JP2005290313A - Primer for bonding footwear part - Google Patents
Primer for bonding footwear part Download PDFInfo
- Publication number
- JP2005290313A JP2005290313A JP2004110852A JP2004110852A JP2005290313A JP 2005290313 A JP2005290313 A JP 2005290313A JP 2004110852 A JP2004110852 A JP 2004110852A JP 2004110852 A JP2004110852 A JP 2004110852A JP 2005290313 A JP2005290313 A JP 2005290313A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- primer
- thermoplastic elastomer
- copolymerizable
- monoethylenically unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 16
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 17
- -1 polyethylene Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000006260 foam Substances 0.000 description 13
- 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 10
- 238000001035 drying Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229920000180 alkyd Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000012965 benzophenone Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 150000001451 organic peroxides Chemical class 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000014593 oils and fats Nutrition 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 2
- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 2
- BVEIKFLZWBDLJG-UHFFFAOYSA-N 1-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC BVEIKFLZWBDLJG-UHFFFAOYSA-N 0.000 description 2
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
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- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、オレフィン系エラストマーよりなる履物用部品の接着用プライマーに関するものである。 The present invention relates to an adhesive primer for footwear parts made of an olefin-based elastomer.
履物用部品、例えば、スポーツシューズ等の靴底（主にミッドソール）には樹脂の架橋発泡体が使用されている。代表的な発泡体としては加硫ゴムおよび軟質オレフィン系プラスチック、たとえばエチレン・酢酸ビニル共重合体（ＥＶＡ）の発泡体が広く用いられてきた。最近コストや性能面の問題から代替素材としてエチレン・α−オレフィン共重合体が提案されている。しかしながらこのようなオレフィン系エラストマーは非極性であるため従来の接着剤では接着が極めて困難である。 Resin crosslinked foams are used for footwear parts such as sports shoes (mainly midsole) such as sports shoes. As typical foams, vulcanized rubbers and soft olefin plastics such as foams of ethylene / vinyl acetate copolymer (EVA) have been widely used. Recently, ethylene / α-olefin copolymers have been proposed as an alternative material due to cost and performance problems. However, since such an olefin-based elastomer is non-polar, it is extremely difficult to bond with a conventional adhesive.
一般にオレフィン系樹脂を塗装、接着する際には、その表面を活性化することにより表面への付着性を改良するといったことが行われてきた。例えば、自動車用バンパーではその表面をトリクロロエタン等のハロゲン系有機溶剤でエッチング処理することにより塗膜との密着性を高めたり、又はコロナ放電処理やプラズマ処理、もしくはオゾン処理等の前処理をした後において、目的の塗装や接着を行うといったことがなされてきた。しかしながら、これら従来に知られる、汎用の前処理を用いた塗装や接着においては多大な設備費がかかるばかりでなく、施行に長時間を要し、更には仕上がりが一様でなく、表面処理状態に差を生じやすい原因となっていた。そこで、上記した問題が改善される組成物のものとして、例えば塩素化変性ポリオレフィンを主成分とした組成物が提案されてきた。しかしながら、これらは塩素を含有するため環境への負荷や塗膜にした際の柔軟性が乏しい等の問題があり、使用される分野が限られていた。したがって、従来の上述した問題点を解消できる接着用プライマーの出現が望まれていた。
本発明の課題は、上記の背景技術に記載した問題点を解決し、無処理の各種オレフィン系樹脂に対する優れた密着性を示す履物用部品接着用プライマーを提供することにある。 An object of the present invention is to solve the problems described in the background art described above, and to provide a footwear component adhesion primer that exhibits excellent adhesion to various untreated olefinic resins.
本発明者らは、前記課題を達成する接着用プライマーの開発に鋭意研究及び検討を重ねてきた結果、熱可塑性エラストマー（Ａ）、或いは熱可塑性エラストマー（Ａ）の少なくとも一部が官能基で変性されたものと、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）の重合体と、有機溶媒からなる樹脂が極めて有用であることを見出し、本発明を完成するに至った。 As a result of intensive studies and studies on the development of an adhesion primer that achieves the above-mentioned problems, the present inventors have determined that at least a part of the thermoplastic elastomer (A) or the thermoplastic elastomer (A) is modified with a functional group. And a copolymer of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer (B), and a resin comprising an organic solvent. It has been found useful, and the present invention has been completed.
即ち、本発明は、以下の［１］〜［６］で特定される。
［１］熱可塑性エラストマー（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）の重合体と有機溶媒からなる履物用部品接着用プライマー。
［２］熱可塑性エラストマー（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）の重合体と光重合開始剤（Ｄ）と有機溶媒からなる履物用部品接着用プライマー。
［３］（１）有機溶媒中、熱可塑性エラストマー（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）とを重合させるか、又は、（２）有機溶媒中、熱可塑性エラストマー（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）とを重合させたのちラジカルを発生させ反応させるか、又は、（３）有機溶媒中、熱可塑性エラストマー（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させてなる樹脂である履物用部品接着用プライマー。
［４］熱可塑性エラストマー（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）又は共重合性モノマー（Ｂ）で構成された重合体（Ｃ）とを、（Ａ）／（Ｂ）＝１／９〜９／１、或いは（Ａ）／（Ｃ）＝１／９〜９／１の重量比で重合させてなる履物用部品接着用プライマー。
［５］熱可塑性エラストマー（Ａ）に、少なくとも一部が官能基で変性されたものを用いた履物用部品接着用プライマー。
［６］前記履物用部品がオレフィン系樹脂からなることを特徴とする請求項１又は２記載の履物用部品接着用プラマー
である。
That is, the present invention is specified by the following [1] to [6].
