JP4078138B2 - Photocurable resin coating composition having antifouling property and easy cleaning property, and cured coating film - Google Patents
Photocurable resin coating composition having antifouling property and easy cleaning property, and cured coating film Download PDFInfo
- Publication number
- JP4078138B2 JP4078138B2 JP2002201254A JP2002201254A JP4078138B2 JP 4078138 B2 JP4078138 B2 JP 4078138B2 JP 2002201254 A JP2002201254 A JP 2002201254A JP 2002201254 A JP2002201254 A JP 2002201254A JP 4078138 B2 JP4078138 B2 JP 4078138B2
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- Prior art keywords
- meth
- photocurable resin
- coating film
- acrylate
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000576 coating method Methods 0.000 title claims description 43
- 239000011248 coating agent Substances 0.000 title claims description 40
- 229920005989 resin Polymers 0.000 title claims description 25
- 239000011347 resin Substances 0.000 title claims description 25
- 239000008199 coating composition Substances 0.000 title claims description 17
- 230000003373 anti-fouling effect Effects 0.000 title description 12
- 238000004140 cleaning Methods 0.000 title 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 42
- 229920002050 silicone resin Polymers 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 238000000016 photochemical curing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 21
- 229920001296 polysiloxane Polymers 0.000 description 17
- 239000003973 paint Substances 0.000 description 16
- -1 polysiloxane Polymers 0.000 description 14
- 229920000180 alkyd Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-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
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N fumaric acid group Chemical group C(\C=C\C(=O)O)(=O)O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光硬化性樹脂コーティング組成物および該組成物から得られた硬化塗膜に関する。詳しくは、本発明は防汚性（拭取り性）を有し、表面硬度が高く、タック感がなく、且つ生産性に優れたコーティング塗膜およびこのような塗膜を形成することができるコーティング組成物に関する。
【０００２】
【従来の技術】
透明樹脂系塗料として多種多様な塗料が知られているが、近年、生産性が高く比較的表面硬度が得られ易い点から、光硬化性樹脂塗料がハードトップコート材料として用いられるようになってきた。一方、防汚性を有する透明樹脂塗膜としては熱硬化型ポリシロキサン組成物が広く使用されており、最近では光硬化型のポリシロキサン組成物も商品化されている。
しかしながら、光硬化型のポリシロキサン組成物は一般に高価であり、アクリル樹脂系光硬化樹脂塗膜に比べると表面硬度が得られにくいという欠点がある。アクリル樹脂系光硬化樹脂にポリシロキサン成分を添加して防汚性を付与することも考えられるが、ポリシロキサン組成物は一般にアクリル系樹脂と相溶しがたく、硬化反応の機構も異なるために、均質な透明塗膜が得られない。さらにポリシロキサン成分の添加により、硬化塗膜の表面硬度を損なうこともある。
【０００３】
【発明が解決しようとする課題】
そこで、本発明の発明者らは、防汚性に優れ、表面硬度が高く、且つタック感のない光硬化性の透明樹脂コーティング材料を提供することを目的とした。
【０００４】
【課題を解決するための手段】
