするものと推定した。From the above analysis results, it was estimated that sample (T-1) was mainly composed of an alkoxytitanium derivative in which one of the isopropoxy groups of TPT was substituted with a crotonic acid residue.
(t))試料(T−2)
試料(T−1)の合成において、TPTに代えてテトラ
ノルマルブトキシチタン(TBT)34部0部、クロト
ン酸に代えてソルビン酸224部(対TBTモル比−2
)を使用した以外には、試料(T−1)と同一の条件で
反応および後処理を行い、25℃における粘度が3.2
ボイズ、Ti含有量10.8%の淡黄色透明な液状物(
T−2)を得た。(t)) Sample (T-2) In the synthesis of sample (T-1), 34 parts and 0 parts of tetra-n-butoxytitanium (TBT) were used instead of TPT, and 224 parts of sorbic acid was used instead of crotonic acid (molar ratio to TBT). -2
) was used, but the reaction and post-treatment were carried out under the same conditions as for sample (T-1), and the viscosity at 25°C was 3.2.
Boies, a pale yellow transparent liquid with a Ti content of 10.8% (
T-2) was obtained.
(C1試料(T−3)
試料(T−1)の合成に用いたものと同一の反応装置に
、TPTの平均縮合度4のチタノキサンイソプロポキシ
ド(TPTポリマー)830部を仕込み、クロトン酸4
30部(TPTポリマーの対イソプロキシ基モル比−0
,5)を徐々に添加し、60℃に加温して3時間攪拌保
持した後、副生イソプロパツールを減圧下に留去し、2
5℃における粘度が162ボイズの淡黄色透明な液状物
(T−3)を得た。(C1 sample (T-3) 830 parts of titanoxane isopropoxide (TPT polymer) with an average degree of condensation of TPT of 4 was charged into the same reactor as that used for the synthesis of sample (T-1), and croton acid 4
30 parts (TPT polymer molar ratio to isoproxy groups -0
, 5) was gradually added, heated to 60°C and kept stirring for 3 hours, and the by-product isopropanol was distilled off under reduced pressure.
A pale yellow transparent liquid (T-3) having a viscosity of 162 voids at 5°C was obtained.
得られた(T−3)をIR分析の結果、不飽和二重結合
およびエステル結合に基づく吸収が認められ、また、強
熱残分(TiO□)法による分析の結果、Ti含有量は
19.8%であった。 以上の分析結果から、試料(T
−3)は、TPTポリマーのイソプロポキシ基の1部が
、クロトン酸残基で置換されたアルコキシチタン誘導体
のポリマーを主成分とするものと推定した。As a result of IR analysis of the obtained (T-3), absorption based on unsaturated double bonds and ester bonds was observed, and as a result of analysis using the ignition residue (TiO□) method, the Ti content was 19 It was .8%. From the above analysis results, the sample (T
-3) was estimated to be mainly composed of an alkoxytitanium derivative polymer in which a part of the isopropoxy group of the TPT polymer was substituted with a crotonic acid residue.
(d) 比較試料(C−1)
試料(T−1)の合成において、クロトン酸80部(対
TPTモル比=1)に代えて、メタクリル酸240部(
対TPTモル比−3)を用いた以外には、試料(T−1
)と同一の条件で反応および後処理を行い、淡黄色透明
な液状物(C−1)を得た。(d) Comparative sample (C-1) In the synthesis of sample (T-1), 240 parts of methacrylic acid (molar ratio to TPT = 1) was replaced with 80 parts of crotonic acid (molar ratio to TPT = 1).
Samples (T-1 to TPT molar ratio -3) were used.
The reaction and post-treatment were carried out under the same conditions as in ) to obtain a pale yellow transparent liquid (C-1).
得られた(C−1)は、試料(T−1)と同一の条件で
分析した結果、イソプロポキシチタントリ (メタクリ
レート)と推定された。The obtained (C-1) was analyzed under the same conditions as sample (T-1) and was estimated to be isopropoxytitanium tri(methacrylate).
この(C−1)は、25℃で保存した結果、3日後にゲ
ル化し、表面処理剤として使用できなかった。When this (C-1) was stored at 25°C, it gelled after 3 days and could not be used as a surface treatment agent.
