JPH02255772A - Covering composition of active energy ray-hardening type - Google Patents
Covering composition of active energy ray-hardening typeInfo
- Publication number
- JPH02255772A JPH02255772A JP8016989A JP8016989A JPH02255772A JP H02255772 A JPH02255772 A JP H02255772A JP 8016989 A JP8016989 A JP 8016989A JP 8016989 A JP8016989 A JP 8016989A JP H02255772 A JPH02255772 A JP H02255772A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- energy ray
- active energy
- unsaturated double
- 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
- 239000000203 mixture Substances 0.000 title abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000008199 coating composition Substances 0.000 claims description 13
- -1 polypropylene Polymers 0.000 claims description 9
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 20
- 239000002966 varnish Substances 0.000 abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 5
- 229940116351 sebacate Drugs 0.000 abstract description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000004611 light stabiliser Substances 0.000 abstract 2
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-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
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 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
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、活性エネルギー線硬化型印刷インキ、オーバ
ープリントニス（ＯＰニス）、塗料等の被覆組成物に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to coating compositions for active energy ray-curable printing inks, overprint varnishes (OP varnishes), paints, and the like.
（従来の技術）
紫外線または電子線等の活性エネルギー硬化型印刷イン
キ、ＯＰニス塗料等の被覆剤は、近年その省エネルギー
、省スペース、速硬化による印刷直後の箔押し等の後加
工の可能なことによる短納期化、あるいは公害対策等の
理由によって急速にその用途を拡大しているのが現状で
ある。(Prior art) Active energy curable printing inks such as ultraviolet rays or electron beams, coating materials such as OP varnish paints, etc. have recently become popular due to their energy-saving, space-saving, and fast-curing properties that allow for post-processing such as foil stamping immediately after printing. Currently, its uses are rapidly expanding due to reasons such as shorter delivery times and pollution control measures.
特に、プラスチックもしくは金属にこのような被覆剤を
適用した場合、紙を対象とする従来の物性、すなわち、
「画像形成」、「着色」のみの要求からより強固な接着
、スクラッチ、耐摩擦性環−段と高度な各種物性の要求
へと変化してきている。In particular, when such coatings are applied to plastics or metals, conventional physical properties intended for paper, i.e.
The requirements for only "image formation" and "coloring" are changing to requirements for stronger adhesion, scratch and friction resistance, and various advanced physical properties.
しかしながら、これらの被覆剤は硬化直後の接着性が実
用上十分であっても、経時によってその接着性が著しく
劣化すると云う問題点がある。この接着性の改良のため
には、被覆体、被印刷体の表面処理、被覆組成物の材料
の選択、接着性改良剤の添加などが試みられているが、
特に接着性に乏しいポリエチレン、ポリプロピレンなど
を被覆体あるいは被印刷体とした場合には、長期に亘る
使用、あるいはその代用試験である高温度、高湿度の促
進テストの後には特に接着性、スクラッチ、耐摩擦性の
低下を抑制することができない現状にある。However, even if these coating materials have practically sufficient adhesion immediately after curing, there is a problem in that the adhesion deteriorates significantly over time. Attempts have been made to improve this adhesion by surface treatment of the coating and printing material, selection of materials for the coating composition, addition of adhesion improvers, etc.
In particular, when polyethylene, polypropylene, etc., which have poor adhesion, are used as coatings or printed materials, adhesion, scratches, At present, it is not possible to suppress the decline in abrasion resistance.
（発明が解決しようとする課題）
本発明は、係る状況を考慮してなされたものであり、長
期間に亘る使用における接着性、スクラッチ、耐摩擦性
等の低下が極めて少ない活性エネルギー線硬化型インキ
、オーバープリントニス等の被覆組成物を提供するもの
である。(Problems to be Solved by the Invention) The present invention has been made in consideration of the above situation, and provides an active energy ray-curable type product that exhibits extremely little deterioration in adhesion, scratch resistance, abrasion resistance, etc. during long-term use. The present invention provides coating compositions such as inks and overprint varnishes.