本発明者らは、(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマーを主成分とする光硬化性樹脂組成物に防汚性を付与するために防汚成分を均一添加することおよび表面硬度を損なわない架橋構造を達成するために鋭意検討した結果、一般式（Ｉ）で表わされるアルキッド樹脂変性シリコーン樹脂が、(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマーに良好に相溶し、かつ表面硬度の高い硬化皮膜を形成できることを見出した。
【０００５】
即ち、本発明は、（ａ）下記一般式（Ｉ）
【化２】
で表わされるアルキッド変性シリコーン樹脂、（ｂ）(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマー、および（ｃ）光重合開始剤、を含有してなり、全固形分中のアルキッド変性シリコーン樹脂の含有量が６〜３０重量％である光硬化性樹脂コーティング組成物に関する。
【０００６】
更に、本発明は、上記組成物に更に溶剤を含み、固形分濃度が６０〜１００重量％である上記光硬化性樹脂コーティング組成物に関する。
特に、本発明は、光硬化後２Ｈ以上の鉛筆硬度の塗膜が得られる上記いずれかに記載の光硬化性樹脂コーティング組成物に関する。
また、本発明は、上記いずれかに記載の光硬化性樹脂コーティング組成物を光硬化して得られる鉛筆硬度が２Ｈ以上の硬化塗膜に関する。
【０００７】
【発明の実施の形態】
本発明は、光硬化性樹脂を塗料として用いる際に、一般式（Ｉ）で表わされるアルキッド変性シリコーン樹脂を添加してなることを特徴とする光硬化性コーティング組成物を提供する。
一般に光硬化性樹脂はその主成分として(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマーを含み、これらは一般に極性が高いために非極性成分と相溶しがたい。したがって、これに防汚成分としてポリシロキサン組成物を添加した場合、良好な相溶状態が得られないために塗料として被塗装物に塗装すると、成分分離によりハジキや塗装むら、凝集物などが塗装面に生じ、得られた塗装品は工業製品としては使用に耐えない。
【０００８】
ポリシロキサン分子の一部に極性基を導入することにより、各種硬化性樹脂との相溶性を改善することができることは広く一般に知られており、それら極性基の種類や変性手法によって、硬化後の硬度の低いものから高いものまで選択することができる。
【０００９】
本発明における(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマーに対しては、特に一般式（Ｉ）で表わされるアルキッド変性シリコーン樹脂が優れた相溶性を示すこと、かつその極性変性基であるアルキッド基が、(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマーのアクリル基と反応して相互に架橋構造をなすことから、塗膜硬化後に光硬化成分の硬度を損なわないことを見出した。さらに、通常アルキッド変性シリコーン樹脂を単独で硬化させる場合には１００℃以上で数分加熱する必要があるが、(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマーのアクリル基がアルキッド変性シリコーン樹脂の重合硬化を促進するために、シリコーン成分の架橋が低温で達成され、それらの十分な防汚効果が得られ、かつ表面へのブリード等が生じない。
【００１０】
本発明における(メタ)アクリレートオリゴマーとは、アクリロイル基（CH2=CHCO-）あるいはメタクリロイル基（CH2=CCH3CO-）を分子内に１〜数個有する分子量が数百から千数百の化合物であり、代表的にはエポキシ、エポキシ化油、ウレタン、ポリエステル、ポリエーテル等のモノ(メタ)アクリレート、ジ(メタ)アクリレート、トリ(メタ)アクリレートおよびさらに多官能の(メタ)アクリレートが挙げられる。
【００１１】
(メタ)アクリレートモノマーとしては、アクリロイル基（CH2=CHCO-）あるいはメタクリロイル基（CH2=CCH3CO-）を分子内に１〜数個有する反応性モノマーであり、代表的にはモノ(メタ)アクリレートとして、２-(２-エトキシエトキシ)エチルアクリレート、ステアリル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ラウリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、２-フェノキシエチル(メタ)アクリレート、イソデシル(メタ)アクリレート、イソオクチルアクリレート、イソボルニル(メタ)アクリレート、２-ヒドロキシエチル(メタ)アクリレート、２-ヒドロキシプロピル(メタ)アクリレート、トリデシルアクリレート、カプロラクトンアクリレート、エトキシ化ノニルフェノールアクリレート等；ジ(メタ)アクリレートとしては、１,６-ヘキサンジオールジ(メタ)アクリレート、１,３-ブタンジ(メタ)アクリレート、１,４-ブタンジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジアクリレート、エトキシ化ビスフェノールＡジ(メタ)アクリレート等；トリ(メタ)アクリレートとしては、トリメチロールプロパントリ(メタ)アクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシ化トリメチロールプロパントリアクリレート、トリス（２-ヒドロキシエチル）イソシアヌレートトリアクリレート、ペンタエリスリトールトリアクリレート等、４官能以上の(メタ)アクリレートとしては、ペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールヒドロキシペンタアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート等が挙げられる。