実施例2 光学ガラスファイバー用被覆剤la) 光
重合性樹脂の合成
攪拌機、温度計、還流冷却器および空気吹き込み管を設
けた反応容器に、ビス(4−イソシアナートシクロヘキ
シル)メタン(水添MDI)293部、ジブチル錫ジラ
ウレート(重合触媒)0.65部およびp−メトキシフ
ェノール(PMP)1゜8部を仕込み、攪拌下、乾燥空
気を吹き込みながらヒドロキシエチルアクリレート(H
EA)130部を2時間にわたって添加した。反応が進
み温度が約70℃に上昇した時点で、この温度に保持し
さらに1時間攪拌を続け、重合性不飽和結合を有するプ
レポリマーを得た。Example 2 Coating agent for optical glass fiber la) Synthesis of photopolymerizable resin Bis(4-isocyanatocyclohexyl)methane (hydrogenated MDI) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and an air blowing tube. Hydroxyethyl acrylate (H
EA) 130 parts were added over 2 hours. When the reaction progressed and the temperature rose to about 70°C, stirring was continued for an additional hour while maintaining this temperature to obtain a prepolymer having polymerizable unsaturated bonds.
このプレポリマーに、数平均分子量2.800、水酸基
含有量0.80meq/g、トラ7ス1.4−結合60
%、シス1.4−結合20%、1.2−結合20%の水
酸基含有液状ポリブタジェン(1,4−PB)(商品名
・Po1y bd−45HT、出光興産■製)300部
と数平均分子量684、水酸基価164のポリプロピレ
ングリコール(PPG)との混合物を3時間にわたって
添加し、温度が約70゛Cに達した時点で、この温度に
さらに1時間攪拌保持し、プレポリマーと1.4− P
Bとが反応した重合性不飽和結合含有ポリブタジェン
、およびプレポリマーとPPGとの反応生成物である重
合性不飽和結合含有ポリプロピレンエーテルとの混合樹
脂(光ラジカル重合性高分子マトリックス)を得た。This prepolymer has a number average molecular weight of 2.800, a hydroxyl group content of 0.80 meq/g, and a tras7s 1.4-bond of 60.
%, hydroxyl group-containing liquid polybutadiene (1,4-PB) with 20% cis 1.4-bonds and 20% 1.2-bonds (trade name: Poly bd-45HT, manufactured by Idemitsu Kosan ■) 300 parts and number average molecular weight 684 and polypropylene glycol (PPG) having a hydroxyl value of 164 was added over a period of 3 hours, and when the temperature reached approximately 70°C, the mixture was stirred and maintained at this temperature for an additional hour to mix the prepolymer and 1.4- P
A mixed resin (photoradical polymerizable polymer matrix) was obtained, which was a mixture of the polymerizable unsaturated bond-containing polybutadiene reacted with B and the polymerizable unsaturated bond-containing polypropylene ether, which is a reaction product of the prepolymer and PPG.
Tb) 光硬化性樹脂組成物の調製
前項で合成した光ラジカル重合性高分子マトリックス6
00部に、実施例1で合成した表面処理剤・試料(T−
1)〜(T−3)ならびに比較試料・プロボキシチクン
トリ (イソステアレート)(C−2)およびT−メタ
クリロキシプロピルトリメトキシシラン(C−3)のそ
れぞれを5部、フェノキシエチルアクリレート(反応性
希釈剤)480部およびN−ビニルピロリドン(N−V
P)120部を加えて良く混合し、さらにベンジルジメ
チルケクール(BMK・光重合開始剤)36部を添加混
合した後、5μmのフィルターを通して濾過し光学ガラ
スファイバー用被覆剤(光硬化性樹脂S、■酸物)なら
びに比較用被覆剤(CR−2)および(CR−3)を調
製した。Tb) Preparation of photocurable resin composition Photoradical polymerizable polymer matrix 6 synthesized in the previous section
00 parts, the surface treatment agent/sample synthesized in Example 1 (T-
1) to (T-3) and comparative sample - 5 parts each of proboxythicuntri (isostearate) (C-2) and T-methacryloxypropyltrimethoxysilane (C-3), phenoxyethyl acrylate ( 480 parts of reactive diluent) and N-vinylpyrrolidone (N-V
Add 120 parts of P) and mix well, and then add and mix 36 parts of benzyldimethylkecool (BMK/photopolymerization initiator), filter through a 5 μm filter, and obtain a coating material for optical glass fiber (photocurable resin S). , (2) acid compound) and comparative coating materials (CR-2) and (CR-3) were prepared.