（課題を解決するための手段）
本発明は、活性エネルギー線硬化型被覆組成物にヒンダ
ードアミン系紫外線安定剤を添加することによって、紫
外線あるいは電子線などの照射による硬化性には悪影響
を与えず、かつ特異的に接着性の経時劣化を抑制すると
云う新規な知見に基づくものである。すなわち本発明は
、エチレン性不飽和二重結合を有する化合物および必要
に応じて光重合開始剤、並びにヒンダードアミン系紫外
線安定剤を０．１〜５重量％を含有することを特徴とす
る被覆組成物に関するものである。(Means for Solving the Problems) The present invention adds a hindered amine ultraviolet stabilizer to an active energy ray-curable coating composition, so that the curability by irradiation with ultraviolet rays or electron beams is not adversely affected. This is based on the novel finding that it specifically suppresses the deterioration of adhesive properties over time. That is, the present invention provides a coating composition characterized by containing 0.1 to 5% by weight of a compound having an ethylenically unsaturated double bond and, if necessary, a photopolymerization initiator and a hindered amine ultraviolet stabilizer. It is related to.
本発明で使用されるヒンダードアミン系紫外線安定剤と
しては、ビス（２，２，６，６−テトラメチル−４−′
−ピペリジル）セバケート、ビス（１，２゜２．６．６
−ベンタメチルー４−ピペリジル）セバケート、コハク
酸ジメチルート（２−ヒドロキシエチル）−４−（ヒド
ロキシ−２，２，６，６−チトラメチルビペリジン重縮
合物等が挙げられる。これらの安定剤は従来ポリオレフ
ィンあるいはポリウレタンなどの成形用樹脂に添加する
ための耐候性の向上剤として用いられているものである
が、本発明のような活性エネルギー線硬化性被覆組成物
に添加する試みはなく、また接着性の経時劣化を抑制す
る効果を示すと云うことは知られていない。The hindered amine UV stabilizer used in the present invention includes bis(2,2,6,6-tetramethyl-4-'
-piperidyl) sebacate, bis(1,2゜2.6.6
-bentamethyl-4-piperidyl) sebacate, dimethylto(2-hydroxyethyl) succinate-4-(hydroxy-2,2,6,6-titramethylbiperidine polycondensate, etc.).These stabilizers are conventionally used. Although it is used as a weather resistance improver to be added to molding resins such as polyolefin or polyurethane, there has been no attempt to add it to active energy ray-curable coating compositions such as the present invention, and It is not known that it exhibits the effect of suppressing the deterioration of physical properties over time.
この安定剤の使用量は被覆剤組成物に対して０．１〜５
重量％である。０．１重量％未満では実用上十分の効果
が発揮されず、５重量％を越えて添加しても効果の向上
がなく逆に被覆組成物もしくは硬化塗膜の物性を悪化さ
せる。The amount of this stabilizer used is 0.1 to 5% based on the coating composition.
Weight%. If it is less than 0.1% by weight, a sufficient practical effect will not be exhibited, and if it is added in excess of 5% by weight, the effect will not be improved and, on the contrary, the physical properties of the coating composition or cured coating will deteriorate.
本発明で使用されるエチレン性不飽和二重結合を有する
化合物としては、モノマー、オリゴマーまたはプレポリ
マーの少なくとも１種が用いられる。As the compound having an ethylenically unsaturated double bond used in the present invention, at least one of monomers, oligomers, and prepolymers is used.
モノマーとしては一般的な活性エネルギー線硬化型イン
キ等に使用されるモノマー類、すなわち、（メタ）アク
リル酸エステル、例えば、エチレングリコール（メタ）
アクリレート、プロピレングリコール（メタ）アクリレ
ート、１．４ブタンジオール（メタ）アクリレート、ネ
オペンチルグリコールジ（メタ）アクリレート、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、ジプロピレングリ
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、トリメチロールプロパント
リ （メタ）アクリレート、トリメチロールエタントリ
（メタ）アクリレート、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
ラアクリレート等の多価アルコールの（メタ）アクリレ
ートあるいは一分子内に（メタ）アクリロイル基を有す
るウレタン変性多価アクリレートもしくはエポキシアク
リレート、フェノールのアルキレンオキサイド付加体の
（メタ）アクリレート等を使用することができる。これ
らのモノマー類は通常は常温で液状のものが多い。The monomers include monomers used in general active energy ray-curable inks, such as (meth)acrylic acid esters, such as ethylene glycol (meth)
acrylate, propylene glycol di(meth)acrylate, 1.4butanediol(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate ) acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, etc. ) Acrylate, urethane-modified polyacrylate or epoxy acrylate having a (meth)acryloyl group in one molecule, (meth)acrylate of an alkylene oxide adduct of phenol, etc. can be used. Most of these monomers are usually liquid at room temperature.