【００１２】
本発明で使用するアルキッド変性シリコーン樹脂は、上記一般式（Ｉ）で表され、式中、Ｒ１は水素原子、炭素数が１〜４のアルキル基またはフェニル基、Ｒ２およびＲ３は炭素数１〜２２のアルキル基またはアルケニル基、またはフェニル基を表し、同一であっても異なってもよく、ｎは１〜１０００の整数である。Ｒ２およびＲ３は、好ましくはフタル酸残基、イソフタル酸残基、テレフタル酸残基等の芳香族２塩基酸残基、マレイン酸残基、フマル酸残基等の脂肪族２塩基酸残基、または植物油由来の脂肪酸残基等である。
【００１３】
アルキッド変性シリコーン樹脂は、シリコーン樹脂（オルガノポリシロキサン）の官能基であるシラノール基あるいはアルコキシ基をアルキッド樹脂のアルコール性水酸基と脱水縮合あるいは脱アルコール縮合させることによって得られるものである。
アルキッド変性シリコーン樹脂としては、オルガノポリシロキサンとアルキッドとを脱水縮合反応させて変性したもの、オルガノアルコキシポリシロキサンとアルキッドとを脱アルコール縮合反応させて変性したもの、オルガノポリシロキサン、多価アルコール、脂肪酸および多塩基酸を脱水縮合反応させて変性したもののいずれも使用することができる。
また、本発明の組成物には、硬化促進剤としてメラミン樹脂が適量含有されていても、あるいは後添加されてもよい。
【００１４】
本発明の組成物中におけるシリコーン樹脂の配合量は、全固形分中６から３０重量％が好ましく、８〜２０重量％が特に好ましい。６重量％より少ないとシリコーン成分による防汚機能が十分に発揮されず、３０重量％を越えると光硬化性成分の硬化性の低下につながり、さらに成分分離による塗膜性状の低下や塗膜硬度の低下も招く恐れがある。
【００１５】
上記の組成物には、光硬化性組成物とするために更に光開始剤が配合される。光開始剤としては、紫外線等の特定波長を吸収して電子的励起状態となり、ラジカルを発生する化合物であり、代表的にはアセトフェノン類、ベンゾイン類、ベンゾフェノン類、チオキサンソン類等が挙げられる。添加量としては(メタ)アクリレート成分に対して１〜５重量％が好ましい。より好ましくは１.５〜４重量％である。また、光開始剤の機能を促進する目的で、適宜、光開始助剤や鋭感剤を加えても良いし、シェルフライフの延長を目的に重合禁止剤等を配合しても良い。
【００１６】
上記の塗料成分に加え、塗料の光硬化性を阻害しない程度に、適宜、着色の目的で染料が添加されていたり、レベリング剤等の表面調整剤が含まれていても良い。
【００１７】
さらに、塗料として用いる際には、塗工性をコントロールするために通常粘度調整を行なう。そのため、溶剤を適宜加えて希釈することできる。溶剤としては各種のものが使用可能であるが、(メタ)アクリレートおよび変性シリコーン樹脂をともに良く溶解し、両者を分離させない溶媒としては、シクロヘキサノン、イソホロン、エタノール、トルエン、キシレン、酢酸エチルが挙げられる。この時、溶剤を多量に使用した場合、後工程で溶剤を除去する際に温度や時間がかかり、また揮発分も多くなるため、はなはだ不経済である。また、溶剤除去が不十分で固形分（架橋成分）中に溶剤が残ったまま光硬化させると、塗膜硬度が低下したり、ピンホールなどの塗膜欠陥を生じる原因になることがある。したがって、溶剤添加量は配合された塗料中に０〜４０重量％の範囲であることが好ましい。すなわち固形分濃度が６０〜１００重量％であることが好ましい。
【００１８】
本発明による塗料を被塗装物に適用する場合、塗工方法は一般的な方法なら何でも使用でき、例えばロールコーター法、コンマコーター法、スプレー法、ディッピング法、刷毛塗りなどが挙げられる。
被塗装物としては、特に限定されるものではないが、金属板、床・タイル・化粧板などの平面材、さらにはプラスチック成形品や金属加工品等の構造体などが代表的に挙げられ、特に鋼板やアルミ板等の金属用の塗料、床・タイル・化粧板などのトップコート塗料、プラスチック成形品のトップコート塗料に好適である。
【００１９】
塗膜の硬化は、被塗装物に紫外線ないしは電子線を照射することにより達成される。ただし、溶剤を含んだ組成の場合には、これら放射線を照射する前に適当な手段により溶剤を除去しておく必要がある。例えば、熱風乾燥炉にて加温する、遠赤外線ヒーター等より加熱するなどの手段が挙げられる。溶剤除去のための加熱の温度、時間などは溶剤の種類によって適宜調整されるべきである。また、あまり高温に長時間曝すと、光開始剤が揮発するなどして塗料の光硬化性が失活したり、被塗装物素材の物性低下を招いたりする恐れがあるため、通常は１５０℃程度以下に抑えることが望ましい。
【００２０】
放射線を照射する際には、塗料表面の酸素障害を防ぐために、適宜、遮光性の少ない透明フィルムなどを貼り合わせていても良いし、あるいは窒素など不活性ガスにより酸素濃度を低減したチャンバー内で行っても良い。
【００２１】
以下、実施例により本発明をより詳細に且つ具体的に説明する。
【実施例】
実施例 １
下記の配合（１）にて、光硬化性樹脂コーティング組成物を調合した。
得られた塗料は薄黄色の透明で均一な液体であった。粘度（室温）は７００ｍＰａ・ｓであった。これを予めプライマー処理された鋼板に、ロールコーター法により樹脂固形分付着量が厚さ５０μｍとなるように調整して塗布した。塗装後、熱風乾燥炉中、１４０℃で約２分加熱して溶剤（キシレン）を除去した後、紫外線照射機（フュージョン・ジャパン社製；無電極ランプ、１２０Ｗ／ｃｍ）にて約２秒間紫外線を照射して塗料を硬化させた。塗膜の物性を評価した結果を表１に示す。
【００２３】
タック感は指により触覚的に評価した。
鉛筆硬度の測定は、東洋精機製「鉛筆引っかき試験機」を用い、ＪＩＳ Ｋ５４００の方法にしたがって行った。
