JP4740661B2 - Photo-curing primer for ethylene resin - Google Patents
Photo-curing primer for ethylene resin Download PDFInfo
- Publication number
- JP4740661B2 JP4740661B2 JP2005186413A JP2005186413A JP4740661B2 JP 4740661 B2 JP4740661 B2 JP 4740661B2 JP 2005186413 A JP2005186413 A JP 2005186413A JP 2005186413 A JP2005186413 A JP 2005186413A JP 4740661 B2 JP4740661 B2 JP 4740661B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- resin
- ethylene
- acrylate
- meth
- 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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- 229920005989 resin Polymers 0.000 title claims description 194
- 239000011347 resin Substances 0.000 title claims description 194
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 77
- 239000005977 Ethylene Substances 0.000 title claims description 77
- 238000000016 photochemical curing Methods 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims description 107
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 106
- 229920001971 elastomer Polymers 0.000 claims description 49
- 239000000806 elastomer Substances 0.000 claims description 47
- 239000003999 initiator Substances 0.000 claims description 42
- 239000003960 organic solvent Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 description 82
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 75
- -1 polyethylene terephthalate Polymers 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 238000004519 manufacturing process Methods 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 27
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 26
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000003505 polymerization initiator Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 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 15
- 239000000243 solution Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 229920000180 alkyd Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
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- 239000003921 oil Substances 0.000 description 8
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- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 150000001451 organic peroxides Chemical class 0.000 description 7
- 229940059574 pentaerithrityl Drugs 0.000 description 7
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
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- 239000003925 fat Substances 0.000 description 3
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
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- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
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- 125000002889 tridecyl 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])[H] 0.000 description 1
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Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Description
本発明は、スチレン系エラストマー、α，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー、光重合性不飽和結合を有する光重合性モノマーと、光重合開始剤からなるエチレン系樹脂用光硬化型プライマーに関する。さらに詳しくは、光硬化性に優れ、エチレン系樹脂に高い密着性を発現する光硬化型プライマーに関するものである。 The present invention relates to a copolymerizable monomer comprising a styrene-based elastomer, a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer, and a photopolymerizable property having a photopolymerizable unsaturated bond. The present invention relates to a photocurable primer for ethylene resin comprising a monomer and a photopolymerization initiator. More specifically, the present invention relates to a photocurable primer that is excellent in photocurability and exhibits high adhesion to an ethylene resin.
光硬化型樹脂は各種塗料、接着剤、印刷インキ、オーバープリント（ＯＰ）ニス等に幅広く用いられる。これら被塗工材料としては、金属、木、紙、プラスチック等があり、基本性能として基材への密着が必要である。プラスチックでは、アクリロニトリル−ブタジエン−スチレン共重合（ＡＢＳ）樹脂、ポリカーボネート（ＰＣ）樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、繊維強化複合材料（ＦＲＰ）等が主に使用されており、これらの光沢、意匠性付与、硬度、擦り傷性付与等の表面性を向上させる為に使用されている。また、これら基材への密着性を付与する目的でプライマーとしても使用されている。
光硬化型樹脂は、光で硬化するため加熱が不要で、硬化が数秒で完了するという特長から、生産性、省エネルギー性に優れる材料としても知られている。
近年では、被塗工材料にポリオレフィンが使用されてきている。しかしながら、これらに十分な密着力を発現するものがなく、例えばこれまでいくつかの提案がなされているが（特許文献１，２）、実用的に未だ満足すべきものはない。また、被塗工材料がエチレン系の樹脂になると前記提案された材料でも殆ど密着するものはない。
The photo-curing resin is known as a material excellent in productivity and energy saving because it is cured by light and does not require heating and can be cured in a few seconds.
In recent years, polyolefin has been used as a material to be coated. However, none of them exhibit sufficient adhesion, and for example, some proposals have been made so far (Patent Documents 1 and 2). Further, when the material to be coated is an ethylene-based resin, there is hardly any of the proposed materials that are in close contact.
本発明の課題は、前記の背景技術に記載した問題点を解決し、エチレン系樹脂に優れた密着性を発現する光硬化型プライマーを提供することある。 The subject of this invention is providing the photocurable primer which solves the problem described in the said background art, and expresses the adhesiveness excellent in ethylene-type resin.
本発明者らは、前記課題を達成するために鋭意研究及び検討を重ねてきた結果、スチレン系エラストマー（Ａ）、α，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）、２〜６の光重合性不飽和結合を含みアクリル基を有する光重合性モノマー（Ｄ）と、光重合開始剤（Ｅ）からなる光硬化型プライマーを用いる事が、極めて有用なものであることを見出し、本発明を完成するに至った。
即ち、スチレン系エラストマー（Ａ）、α，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）、２〜６の光重合性不飽和結合を含みアクリル基を有する光重合性モノマー（Ｄ）と、光重合開始剤（Ｅ）からなり、（Ａ）のスチレン含有量が２〜５０重量％、かつ重量平均分子量（Ｍｗ）が１〜７０万のエチレン系樹脂用光硬化型プライマーである。
また、スチレン系エラストマー（Ａ）、共重合性モノマー（Ｂ）、光重合性モノマー（Ｄ）との割合が、（Ａ）／（Ｂ）＝９９．５／０．５〜３０／７０、（（Ａ）＋（Ｂ））／（Ｄ）＝９５／５〜３０／７０の重量比であるエチレン系樹脂用光硬化型プライマーが好ましい。
更に、有機溶媒（Ｆ）を含有してなるエチレン系樹脂用光硬化型プライマーである。
また、エチレン系樹脂上に本発明の光硬化型プライマーを塗布し、さらにこれに光を照射して硬化させたものを含む成型体であり、該エチレン系樹脂が発泡体であってもよい。
As a result of intensive studies and studies to achieve the above-mentioned problems, the present inventors have found that the styrene elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymerization are possible. A photopolymerizable monomer (B) comprising a photopolymerizable monomer, a photopolymerizable monomer (D) having a photopolymerizable unsaturated bond of 2 to 6 and having an acrylic group, and a photopolymerization initiator (E) It has been found that the use of a mold primer is extremely useful, and the present invention has been completed.
That is, a copolymerizable monomer (B) comprising a styrene elastomer (A), a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, and photopolymerizability of 2-6 It consists of a photopolymerizable monomer (D) having an unsaturated bond and an acrylic group, and a photopolymerization initiator (E), and (A) has a styrene content of 2 to 50% by weight and a weight average molecular weight (Mw). 1 to 70 thousands of e styrene-based resin for photocurable primer.
Moreover, the ratio with a styrene-type elastomer (A), a copolymerizable monomer (B), and a photopolymerizable monomer (D) is (A) / (B) = 99.5 / 0.5-30 / 70, ( (A) + (B)) / (D) = 95 / 5-30 / 70 The weight ratio of the photocuring primer for ethylene resins is preferable.
Furthermore, it is a photocurable primer for an ethylene-based resin comprising an organic solvent (F).
Moreover, it is a molding containing the thing which apply | coated the photocurable primer of this invention on ethylene-type resin, and also irradiated this with light and hardened | cured, and this ethylene-type resin may be a foam.
本発明により、エチレン系樹脂に優れた密着性を発現する光硬化型プライマーを得ることができる。 According to the present invention, a photocurable primer that exhibits excellent adhesion to an ethylene-based resin can be obtained.
以下に、本発明の詳細を説明する。 Details of the present invention will be described below.
＜スチレン系エラストマー（Ａ）＞
本発明に用いられるスチレン系エラストマー（Ａ）としては、スチレン−共役ジエンブロック共重合体、スチレン−共役ジエンランダム共重合体、およびこれら共重合体の水素添加物等が挙げられる。スチレン−共役ジエンブロック共重合体の水素添加物の構成としては、スチレン−共役ジエンのジブロック共重合体、スチレン−共役ジエン−スチレンのトリブロック共重合体、およびこれら共重合体の水素添加物等が挙げられる。ここで用いられる共役ジエンとしては、ブタジエン、イソプレン等が挙げられる。中でも、スチレン−イソプレンのジブロック共重合体の水素添加物、スチレン−イソプレン−スチレンのトリブロック共重合体の水素添加物、スチレン−ブタジエンのジブロック共重合体の水素添加物、スチレン−ブタジエン−スチレンのトリブロック共重合体の水素添加物、スチレン−ブタジエンのランダム共重合体の水素添加物が好ましい。
<Styrene elastomer (A)>
Examples of the styrenic elastomer (A) used in the present invention include styrene-conjugated diene block copolymers, styrene-conjugated diene random copolymers, and hydrogenated products of these copolymers. The constitution of hydrogenated styrene-conjugated diene block copolymer is as follows: styrene-conjugated diene diblock copolymer, styrene-conjugated diene-styrene triblock copolymer, and hydrogenated products of these copolymers Etc. Examples of the conjugated diene used here include butadiene and isoprene. Among them, hydrogenated styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene-styrene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer, styrene-butadiene- A hydrogenated product of a styrene triblock copolymer and a hydrogenated product of a random copolymer of styrene-butadiene are preferred.
ここで用いられるスチレン系エラストマーは、そのスチレンの含有量が通常２〜５０重量％、好ましくは３〜４０重量％の範囲のものである。 また、ＧＰＣによる重量平均分子量（以下、Ｍｗと略記する）が１０，０００〜７００，０００の範囲が好ましく、スチレン−イソプレン−スチレン共重合体の水素添加物では１５，０００〜５００，０００、さらには２０，０００〜４００，０００が好ましい。また、スチレン−ブタジエン共重合体の水素添加物では１０，０００〜７００，０００、さらには５０，０００〜５００，０００が好ましい。前記のスチレン系エラストマー（Ａ）は、単独或いは２種以上併用することができる。 The styrene elastomer used here has a styrene content of usually 2 to 50% by weight, preferably 3 to 40% by weight. The weight average molecular weight by GPC (hereinafter abbreviated as Mw) is preferably in the range of 10,000 to 700,000, and in the case of hydrogenated styrene-isoprene-styrene copolymer, 15,000 to 500,000, Is preferably 20,000 to 400,000. Moreover, in the hydrogenated product of a styrene-butadiene copolymer, 10,000-700,000, Furthermore, 50,000-500,000 are preferable. The styrene elastomer (A) can be used alone or in combination of two or more.
＜共重合性モノマー（Ｂ）＞
本発明に用いられる、α，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）を以下に例示する。
<Copolymerizable monomer (B)>
Examples of the copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention are shown below.
α，β−モノエチレン性不飽和基を有する単量体として、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウロイル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、イソボロニル（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、ジシクロペンテニル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等の（メタ）アクリル酸エステル類、ヒドロキシエチルアクリレート、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、４−ヒドロキシブチルアクリレート、ラクトン変性ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート等の水酸基含有ビニル類、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸、フマル酸、ω−カルボキシ−ポリカプロラクトンモノアクリレート、フタル酸モノヒドロキシエチルアクリレート等のカルボキシル基含有ビニル類およびこれらのモノエステル化物、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート等のエポキシ基含有ビニル類、ビニルイソシアナート、イソプロペニルイソシアナート等のイソシアナート基含有ビニル類、スチレン、α−メチルスチレン、ビニルトルエン、ｔ−ブチルスチレン等の芳香族ビニル類、アクリルアミド、メタクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルアミド、マレイン酸アミド等のアミド類、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、Ｎ、Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ、Ｎ−ジエチルアミノエチル（メタアクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ、Ｎ−ジプロピルアミノエチル（メタ）アクリレート、Ｎ、Ｎ−ジブチルアミノエチル（メタ）アクリレート、Ｎ、Ｎ−ジヒドロキシエチルアミノエチル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート類、スチレンスルホン酸、スチレンスルホン酸ソーダ、２−アクリルアミド−２−メチルプロパンスルホン酸等の不飽和スルホン酸類、モノ（２−メタクリロイロキシエチル）アシッドホスフェート、モノ（２−アクリロイロキシエチル）アシッドホスフェート等の不飽和リン酸類、その他アクリロニトリル、メタクリルニトリル、２−メトキシエチルアクリレート、２−エトキシエチルアクリレート、エチレン、プロピレン、Ｃ４〜Ｃ２０のα−オレフィン、１，２，２，６，６−ペンタメチル−４−ピペリジル（メタ）アクリレート、２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、２−（２’−ヒドロキシ−５’−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等が挙げられる。また、前記単量体、或いはその共重合体をセグメントに有し、末端にビニル基を有するマクロモノマー類等も使用できる。 As monomers having α, β-monoethylenically unsaturated groups, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , Tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, pheny (Meth) acrylic acid such as ru (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Esters, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc. Hydroxyl group-containing vinyls, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxy ester Carboxyl group-containing vinyls such as acrylates and their monoesterified products, epoxy group-containing vinyls such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, isocyanate groups such as vinyl isocyanate and isopropenyl isocyanate Vinyls, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, amides such as acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, diacetoneacrylamide, maleic acid amide , Vinyl esters such as vinyl acetate and vinyl propionate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl) Aminoalkyl (meth) such as pill (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate Acrylates, styrene sulfonic acid, sodium styrene sulfonate, unsaturated sulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) Unsaturated phosphoric acids such as acid phosphate, other acrylonitrile, methacrylonitrile, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, ethylene, propylene, α-olefin of C 4 to C 20 , 1, 2, 2, 6, 6 -Penta Methyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole Etc. Moreover, the macromonomer etc. which have the said monomer or its copolymer in a segment, and have a vinyl group at the terminal can also be used.