得られた被覆剤の25℃における粘度を第1表に示す。Table 1 shows the viscosity of the resulting coating at 25°C.
(C1硬化物の物性測定
前項で調製した被覆剤をブリキ板上に、ドクターブレー
ドを用いてO,1mm厚さに塗布し、ついで80w/a
mのメタルハライドランプを用いランプ間距離40cm
で10秒間紫外線を照射して硬化させた。得られた硬化
皮膜を水銀アマルガム法により’/jl離し、試験用シ
ートを作成した。(Measurement of physical properties of C1 cured product The coating material prepared in the previous section was applied to a tin plate using a doctor blade to a thickness of 0.1 mm, and then 80 w/a
Distance between lamps is 40cm using metal halide lamps.
It was cured by irradiating it with ultraviolet light for 10 seconds. The obtained cured film was separated by '/jl using the mercury amalgam method to prepare a test sheet.
作成した試験用シートを用い下記の物性を測定した。測
定結果を、第1表中に示す。The following physical properties were measured using the prepared test sheet. The measurement results are shown in Table 1.
弾性率測定:JIS K−7113に準拠し、弾性率
を測定した。Elastic modulus measurement: The elastic modulus was measured in accordance with JIS K-7113.
耐熱試験 :3Q’Cに設定した加熱老化試験機に窒素
雰囲気下に試験シー1−を10日間保持して老化した、
さらに20℃×50%RHの恒温室に24時間放置した
後、弾性率を測定した。Heat resistance test: Test sheet 1- was kept in a heat aging tester set at 3Q'C in a nitrogen atmosphere for 10 days and aged.
Further, after being left in a constant temperature room at 20° C. and 50% RH for 24 hours, the elastic modulus was measured.
動的粘弾性:動的粘弾性測定装置(東洋ボールドウィン
0菊製)を用い、周波数35 I(z 、昇温速度2℃
/分、動的変位±0.025mm、測定温度−100℃
〜+100℃の条件で測定し、測定結果よりガラス転位
温度を求めた。Dynamic viscoelasticity: Using a dynamic viscoelasticity measuring device (manufactured by Toyo Baldwin 0 Kiku), frequency 35 I (z, heating rate 2°C)
/min, dynamic displacement ±0.025mm, measurement temperature -100℃
It was measured under the conditions of ~+100°C, and the glass transition temperature was determined from the measurement results.
(dl 密着性試験
石英ガラス板上に、前記Cb1項で調製した被覆剤をド
クターブレードを用いてQ、l rn rn厚さに塗布
し、80 w / c mのメタルハライドランプを用
いランプ間距離40cmで10秒間紫外線を照射して硬
化させた。(dl Adhesion Test The coating material prepared in Section Cb1 above was applied to a thickness of Q, lrn rn using a doctor blade on a quartz glass plate, and the distance between the lamps was 40cm using an 80 w/cm metal halide lamp. It was cured by irradiating it with ultraviolet light for 10 seconds.
この被覆ガラス板を、20°C×50%RHの恒温室に
24時間放置し、さらに蒸留水に浸漬、5日間放置した
後、サンプルrj+ば20mm、引張速度100mm/
分の条件で剥離試験を行った。This coated glass plate was left in a constant temperature room at 20°C x 50% RH for 24 hours, and then immersed in distilled water for 5 days.
A peel test was conducted under the conditions of 10 minutes.
測定結果を、第1表中に示す。The measurement results are shown in Table 1.
(以下余白)
(f) 光学ガラスファイバーの被覆未被覆の外径1
25μmの光学ガラスファイバーに、fbl項で調製し
た被覆剤を被覆後の外径が400μmとなるように塗布
し、80w/cmのメタルハライドランプを用いて紫外
線を照射して被覆ファイバーを得た。(Left below) (f) Uncoated outer diameter of optical glass fiber 1
The coating material prepared in the FBL section was applied to a 25 μm optical glass fiber so that the outer diameter after coating was 400 μm, and the coated fiber was irradiated with ultraviolet rays using an 80 W/cm metal halide lamp.