本発明に使用されるエチレン性不飽和二重結合を有する
オリゴマーまたはプレポリマーとしては、多価アルコー
ルと多塩基酸からなるポリエステルの（メタ）アクリレ
ートであるポリエステル（メタ）アクリレート、ビスフ
ェノールＡ型、ノボラック型あるいは脂環型のエポキシ
樹脂の（メタ）アクリレートであるエポキシ（メタ）ア
クリレートあるいはイソシアネート化合物と例えば２ヒ
ドロキシエチルアクリレート等のヒドロキシル基との反
応物であるポリウレタン（メタ）アクリレート等が一般
的であり、その他アルキッド（メタ）アクリレート、ポ
リオール（メタ）アシクリレート、ポリエーテル（メタ
）アクリレート等を単独もしくは混合して使用すること
ができる。Examples of the oligomer or prepolymer having an ethylenically unsaturated double bond used in the present invention include polyester (meth)acrylate, which is a (meth)acrylate of a polyester consisting of a polyhydric alcohol and a polybasic acid, bisphenol A type, and novolac. Generally, epoxy (meth)acrylate, which is a (meth)acrylate of type or alicyclic type epoxy resin, or polyurethane (meth)acrylate, which is a reaction product of an isocyanate compound and a hydroxyl group such as 2-hydroxyethyl acrylate, etc. , other alkyd (meth)acrylates, polyol (meth)acrylates, polyether (meth)acrylates, etc. can be used alone or in combination.
エチレン性不飽和二重結合を有するプレポリマーオリゴ
マー、モノマーを単独もしくは混合して使用することも
できる。Prepolymer oligomers and monomers having ethylenically unsaturated double bonds can be used alone or in combination.
本発明において、必要に応じて使用される添加剤として
の光重合開始剤としてはイソブチルベンゾインエーテル
、イソプロピルベンゾインエーテル、ベンゾインエチル
エーテル、ベンゾインメチルエーテル等のベンゾインエ
ーテル型、ベンジル、２．２−ジメトキシ−２−フェニ
ルアセトフェノン、ヒドロキシシクロへキシルフェニル
ケトン等のベンジルケタノール型、ジェトキシアセトフ
ェノン、２−ヒドロキシ−２・メチルートフェニルプロ
パン−１−オン等のアセトフェノン誘導体、ベンゾフェ
ノン、クロロチオキサントン、２−クロロチオキサント
ン、イソプロピルチオキサントン等のケトン系、さらに
はこれと光重合を促進するための光増感剤として三級ア
ミンを併用してもよい。さらに製造時あるいは貯蔵中の
暗反応によるゲル化防止のためにハイドロキノン、ｐ−
ベンゾキノン、フェノチアジン、ｔブチルカテコール等
の熱重合禁止剤を添加してもよい。In the present invention, photopolymerization initiators as additives used as necessary include benzoin ether type, benzyl, 2,2-dimethoxy-, etc. 2-phenylacetophenone, benzylketanol type such as hydroxycyclohexylphenyl ketone, acetophenone derivatives such as jetoxyacetophenone, 2-hydroxy-2-methylphenylpropan-1-one, benzophenone, chlorothioxanthone, 2-chlorothioxanthone , a ketone such as isopropylthioxanthone, or a tertiary amine as a photosensitizer for promoting photopolymerization. In addition, hydroquinone, p-
A thermal polymerization inhibitor such as benzoquinone, phenothiazine, or t-butylcatechol may be added.
さらに印刷、塗工する際のインキ適性、塗装適性を与え
るために炭酸カルシウム、硫酸バリウム、アルミナ、タ
ルク等の体質顔料、さらに有機顔料、無機顔料を使用し
ても良く、エチレン性不飽和二重結合を有しない常温固
体の樹脂を溶解して併用してもよい。Furthermore, extender pigments such as calcium carbonate, barium sulfate, alumina, and talc, as well as organic pigments and inorganic pigments, may be used to provide ink suitability and painting suitability during printing and coating. A resin that is solid at room temperature and has no bond may be dissolved and used in combination.