本発明に用いられるその他共重合可能な単量体からなる共重合性モノマーとしては、無水マレイン酸、無水シトラコン酸等の無水カルボン酸類等が挙げられる。また、ここに記載されたメチル（メタ）アクリレートのような記載は、メチルアクリレート及びメチルメタアクリレートを示す。前記の共重合性モノマー（Ｂ）は、単独或いは２種以上併用することができる。 Examples of the copolymerizable monomer composed of other copolymerizable monomers used in the present invention include carboxylic anhydrides such as maleic anhydride and citraconic anhydride. Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate. The copolymerizable monomers (B) can be used alone or in combination of two or more.
＜重合体（Ｃ）＞
本発明で用いられる重合体（Ｃ）は、前記記載のα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）により構成される。本発明において、スチレン系エラストマー（Ａ）と、α，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）或いはこれらの重合体（Ｃ）の割合は、重量比で（Ａ）／（Ｂ）＝９９．５／０．５〜３０／７０、或いは（Ａ）／（Ｃ）＝９０／１０〜３０／７０、好ましくは（Ａ）／（Ｂ）＝９９／１〜４０／６０、或いは（Ａ）／（Ｃ）＝８５／１５〜４０／６０である。スチレン系エラストマー（Ａ）の含有量が少なくなる、或いはα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）或いはこれらの重合体（Ｃ）の含有量が多くなるとエチレン系樹脂との密着性が低下するものとなるため、前記範囲が好ましい。
<Polymer (C)>
The polymer (C) used in the present invention is composed of a copolymerizable monomer (B) comprising the above-mentioned monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer. Is done. In the present invention, a copolymerizable monomer (B) comprising a styrene elastomer (A), a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, or a polymer thereof. The ratio of (C) is (A) / (B) = 99.5 / 0.5 to 30/70, or (A) / (C) = 90/10 to 30/70, preferably ( A) / (B) = 99/1 to 40/60, or (A) / (C) = 85/15 to 40/60. Copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomer (B) or a styrene-based elastomer (A) content is reduced. The above-mentioned range is preferable because the adhesiveness to the ethylene resin is lowered when the content of the polymer (C) is increased.
また、（Ａ）／（Ｂ）＝９９．５／０．５〜９０／１０の範囲においては、共重合性モノマー（Ｂ）の中でも以下に挙げた共重合性モノマー（Ｂ１）を使用する事が好ましく、使用量としては、（Ｂ）中の３０〜１００重量％で使用する事が好ましい。（Ｂ１）は、単独或いは２種以上併用することができる。 In the range of (A) / (B) = 99.5 / 0.5 to 90/10, among the copolymerizable monomers (B), the following copolymerizable monomers (B1) should be used. It is preferable to use it in an amount of 30 to 100% by weight in (B). (B1) can be used alone or in combination of two or more.
共重合性モノマー（Ｂ１）としては、ヒドロキシエチルアクリレート、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、４−ヒドロキシブチルアクリレート、ラクトン変性ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート等の水酸基含有ビニル類、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸、フマル酸、ω−カルボキシ−ポリカプロラクトンモノアクリレート、フタル酸モノヒドロキシエチルアクリレート等のカルボキシル基含有ビニル類、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート等のエポキシ基含有ビニル類、アクリルアミド、メタクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルアミド、マレイン酸アミド等のアミド類、無水マレイン酸、無水シトラコン酸等の無水カルボン酸類等が挙げられる。 Examples of the copolymerizable monomer (B1) include hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy Hydroxyl group-containing vinyls such as -3-phenoxypropyl acrylate, carboxyl group-containing vinyls such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate, and monohydroxyethyl phthalate , Epoxy group-containing vinyls such as glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylo Le acrylamide, diacetone acrylamide, amides such as maleic acid amide, maleic anhydride, carboxylic anhydrides such as citraconic anhydride.
＜光重合性モノマー（Ｄ）＞
本発明における光重合性モノマー（Ｄ）は、２〜６の光重合性不飽和結合を含むものである。光重合性不飽和結合が１つの場合、プライマー内で架橋が起こらないため塗膜の強度が低くなり、高い密着力を発現しない。これに対し、光重合性不飽和結合を少なくとも２つ以上含有するものは、塗膜内部で架橋を起こすため塗膜の強度が高くなり、高い密着力を発現する。また、一部は基材と架橋を起こすため、密着力が向上する。
<Photopolymerizable monomer (D)>
Photopolymerizable monomer (D) in the present invention is a Dressings containing photopolymerizable unsaturated bonds 2-6. In the case where there is one photopolymerizable unsaturated bond, since no crosslinking occurs in the primer, the strength of the coating film is lowered and high adhesion is not exhibited. On the other hand, those containing at least two photopolymerizable unsaturated bonds cause cross-linking inside the coating film, so that the strength of the coating film is increased and high adhesion is exhibited. Moreover, since a part raise | generates a base material and bridge | crosslinking, adhesive force improves.
本発明における光重合性モノマー（Ｄ）としては、アクリル基を有する化合物である。例えば、ブタンジオールジ（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、１，６−へキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリ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、ビス（（メタ）アクリロキシエチル）ビスフェノールＡ、テトラエチレングリコールジアクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパンジトリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、エチレンオキサイド変性グリセリントリ（メタ）アクリレート、プロピレンオキサイド変性グリセリントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（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、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、これら（メタ）アクリレートの一部をアルキル基やε−カプロラクトンで置換した多官能（メタ）アクリレート、その他活性二重結合を持つトリエチレングリコールジビニルエーテル、ヒドロキシエチルジビニルエーテル、ジビニルベンゼン等が挙げられる。 The photopolymerizable monomer (D) in the present invention is a compound having an acrylic group. For example, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dimethylol tricyclodecanedi (Meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, bis ((meth) acryloxyethyl) bisphenol A, tetraethylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, ethylene Xoxide modified trimethylolpropane ditri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, ethylene oxide modified glycerin tri (meth) acrylate, propylene oxide modified glycerin tri (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, one of these (meth) acrylates Polyfunctional (meth) acrylate substituted with alkyl group or ε-caprolactone on the part, and other trie with active double bond Tylene glycol divinyl ether, hydroxyethyl divinyl ether, divinylbenzene and the like can be mentioned.
さらには、フタル酸、アジピン酸等の多塩基酸と、エチレングリコール、ブタジオール等の多価アルコールと、（メタ）アクリル酸化合物との反応で得られるポリエステルポリ（メタ）アクリレート、エポキシ樹脂と（メタ）アクリル酸化合物との反応で得られるエポキシポリ（メタ）アクリレート、ポリシロキサンと（メタ）アクリル酸化合物との反応によって得られるポリシロキサンポリ（メタ）アクリレート、ポリアミドと（メタ）アクリル酸化合物との反応によって得られるポリアミドポリ（メタ）アクリレート等が挙げられる。 Furthermore, polyester poly (meth) acrylate, epoxy resin (meta) obtained by reaction of polybasic acids such as phthalic acid and adipic acid, polyhydric alcohols such as ethylene glycol and butadiol, and (meth) acrylic acid compounds. ) Epoxy poly (meth) acrylate obtained by reaction with acrylic acid compound, polysiloxane poly (meth) acrylate obtained by reaction of polysiloxane and (meth) acrylic acid compound, polyamide and (meth) acrylic acid compound Examples thereof include polyamide poly (meth) acrylate obtained by the reaction.
本発明においては、前記光重合性モノマー（Ｄ）を１種以上適用するが、架橋を起こすため光重合性不飽和結合を３つ以上含有するものがより好ましい。これらの中でも、ウレタンアクリレート（Ｐ）、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（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、エチレンオキサイド変性トリメチロールプロパンジトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートが好ましく用いられる。 In the present invention, at least one photopolymerizable monomer (D) is applied, but it preferably contains three or more photopolymerizable unsaturated bonds in order to cause crosslinking. Among these, urethane acrylate (P), trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide modified trimethylolpropane ditri (meth) acrylate, dipentaerythritol Penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used.
ウレタンアクリレート（Ｐ）は、ジイソシアネート化合物とグリコール種の付加反応により重合を行い、残存するイソシアネート基にさらに水酸基等の活性水素基を有する（メタ）アクリレートを付加することで合成される。ジイソシアネート化合物は、例えば、ヘキサメチレンジイソシアネート（ＨＤＩ）、１，３−ジイソシアナトメチルシクロヘキサン（Ｈ6 ＸＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、トルエンジイソシアネート（ＴＤＩ）等が挙げられる。これらのなかでも、ヘキサメチレンジイソシアネート、１，３−ジイソシアナトメチルシクロヘキサン、イソホロンジイソシアネートが好ましい。 Urethane acrylate (P) is synthesized by performing polymerization by addition reaction of a diisocyanate compound and a glycol species, and further adding (meth) acrylate having an active hydrogen group such as a hydroxyl group to the remaining isocyanate group. Examples of the diisocyanate compound include hexamethylene diisocyanate (HDI), 1,3-diisocyanatomethylcyclohexane (H 6 XDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), and the like. Among these, hexamethylene diisocyanate, 1,3-diisocyanatomethylcyclohexane, and isophorone diisocyanate are preferable.
グリコール種は、例えば、ピバリン酸ネオペンチルグリコールエステル、ポリカプロラクトンポリオール等のポリエステルポリオール；ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等のポリエーテルポリオール；ポリヘキサメチレンカーボネートグリコール等のポリカーボネートポリオール；エチレングリコール、プロパンジオール、１，４−ブチレングリコール、１，３−ブチレングリコール、１，２−ブチレングリコール、１，６−ヘキサンジオール、メチルペンタンジオール、ネオペンチルグリコール、３，３−ジメチロールヘプタン、炭素数が７〜２２のアルカンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、シクロヘキサンジメタノール、炭素数が１７〜２０のアルカン−１，２−ジオール、水素化ビスフェノールＡ、１，４−ジヒドロキシ−２−ブテン、２，６−ジメチル−１−オクテン−３，８−ジオール、ビスフェノールＡ、グリセリン、２−メチル−２−ヒドロキシメチル−１，３−プロパンジオール、２，４−ジヒドロキシ−３−ヒドロキシメチルペンタン、１，２，６−ヘキサントリオール、１，１，１−トリス（ヒドロキシメチル）プロパン、２，２−ビス（ヒドロキシメチル）−３−ブタノール、その他の炭素数が８〜２４の脂肪族トリオール、テトラメチロールメタン、Ｄ−ソルビトール、キシリトール、Ｄ−マンニトール、Ｄ−マンニット等である。水酸基等の活性水素基を有する（メタ）アクリレートとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有ビニル類が挙げられる。 Examples of the glycol species include polyester polyols such as pivalic acid neopentyl glycol ester and polycaprolactone polyol; polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol; polycarbonate polyols such as polyhexamethylene carbonate glycol; ethylene glycol Propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, methylpentanediol, neopentyl glycol, 3,3-dimethylolheptane, carbon number 7-22 alkanediol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol Alkane-1,2-diol having 17 to 20 carbon atoms, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, glycerin 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane 2,2-bis (hydroxymethyl) -3-butanol, other aliphatic triols having 8 to 24 carbon atoms, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol, D-mannitol and the like. Examples of the (meth) acrylate having an active hydrogen group such as a hydroxyl group include hydroxyl group-containing vinyls such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. .