本発明の被覆剤を使用して得られた被覆ファイバーは、
被覆による伝送損失の変化は認められず、また−50〜
+60℃の温度範囲における伝送損失の変化は、±0.
05dB/kmであった。The coated fiber obtained using the coating material of the present invention is
No change in transmission loss due to coating was observed, and -50~
The change in transmission loss in the +60°C temperature range is ±0.
It was 05dB/km.
実施例3 光硬化性レジストインキ
fa) 光硬化性レジストインキの調製フェノールノ
ボラック型エポキシ樹脂のアクリル酸付加物50部とト
リメチロールプロパントリアクリレート
性高分子マトリックス)に、ヒドロキシピバリン酸エス
テルネオペンチルグリコールジアクリレート(反応性希
釈剤)25部を加えて混合し、さらに2−エチルアント
ラキノン(光重合開始剤)5部ならびに実施例1で合成
した表面処理剤および実施例2で使用した比較試料の表
面処理剤のそれぞれの0.5部を用いて予め表面処理を
施したタルク50部とフタロシアニングリーン1部との
混合物を加え、3本ロールを通して混練し、紫外線硬化
型レジストインキ(光硬化性樹脂組成物)ならびに比較
用インキを調製した。Example 3 Preparation of photocurable resist ink (fa) Preparation of photocurable resist ink 50 parts of acrylic acid adduct of phenol novolac type epoxy resin and trimethylolpropane triacrylate polymer matrix) were added with hydroxypivalic acid ester neopentyl glycoldi. Add and mix 25 parts of acrylate (reactive diluent), and further 5 parts of 2-ethylanthraquinone (photopolymerization initiator) and surface treatment of the surface treatment agent synthesized in Example 1 and the comparative sample used in Example 2. A mixture of 50 parts of talc and 1 part of phthalocyanine green, which had been surface-treated in advance using 0.5 parts of each agent, was added and kneaded through three rolls to form an ultraviolet curable resist ink (photocurable resin composition). ) and comparative inks were prepared.
fbl レジスト特性
前項で調製したインキを、銅張積層板上に15μmの厚
さに塗布し、高圧水銀灯(8部w/cm×3灯)を用い
、約20v’mの距離から10秒間紫外線を照射し硬化
した。fbl Resist properties The ink prepared in the previous section was applied to a thickness of 15 μm on a copper-clad laminate, and ultraviolet rays were irradiated for 10 seconds from a distance of approximately 20 V'm using a high-pressure mercury lamp (8 parts W/cm x 3 lamps). It was irradiated and cured.
得られたレジスト付積層板を用い、下記の特性を測定し
た。測定結果を第2表に示す。Using the obtained resist-coated laminate, the following properties were measured. The measurement results are shown in Table 2.
密 着 性:ゴバン目セロテープ剥離試験により測定し
た。Adhesion: Measured by a cross-cut sellotape peel test.
耐 熱 性:260℃のハンダ浴に45秒間ディップし
、剥離、ふくれ等の有無
を目視観察した。Heat resistance: Dipped in a 260°C solder bath for 45 seconds and visually observed for peeling, blistering, etc.
電気絶縁性:直流電圧500vを1分間印加し、電気絶
縁抵抗値を測定した。Electrical insulation: A DC voltage of 500 V was applied for 1 minute, and the electrical insulation resistance value was measured.
実施例4 白系塗料
ta+ 塗料の1周:襲
アクリル酸メチル、アクリル酸エチル、メタクリル酸メ
チルおよびメタクリル酸N,N’−ジメチルアミノエチ
ルを共重合させて得た数平均分子量が73、000、ガ
ラス転移点5℃のコポリマー(光ラジカル重合性高分子
マトリックス)33.5%を含有するトルエン溶液をコ
ポリマーとして44部、トリメチロールプロパントリメ
タクリレート11部および実施例1で合成した表面処理
剤および実施例2で使用した比較試料の表面処理剤のそ
れぞれの0.45部を用いて予め表面処理を施したチタ
ン白45部を、三本ロールを用いて混練し塗料化した。Example 4 White paint ta+ One cycle of paint: Copolymerized methyl acrylate, ethyl acrylate, methyl methacrylate, and N,N'-dimethylaminoethyl methacrylate with a number average molecular weight of 73,000, glass 44 parts of a toluene solution containing 33.5% copolymer (photoradically polymerizable polymer matrix) with a transition point of 5°C, 11 parts of trimethylolpropane trimethacrylate, and the surface treatment agent synthesized in Example 1 and Examples 45 parts of titanium white, which had been surface-treated in advance using 0.45 parts of each of the comparative sample surface treatment agents used in 2, was kneaded using a triple roll to form a paint.