本発明の活性エネルギー線硬化型被覆組成物の組成は、
塗料あるいは印刷インキの場合には、エチレン性不飽和
二重結合を有する化合物３０〜９５重量％、ヒンダード
アミン系紫外線安定剤０．１〜５重量％、光重合開始剤
０〜１０重量％、体質顔料、無機顔料または有機顔料な
どの各種添加剤０〜６０重量％である。The composition of the active energy ray-curable coating composition of the present invention is:
In the case of paint or printing ink, 30 to 95% by weight of a compound having an ethylenically unsaturated double bond, 0.1 to 5% by weight of a hindered amine ultraviolet stabilizer, 0 to 10% by weight of a photopolymerization initiator, and an extender pigment. , 0 to 60% by weight of various additives such as inorganic pigments or organic pigments.
本発明の被覆組成物は、特にポリエチレン、ポリ塩化ビ
ニル、ポリプロピレン、ポリエステル、ポリカーボネー
ト、ポリイミドなどのフィルム、シートまたはその他の
成形品に適用すると優れた性能を示し、ビデオ、カセッ
トケート、コンパクトまたはミニフロッピーディスク用
ケースのポリプロピレン製シートへの平版インキ、ＯＰ
ニスとして耐摩擦性、スクラッチ性に優れている。The coating composition of the present invention exhibits excellent performance when applied to films, sheets or other molded articles, particularly of polyethylene, polyvinyl chloride, polypropylene, polyester, polycarbonate, polyimide, etc. Lithographic ink on polypropylene sheet for disc case, OP
As a varnish, it has excellent abrasion resistance and scratch resistance.
また、本発明の被覆組成物は、平版インキ、樹脂凸版イ
ンキ、スクリーンインキ、ＯＰニス、塗料として使用さ
れる。Furthermore, the coating composition of the present invention can be used as lithographic ink, resin letterpress ink, screen ink, OP varnish, and paint.
次に本発明を更に具体的に説明するために以下に実施例
を示す。例中「部」、「％」とは重量部、重量％を示す
。Next, Examples will be shown below to further specifically explain the present invention. In the examples, "part" and "%" indicate parts by weight and weight %.
合成例
攪拌棒、温度計、空気吹込管、エステル管を備えた４つ
ロフラスコ中にネオペンチルグリコール２０８部、テレ
フタル酸１６６部、トルエン４０部、パラトルエンスル
ホン酸０．９部、次亜リン酸０．９部を仕込み、窒素ガ
スを吹込みながら、１８０℃まで加熱し、６時間反応さ
せる。反応は酸価１０以下になるまで継続する。次いで
アクリル酸１４２部、シクロヘキサン５４部、ハイドロ
キノン０．１部を加え、１００℃で反応を続け、酸価２
５．０以下になるまで継続した後、減圧下でトルエン、
シクロヘキサンを除去する。次いで新中村化学製モノマ
ーＡ−ＢＰＥ−４１００部を加えて組成物Ｉを得た。Synthesis Example 208 parts of neopentyl glycol, 166 parts of terephthalic acid, 40 parts of toluene, 0.9 part of para-toluenesulfonic acid, hypophosphorous acid in a four-bottle flask equipped with a stirring bar, thermometer, air blowing tube, and ester tube. Add 0.9 part of the mixture, heat to 180° C. while blowing nitrogen gas, and react for 6 hours. The reaction continues until the acid value becomes 10 or less. Next, 142 parts of acrylic acid, 54 parts of cyclohexane, and 0.1 part of hydroquinone were added, and the reaction was continued at 100°C until the acid value reached 2.
After continuing until it becomes 5.0 or less, add toluene under reduced pressure,
Remove cyclohexane. Next, 100 parts of monomer A-BPE-4 manufactured by Shin Nakamura Chemical Co., Ltd. was added to obtain Composition I.
組成物■は酸価２１．０．２５℃における粘度１５００
ポイズの粘調な液体であった。Composition (1) has an acid value of 21 and a viscosity of 1500 at 0.25°C.
It was a viscous liquid of poise.