本発明の光重合性モノマー（Ｄ）の使用量は、エチレン系樹脂への優れた密着性を発現させるため、通常、スチレン系エラストマー（Ａ）とα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）或いはこれらの重合体（Ｃ）に対して、重量比で（（Ａ）＋（Ｂ））／（Ｄ）＝９５／５〜３０／７０、或いは（（Ａ）＋（Ｃ））／（Ｄ）＝９５／５〜３０／７０、好ましくは（（Ａ）＋（Ｂ））／（Ｄ）＝９０／１０〜４０／６０、或いは（（Ａ）＋（Ｃ））／（Ｄ）＝９０／１０〜４０／６０である。 The amount of the photopolymerizable monomer (D) used in the present invention usually has a styrene elastomer (A) and an α, β-monoethylenically unsaturated group in order to develop excellent adhesion to an ethylene resin. ((A) + (B)) / (D) = weight ratio with respect to the copolymerizable monomer (B) comprising these monomers and other copolymerizable monomers, or these polymers (C). 95/5 to 30/70, or ((A) + (C)) / (D) = 95/5 to 30/70, preferably ((A) + (B)) / (D) = 90/10 -40/60 or ((A) + (C)) / (D) = 90 / 10-40 / 60.
＜光重合開始剤（Ｅ）＞
本発明の光重合開始剤（Ｅ）としては、紫外線、電子線、放射線等でラジカルを発生することが可能な化合物であり、具体例としては、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、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、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、ｐ−メトキシベンゾフェノン、ジエトキシアセトフェノン、２,２−ジメトキシ−２−フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、４,４−ビス（ジメチルアミノベンゾフェノン）、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン等のカルボニル類、ジフェニルジスルフィド、ジベンジルジスルフィド、テトラメチルチウラムジスルフィド等のスルフィド類、アゾビスイソブチロニトリル、アゾビス−２,４−ジメチルバレロニトリル等のアゾ類、ベンゾキノン、アントラキノン、クロロアントラキノン、エチルアントラキノン、ブチルアントラキノン等のキノン類、ベンゾイルパーオキシド、ジターシャリーブチルパーオキシド等のパーオキシド類、２,４,６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２,６−ジメトキシベンゾイル）−２,４,４−トリメチルペンチルホスフィンオキサイド等のアシルホスフィンオキサイド類、チオキサントン、２−メチルチオキサントン、２−クロロチオキサントン等のチオキサントン類等を挙げることができるが、これらは単独あるいは２種以上で併用してもよい。また、これらに、トリエチルアミン、トリメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、ピリジン、キノリン、トリメチルベンジルアンモニウムクロライド等のアミン類、トリフェニルホスフィン等のアリルホスフィン類、β−チオジグリコール等のチオールエーテル類等を併用しても良い。
<Photopolymerization initiator (E)>
The photopolymerization initiator (E) of the present invention is a compound capable of generating radicals by ultraviolet rays, electron beams, radiation, etc., and specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl. Ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4, 4-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydride Carbonyls such as xyl-2-methylpropan-1-one, sulfides such as diphenyl disulfide, dibenzyl disulfide and tetramethylthiuram disulfide, azo such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile Quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethylanthraquinone and butylanthraquinone, peroxides such as benzoyl peroxide and ditertiary butyl peroxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and other acylphosphine oxides, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone and other thiols Although xanthone etc. can be mentioned, these may be used alone or in combination of two or more. In addition, these include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline, trimethylbenzylammonium chloride, allylphosphines such as triphenylphosphine, thiol ethers such as β-thiodiglycol, etc. May be used in combination.
前記の中でも、ベンゾフェノン、メチルフェニルグリオキシレート、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２,４,６−トリメチルベンゾイルジフェニルホスフィンオキサイドが好ましく、これらを単独あるいは２種以上併用してもよい。 Among the above, benzophenone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable, These may be used alone or in combination of two or more.
前記光重合開始剤（Ｅ）の使用量は、スチレン系エラストマー（Ａ）とα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）或いはこれらの重合体（Ｃ）と（Ｄ）との総重量に対して、通常０．１〜２０重量％、好ましくは１〜１５重量％であり、更に好ましくは１〜１０重量％である。 The amount of the photopolymerization initiator (E) used is a copolymerizable monomer comprising a styrene elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers. (B) or the total weight of these polymers (C) and (D) is usually 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1 to 10% by weight. It is.
＜有機溶媒（Ｆ）＞
本発明に用いる有機溶媒（Ｆ）としては、キシレン、トルエン、エチルベンゼン等の芳香族炭化水素、ヘキサン、ヘプタン、オクタン、デカン、イソオクタン、イソデカン等の脂肪族炭化水素、シクロヘキサン、シクロヘキセン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素、酢酸エチル、ｎ−酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３メトキシブチルアセテート等のエステル系、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒等の有機溶剤を用いることができ、またこれらの２種以上からなる混合物であっても構わない。これらの中でも、芳香族炭化水素、脂肪族炭化水素、及び脂環式炭化水素が好ましく、脂肪族炭化水素、脂環式炭化水素がより好適に用いられる。有機溶媒の量は、スチレン系エラストマー（Ａ）を有機溶媒に溶解させたときの不揮発分が５〜６０重量％となる範囲で用いることができる。
<Organic solvent (F)>
Examples of the organic solvent (F) used in the present invention include aromatic hydrocarbons such as xylene, toluene and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane, decane, isooctane and isodecane, cyclohexane, cyclohexene, methylcyclohexane and ethyl. Cycloaliphatic hydrocarbons such as cyclohexane, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, etc., ketones such as methyl ethyl ketone, methyl isobutyl ketone An organic solvent such as a system solvent can be used, and a mixture of two or more of these may be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferably used. The amount of the organic solvent can be used in such a range that the nonvolatile content when the styrene elastomer (A) is dissolved in the organic solvent is 5 to 60% by weight.
本発明で用いる重合開始剤としては、ジ−ｔｅｒｔ−ブチルパーオキサイド、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウロイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエイト、２，５−ジメチル−２，５−ジ（パーオキシベンゾエート）ヘキシン−３、クメンハイドロパーオキサイド等の有機過酸化物、アゾビスイソブチロニトリル、４，４’−アゾビス（４−シアノペンタ酸）、２，２’−アゾビス（２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオアミド）等のアゾ化合物が挙げられる。これらは、単独或いは２種以上併用して用いることができる。 Examples of the polymerization initiator used in the present invention include di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, and tert-butyl peroxybenzo. Eight, organic peroxides such as 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, cumene hydroperoxide, azobisisobutyronitrile, 4,4′-azobis (4-cyanopenta Acid) and 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propioamide) and the like. These can be used alone or in combination of two or more.
また、更にラジカルを発生させて反応を行う場合のラジカル発生方法は、例えば、光重合開始剤（Ｅ）の存在下に光を照射する方法、又は有機過酸化物を添加する方法等、公知の方法を使用することができる。前記光重合開始剤（Ｅ）の使用量は、前記スチレン系エラストマー（Ａ）と、共重合性モノマー（Ｂ）或いは重合体（Ｃ）との総重量に対し、通常、０．０１〜１０重量％、より好ましくは０．１〜５重量％の範囲で用いる事で安定性に大きな効果が現れる。 Further, the radical generation method in the case of performing the reaction by further generating radicals is a known method such as a method of irradiating light in the presence of the photopolymerization initiator (E) or a method of adding an organic peroxide. The method can be used. The amount of the photopolymerization initiator (E) used is usually 0.01 to 10 weights with respect to the total weight of the styrene elastomer (A) and the copolymerizable monomer (B) or polymer (C). %, More preferably 0.1 to 5% by weight, a great effect on stability appears.
また、有機過酸化物としては、分子内にｔｅｒｔ−ブチル基及び／又はベンジル基を有する、ジ−ｔｅｒｔ−ブチルパーオキサイド、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエイト、ラウロイルパーオキサイド、クメンハイドロパーオキサイド等が挙げられる。これらは、単独あるいは２種以上を混合して用いることができる。
本発明では、前記した有機過酸化物のうちでも、ジ−ｔｅｒｔ−ブチルパーオキサイドやｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエートがより好適に用いられる。すなわち、分子内にｔｅｒｔ−ブチル基及び／又はベンジル基を有する有機過酸化物は水素引抜能力が比較的高く、スチレン系エラストマーとのグラフト率を向上させる効果がある。
Organic peroxides include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dioctyl having a tert-butyl group and / or a benzyl group in the molecule. Milperoxide, tert-butylperoxybenzoate, lauroyl peroxide, cumene hydroperoxide and the like can be mentioned. These can be used alone or in admixture of two or more.
In the present invention, among the above-described organic peroxides, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are more preferably used. That is, an organic peroxide having a tert-butyl group and / or a benzyl group in the molecule has a relatively high hydrogen abstraction ability, and has an effect of improving the graft ratio with the styrene elastomer.
前記有機過酸化物の使用量は、スチレン系エラストマー（Ａ）と、共重合性モノマー（Ｂ）或いは重合体（Ｃ）との総重量に対し、通常２〜５０重量％、より好ましくは３〜３０重量％の範囲で用いる事で安定性に大きな効果が現れる。前記した範囲で有機過酸化物を使用する場合は、なるべく時間をかけ、これを少量ずつ添加することが好ましい。 The amount of the organic peroxide used is usually 2 to 50% by weight, more preferably 3 to the total weight of the styrene elastomer (A) and the copolymerizable monomer (B) or polymer (C). When used in the range of 30% by weight, a great effect on stability appears. When using an organic peroxide in the above-mentioned range, it is preferable to spend as much time as possible and add it little by little.
本発明のエチレン系樹脂用光硬化型プライマーを得る方法としては、（１）有機溶媒中、スチレン系エラストマー（Ａ）にα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）と重合開始剤をフィードしながら重合せしめたものに、或いは（２）有機溶媒中、スチレン系エラストマー（Ａ）とα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）に、重合開始剤をフィードしながら重合せしめたものに、光重合性不飽和結合を有する光重合性モノマー（Ｄ）と光重合開始剤（Ｅ）を混合して製造することができる。また、（３）有機溶媒中、スチレン系エラストマー（Ａ）にα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）と重合開始剤をフィードしながら重合せしめた後、或いは（４）有機溶媒中、スチレン系エラストマー（Ａ）とα，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）に、重合開始剤をフィードしながら重合せしめた後、更にラジカルを発生させ反応を行ったものに、光重合性不飽和結合を有する光重合性モノマー（Ｄ）と光重合開始剤（Ｅ）を混合して製造することができる。また、（５）有機溶媒中、スチレン系エラストマー（Ａ）と、α，β−モノエチレン性不飽和基を有する単量体及びその他共重合可能な単量体からなる共重合性モノマー（Ｂ）で構成された重合体（Ｃ）とをラジカルを発生させ反応を行ったものに、光重合性不飽和結合を有する光重合性モノマー（Ｄ）と光重合開始剤（Ｅ）を混合して製造することができる。さらには、前記のスチレン系エラストマーの代わりに、共重合性モノマー（Ｂ１）が一部に反応したスチレン系エラストマーを用いて製造することもできる。 As a method for obtaining the photocurable primer for ethylene resin of the present invention, (1) a monomer having an α, β-monoethylenically unsaturated group in styrene elastomer (A) and other copolymer in an organic solvent Copolymerizable monomer (B) composed of possible monomers and polymerized while feeding polymerization initiator, or (2) Styrenic elastomer (A) and α, β-monoethylenic in organic solvent Light having a photopolymerizable unsaturated bond is obtained by polymerizing a monomer having an unsaturated group and another copolymerizable monomer (B) while feeding a polymerization initiator to the copolymerizable monomer (B). It can be produced by mixing the polymerizable monomer (D) and the photopolymerization initiator (E). (3) a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers in the styrene elastomer (A) in an organic solvent; After polymerization while feeding a polymerization initiator, or (4) a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers in an organic solvent with a styrene elastomer (A) After the polymerization is carried out while feeding the polymerization initiator to the copolymerizable monomer (B) consisting of a polymer, a radical is further generated to react with the photopolymerizable monomer having a photopolymerizable unsaturated bond (D ) And a photopolymerization initiator (E). (5) a copolymerizable monomer (B) comprising a styrene elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers in an organic solvent; Produced by mixing a polymer (C) composed of a photopolymerizable monomer (D) having a photopolymerizable unsaturated bond and a photopolymerization initiator (E) with a radical generated and reacted. can do. Furthermore, it can also be produced using a styrene elastomer in which the copolymerizable monomer (B1) has partially reacted instead of the styrene elastomer.