fb) 塗膜物性
前項で調製した塗料のそれぞれを、エポキシ系プライマ
ーを2μmの厚さに塗布し、熱硬化させた塗膜を有する
O.’6mm厚さの電気亜鉛めっき鋼板に、バーコータ
ーを用いて塗布し、130℃の熱風オーブンに3分間保
持して溶剤を揮発させた。fb) Paint film physical properties Each of the paints prepared in the previous section was coated with an epoxy primer to a thickness of 2 μm and cured by heat. It was coated on a 6 mm thick electrogalvanized steel plate using a bar coater and held in a hot air oven at 130° C. for 3 minutes to volatilize the solvent.
ついで、電圧300KV、電流65mAのICT電子線
加速機を用い、窒素雰囲気下に、2 M r adの電
子線を照射し、塗膜を硬化させた。Then, using an ICT electron beam accelerator with a voltage of 300 KV and a current of 65 mA, a 2 M rad electron beam was irradiated in a nitrogen atmosphere to cure the coating film.
硬化塗膜について、下記のJIS K−5400に準
拠した塗膜特性他の塗膜特性を測定した。Regarding the cured coating film, coating film properties and other coating film properties based on the following JIS K-5400 were measured.
測定結果を、第3表に示す。The measurement results are shown in Table 3.
鉛筆硬度 :荷重1kgにおける塗膜破壊硬度密 着
性:ゴバン目セロテープ剥離試験耐屈曲性 :折曲角度
180度における塗膜に異常を認めない中心棒直径
衝撃強さ :荷重500gxl/2’ における塗nり
に異常を認めない高さ
耐アルカリ性:5%〜a01水溶液(常温)に1週間浸
??1後の外観
耐 酸 性:5%11□SO,水溶液(常IjL)に1
週間浸漬後の外観
耐塩水性 ;片側211離幅が3rnmに達するまでの
時間(JIs J−2371に
$拠)
耐 候 性:促進耐候試験を行い、500時間後の塗膜
面について指触し、白亜
化の有無を調べた。Pencil hardness: Paint film breaking hardness adhesion at a load of 1 kg
Properties: Vertical Cellotape peel test Flexibility: Center rod diameter with no abnormality observed at bending angle of 180 degrees Impact strength: Height with no abnormality observed on coating at a load of 500gxl/2' Alkali resistance: Soak in 5%~A01 aqueous solution (room temperature) for one week? ? Appearance after 1 Acid resistance: 5% 11□SO, 1 in aqueous solution (normal IjL)
Appearance salt water resistance after immersion for one week: Time required for one side 211 separation to reach 3 rnm (based on JIs J-2371) Weather resistance: Accelerated weather resistance test was conducted, and the coating surface was touched with the finger after 500 hours. The presence or absence of chalking was examined.
前記実施例1に示したように、過剰の不飽和カルボン酸
残基を導入したアルコキシチタン誘導体(比較試料(C
−1))は、短時間の間にゲル化し、表面処理剤として
使用できないのに対し、本発明の表面処理剤は、光学グ
ラスファイバー被覆剤に添加した場合(実施例2参照)
には、その弾性率や耐熱性を低下させることなく、耐水
性を向上させ、光硬化性レジストインキに添加した場合
(実施例3参照)には、その密着性、電気絶縁性を向上
させ、また、白糸塗料に添加した場合(実施例4参照)
には、密着性、耐屈曲性等を始めほとんどの塗膜特性を
向上させる。これに対し、従来から表面処理剤として使
用されているイソプロポキシチタントリ (イソステア
レート) (比較試料(C−2))やγ−メタクリロキ
シプロピルトリメトキシシラン(比較試料(C−3))
においては、一部その添加効果の認められる項目もない
ではないが、全般的な添加効果は認められない。As shown in Example 1, an alkoxytitanium derivative (comparative sample (C
-1)) gels in a short period of time and cannot be used as a surface treatment agent, whereas the surface treatment agent of the present invention when added to an optical glass fiber coating (see Example 2)
It improves water resistance without reducing its elastic modulus or heat resistance, and when added to photocurable resist ink (see Example 3), it improves its adhesion and electrical insulation. Also, when added to white thread paint (see Example 4)
It improves most coating film properties, including adhesion and bending resistance. In contrast, isopropoxytitanium tri(isostearate) (comparative sample (C-2)) and γ-methacryloxypropyltrimethoxysilane (comparative sample (C-3)), which have been conventionally used as surface treatment agents.