実施例】
合成例の組成物１３９．９部、シリコンアクリレート（
エベクリル３６０、ＵＣＢ社製商品名）０．５部、アク
リル系モノマ−（ＯＴＡ４８０、ＵＣＢ社製商品名）９
．５部、チタンホワイト４５部、紫外線開始剤（イルガ
キュア６５１、チバガイギー社製商品名）５部、ハイド
ロキノン０．１部、ビス（２，２゜６．６−テトラメチ
ル−４−ピペリジル）セバケート１部を常法により３本
ロールミルにて混練し、インキＡ−１を得た。Example] 139.9 parts of the composition of the synthesis example, silicon acrylate (
Ebecryl 360 (trade name manufactured by UCB) 0.5 part, acrylic monomer (OTA480, trade name manufactured by UCB) 9
．． 5 parts, titanium white 45 parts, ultraviolet initiator (Irgacure 651, trade name manufactured by Ciba Geigy) 5 parts, hydroquinone 0.1 part, bis(2,2゜6.6-tetramethyl-4-piperidyl) sebacate 1 part were kneaded in a three-roll mill in a conventional manner to obtain ink A-1.
実施例２
合成例１の組成物１６９．４部、アクリル系モノマー（
三菱油化製５Ａ−１００２商品名）２３．５部、イルガ
キュア６５１５部、ハイドロキノン０．１部 エベクリ
ル３６０２．０部コハク酸ジメチルート（２−ヒドロキ
シエチル）−４＝、（ヒドロキシ−２，２，６，６−チ
トラメチルピペリジン重縮合物２部を３本ロールミルに
て混練し、ＯＰニスＢ−１を得た。Example 2 169.4 parts of the composition of Synthesis Example 1, acrylic monomer (
Mitsubishi Yuka 5A-1002 (trade name) 23.5 parts, Irgacure 6515 parts, hydroquinone 0.1 part Ebecryl 3602.0 parts Dimethyl succinate (2-hydroxyethyl)-4=, (hydroxy-2,2,6 , 2 parts of 6-titramethylpiperidine polycondensate were kneaded in a three-roll mill to obtain OP varnish B-1.
比較例１
インキＡ−１を作製する際に紫外線安定剤を加えないも
のをインキＡ−２とする。Comparative Example 1 Ink A-2 was prepared without adding an ultraviolet stabilizer to Ink A-1.
比較例２
０ＰニスＢ−１を作製する際に紫外線安定剤を加えない
ものをＯＰニスＢ−２とする。Comparative Example 2 OP varnish B-2 was prepared without adding an ultraviolet stabilizer when producing OP varnish B-1.
比較例３
インキＡ−１を作製する際の紫外線安定剤としてニッケ
ル系の紫外線安定剤にッケルビス（オクチルフェニル）
サルファイドを用いた以外は同様にして得たものをイン
キＡ−３とする。Comparative Example 3 Nickel bis(octylphenyl) was added to the nickel-based UV stabilizer as a UV stabilizer when producing Ink A-1.
Ink A-3 was obtained in the same manner except that sulfide was used.
以上のインキおよびＯＰニスをＲ１テスターにて全面ロ
ール０．３ｃｃを被印刷体に展色側を行う。紫外線照射
は水銀空冷ランプ１２０Ｗ／ａｍ ｌ灯にて通過速度２
０ｍ／分の条件にて行った。表中接着性は、セロファン
粘着テープによる基盤目テストの結果であり、○は実用
上使用範囲にあること、Δは問題はあるが実用に供する
ことのできることを示す。The above ink and OP varnish were spread on a printing medium using a 0.3 cc roll of the entire surface using an R1 tester. Ultraviolet irradiation was performed using a mercury air-cooled lamp of 120 W/aml at a passing speed of 2.
The test was carried out at a speed of 0 m/min. The adhesion properties in the table are the results of a substrate test using cellophane adhesive tape, where ◯ indicates that it is within the range of practical use, and ∆ indicates that it can be used for practical use although there are problems.
また、促進テストはアトラスフェトメーターにて７２時
間試験後行った。以下に評価結果を表１に示す。Further, the accelerated test was conducted after 72 hours of testing using an Atlas fetometer. The evaluation results are shown in Table 1 below.
なお、インキＡ−３は、インキＡ−２と同様の結果であ
った。Note that ink A-3 gave similar results to ink A-2.