本発明のエチレン系樹脂用光硬化型プライマーを製造するにあたり、油脂類、油脂類の誘導体、エポキシ樹脂、ポリエステルからなる群から選ばれる少なくとも１つ以上を第３成分として用いることができる。第３成分として用いられる油脂類としては、アマニ油、大豆油、ヒマシ油及びこれらの精製物が挙げられる。
第３成分として用いられる油脂類の誘導体としては、無水フタル酸等の多塩基酸とグリセリン、ペンタエリスリトール、エチレングリコール等の多価アルコールを骨格としたものを油脂（脂肪酸）で変性した短油アルキッド樹脂、中油アルキッド樹脂、長油アルキッド樹脂等、或いはこれにさらに天然樹脂、合成樹脂および重合性モノマーで変性したロジン変性アルキッド樹脂、フェノール変性アルキッド樹脂、エポキシ変性アルキッド樹脂、アクリル化アルキッド樹脂、ウレタン変性アルキッド樹脂等が挙げられる。
In producing the photocurable primer for ethylene resin of the present invention, at least one selected from the group consisting of fats and oils, derivatives of fats and oils, epoxy resins, and polyesters can be used as the third component. Examples of the fats and oils used as the third component include linseed oil, soybean oil, castor oil, and purified products thereof.
Oils and fats used as the third component are short oil alkyds obtained by modifying polybasic acids such as phthalic anhydride and polyhydric alcohols such as glycerin, pentaerythritol and ethylene glycol with oils (fatty acids). Resin, medium oil alkyd resin, long oil alkyd resin, etc., or rosin modified alkyd resin modified with natural resin, synthetic resin and polymerizable monomer, phenol modified alkyd resin, epoxy modified alkyd resin, acrylated alkyd resin, urethane modified Examples include alkyd resins.
また、第３成分として用いられるエポキシ樹脂としては、ビスフェノールＡ、ビスフェノールＦ、ノボラック等をグリシジルエーテル化したエポキシ樹脂、ビスフェノールＡにプロピレンオキサイド、またはエチレンオキサイドを付加しグリシジルエーテル化したエポキシ樹脂等を挙げることができる。また、多官能アミンをエポキシ基に付加したアミン変性エポキシ樹脂等を用いても良い。さらに、脂肪族エポキシ樹脂、脂環エポキシ樹脂、ポリエーテル系エポキシ樹脂等が挙げられる。 Examples of the epoxy resin used as the third component include an epoxy resin obtained by glycidyl etherification of bisphenol A, bisphenol F, novolac, etc., an epoxy resin obtained by adding propylene oxide or ethylene oxide to bisphenol A, and the like. be able to. Moreover, you may use the amine modified epoxy resin etc. which added the polyfunctional amine to the epoxy group. Furthermore, an aliphatic epoxy resin, an alicyclic epoxy resin, a polyether type epoxy resin, etc. are mentioned.
また、第３成分として用いられるポリエステルは、カルボン酸成分とアルコール成分を縮重合したものであり、カルボン酸成分として例えば、テレフタル酸、イソフタル酸、無水フタル酸、ナフタレンジカルボン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、１，１０−デカンジカルボン酸、シクロヘキサンジカルボン酸、トリメリット酸、マレイン酸、フマル酸等の多価カルボン酸およびその低級アルコールエステル、パラオキシ安息香酸等のヒドロキシカルボン酸、および安息香酸等の１価カルボン酸等を用いる事ができ、また２種類以上併用する事も可能である。 The polyester used as the third component is obtained by condensation polymerization of a carboxylic acid component and an alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, succinic acid, and glutaric acid. Adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, polyvalent carboxylic acid such as trimellitic acid, maleic acid, fumaric acid and the like, lower alcohol ester thereof, hydroxycarboxylic acid such as paraoxybenzoic acid, and Monovalent carboxylic acids such as benzoic acid can be used, and two or more kinds can be used in combination.
また、アルコール成分として例えば、エチレングリコール、ジエチレングリコール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，１０−デカンジオール、３−メチル−ペンタンジオール、２，２’−ジエチル−１，３−プロパンジオール、２−エチル−１，３−ヘキサンジオール、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＡのプロピレンオキサイド付加物、水添ビスフェノールＡのエチレンオキサイド付加物、水添ビスフェノールＡのプロピレンオキサイド付加物等を用いることができ、また２種類以上併用する事も可能である。 Examples of the alcohol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 -Decanediol, 3-methyl-pentanediol, 2,2'-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, Pentaerythritol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, etc. can be used. It is also possible to use.
また、水酸基を有する前記ポリエステルに、分子内に重合性不飽和結合を有する無水カルボン酸を付加させることによって得られた分子内に重合性不飽和結合を含有させた樹脂も使用可能である。前記、第３成分は、１種類でも使用できるし、２種類以上で併用しても何ら構わない。また、反応器中へフィードしながら添加することも、また最初に反応器内に仕込んで使用することも可能である。また第３成分の添加量は、樹脂成分に対し通常０．５〜６０重量％、好ましくは２〜４０重量％で用いる。特に、第３成分として油脂類及び油脂類の誘導体を用いて得られた樹脂改質剤は、とりわけエチレン系樹脂との相溶性が良く、塗料との密着が良好で、特にヒマシ油を含むものは効果が大きい。
以上説明したような方法で得られたエチレン系樹脂用光硬化型プライマーについては、例えば、反応時の溶媒を脱溶媒した後、所望の溶剤を添加して樹脂を溶解・分散させる方法、或いは所望の溶媒を添加した後、反応時の溶媒を脱溶媒する方法等により、所望の溶媒組成の樹脂溶液に変更することもできる。
Moreover, the resin which contained the polymerizable unsaturated bond in the molecule | numerator obtained by adding the carboxylic anhydride which has a polymerizable unsaturated bond in a molecule | numerator to the said polyester which has a hydroxyl group can also be used. The third component can be used alone or in combination of two or more. Further, it can be added while being fed into the reactor, or it can be first charged into the reactor and used. The amount of the third component added is usually 0.5 to 60% by weight, preferably 2 to 40% by weight, based on the resin component. In particular, resin modifiers obtained using oils and fats and derivatives of oils as the third component are particularly compatible with ethylene resins, have good adhesion to paints, and particularly contain castor oil Is very effective.
For the photocurable primer for ethylene resin obtained by the method as described above, for example, after removing the solvent at the time of reaction, a desired solvent is added to dissolve or disperse the resin, or desired After adding the solvent, it can be changed to a resin solution having a desired solvent composition by a method of removing the solvent during the reaction or the like.
本発明のエチレン系樹脂用光硬化型プライマーは、必要に応じて、アゾ顔料、フタロシアニンブルー等の有機顔料、アゾ染料、アントラキノン系染料等の染料、酸化チタン、モリブデン、カーボンブラック等の無機顔料等の着色剤、重合禁止剤、光安定剤、酸化防止剤、黄変防止剤、耐候安定剤、耐熱防止剤等の各種安定剤、消泡剤、増粘剤、沈降防止剤、帯電防止剤、防曇剤、分散剤、湿潤剤、界面活性剤、防カビ剤、抗菌剤、防腐剤、触媒、充填剤、ワックス、ブロッキング防止剤、だれ防止剤、カップリング剤、可塑剤、レベリング剤、ハジキ防止剤、スリップ剤等の成分を含有させることができる。 The photo-curing primer for ethylene resin of the present invention includes organic pigments such as azo pigments and phthalocyanine blue, dyes such as azo dyes and anthraquinone dyes, inorganic pigments such as titanium oxide, molybdenum, and carbon black as necessary. Colorants, polymerization inhibitors, light stabilizers, antioxidants, yellowing inhibitors, weathering stabilizers, heat stabilizers and other stabilizers, antifoaming agents, thickeners, antisettling agents, antistatic agents, Antifogging agent, dispersant, wetting agent, surfactant, antifungal agent, antibacterial agent, antiseptic, catalyst, filler, wax, antiblocking agent, anti-dripping agent, coupling agent, plasticizer, leveling agent, repellent Components such as an inhibitor and a slip agent can be contained.
本発明の光硬化型プライマーをエチレン系樹脂の成型体に塗布する方法に限定はなく、ハケ塗り、スプレーコート、ディップコート、ロールコートなどの常法によって行われる。塗布は通常、常温にて容易に行なうことができ、塗布後に紫外線を照射するのが好適である。膜厚は、優れた密着性を発現させるために乾燥後の膜厚が０．０１〜５０μｍのものが好ましく、更には０．０５〜３０μｍが好ましい。また、乾燥方法についても特に限定はなく、自然乾燥や加熱強制乾燥等、適宜の方法で乾燥することができる。 There is no limitation on the method of applying the photocurable primer of the present invention to a molded body of an ethylene resin, and it is carried out by a conventional method such as brush coating, spray coating, dip coating or roll coating. Application can usually be easily performed at room temperature, and it is preferable to irradiate ultraviolet rays after application. The film thickness is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm after drying in order to develop excellent adhesion. Moreover, there is no limitation in particular also about the drying method, It can dry by appropriate methods, such as natural drying and heat forced drying.
成型体に塗布された被膜を硬化させる手段としては、紫外線、電子線、放射線等の活性エネルギー線を照射する公知の方法を用いることができ、紫外線発生源としては実用的、経済性の面から紫外線ランプが一般に用いられている。具体的には、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、ガリウムランプ、メタルハライドランプ、太陽光等の紫外線などが挙げられる。照射雰囲気は空気でもよいし、窒素、アルゴン等の不活性ガスでもよい。また、前記の塗膜に紫外線を照射する方法について特に限定はなく、被塗物が変形したり、変色したりしない程度の強度で照射する。 As a means for curing the coating applied to the molded body, a known method of irradiating active energy rays such as ultraviolet rays, electron beams, and radiations can be used, and the ultraviolet ray generation source is practical and economical. An ultraviolet lamp is generally used. Specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, and ultraviolet rays such as sunlight. The irradiation atmosphere may be air or an inert gas such as nitrogen or argon. Moreover, there is no limitation in particular about the method of irradiating the said coating film with an ultraviolet-ray, It irradiates with the intensity | strength of the grade which a to-be-coated article does not deform | transform or discolor.
本発明のエチレン系樹脂用光硬化型プライマーは、その特徴からエチレン系樹脂に高い密着力を示す。エチレン系樹脂とは、エチレン骨格を含有する樹脂からなり、例えば、ポリエチレン、エチレン−プロピレン、エチレン−ブテン、エチレン−オクテン、エチレン−プロピレン−ブテン、エチレン−酢酸ビニル、エチレン−アクリル酸、エチレン−メタクリル酸、エチレン−トリシクロデカン、エチレン−テトラシクロドデセン、エチレン−プロピレン−ヘキサジエン、エチレン−プロピレン−エチリデンノルボルネン、エチレン−プロピレン−シクロペンタジエン等である。 The photocurable primer for ethylene resins of the present invention exhibits high adhesion to ethylene resins due to its characteristics. The ethylene-based resin is made of a resin containing an ethylene skeleton, such as polyethylene, ethylene-propylene, ethylene-butene, ethylene-octene, ethylene-propylene-butene, ethylene-vinyl acetate, ethylene-acrylic acid, ethylene-methacrylic. Examples thereof include acids, ethylene-tricyclodecane, ethylene-tetracyclododecene, ethylene-propylene-hexadiene, ethylene-propylene-ethylidene norbornene, and ethylene-propylene-cyclopentadiene.
本発明のエチレン系樹脂用光硬化型プライマーは、前記エチレン系樹脂からなるシート状成型体、フィルム状成型体、各種射出成型体、或いはこれらに合成ゴム等を含有する樹脂からなるシート状成型体、フィルム状成型体、各種射出成型体、或いはこれらの発泡体等に優れた密着力を発現する。なかでも、ポリエチレン、エチレン−プロピレン共重合体、エチレン−ブテン共重合体、エチレン−オクテン共重合体、エチレン−プロピレン−ブテン共重合体、エチレン−酢酸ビニルからなる発泡体へ高い密着力を発現する。
本発明の光硬化型プライマーよって得られた塗膜は、エチレン系樹脂に優れた密着性を発現するため、自動車部品、電化製品、玩具、化粧品容器、靴、カバン、建築材料、光学材料などの用途で好適に使用できるものである。
The photocurable primer for ethylene resin of the present invention is a sheet-like molded body made of the ethylene-based resin, a film-like molded body, various injection-molded bodies, or a sheet-like molded body made of a resin containing synthetic rubber or the like. It exhibits excellent adhesion to film-like molded products, various injection-molded products, or foams thereof. Among them, it exhibits high adhesion to foams composed of polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-vinyl acetate. .