防汚性の評価については、ホワイトボード用マーカー（色は黒、赤、青の３色）を用いて塗装表面上を長さ１０ｃｍ（幅１ｃｍ）にわたって任意に線を引き、重さ３０ｇのマーカーイレイザーで往復何回でインクの痕跡が消えるかを視覚により評価した。
表１に示すように、塗膜はタック感がなく、汚れも容易に拭き取れ、鉛筆硬度も実用的に好ましい２Ｈに達していた。
【００２４】
比較例 ５
下記配合（２）を用い、実施例１とまったく同様にして硬化塗膜を形成させた。
〔コーティング組成物配合（２）〕
ウレタンアクリレートオリゴマー（新中村化学工業(株)製「NKオリゴU-6HA」） １００重量部
トリメチロールプロパントリアクリレート（日本化薬(株)製「KS-TMPTA」） ２０重量部
光開始剤（チバスペシャリティケミカルズ(株)製「Irgacure 184」） ４重量部
アクリル変性シリコーンレジン（GE東芝シリコーン(株)製「TSR171；固形分50wt%」）
３５重量部
希釈溶剤（キシレン） ４０重量部
その結果、溶剤乾燥中に若干成分分離が生じ、塗膜面の平滑性が低下した。
得られた硬化塗膜の性能を実施例１と同様にして測定し、結果を表１に記載した。実施例１の塗膜同様、塗膜はタック感がなく、汚れも容易に拭き取れ、鉛筆硬度も実用的に好ましい２Ｈに達していた。
【００２５】
実施例 ２
アルキッド変性シリコーンレジン配合量を減量した下記配合（３）を用いた以外は、実施例１とまったく同様にして硬化塗膜を形成させた。
〔コーティング組成物配合（３）〕
ウレタンアクリレートオリゴマー（新中村化学工業(株)製「NKオリゴU-6HA」） １００重量部
トリメチロールプロパントリアクリレート（日本化薬(株)製「KS-TMPTA」） ２０重量部
光開始剤（チバスペシャリティケミカルズ(株)製「Irgacure 184」） ４重量部
アルキッド変性シリコーンレジン（GE東芝シリコーン(株)製「TSR180」；固形分50wt%）
１０重量部
希釈溶剤（キシレン） ４０重量部
得られた硬化塗膜の性能を実施例１と同様にして測定し、結果を表１に記載した。塗膜は、実施例１および比較例５に較べて拭取り性が心持ち低下したが、塗膜はタック感がなく、鉛筆硬度も実用的に好ましい２Ｈに達していた。
【００２６】
比較例 １
下記の配合（４）にて、光硬化性樹脂コーティング組成物を調合した。
【００２７】
比較例 ２
シリコーン樹脂としてアクリル変性シリコ−ン樹脂〔ＧＥ東芝シリコーン(株)製「TSR171」；固形分５０wt%〕を２０重量部用いた以外は実施例１と同様にしてコーティング組成物を調製し、塗膜を形成した。
得られた硬化塗膜の性能を実施例１と同様にして測定し、結果を表２に記載した。塗膜には若干のタック感が残った他、拭取り性も不十分であった。
【００２８】
比較例 ３
エポキシ変性シリコーンレジンを用いた下記配合（６）を調合した。
【００２９】
比較例 ４
一般的な熱縮合硬化型シリコーンコーティング剤である剥離紙離型剤用シリコーンを用いて、下記配合（７）を調製した。しかしながら、光硬化性樹脂成分との相溶性が悪く、均一な溶液にならなかった。
【表１】
【表２】
【発明の効果】
以上のように本発明を用いることにより、防汚性に優れ、タック感がなく、かつ表面硬度の高い光硬化性の透明樹脂コーティング塗膜を得ることができ、金属用塗料、床・タイル・化粧板などのトップコート塗料、プラスチック成形品のトップコート塗料などに適用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocurable resin coating composition and a cured coating film obtained from the composition. Specifically, the present invention is a coating film having antifouling properties (wiping properties), high surface hardness, no tackiness, and excellent productivity, and a coating capable of forming such a coating film. Relates to the composition.
[0002]
[Prior art]
A wide variety of paints are known as transparent resin-based paints, but in recent years, photocurable resin paints have come to be used as hard top coat materials because of their high productivity and relatively easy surface hardness. It was. On the other hand, thermosetting polysiloxane compositions are widely used as transparent resin coatings having antifouling properties. Recently, photocurable polysiloxane compositions have also been commercialized.