Although there are some items where the effect of the addition is recognized, no overall effect of the addition is observed.
すなわち、これらの効果は、本発明の表面処理剤による
事前の表面処理または樹脂系への添加により、無機物質
の表面が改質され、光重合性樹脂と無機物質との馴染み
が向上すること、および表面処理剤の主成分であるアル
コキシチタン誘導体の有する不飽和二重結合が、光重合
性樹脂と共重合することにより、無機物質と光重合性の
高分子マトリックスとが有機的に結合し発現する。That is, these effects are that the surface of the inorganic substance is modified by prior surface treatment with the surface treatment agent of the present invention or its addition to the resin system, and the compatibility between the photopolymerizable resin and the inorganic substance is improved; When the unsaturated double bonds of the alkoxy titanium derivative, which is the main component of the surface treatment agent, copolymerize with the photopolymerizable resin, the inorganic substance and the photopolymerizable polymer matrix organically bond and develop. do.
したがって、本発明の表面処理剤を配合した光硬化性樹
脂組成物(第2発明)は、無機物質と光重合性樹脂との
界面に適用される分野、たとえば、光学ガラスファイバ
ー被覆剤、フィラーを含有するレジストインキ、顔料を
含有する塗料、その他無機機材と透明な機材との接着剤
等に好適に使用することができる。Therefore, the photocurable resin composition containing the surface treatment agent of the present invention (second invention) can be used in fields where it is applied to the interface between an inorganic substance and a photopolymerizable resin, such as optical glass fiber coatings and fillers. It can be suitably used in resist inks containing pigments, paints containing pigments, adhesives between other inorganic materials and transparent materials, and the like.
本発明は、無機物質の表面を改質し光重合性樹脂との馴
染みを向上させる表面処理剤(第1発明)およびこの表
面処理剤を含有する光硬化性樹脂組成物(第2発明)を
提供するものであり、その産業的意義は極めて大きい。The present invention provides a surface treatment agent (first invention) that modifies the surface of an inorganic substance to improve its compatibility with a photopolymerizable resin, and a photocurable resin composition containing this surface treatment agent (second invention). The industrial significance of this is extremely large.
Claims (2)
ここに、Rは、炭素数1〜8の直鎖または分枝を有する
アルキル基を表す。)、残部が下記一般式で表される不
飽和カルボン酸残基: ▲数式、化学式、表等があります▼ (ここに、R′は、H−、CH_3−、C_H_5−、
CH_3CH=CH−またはC_6H_5−CH=CH
−を、R″は、H−またはCH_3−を表す。)である
平均縮合度が6以下のアルコキシチタン誘導体を含有す
ることを特徴とする表面処理剤(1) 35-90% of the substituents are alkoxy groups: -OR(
Here, R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms. ), and the remainder is an unsaturated carboxylic acid residue represented by the following general formula: ▲Mathematical formulas, chemical formulas, tables, etc.▼ (Here, R' is H-, CH_3-, C_H_5-,
CH_3CH=CH- or C_6H_5-CH=CH
-, R'' represents H- or CH_3-), and the average degree of condensation is 6 or less.