The coating film obtained by the photo-curing primer of the present invention expresses excellent adhesion to ethylene-based resins, so that it can be used for automobile parts, electrical appliances, toys, cosmetic containers, shoes, bags, building materials, optical materials, etc. It can be suitably used for the purpose.
以下、本発明のエチレン系樹脂用光硬化型プライマーの製法および各種試験例を挙げ、更に説明するが、本発明はこれら実施例に限定されるものではない。
[製造例１]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、スチレン系エラストマーとしてセプトン２００２（（株）クラレ製、スチレン含有量：３０％）を８０部と、有機溶剤としてメチルシクロヘキサンを１５０部仕込み、窒素置換しながら９５℃に加熱昇温した。次いでこの中に、重合可能な単量体としてメチルメタアクリレート４部、エチルアクリレート７部、ヒドロキシエチルアクリレート７部、メタクリル酸２部と重合開始剤としてｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート（以下、ＰＢＯと略記する）０．２部の混合液を４時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．１部添加した。ＰＢＯの添加後より２時間放置して反応させ、樹脂液（１）を得た。
Hereinafter, although the manufacturing method and various test examples of the photocurable primer for ethylene-based resins of the present invention will be described and further described, the present invention is not limited to these examples.
[Production Example 1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 80 parts of Septon 2002 (manufactured by Kuraray Co., Ltd., styrene content: 30%) as a styrene elastomer, and an organic solvent 150 parts of methylcyclohexane was charged and heated to 95 ° C. while replacing with nitrogen. Next, 4 parts of methyl methacrylate, 7 parts of ethyl acrylate, 7 parts of hydroxyethyl acrylate, 2 parts of methacrylic acid and tert-butylperoxy-2-ethylhexanoate as a polymerization initiator 0.2 parts of the mixed solution (hereinafter abbreviated as PBO) was fed over 4 hours. 0.1 parts of PBO was added 1 hour and 2 hours after the end of the feed. After the addition of PBO, the mixture was allowed to react for 2 hours to obtain a resin liquid (1).
[製造例２]
スチレン系エラストマーをダイナロン１３２０Ｐ（ＪＳＲ（株）製、スチレン含有量：１０％）に、有機溶剤であるメチルシクロヘキサンを４００部に変更した以外は、製造例１と同様の方法で樹脂分散体を得、これを樹脂液（２）とした。
[Production Example 2]
A resin dispersion was obtained in the same manner as in Production Example 1, except that the styrene elastomer was changed to Dynalon 1320P (manufactured by JSR Corporation, styrene content: 10%) and methylcyclohexane as the organic solvent was changed to 400 parts. This was designated as resin liquid (2).
[製造例３]
スチレン系エラストマーをタフテックＨ１０５２（旭化成ケミカルズ（株）製、スチレン含有量：２０％）に変更した以外は、製造例１と同様の方法で樹脂分散体を得、これを樹脂液（３）とした。
[Production Example 3]
A resin dispersion was obtained in the same manner as in Production Example 1 except that the styrene-based elastomer was changed to Tuftec H1052 (manufactured by Asahi Kasei Chemicals Corporation, styrene content: 20%), and this was used as the resin liquid (3). .
[製造例４]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、スチレン系エラストマーとしてセプトン２００２を４０部と、有機溶剤としてメチルシクロヘキサンを１５０部仕込み、窒素置換しながら９５℃に加熱昇温した。次いでこの中に、重合可能な単量体としてメチルメタアクリレート２１部、エチルアクリレート３０部、ヒドロキシエチルアクリレート７部、メタクリル酸２部と重合開始剤としてＰＢＯを０．６部の混合液を４時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．１部添加した。ＰＢＯの添加後より２時間放置して反応させ、樹脂液（４）を得た。
[Production Example 4]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube is charged with 40 parts of Septon 2002 as a styrene elastomer and 150 parts of methylcyclohexane as an organic solvent, and the temperature is changed to 95 ° C. while purging with nitrogen. The temperature was raised by heating. Next, in this, a mixed solution of 21 parts of methyl methacrylate as a polymerizable monomer, 30 parts of ethyl acrylate, 7 parts of hydroxyethyl acrylate, 2 parts of methacrylic acid and 0.6 part of PBO as a polymerization initiator was used for 4 hours. I fed it. 0.1 parts of PBO was added 1 hour and 2 hours after the end of the feed. After the addition of PBO, the reaction was allowed to stand for 2 hours to obtain a resin liquid (4).
[製造例５]
スチレン系エラストマーをダイナロン１３２０Ｐに、有機溶剤であるメチルシクロヘキサンを４００部に変更した以外は、製造例４同様の方法で樹脂分散体を得、これを樹脂液（５）とした。
[Production Example 5]
A resin dispersion was obtained in the same manner as in Production Example 4 except that the styrene elastomer was changed to Dynalon 1320P and the methylcyclohexane as the organic solvent was changed to 400 parts, and this was used as a resin liquid (5).
[製造例６]
スチレン系エラストマーをタフテックＨ１０５２に変更した以外は、製造例４と同様の方法で樹脂分散体を得、これを樹脂液（６）とした。
[Production Example 6]
A resin dispersion was obtained in the same manner as in Production Example 4 except that the styrene elastomer was changed to Tuftec H1052, and this was designated as resin liquid (6).
[製造例７]
攪拌装置を備えた１．５Ｌ容量のオートクレーブに、スチレン系エラストマーとしてセプトン２００２を２５０部と、有機溶剤としてトルエンを５００部仕込み、攪拌下、１６０℃に加熱昇温した。次いでこの中に、ヒドロキシプロピルアクリレート２５部と重合開始剤としてジ−ｔｅｒｔ−ブチルパーオキサイド（以下、ＰＢＤと略記する）６．５部を、それぞれ５時間かけてフィードした。フィード終了より２時間反応させた後、希釈溶剤としてトルエンを３２５部添加し樹脂液（７）を得た。
[Production Example 7]
A 1.5 L autoclave equipped with a stirrer was charged with 250 parts of Septon 2002 as a styrene elastomer and 500 parts of toluene as an organic solvent, and heated to 160 ° C. with stirring. Next, 25 parts of hydroxypropyl acrylate and 6.5 parts of di-tert-butyl peroxide (hereinafter abbreviated as PBD) as a polymerization initiator were fed into each of them over 5 hours. After reacting for 2 hours from the end of the feed, 325 parts of toluene was added as a diluent solvent to obtain a resin liquid (7).
[製造例８]
攪拌装置を備えた１．５Ｌ容量のオートクレーブに、スチレン系エラストマーとしてダイナロン１３２０Ｐを１００部と、有機溶剤としてトルエンを５００部仕込み、攪拌下、１６０℃に加熱昇温した。次いでこの中に、ヒドロキシプロピルアクリレート１０部と重合開始剤としてＰＢＤ２．６部を、それぞれ５時間かけてフィードした。フィード終了より２時間反応させた後、希釈溶剤としてトルエンを１２３部添加し樹脂液（８）を得た。
[Production Example 8]
A 1.5 L autoclave equipped with a stirrer was charged with 100 parts of Dynalon 1320P as a styrene elastomer and 500 parts of toluene as an organic solvent, and heated to 160 ° C. with stirring. Next, 10 parts of hydroxypropyl acrylate and 2.6 parts of PBD as a polymerization initiator were fed into each of them over 5 hours. After reacting for 2 hours from the end of the feed, 123 parts of toluene was added as a diluent solvent to obtain a resin liquid (8).
[製造例９]
スチレン系エラストマーをタフテックＨ１０５２に変更した以外は、製造例７と同様の方法で樹脂分散体を得、これを樹脂液（９）とした。
[Production Example 9]
A resin dispersion was obtained in the same manner as in Production Example 7 except that the styrene-based elastomer was changed to Tuftec H1052, and this was used as a resin liquid (9).
[製造例１０]
攪拌装置を備えた１．５Ｌ容量のオートクレーブに、スチレン系エラストマーとしてセプトン２００２を２５０部と、有機溶剤としてトルエンを５００部仕込み、攪拌下、１４５℃に加熱昇温した。次いでこの中に、無水マレイン酸２３部をトルエン１００部に溶解した溶液と重合開始剤であるＰＢＤ８部とトルエン５０部に溶解した溶液それぞれ４時間かけてフィードした。フィード終了より２時間反応させた後、希釈溶剤としてトルエンを１６９部添加し樹脂液（１０）を得た。
[Production Example 10]
A 1.5 L autoclave equipped with a stirrer was charged with 250 parts of Septon 2002 as a styrene elastomer and 500 parts of toluene as an organic solvent, and heated to 145 ° C. with stirring. Then, a solution in which 23 parts of maleic anhydride was dissolved in 100 parts of toluene, a solution of 8 parts of PBD as a polymerization initiator, and a solution in 50 parts of toluene were fed into each of them for 4 hours. After reacting for 2 hours from the end of the feed, 169 parts of toluene was added as a diluent solvent to obtain a resin liquid (10).
[製造例１１]
攪拌装置を備えた１．５Ｌ容量のオートクレーブに、スチレン系エラストマーとしてダイナロン１３２０Ｐを１００部と、有機溶剤としてトルエンを５００部仕込み、攪拌下、１４５℃に加熱昇温した。次いでこの中に、無水マレイン酸１０部をトルエン８８部に溶解した溶液と重合開始剤であるＰＢＤ３．５部とトルエン３５部に溶解した溶液それぞれ４時間かけてフィードした。フィード終了より２時間反応させ、樹脂液（１１）を得た。
[Production Example 11]
A 1.5 L autoclave equipped with a stirrer was charged with 100 parts of Dynalon 1320P as a styrenic elastomer and 500 parts of toluene as an organic solvent, and heated to 145 ° C. with stirring. Then, 10 parts of maleic anhydride dissolved in 88 parts of toluene, 3.5 parts of PBD as a polymerization initiator, and a solution dissolved in 35 parts of toluene were fed into each of them over 4 hours. Reaction was performed for 2 hours from the end of feeding to obtain a resin liquid (11).
[製造例１２]
スチレン系エラストマーをタフテックＨ１０５２に変更した以外は、製造例１０と同様の方法で樹脂分散体を得、これを樹脂液（１２）とした。
[Production Example 12]
A resin dispersion was obtained in the same manner as in Production Example 10 except that the styrene-based elastomer was changed to Tuftec H1052, and this was used as a resin liquid (12).
[製造例１３]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、スチレン系エラストマーとしてダイナロン１３２０Ｐを８０部と、有機溶剤としてアイソパーＥ（エクソン化学製）を４００部仕込み、窒素置換しながら１１０℃に加熱昇温した。次いでこの中に、重合可能な単量体としてメチルメタアクリレート４部、エチルアクリレート７部、ヒドロキシエチルアクリレート７部、メタクリル酸２部と重合開始剤としてＰＢＯを０．２部の混合液を４時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．１部添加した。さらに１時間後にＰＢＯを０．３部添加して反応させた。ＰＢＯの添加後より２時間放置して反応させ、希釈溶剤としてメチルシクロヘキサンを１６７部添加し、樹脂液（１３）を得た。
[Production Example 13]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 80 parts of Dynalon 1320P as a styrene elastomer and 400 parts of Isopar E (manufactured by Exxon Chemical) as an organic solvent. The temperature was raised to 110 ° C. while heating. Then, 4 parts of methyl methacrylate as a polymerizable monomer, 7 parts of ethyl acrylate, 7 parts of hydroxyethyl acrylate, 2 parts of methacrylic acid and 0.2 part of PBO as a polymerization initiator are mixed for 4 hours. I fed it. 0.1 parts of PBO was added 1 hour and 2 hours after the end of the feed. Further, after 1 hour, 0.3 parts of PBO was added and reacted. The reaction was allowed to stand for 2 hours after the addition of PBO, and 167 parts of methylcyclohexane was added as a diluent solvent to obtain a resin liquid (13).