However, the photocurable polysiloxane composition is generally expensive and has a drawback that it is difficult to obtain surface hardness as compared with an acrylic resin-based photocurable resin coating film. Although it is conceivable to add anti-fouling properties by adding a polysiloxane component to the acrylic resin-based photo-curing resin, the polysiloxane composition is generally incompatible with acrylic resins and the curing reaction mechanism is different. A homogeneous transparent coating film cannot be obtained. Furthermore, the addition of the polysiloxane component may impair the surface hardness of the cured coating film.
[0003]
[Problems to be solved by the invention]
Accordingly, the inventors of the present invention have aimed to provide a photocurable transparent resin coating material that is excellent in antifouling property, has a high surface hardness, and does not have a tackiness.
[0004]
[Means for Solving the Problems]
The present inventors uniformly added an antifouling component and imparted antifouling property to a photocurable resin composition containing a (meth) acrylate oligomer and / or a (meth) acrylate monomer as a main component and surface hardness. As a result of intensive studies to achieve a crosslinked structure that does not impair the alkyd resin, the alkyd resin-modified silicone resin represented by the general formula (I) is well compatible with the (meth) acrylate oligomer and / or (meth) acrylate monomer, It was also found that a cured film having a high surface hardness can be formed.
[0005]
That is, the present invention provides (a) the following general formula (I)
[Chemical 2]
Of the alkyd-modified silicone resin in the total solid content, comprising (b) a (meth) acrylate oligomer and / or (meth) acrylate monomer, and (c) a photopolymerization initiator. The present invention relates to a photocurable resin coating composition having a content of 6 to 30% by weight.
[0006]
Furthermore, this invention relates to the said photocurable resin coating composition which further contains a solvent in the said composition and whose solid content concentration is 60 to 100 weight%.
In particular, the present invention relates to the photocurable resin coating composition according to any one of the above, wherein a coating film having a pencil hardness of 2H or higher is obtained after photocuring.
The present invention also relates to a cured coating film having a pencil hardness of 2H or more obtained by photocuring any of the photocurable resin coating compositions described above.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a photocurable coating composition comprising an alkyd-modified silicone resin represented by the general formula (I) when a photocurable resin is used as a paint.