特に、本発明の被覆剤は、ビデオカセット、コンパクト
フロッピーディスク、ミニフロッピーディスク用ケース
のポリプロピレン製シートまたはフィルムに対して有用
である。この印刷物または塗装物としては、接着性、耐
摩擦性、スクラッチ性が要求されているが、満足し得る
被覆剤がほとんどないのが実状であったため、好ましい
適用対象である。In particular, the coatings of the present invention are useful for polypropylene sheets or films for cases for video cassettes, compact floppy disks, and mini-floppy disks. Adhesion, abrasion resistance, and scratch resistance are required for printed matter or painted objects, but in reality there are almost no coating materials that can satisfy these requirements, so this is a preferable application target.
Claims (1)
要に応じて光重合開始剤、並びにヒンダードアミン系紫
外線安定剤を０．１〜５重量％含有することを特徴とす
る活性エネルギー線硬化型被覆組成物。 ２、ビデオカセット、コンパクトフロッピーディスクま
たはミニフロッピーディスク用ケースのポリプロピレン
製板、フィルムまたはシート用である請求項１記載の被
覆組成物。[Claims] 1. An activity characterized by containing 0.1 to 5% by weight of a compound having an ethylenically unsaturated double bond, optionally a photopolymerization initiator, and a hindered amine ultraviolet stabilizer. Energy ray curable coating composition. 2. The coating composition according to claim 1, which is used for polypropylene plates, films, or sheets of cases for video cassettes, compact floppy disks, or mini-floppy disks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8016989A JPH02255772A (en) | 1989-03-30 | 1989-03-30 | Covering composition of active energy ray-hardening type |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8016989A JPH02255772A (en) | 1989-03-30 | 1989-03-30 | Covering composition of active energy ray-hardening type |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02255772A true JPH02255772A (en) | 1990-10-16 |
Family
ID=13710825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8016989A Pending JPH02255772A (en) | 1989-03-30 | 1989-03-30 | Covering composition of active energy ray-hardening type |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02255772A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03140380A (en) * | 1989-10-26 | 1991-06-14 | Dainippon Printing Co Ltd | Composition for forming surface protective film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59138205A (en) * | 1983-01-20 | 1984-08-08 | チバ−ガイギ− アクチエンゲゼルシヤフト | Coating composition and curing method |
| JPS59184227A (en) * | 1983-04-04 | 1984-10-19 | Mitsubishi Chem Ind Ltd | Film-forming composition and surface modification of synthetic resin molding by using same |
| JPS621402A (en) * | 1985-06-26 | 1987-01-07 | Hitachi Ltd | Gas-liquid contact device |
| JPS629124A (en) * | 1985-07-03 | 1987-01-17 | Hitachi Ltd | Gas turbine combustor |
| JPS6386763A (en) * | 1986-09-30 | 1988-04-18 | Mitsubishi Rayon Co Ltd | Coating material composition for forming cured coating film |
| JPH02129235A (en) * | 1988-11-08 | 1990-05-17 | Mitsubishi Rayon Co Ltd | Preparation of coating composition and wear-resistant synthetic resin molded item |
-
1989
- 1989-03-30 JP JP8016989A patent/JPH02255772A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59138205A (en) * | 1983-01-20 | 1984-08-08 | チバ−ガイギ− アクチエンゲゼルシヤフト | Coating composition and curing method |
| JPS59184227A (en) * | 1983-04-04 | 1984-10-19 | Mitsubishi Chem Ind Ltd | Film-forming composition and surface modification of synthetic resin molding by using same |
| JPS621402A (en) * | 1985-06-26 | 1987-01-07 | Hitachi Ltd | Gas-liquid contact device |
| JPS629124A (en) * | 1985-07-03 | 1987-01-17 | Hitachi Ltd | Gas turbine combustor |
| JPS6386763A (en) * | 1986-09-30 | 1988-04-18 | Mitsubishi Rayon Co Ltd | Coating material composition for forming cured coating film |
| JPH02129235A (en) * | 1988-11-08 | 1990-05-17 | Mitsubishi Rayon Co Ltd | Preparation of coating composition and wear-resistant synthetic resin molded item |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03140380A (en) * | 1989-10-26 | 1991-06-14 | Dainippon Printing Co Ltd | Composition for forming surface protective film |
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