[製造例１４]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、スチレン系エラストマーとしてダイナロン１３２０Ｐを８０部と、有機溶剤としてトルエンを３８０部、重合可能な単量体としてメチルメタアクリレート４部、エチルアクリレート７部、ヒドロキシエチルアクリレート７部、メタクリル酸２部を仕込み、窒素置換しながら９５℃に加熱昇温した。次いでこの中に、重合開始剤であるＰＢＯを０．２部とトルエン２０部を混合した混合液を５時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．１部添加した。ＰＢＯの添加後より２時間放置して反応させ、希釈溶剤としてメチルシクロヘキサンを１６７部添加し、樹脂液（１４）を得た。
[Production Example 14]
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube, 80 parts of Dynalon 1320P as a styrene elastomer, 380 parts of toluene as an organic solvent, and methylmeta as a polymerizable monomer 4 parts of acrylate, 7 parts of ethyl acrylate, 7 parts of hydroxyethyl acrylate and 2 parts of methacrylic acid were charged, and the temperature was raised to 95 ° C. while replacing with nitrogen. Next, a mixed liquid in which 0.2 parts of PBO as a polymerization initiator and 20 parts of toluene were mixed was fed into this over 5 hours. 0.1 parts of PBO was added 1 hour and 2 hours after the end of the feed. The reaction was allowed to stand for 2 hours after the addition of PBO, and 167 parts of methylcyclohexane was added as a diluent solvent to obtain a resin liquid (14).
[製造例１５]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、トルエンを５０部、酢酸ブチルを５０部仕込み、窒素置換しながら１００℃に加熱昇温した。次いでこの中に、重合可能な単量体としてメチルメタアクリレート２０部、エチルアクリレート３５部、ヒドロキシエチルアクリレート３５部、メタクリル酸１０部と重合開始剤としてＰＢＯを０．５部の混合液を４時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．２部添加した。ＰＢＯの添加後より２時間放置して反応させ樹脂溶液（Ａ）を得た。
[Production Example 15]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was charged with 50 parts of toluene and 50 parts of butyl acetate, and heated to 100 ° C. while replacing with nitrogen. Next, a mixed solution of 20 parts of methyl methacrylate as a polymerizable monomer, 35 parts of ethyl acrylate, 35 parts of hydroxyethyl acrylate, 10 parts of methacrylic acid and 0.5 part of PBO as a polymerization initiator for 4 hours. I fed it. 0.2 parts of PBO were added 1 hour and 2 hours after the end of the feed. The resin solution (A) was obtained by reacting for 2 hours after the addition of PBO.
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコにダイナロン１３２０Ｐを８０部と、有機溶剤としてトルエンを４００部仕込み、窒素置換しながら１１０℃に加熱昇温した。次いでこの中に、樹脂溶液（Ａ）４０部を１時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ１部添加した。更に１時間後にＰＢＯを２部添加し反応させた。ＰＢＯの添加後より２時間放置して反応させ、希釈溶剤としてメチルシクロヘキサンを１４７部添加し、樹脂液（１５）を得た。 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 80 parts of Dynalon 1320P and 400 parts of toluene as an organic solvent, and heated to 110 ° C. while replacing with nitrogen. Next, 40 parts of the resin solution (A) was fed into this over 1 hour. One part of PBO was added 1 hour and 2 hours after the end of the feed. After an additional hour, 2 parts of PBO was added and reacted. The reaction was allowed to stand for 2 hours after the addition of PBO, and 147 parts of methylcyclohexane was added as a diluent solvent to obtain a resin liquid (15).
[製造例１６]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、製造例８で得られた樹脂液（８）７３３部を仕込み、窒素置換しながら９５℃に加熱昇温した。次いでこの中に、重合可能な単量体としてメチルメタアクリレート４部、エチルアクリレート７部、ヒドロキシエチルアクリレート７部、メタクリル酸２部と重合開始剤としてＰＢＯを０．２部の混合液を４時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．１部添加した。ＰＢＯの添加後より２時間放置して反応させ、樹脂液（１６）を得た。
[Production Example 16]
Into a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introducing tube, 733 parts of the resin liquid (8) obtained in Production Example 8 was charged, and heated to 95 ° C. while replacing with nitrogen. . Then, 4 parts of methyl methacrylate as a polymerizable monomer, 7 parts of ethyl acrylate, 7 parts of hydroxyethyl acrylate, 2 parts of methacrylic acid and 0.2 part of PBO as a polymerization initiator are mixed for 4 hours. I fed it. 0.1 parts of PBO was added 1 hour and 2 hours after the end of the feed. After the addition of PBO, the mixture was allowed to react for 2 hours to obtain a resin liquid (16).
[製造例１７]
攪拌機、温度計、還流冷却装置、及び窒素導入管を備えた４つ口フラスコに、製造例１１で得られた樹脂液（１１）７３３部を仕込み、窒素置換しながら９５℃に加熱昇温した。次いでこの中に、重合可能な単量体としてメチルメタアクリレート４部、エチルアクリレート７部、ヒドロキシエチルアクリレート７部、メタクリル酸２部と重合開始剤としてＰＢＯを０．２部の混合液を４時間かけてフィードした。フィード終了より１時間後と２時間後にＰＢＯをそれぞれ０．１部添加した。ＰＢＯの添加後より２時間放置して反応させ、樹脂液（１７）を得た。
[Production Example 17]
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen inlet tube was charged with 733 parts of the resin liquid (11) obtained in Production Example 11, and heated to 95 ° C. while replacing with nitrogen. . Then, 4 parts of methyl methacrylate as a polymerizable monomer, 7 parts of ethyl acrylate, 7 parts of hydroxyethyl acrylate, 2 parts of methacrylic acid and 0.2 part of PBO as a polymerization initiator are mixed for 4 hours. I fed it. 0.1 parts of PBO was added 1 hour and 2 hours after the end of the feed. After adding PBO, the mixture was allowed to react for 2 hours to obtain a resin liquid (17).
[製造例１８]
スチレン系エラストマーをオレフィン系エラストマーであるベストプラスト７５０（デグサヒュルス製）に、重合終了後に希釈溶剤としてメチルシクロヘキサンを１５０部添加する事に変更した以外は、製造例１と同様の方法で樹脂分散体を得、これを樹脂液（１８）とした。
[Production Example 18]
A resin dispersion was prepared in the same manner as in Production Example 1 except that styrene elastomer was changed to Best Plast 750 (manufactured by Degussa Huls), an olefin elastomer, by adding 150 parts of methylcyclohexane as a diluent solvent after the completion of polymerization. This was used as a resin liquid (18).
[製造例１９]
スチレン系エラストマーをオレフィン系エラストマーであるベストプラスト７５０に、重合終了後に希釈溶剤としてメチルシクロヘキサンを１５０部添加する事に変更した以外は、製造例４と同様の方法で樹脂分散体を得、これを樹脂液（１９）とした。
[Production Example 19]
A resin dispersion was obtained in the same manner as in Production Example 4, except that styrene elastomer was changed to Best Plast 750, which is an olefin elastomer, by adding 150 parts of methylcyclohexane as a diluent solvent after the completion of polymerization. Resin liquid (19) was obtained.
[製造例２０]
スチレン系エラストマーをオレフィン系エラストマーであるベストプラスト７５０に、重合終了後に添加する希釈溶剤を１０５８部に変更した以外は、製造例７と同様の方法で樹脂分散体を得、これを樹脂液（２０）とした。
[Production Example 20]
A resin dispersion was obtained in the same manner as in Production Example 7, except that the styrene elastomer was changed to Bestplast 750, which is an olefin elastomer, and the dilution solvent added after the polymerization was changed to 1058 parts. ).
[製造例２１]
スチレン系エラストマーをオレフィン系エラストマーであるベストプラスト７５０に、重合終了後に添加する希釈溶剤を８９７部に変更した以外は、製造例１０と同様の方法で樹脂分散体を得、これを樹脂液（２１）とした。
以上製造例に記載した組成を表−１にまとめた。
[Production Example 21]
A resin dispersion was obtained in the same manner as in Production Example 10 except that the styrene elastomer was changed to Bestplast 750, which is an olefin elastomer, and the dilution solvent added after the polymerization was changed to 897 parts. ).
The compositions described in the production examples are summarized in Table 1.
[実施例１]
樹脂液（１）１００部に、光重合性モノマーであるアロニックスＭ４００（東亞合成（株）製 光重合性不飽和結合数５以上）を１７部混合し、光重合開始剤であるイルガキュア１８４（チバ・スペシャルティ・ケミカルズ（株）製）を２．８５部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 1]
In 100 parts of the resin liquid (1), 17 parts of Aronix M400 which is a photopolymerizable monomer (manufactured by Toagosei Co., Ltd., photopolymerizable unsaturated bond number 5 or more) is mixed, and Irgacure 184 which is a photopolymerization initiator (Ciba). -Specialty Chemicals Co., Ltd. 2.85 parts was mixed, and the photocurable primer for ethylene-type resin was obtained.
[実施例２]
樹脂液（２）１００部に、光重合性モノマーであるアロニックスＭ４００を８．６部混合し、光重合開始剤であるイルガキュア１８４を１．４３部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 2]
8.6 parts of Aronix M400 which is a photopolymerizable monomer is mixed with 100 parts of the resin liquid (2), and 1.43 parts of Irgacure 184 which is a photopolymerization initiator is mixed, and a photocurable primer for an ethylene-based resin is added. Obtained.
[実施例３]
樹脂液を（３）に変更した以外は、実施例１同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 3]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 1 except that the resin liquid was changed to (3).
[実施例４]
樹脂液を（４）に変更した以外は、実施例１同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 4]
Except having changed the resin liquid into (4), the photocurable primer for ethylene resin was obtained by the same method as Example 1.
[実施例５]
樹脂液を（４）に変更した以外は、実施例２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 5]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 2 except that the resin solution was changed to (4).
[実施例６]
樹脂液を（６）に変更した以外は、実施例１同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 6]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 1 except that the resin solution was changed to (6).
[実施例７]
樹脂液（７）１００部に、光重合性モノマーであるアロニックスＭ４００を１０．７部混合し、光重合開始剤であるイルガキュア１８４を１．７９部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 7]
10.7 parts of Aronix M400 which is a photopolymerizable monomer is mixed with 100 parts of the resin liquid (7), 1.79 parts of Irgacure 184 which is a photopolymerization initiator is mixed, and a photocurable primer for an ethylene-based resin is added. Obtained.
[実施例８]
樹脂液（８）１００部に、光重合性モノマーであるアロニックスＭ４００を６．４部混合し、光重合開始剤であるイルガキュア１８４を１．０７部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 8]
6.4 parts of Aronix M400 which is a photopolymerizable monomer is mixed with 100 parts of the resin liquid (8), 1.07 parts of Irgacure 184 which is a photopolymerization initiator is mixed, and a photocurable primer for ethylene resin is added. Obtained.
[実施例９]
樹脂液を（９）に変更した以外は、実施例７同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 9]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 7 except that the resin liquid was changed to (9).
[実施例１０]
樹脂液を（１０）に変更した以外は、実施例７同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 10]
A photocurable primer for an ethylene-based resin was obtained in the same manner as in Example 7 except that the resin liquid was changed to (10).
[実施例１１]
樹脂液を（１１）に変更した以外は、実施例８同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 11]
Except having changed the resin liquid into (11), the photocurable primer for ethylene resin was obtained by the same method as Example 8.
[実施例１２]
樹脂液を（１２）に変更した以外は、実施例７同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 12]
Except having changed the resin liquid into (12), the photocurable primer for ethylene-type resins was obtained by the same method as Example 7.
[実施例１３]
樹脂液（１３）１００部に、光重合性モノマーであるアロニックスＭ４００を６．４部混合し、光重合開始剤であるイルガキュア１８４を１．０７部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 13]
6.4 parts of Aronix M400 which is a photopolymerizable monomer is mixed with 100 parts of the resin liquid (13), 1.07 parts of Irgacure 184 which is a photopolymerization initiator is mixed, and a photocurable primer for ethylene resin is added. Obtained.
[実施例１４]
樹脂液を（１４）に変更した以外は、実施例１３同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 14]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 13 except that the resin liquid was changed to (14).
[実施例１５]
樹脂液を（１５）に変更した以外は、実施例１３同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 15]
Except having changed the resin liquid into (15), the photocurable primer for ethylene resin was obtained by the same method as Example 13.