In general, a photocurable resin contains a (meth) acrylate oligomer and / or a (meth) acrylate monomer as a main component, and these are generally incompatible with nonpolar components because of their high polarity. Therefore, if a polysiloxane composition is added as an antifouling component to this, a good compatibility state cannot be obtained. The resulting coated product cannot be used as an industrial product.
[0008]
It is widely known that the compatibility with various curable resins can be improved by introducing a polar group into a part of the polysiloxane molecule. Depending on the type of the polar group and the modification method, You can select from low to high hardness.
[0009]
For the (meth) acrylate oligomer and / or (meth) acrylate monomer in the present invention, the alkyd-modified silicone resin represented by the general formula (I) exhibits excellent compatibility, and is a polar modifying group. It has been found that the alkyd group reacts with the acrylic group of the (meth) acrylate oligomer and / or (meth) acrylate monomer to form a cross-linked structure with each other, so that the hardness of the photocuring component is not impaired after the coating is cured. Furthermore, when the alkyd-modified silicone resin is usually cured alone, it is necessary to heat it at 100 ° C. or higher for several minutes. However, the acrylic group of the (meth) acrylate oligomer and / or the (meth) acrylate monomer is the alkyd-modified silicone resin. In order to accelerate the polymerization and curing, the crosslinking of the silicone component is achieved at a low temperature, their sufficient antifouling effect is obtained, and bleeding to the surface does not occur.
[0010]
The (meth) acrylate oligomer in the present invention has a molecular weight of one to several acryloyl groups (CH 2 ═CHCO—) or methacryloyl groups (CH 2 ═CCH 3 CO—) in the molecule of hundreds to thousands. These are typically compounds such as mono (meth) acrylates such as epoxies, epoxidized oils, urethanes, polyesters, and polyethers, di (meth) acrylates, tri (meth) acrylates, and more multifunctional (meth) acrylates. It is done.
[0011]
The (meth) acrylate monomer is a reactive monomer having 1 to several acryloyl groups (CH 2 ═CHCO—) or methacryloyl groups (CH 2 ═CCH 3 CO—) in the molecule. 2- (2-Ethoxyethoxy) ethyl acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate 2-phenoxyethyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tridecyl acrylate, caprolactone acrylate Ethoxylated nonyl Enol acrylate, etc .; As di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butanedi (meth) acrylate, 1,4-butanedi (meth) acrylate, diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A di (meth) acrylate, etc .; as tri (meth) acrylate Are trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, Examples of tetra- or higher functional (meth) acrylates such as pentaerythritol triacrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, ethoxylated pentaerythritol tetraacrylate, and the like.
[0012]
The alkyd-modified silicone resin used in the present invention is represented by the above general formula (I), wherein R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R 2 and R 3 are carbon. Represents an alkyl group or an alkenyl group of formula 1 to 22, or a phenyl group, which may be the same or different, and n is an integer of 1 to 1000. R 2 and R 3 are preferably an aliphatic dibasic acid residue such as an aromatic dibasic acid residue such as a phthalic acid residue, an isophthalic acid residue or a terephthalic acid residue, a maleic acid residue or a fumaric acid residue. Group or a fatty acid residue derived from vegetable oil.
[0013]
The alkyd-modified silicone resin is obtained by dehydrating or dealcoholizing a silanol group or alkoxy group, which is a functional group of a silicone resin (organopolysiloxane), with an alcoholic hydroxyl group of the alkyd resin.
Alkyd-modified silicone resins include those modified by dehydration condensation reaction of organopolysiloxane and alkyd, those modified by dealcoholization condensation reaction of organoalkoxypolysiloxane and alkyd, organopolysiloxane, polyhydric alcohol, fatty acid Any of those modified by dehydration condensation reaction of a polybasic acid can be used.
The composition of the present invention may contain an appropriate amount of a melamine resin as a curing accelerator, or may be added afterwards.