はポリマー、および成分B:置換基の35〜90%がア
ルコキシ基:−OR(ここに、Rは、炭素数1〜8の直
鎖または分枝を有するアルキル基を表す。)、残部が下
記一般式で表される不飽和カルボン酸残基: ▲数式、化学式、表等があります▼ (ここに、R′は、H−、CH_3−、C_6H_5−
、CH_3CH=CH−またはC_6H_5−CH=C
H−を、R″は、H−またはCH_3−を表す。)であ
る平均縮合度が6以下のアルコキシチタン誘導体を含有
することを特徴とする光硬化性樹脂組成物(2) Component A: photoradically polymerizable monomer and/or polymer, and component B: 35 to 90% of the substituents are alkoxy groups: -OR (here, R is a straight chain or branched chain having 1 to 8 carbon atoms). (represents an alkyl group with branches), unsaturated carboxylic acid residue whose remainder is represented by the following general formula: ▲Mathical formula, chemical formula, table, etc.▼ (Here, R' is H-, CH_3-, C_6H_5-
, CH_3CH=CH- or C_6H_5-CH=C
A photocurable resin composition containing an alkoxytitanium derivative having an average degree of condensation of 6 or less, where H- represents H- or CH_3-.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62095053A JPS63260940A (en) | 1987-04-20 | 1987-04-20 | Photoreactive surface treating agent and resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62095053A JPS63260940A (en) | 1987-04-20 | 1987-04-20 | Photoreactive surface treating agent and resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63260940A true JPS63260940A (en) | 1988-10-27 |
Family
ID=14127307
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62095053A Pending JPS63260940A (en) | 1987-04-20 | 1987-04-20 | Photoreactive surface treating agent and resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63260940A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989009245A1 (en) * | 1988-04-01 | 1989-10-05 | Nippon Soda Co., Ltd. | Surface-treating agent and filler powder surface-treated with the agent |
CN1064687C (en) * | 1996-08-22 | 2001-04-18 | 埃勒夫阿托化学有限公司 | Unsaturated metal-organic compound derived from titanium and its preparing method |
-
1987
- 1987-04-20 JP JP62095053A patent/JPS63260940A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989009245A1 (en) * | 1988-04-01 | 1989-10-05 | Nippon Soda Co., Ltd. | Surface-treating agent and filler powder surface-treated with the agent |
CN1064687C (en) * | 1996-08-22 | 2001-04-18 | 埃勒夫阿托化学有限公司 | Unsaturated metal-organic compound derived from titanium and its preparing method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2460861A1 (en) | Surface conditioner for coating agents | |
JPH0586416B2 (en) | ||
JP4537209B2 (en) | UV curable epoxy acrylate | |
JP2011517465A (en) | Radiation curable compound | |
JP5012235B2 (en) | Photo-curable moisture-proof insulating coating, electronic component moisture-proof insulated using this photo-curable moisture-proof insulating coating, and manufacturing method thereof | |
WO1998027079A1 (en) | Novel compounds, polymers of them, processes for the preparation of both, and compositions containing the compounds | |
JP4775830B2 (en) | Water-based paint composition and method for forming waterproof coating using the same | |
JPS63260940A (en) | Photoreactive surface treating agent and resin composition | |
JP3674210B2 (en) | Curable composition for optical component manufacturing | |
JP2000302840A (en) | Active energy radiation curing coating composition and process for formation of coated film using the composition | |
JP4310072B2 (en) | Photo-curable putty composition | |
JPH0522743B2 (en) | ||
JP2813429B2 (en) | Manufacturing method of electron beam curing type pre-coated steel sheet | |
EP0825201B2 (en) | Photocurable composition and curing process therefor | |
JPS6049716B2 (en) | Substrate surface treatment method for imparting conductivity | |
JPH11302562A (en) | Photocurable coating composition | |
JPH0473448B2 (en) | ||
JPH09165444A (en) | Production of film or molding by radiation curing | |
JP2003147072A (en) | (meth)acrylate compound, composition, cured product and method of producing (meth)acrylate compound | |
JPH1180118A (en) | New sulfonium salt, cation-polymerizable composition and its cured product | |
JPH0412307B2 (en) | ||
JPH05247402A (en) | Coating material for plastic member of automobile | |
JPS59227915A (en) | Curable liquid resin composition and optical fiber coating material based thereon | |
JPH11130981A (en) | Covering resin composition and coating method using this | |
WO2003085028A1 (en) | Novel polyether compound containing acid group and unsaturated group, process for producing the same, and resin composition |