[実施例１６]
樹脂液（１６）１００部に、光重合性モノマーであるアロニックスＭ４００を７．４部混合し、光重合開始剤であるイルガキュア１８４を１．２４部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 16]
7.4 parts of Aronix M400 which is a photopolymerizable monomer is mixed with 100 parts of the resin liquid (16), and 1.24 parts of Irgacure 184 which is a photopolymerization initiator is mixed, and a photocurable primer for ethylene resin is added. Obtained.
[実施例１７]
樹脂液を（１７）に変更した以外は、実施例１６同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 17]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 16 except that the resin liquid was changed to (17).
[実施例１８]
樹脂液（１）１００部に、光重合性モノマーであるアロニックスＭ４００を１０部混合し、光重合開始剤であるイルガキュア１８４を２．５部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 18]
10 parts of Aronix M400 which is a photopolymerizable monomer was mixed with 100 parts of the resin liquid (1), and 2.5 parts of Irgacure 184 which was a photopolymerization initiator was mixed to obtain a photocurable primer for ethylene resin. .
[実施例１９]
樹脂液（２）１００部に、光重合性モノマーであるアロニックスＭ４００を５部混合し、光重合開始剤であるイルガキュア１８４を１．２５部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 19]
5 parts of Aronix M400 which is a photopolymerizable monomer was mixed with 100 parts of the resin liquid (2), and 1.25 parts of Irgacure 184 which was a photopolymerization initiator was mixed to obtain a photocurable primer for an ethylene-based resin. .
[実施例２０]
樹脂液を（３）に変更した以外は、実施例１６同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 20]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 16 except that the resin liquid was changed to (3).
[実施例２１]
樹脂液を（４）に変更した以外は、実施例１６同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 21]
Except having changed the resin liquid into (4), the photocurable primer for ethylene-type resins was obtained by the same method as Example 16.
[実施例２２]
樹脂液を（５）に変更した以外は、実施例１７同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 22]
A photocurable primer for an ethylene-based resin was obtained in the same manner as in Example 17 except that the resin liquid was changed to (5).
[実施例２３]
樹脂液を（６）に変更した以外は、実施例１６同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 23]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 16 except that the resin liquid was changed to (6).
[実施例２４]
樹脂液（７）１００部に、光重合性モノマーであるアロニックスＭ４００を６．３部混合し、光重合開始剤であるイルガキュア１８４を１．５７部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 24]
To 100 parts of the resin liquid (7), 6.3 parts of Aronix M400 which is a photopolymerizable monomer is mixed, and 1.57 parts of Irgacure 184 which is a photopolymerization initiator are mixed. Obtained.
[実施例２５]
樹脂液（８）１００部に、光重合性モノマーであるアロニックスＭ４００を３．８部混合し、光重合開始剤であるイルガキュア１８４を０．９４部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 25]
In 100 parts of the resin liquid (8), 3.8 parts of Aronix M400, a photopolymerizable monomer, is mixed with 0.94 parts of Irgacure 184, which is a photopolymerization initiator, and a photocurable primer for an ethylene-based resin is added. Obtained.
[実施例２６]
樹脂液を（９）に変更した以外は、実施例２２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 26]
Except having changed the resin liquid into (9), the photocurable primer for ethylene-type resins was obtained by the same method as Example 22.
[実施例２７]
樹脂液を（１０）に変更した以外は、実施例２２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 27]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 22 except that the resin liquid was changed to (10).
[実施例２８]
樹脂液を（１１）に変更した以外は、実施例２３同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 28]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 23 except that the resin liquid was changed to (11).
[実施例２９]
樹脂液を（１２）に変更した以外は、実施例２２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 29]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 22 except that the resin liquid was changed to (12).
[実施例３０]
樹脂液（１６）１００部に、光重合性モノマーであるアロニックスＭ４００を４．３部混合し、光重合開始剤であるイルガキュア１８４を１．０８部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 30]
In 100 parts of the resin liquid (16), 4.3 parts of Aronix M400, which is a photopolymerizable monomer, is mixed with 1.08 parts of Irgacure 184, which is a photopolymerization initiator, and a photocurable primer for an ethylene-based resin is added. Obtained.
[実施例３１]
樹脂液を（１７）に変更した以外は、実施例３０同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 31]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 30, except that the resin liquid was changed to (17).
[実施例３２]
樹脂液（１）１００部に、光重合性モノマーであるアロニックスＭ４００を４０部混合し、光重合開始剤であるイルガキュア１８４を４部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 32]
40 parts of Aronix M400, a photopolymerizable monomer, was mixed with 100 parts of the resin liquid (1), and 4 parts of Irgacure 184, a photopolymerization initiator, was mixed to obtain a photocurable primer for ethylene resin.
[実施例３３]
樹脂液（２）１００部に、光重合性モノマーであるアロニックスＭ４００を２０部混合し、光重合開始剤であるイルガキュア１８４を２部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 33]
20 parts of Aronix M400 which is a photopolymerizable monomer was mixed with 100 parts of the resin liquid (2), and 2 parts of Irgacure 184 which was a photopolymerization initiator was mixed to obtain a photocurable primer for ethylene resin.
[実施例３４]
樹脂液を（３）に変更した以外は、実施例２８同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 34]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 28 except that the resin liquid was changed to (3).
[実施例３５]
樹脂液を（４）に変更した以外は、実施例２８同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 35]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 28 except that the resin liquid was changed to (4).
[実施例３６]
樹脂液を（５）に変更した以外は、実施例２９同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 36]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 29 except that the resin liquid was changed to (5).
[実施例３７]
樹脂液を（６）に変更した以外は、実施例２８同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 37]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 28 except that the resin liquid was changed to (6).
[実施例３８]
樹脂液（７）１００部に、光重合性モノマーであるアロニックスＭ４００を２５部混合し、光重合開始剤であるイルガキュア１８４を２．５部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 38]
25 parts of Aronix M400 which is a photopolymerizable monomer was mixed with 100 parts of the resin liquid (7), and 2.5 parts of Irgacure 184 which was a photopolymerization initiator was mixed to obtain a photocurable primer for ethylene resin. .
[実施例３９]
樹脂液（８）１００部に、光重合性モノマーであるアロニックスＭ４００を１５部混合し、光重合開始剤であるイルガキュア１８４を１．５部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 39]
15 parts of Aronix M400 which is a photopolymerizable monomer was mixed with 100 parts of the resin liquid (8), and 1.5 parts of Irgacure 184 which was a photopolymerization initiator was mixed to obtain a photocurable primer for ethylene resin. .
[実施例４０]
樹脂液を（９）に変更した以外は、実施例３４同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 40]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 34 except that the resin liquid was changed to (9).
[実施例４１]
樹脂液を（１０）に変更した以外は、実施例３４同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 41]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 34 except that the resin liquid was changed to (10).
[実施例４２]
樹脂液を（１１）に変更した以外は、実施例３５同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 42]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 35 except that the resin liquid was changed to (11).
[実施例４３]
樹脂液を（１２）に変更した以外は、実施例３４同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 43]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 34 except that the resin liquid was changed to (12).
[実施例４４]
樹脂液（１６）１００部に、光重合性モノマーであるアロニックスＭ４００を１７．３部混合し、光重合開始剤であるイルガキュア１８４を１．７３部混合し、エチレン系樹脂用光硬化型プライマーを得た。
[Example 44]
100 parts of the resin liquid (16) is mixed with 17.3 parts of photopolymerizable monomer Aronix M400, 1.73 parts of photopolymerization initiator Irgacure 184 is mixed, and a photocurable primer for ethylene resin is added. Obtained.
[実施例４５]
樹脂液を（１７）に変更した以外は、実施例４４同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 45]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 44 except that the resin liquid was changed to (17).
[実施例４６]
光重合性モノマーをアロニックスＭ２２０（東亞合成（株）製 光重合性不飽和結合数２）に変更した以外は、実施例２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 46]
A photocurable primer for an ethylene resin was obtained in the same manner as in Example 2 except that the photopolymerizable monomer was changed to Aronix M220 (manufactured by Toagosei Co., Ltd., photopolymerizable unsaturated bond number 2).
[実施例４７]
光重合性モノマーをアロニックスＭ２２０に変更した以外は、実施例５同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 47]
A photocurable primer for an ethylene-based resin was obtained in the same manner as in Example 5 except that the photopolymerizable monomer was changed to Aronix M220.
[実施例４８]
光重合性モノマーをアロニックスＭ２２０に変更した以外は、実施例８同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 48]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 8 except that the photopolymerizable monomer was changed to Aronics M220.
[実施例４９]
光重合性モノマーをアロニックスＭ２２０に変更した以外は、実施例１１同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 49]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 11 except that the photopolymerizable monomer was changed to Aronics M220.
[実施例５０]
光重合性モノマーをアロニックスＭ２２０に変更した以外は、実施例１６同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 50]
A photocurable primer for an ethylene-based resin was obtained in the same manner as in Example 16 except that the photopolymerizable monomer was changed to Aronix M220.
[実施例５１]
光重合性モノマーをアロニックスＭ２２０に変更した以外は、実施例１７同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 51]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 17 except that the photopolymerizable monomer was changed to Aronics M220.
[実施例５２]
光重合開始剤の添加量を０．５７部に変更した以外は、実施例２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 52]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 2 except that the addition amount of the photopolymerization initiator was changed to 0.57 parts.
[実施例５３]
光重合開始剤の添加量を２．８６部に変更した以外は、実施例２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 53]
A photocurable primer for an ethylene-based resin was obtained in the same manner as in Example 2 except that the addition amount of the photopolymerization initiator was changed to 2.86 parts.
[実施例５４]
光重合開始剤をイルガキュア５００（チバ・スペシャルティ・ケミカルズ（株）製）に変更した以外は、実施例２同様の方法でエチレン系樹脂用光硬化型プライマーを得た。
[Example 54]
A photocurable primer for ethylene resin was obtained in the same manner as in Example 2 except that the photopolymerization initiator was changed to Irgacure 500 (manufactured by Ciba Specialty Chemicals).
[比較例１]
樹脂液（１８）１００部に、光重合性モノマーであるアロニックスＭ４００を１０．７部混合し、光重合開始剤であるイルガキュア１８４を１．７９部混合し、光硬化型プライマーを得た。
[Comparative Example 1]
10.7 parts of Aronix M400 as a photopolymerizable monomer was mixed with 100 parts of the resin liquid (18), and 1.79 parts of Irgacure 184 as a photopolymerization initiator were mixed to obtain a photocurable primer.
[比較例２]
樹脂液を（１９）に変更した以外は、比較例１同様の方法で光硬化型プライマーを得た。
[Comparative Example 2]
A photocurable primer was obtained in the same manner as in Comparative Example 1 except that the resin liquid was changed to (19).
[比較例３]
樹脂液（２０）１００部に、光重合性モノマーであるアロニックスＭ４００を６．４部混合し、光重合開始剤であるイルガキュア１８４を１．０７部混合し、光硬化型プライマーを得た。
[Comparative Example 3]
To 100 parts of the resin liquid (20), 6.4 parts of Aronix M400 as a photopolymerizable monomer was mixed, and 1.07 parts of Irgacure 184 as a photopolymerization initiator were mixed to obtain a photocurable primer.
[比較例４]
樹脂液を（２１）に変更した以外は、比較例３同様の方法で光硬化型プライマーを得た。
[Comparative Example 4]
A photocurable primer was obtained in the same manner as in Comparative Example 3 except that the resin liquid was changed to (21).
[比較例５]
樹脂液（１８）１００部に、光重合開始剤であるイルガキュア１８４を１．２５部混合し、光硬化型プライマーを得た。
[Comparative Example 5]
To 100 parts of the resin liquid (18), 1.25 parts of Irgacure 184 as a photopolymerization initiator was mixed to obtain a photocurable primer.
[比較例６]
樹脂液を（１９）に変更した以外は、比較例５同様の方法で光硬化型プライマーを得た。
[Comparative Example 6]
A photocurable primer was obtained in the same manner as in Comparative Example 5 except that the resin liquid was changed to (19).
[比較例７]
樹脂液（２０）１００部に、光重合開始剤であるイルガキュア１８４を０．７５部混合し、光硬化型プライマーを得た。
[Comparative Example 7]
0.75 parts of Irgacure 184 as a photopolymerization initiator was mixed with 100 parts of the resin liquid (20) to obtain a photocurable primer.
[比較例８]
樹脂液を（２１）に変更した以外は、比較例７同様の方法で光硬化型プライマーを得た。
[Comparative Example 8]
A photocurable primer was obtained in the same manner as in Comparative Example 7 except that the resin liquid was changed to (21).