[0014]
The blending amount of the silicone resin in the composition of the present invention is preferably 6 to 30% by weight, particularly preferably 8 to 20% by weight based on the total solid content. If it is less than 6% by weight, the antifouling function due to the silicone component will not be fully exerted, and if it exceeds 30% by weight, the curability of the photo-curable component will be reduced, and further, the coating properties will be reduced due to component separation and the coating hardness. There is also a risk of lowering.
[0015]
In order to obtain a photocurable composition, a photoinitiator is further added to the above composition. The photoinitiator is a compound that absorbs a specific wavelength such as ultraviolet rays to be in an electronically excited state and generates a radical, and typically includes acetophenones, benzoins, benzophenones, thioxanthones, and the like. The addition amount is preferably 1 to 5% by weight with respect to the (meth) acrylate component. More preferably, it is 1.5 to 4% by weight. For the purpose of promoting the function of the photoinitiator, a photoinitiator assistant or a sharpener may be added as appropriate, or a polymerization inhibitor may be added for the purpose of extending shelf life.
[0016]
In addition to the coating components described above, a dye may be added as appropriate for the purpose of coloring, or a surface conditioner such as a leveling agent may be included to the extent that does not impair the photocurability of the coating.
[0017]
Further, when used as a paint, the viscosity is usually adjusted to control the coatability. Therefore, it can dilute by adding a solvent suitably. Various solvents can be used, but examples of solvents that dissolve both (meth) acrylate and modified silicone resin well and do not separate them include cyclohexanone, isophorone, ethanol, toluene, xylene, and ethyl acetate. . At this time, if a large amount of the solvent is used, it takes a lot of temperature and time to remove the solvent in the subsequent process, and the volatile content increases, which is very uneconomical. Moreover, if the solvent removal is insufficient and the photocuring is performed with the solvent remaining in the solid content (crosslinking component), the coating film hardness may be reduced, or coating defects such as pinholes may be caused. Therefore, the amount of the solvent added is preferably in the range of 0 to 40% by weight in the blended paint. That is, the solid content concentration is preferably 60 to 100% by weight.
[0018]
When the paint according to the present invention is applied to an object to be coated, any general coating method can be used, and examples thereof include a roll coater method, a comma coater method, a spray method, a dipping method, and a brush coating method.
The object to be coated is not particularly limited, but typically includes metal plates, flat materials such as floors, tiles, and decorative plates, and structures such as plastic molded products and metal processed products. It is particularly suitable for metal paints such as steel plates and aluminum plates, top coat paints for floors, tiles, decorative boards, etc., and top coat paints for plastic molded products.
[0019]
Curing of the coating film is achieved by irradiating the object to be coated with ultraviolet rays or electron beams. However, in the case of a composition containing a solvent, it is necessary to remove the solvent by an appropriate means before irradiation with these radiations. For example, means such as heating with a hot air drying furnace or heating with a far infrared heater or the like can be mentioned. The heating temperature and time for removing the solvent should be appropriately adjusted depending on the type of the solvent. In addition, if exposed to a very high temperature for a long time, the photoinitiator may volatilize and the photocurability of the paint may be deactivated or the physical properties of the material to be coated may be reduced. It is desirable to keep it below the level.
[0020]
When irradiating with radiation, in order to prevent oxygen damage on the paint surface, a transparent film with a low light shielding property may be appropriately laminated, or in a chamber where the oxygen concentration is reduced by an inert gas such as nitrogen. You can go.
[0021]
Hereinafter, the present invention will be described in more detail and specifically by way of examples.
【Example】
Example 1
A photocurable resin coating composition was prepared by the following formulation (1).
The obtained paint was a light yellow transparent and uniform liquid. The viscosity (room temperature) was 700 mPa · s. This was applied to a steel sheet that had been previously primed with a roll coater method so that the amount of solid resin adhered was 50 μm in thickness. After coating, the solvent (xylene) is removed by heating at 140 ° C. for about 2 minutes in a hot air drying furnace, and then UV is irradiated for about 2 seconds with an UV irradiation machine (Fusion Japan Co., Ltd .; electrodeless lamp, 120 W / cm). Was applied to cure the paint. The results of evaluating the physical properties of the coating film are shown in Table 1.
[0023]
The tactile sensation was evaluated tactilely with fingers.
The measurement of pencil hardness was performed according to the method of JIS K5400 using a “Pencil Scratch Tester” manufactured by Toyo Seiki.