[比較例９]
樹脂液（１）１００部に、光重合開始剤であるイルガキュア１８４を２部混合し、光硬化型プライマーを得た。
[Comparative Example 9]
Two parts of Irgacure 184 as a photopolymerization initiator were mixed with 100 parts of the resin liquid (1) to obtain a photocurable primer.
[比較例１０]
樹脂液を（４）に変更した以外は、比較例９同様の方法で光硬化型プライマーを得た。
[Comparative Example 10]
A photocurable primer was obtained in the same manner as in Comparative Example 9 except that the resin liquid was changed to (4).
[比較例１１]
樹脂液（７）１００部に、光重合開始剤であるイルガキュア１８４を１．２５部混合し、光硬化型プライマーを得た。
[Comparative Example 11]
1.25 parts of Irgacure 184 as a photopolymerization initiator was mixed with 100 parts of the resin liquid (7) to obtain a photocurable primer.
[比較例１２]
樹脂液を（１０）に変更した以外は、比較例１１同様の方法で光硬化型プライマーを得た。
[Comparative Example 12]
A photocurable primer was obtained in the same manner as in Comparative Example 11 except that the resin liquid was changed to (10).
[比較例１３]
樹脂液（１）１００部に、光重合性不飽和結合を１つ含有する光重合性モノマーとしてエチルヘキシルアクリレートを１７．１部、光重合開始剤であるイルガキュア１８４を２．９部混合し、光硬化型プライマーを得た。
[Comparative Example 13]
In 100 parts of the resin liquid (1), 17.1 parts of ethylhexyl acrylate as a photopolymerizable monomer containing one photopolymerizable unsaturated bond and 2.9 parts of Irgacure 184 as a photopolymerization initiator are mixed. A curable primer was obtained.
[比較例１４]
樹脂液を（４）に変更した以外は、比較例１３同様の方法で光硬化型プライマーを得た。
[Comparative Example 14]
A photocurable primer was obtained in the same manner as in Comparative Example 13 except that the resin liquid was changed to (4).
[比較例１５]
樹脂液（７）１００部に、光重合性不飽和結合を１つ含有する光重合性モノマーとしてエチルヘキシルアクリレートを１２．８部、光重合開始剤であるイルガキュア１８４を１．９部混合し、光硬化型プライマーを得た。
[Comparative Example 15]
100 parts of the resin liquid (7) is mixed with 12.8 parts of ethylhexyl acrylate as a photopolymerizable monomer containing one photopolymerizable unsaturated bond and 1.9 parts of Irgacure 184 as a photopolymerization initiator. A curable primer was obtained.
[比較例１６]
樹脂液を（１０）に変更した以外は、比較例１５同様の方法で光硬化型プライマーを得た。
[Comparative Example 16]
A photocurable primer was obtained in the same manner as in Comparative Example 15 except that the resin liquid was changed to (10).
[比較例１７]
製造例１５に記載の樹脂溶液（Ａ）１００部に、光重合性モノマーであるアロニックスＭ４００を２１．４部混合し、光重合開始剤であるイルガキュア１８４を３．５７部混合し、光硬化型プライマーを得た。
[Comparative Example 17]
100 parts of the resin solution (A) described in Production Example 15 is mixed with 21.4 parts of Aronix M400, which is a photopolymerizable monomer, and 3.57 parts of Irgacure 184, which is a photopolymerization initiator, and is photocurable. A primer was obtained.
[比較例１８]
製造例１５に記載の樹脂溶液（Ａ）１００部に、光重合開始剤であるイルガキュア１８４を２．５部混合し、光硬化型プライマーを得た。
[Comparative Example 18]
2.5 parts of Irgacure 184, which is a photopolymerization initiator, was mixed with 100 parts of the resin solution (A) described in Production Example 15 to obtain a photocurable primer.
＜評価＞
１．樹脂液の安定性
前述で得られた光硬化型プライマーの光重合開始剤を添加する前の組成物で、４０℃の条件で暗室で１週間静置し、溶液の状態を評価した。１週間の経過後、この樹脂組成物溶液につき分離および沈殿がともに確認されなかったものを○、分離および／または沈殿の観察されたもので攪拌にて容易に分散できるものを△、分離および／または沈殿の観察された攪拌にて容易に分散できないものを×とし、その結果を表−２に記載した。
２．接着評価
＜発泡体での評価＞
前述で得られた光硬化型プライマーを、メチルシクロヘキサン／メチルイソブチルケトン（＝４／１：重量比）で希釈し、１０％となるように調整した。次いで、「特開２０００−３４４９２４」の実施例３、比較例２で作成された発泡体をそれぞれ基材Ａ、基材Ｂとして、これらを混合溶剤（メチルシクロヘキサン／イソプロピルアルコール／メチルエチルケトン＝６５／２０／１５）に１分間浸漬した後、乾燥後の膜厚が２μｍとなるように前記溶液を刷毛で塗布して乾燥させた。次いで、８０Ｗ／ｃｍの高圧水銀灯１灯を通過方向と垂直に設置した照射装置（日本電池（株）製、ＥＰＳＨ−６００−３Ｓ型、紫外線照射装置）を用い、光源下１５ｃｍの位置に置いてコンベアスピードを１０ｍ／分の速度で移動させ紫外線を照射した。
前述の紫外線を照射した後の塗膜について、以下の２方法での剥離強度試験と、追従性試験を行った。
<Evaluation>
1. Stability of the resin liquid The composition before adding the photopolymerization initiator of the photocurable primer obtained above was allowed to stand in a dark room at 40 ° C. for 1 week, and the state of the solution was evaluated. After 1 week, the resin composition solution in which neither separation nor precipitation was confirmed was marked with ○, the separation and / or precipitation observed and Δ that could be easily dispersed by stirring, Or the thing which cannot be disperse | distributed easily by stirring by which precipitation was observed was set to x, and the result was described in Table-2.
2. Adhesion evaluation < Evaluation with foam>
The photocurable primer obtained above was diluted with methylcyclohexane / methylisobutylketone (= 4/1: weight ratio) and adjusted to 10%. Next, the foams prepared in Example 3 and Comparative Example 2 of “JP 2000-344924” are used as a base material A and a base material B, respectively, and these are mixed solvents (methylcyclohexane / isopropyl alcohol / methyl ethyl ketone = 65/20). / 15), the solution was applied with a brush and dried so that the film thickness after drying was 2 μm. Next, an irradiation device (manufactured by Nippon Battery Co., Ltd., EPSH-600-3S type, ultraviolet irradiation device) in which one 80 W / cm high-pressure mercury lamp is installed perpendicular to the passing direction is placed at a position 15 cm below the light source. The conveyor speed was moved at a speed of 10 m / min and irradiated with ultraviolet rays.
About the coating film after irradiating the above-mentioned ultraviolet-ray, the peeling strength test by the following 2 methods and the followable | trackability test were done.
評価１
前述の紫外線を照射した後の塗膜上に、水性ウレタン樹脂（東成化学（株）製、製品名；ＢＯＮＤ ＡＣＥ Ｗ−０１）を乾燥後の膜厚が５μｍとなるように刷毛で塗布して乾燥させたものと、アセトン拭きした合成ゴムシート（ＪＳＲ（株）製、商品名；ＮＩＰＯＬ ＢＲ１２２０）に乾燥後の膜厚が１μｍとなるようにプライマー組成物（東成化学（株）製、商品名；Ｄ−ＰＬＹ ００７）を塗布した後、さらに乾燥後の膜厚が５μｍとなるように水性ウレタン樹脂（東成化学（株）製、製品名；ＢＯＮＤ ＡＣＥ Ｗ−０１）を刷毛で塗布して乾燥させたものとを６０℃下、４０ｋｇ／ｍ２の力で１０秒間圧着し、４８時間放置した。得られたもののゴム側に１ｃｍ幅で切れ目を入れ、その端部を剥離した後、端部を２００ｍｍ／分の速度で１８０°方向に引っ張り剥離強度を測定し、剥離強度が５ｋｇ／ｃｍ以上、或いは基材が材料破壊するものを○、５ｋｇ／ｃｍ未満のものを×とし、その結果を表−２に記載した。
Evaluation 1
A water-based urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) was applied onto the coating film after being irradiated with ultraviolet rays with a brush so that the film thickness after drying was 5 μm. Primer composition (manufactured by Tosei Chemical Co., Ltd.) so that the film thickness after drying is 1 μm on a dried synthetic rubber sheet (JSR Co., Ltd., trade name: NIPOL BR1220) wiped with acetone. D-PLY 007) is applied, and further, an aqueous urethane resin (manufactured by Tosei Chemical Co., Ltd., product name; BOND ACE W-01) is applied with a brush so as to have a film thickness after drying of 5 μm and dried. The resultant was pressure-bonded at 60 ° C. with a force of 40 kg / m 2 for 10 seconds and left for 48 hours. The obtained rubber was cut with a width of 1 cm on the rubber side, and the end was peeled off, then the end was pulled at a rate of 200 mm / min in the 180 ° direction to measure the peel strength, and the peel strength was 5 kg / cm or more, Or the thing whose base material destroys material is set as (circle) and less than 5 kg / cm as x, and the result was described in Table-2.
評価２
前述の紫外線を照射した後の塗膜上に、水性ウレタン樹脂（東成化学（株）製、製品名；ＢＯＮＤ ＡＣＥ Ｗ−０１）を乾燥後の膜厚が５μｍとなるように刷毛で塗布して乾燥させたものと、ウレタンシート（Ｄａｅ Ｊｉｎ Ｓｙｎｔｈｅｓｉｓ Ｃｈｅｍｉｃａｌ製、ＤＲＹ方式のシューズ用ポリウレタンシート）に乾燥後の膜厚が１μｍとなるようにプライマー組成物（東成化学（株）製、商品名；ＢＯＮＤ ＡＣＥ ２３２Ｈ）を塗布した後、さらに乾燥後の膜厚が５μｍとなるように水性ウレタン樹脂（東成化学（株）製、製品名；ＢＯＮＤ ＡＣＥ Ｗ−０１）を刷毛で塗布して乾燥させたものとを６０℃下、４０ｋｇ／ｍ２の力で１０秒間圧着し、４８時間放置した。得られたもののウレタンシート側に１ｃｍ幅で切れ目を入れ、その端部を剥離した後、端部を２００ｍｍ／分の速度で１８０°方向に引っ張り剥離強度を測定し、剥離強度が５ｋｇ／ｃｍ以上、或いは基材が材料破壊するものを○、５ｋｇ／ｃｍ未満のものを×とし、その結果を表−２に記載した。
Evaluation 2
A water-based urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) was applied onto the coating film after being irradiated with ultraviolet rays with a brush so that the film thickness after drying was 5 μm. Primer composition (manufactured by Tosei Chemical Co., Ltd., trade name; BOND) so that the film thickness after drying is 1 μm on the dried and urethane sheet (Dae Jin Synthesis Chemical, polyurethane sheet for DRY method shoes) After applying ACE 232H), water-based urethane resin (manufactured by Tosei Chemical Co., Ltd., product name; BOND ACE W-01) was applied with a brush and dried so that the film thickness after drying was 5 μm. Were pressed at 60 ° C. with a force of 40 kg / m 2 for 10 seconds and left for 48 hours. Cut the urethane sheet with a width of 1 cm on the side of the obtained product, peel off the end, then measure the peel strength at 180 ° direction at a speed of 200 mm / min, and the peel strength is 5 kg / cm or more. Alternatively, the material that the material of the base material broke down was evaluated as ◯, the material less than 5 kg / cm as ×, and the result is shown in Table-2.
追従性試験
発泡体の接着試験で剥離強度が５ｋｇ／ｃｍ以上、或いは基材が材料破壊するものについて、シートを９０°に折り曲げた後、再び元の状態に戻す試験を１００回行い、折り曲げ部に剥離が起こらなかったものを○、折り曲げ部に塗膜浮きが起こるものを△、折り曲げ時に剥離が起こるものを×とし、その結果を表−２に記載した。
Follow-up test For foams with a peel strength of 5 kg / cm or more, or for materials that break the material of the base material, the sheet is bent 90 ° and then returned to its original state 100 times. The results are shown in Table 2. The results are shown in Table 2, where no peeling occurred, ◯ for coating film floating at the folded portion, and x for peeling when folding occurred.
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