For the evaluation of antifouling properties, a whiteboard marker (color is black, red, and blue) is used to draw a line on the painted surface over a length of 10 cm (width 1 cm) and weigh 30 g. It was visually evaluated how many times the ink trace disappeared with the eraser.
As shown in Table 1, the coating film had no tackiness, easily wiped off dirt, and the pencil hardness reached 2H, which is practically preferable.
[0024]
Comparative example 5
A cured coating film was formed in the same manner as in Example 1 using the following formulation (2).
[Coating composition blend (2)]
Urethane acrylate oligomer (“NK Oligo U-6HA” manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by weight Trimethylolpropane triacrylate (“KS-TMPTA” manufactured by Nippon Kayaku Co., Ltd.) 20 parts by weight Photoinitiator (Ciba “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd.) 4 parts by weight Acrylic modified silicone resin (“TSR171 manufactured by GE Toshiba Silicone Co., Ltd .; solid content 50 wt%”)
35 parts by weight Diluted solvent (xylene) 40 parts by weight As a result, component separation occurred slightly during the drying of the solvent, and the smoothness of the coating film surface was lowered.
The performance of the obtained cured coating film was measured in the same manner as in Example 1, and the results are shown in Table 1. Similar to the coating film of Example 1, the coating film had no tackiness, easily wiped off dirt, and had a pencil hardness of 2H which was practically preferable.
[0025]
Example 2
A cured coating film was formed in the same manner as in Example 1 except that the following formulation (3) in which the blending amount of the alkyd-modified silicone resin was reduced was used.
[Coating composition blend (3)]
Urethane acrylate oligomer (“NK Oligo U-6HA” manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by weight Trimethylolpropane triacrylate (“KS-TMPTA” manufactured by Nippon Kayaku Co., Ltd.) 20 parts by weight Photoinitiator (Ciba “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd.) 4 parts by weight Alkyd-modified silicone resin (“TSR180” manufactured by GE Toshiba Silicone Co., Ltd .; solid content 50 wt%)
10 parts by weight Diluting solvent (xylene) 40 parts by weight The performance of the obtained cured coating film was measured in the same manner as in Example 1, and the results are shown in Table 1. Although the wiping property of the coating film was lower than that of Example 1 and Comparative Example 5 , the coating film had no tackiness and the pencil hardness reached 2H, which is practically preferable.
[0026]
Comparative example 1
A photocurable resin coating composition was prepared by the following formulation (4).
[0027]
Comparative example 2
A coating composition was prepared in the same manner as in Example 1 except that 20 parts by weight of an acrylic-modified silicone resin (“TSR171” manufactured by GE Toshiba Silicone Co., Ltd .; solid content 50 wt%) was used as the silicone resin. Formed.
The performance of the obtained cured coating film was measured in the same manner as in Example 1, and the results are shown in Table 2. The coating film remained slightly tacky and had insufficient wiping properties.
[0028]
Comparative example 3
The following formulation (6) using an epoxy-modified silicone resin was prepared.
[0029]
Comparative example 4
The following formulation (7) was prepared using a release paper release agent silicone that is a general thermal condensation curable silicone coating agent. However, the compatibility with the photocurable resin component was poor and a uniform solution was not obtained.
[Table 1]
[Table 2]
【The invention's effect】
As described above, by using the present invention, it is possible to obtain a photocurable transparent resin coating film having excellent antifouling property, no tackiness, and high surface hardness. It can be applied to top coat paints such as decorative plates and top coat paints of plastic molded products.
Claims (5)
で表わされるアルキッド変性シリコーン樹脂、（ｂ）(メタ)アクリレートオリゴマーおよび／または(メタ)アクリレートモノマー、および（ｃ）光重合開始剤、を含有してなり、全固形分中のアルキッド変性シリコーン樹脂の含有量が６〜３０重量％である光硬化性樹脂コーティング組成物。(A) The following general formula (I)
Of the alkyd-modified silicone resin in the total solid content, comprising (b) a (meth) acrylate oligomer and / or (meth) acrylate monomer, and (c) a photopolymerization initiator. A photocurable resin coating composition having a content of 6 to 30% by weight.
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