[1] Polymer and organic solvent of copolymerizable monomer (B) comprising thermoplastic elastomer (A), monomer having α, β-monoethylenically unsaturated group and other copolymerizable monomer A primer for bonding footwear parts.
[2] Polymer and photopolymerization of thermoplastic elastomer (A), copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers A primer for adhering footwear parts comprising an initiator (D) and an organic solvent.
[3] (1) A copolymerizable monomer (B) comprising a thermoplastic elastomer (A), a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in an organic solvent. Or (2) a thermoplastic elastomer (A) in an organic solvent, a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers. After the copolymerizable monomer (B) is polymerized, a radical is generated and reacted, or (3) the thermoplastic elastomer (A) and an α, β-monoethylenically unsaturated group in an organic solvent A primer for footwear part adhesion, which is a resin formed by reacting a polymer (C) composed of a monomer and a copolymerizable monomer (B) comprising a copolymerizable monomer to generate radicals.
[4] Copolymerizable monomer (B) or copolymerizable monomer comprising a thermoplastic elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers ( B) The polymer (C) composed of (A) / (B) = 1/9 to 9/1, or (A) / (C) = 1/9 to 9/1 in a weight ratio. Primer for bonding footwear parts made by polymerization.
[5] A primer for adhering to footwear parts, wherein the thermoplastic elastomer (A) is at least partially modified with a functional group.
[6] The footwear component bonding plummer according to claim 1 or 2, wherein the footwear component is made of an olefin resin.
本発明の履物用部品接着用プライマーは塩素を含有せず、無処理の各種オレフィン系樹脂へ優れた密着性を示すものである。 The primer for adhering footwear parts of the present invention does not contain chlorine and exhibits excellent adhesion to various untreated olefin resins.
以下に本発明について詳細に説明する。 The present invention is described in detail below.
本発明の履物用部品接着用プライマーは、有機溶剤中、熱可塑性エラストマー（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、或いは熱可塑性エラストマー（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に、さらにラジカルを発生させて反応を行う方法で製造することができる。また、熱可塑性エラストマー（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）で構成された重合体（Ｃ）を添加した後、ラジカルを発生させて反応を行う方法でも製造することができる。 The primer for adhering footwear parts of the present invention is a copolymer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in a thermoplastic elastomer (A) in an organic solvent. After polymerization while feeding the polymerizable monomer (B) and the polymerization initiator, or the thermoplastic elastomer (A) and a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers After the polymerization is carried out while feeding a polymerization initiator to the copolymerizable monomer (B) composed of the body, it can be produced by a method in which a reaction is performed by further generating radicals. In addition, a polymer composed of a copolymerizable monomer (B) composed of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer (B) on the thermoplastic elastomer (A) ( It can also be produced by a method in which, after adding C), a reaction is performed by generating radicals.
さらに、熱可塑性エラストマー（Ａ）の少なくとも一部が官能基で変性されたものに、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させる、或いは熱可塑性エラストマー（Ａ）の少なくとも一部が官能基で変性されたものと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させる方法やさらにこのようにして得られた樹脂溶液に更にラジカルを発生させ反応を行う方法でも製造することができる。また、熱可塑性エラストマー（Ａ）の少なくとも一部が官能基で変性されたものに、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）で構成された重合体（Ｃ）を添加した後、ラジカルを発生させて反応を行う方法でも製造することができる。 Furthermore, a copolymer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in which at least a part of the thermoplastic elastomer (A) is modified with a functional group A monomer having an α, β-monoethylenically unsaturated group and a polymer in which at least a part of the thermoplastic elastomer (A) is modified with a functional group, while being polymerized while feeding the polymerizable monomer (B) and the polymerization initiator The polymerization is carried out while feeding a polymerization initiator to the copolymerizable monomer (B) consisting of a monomer and other copolymerizable monomers, and further a radical is generated in the resin solution thus obtained to carry out the reaction. It can also be produced by a method. Also, a copolymer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in which at least a part of the thermoplastic elastomer (A) is modified with a functional group It can also be produced by a method in which a polymer (C) composed of a polymerizable monomer (B) is added and then a radical is generated to react.
本発明に用いられる熱可塑性エラストマー（Ａ）としては、ポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリ−３−メチル−１−ブテン、ポリ−３−メチル−１−ペンテン、ポリ−４−メチル−1−ペンテン、エチレン・プロピレン共重合体、エチレン・１−ブテン共重合体、プロピレン・１−ブテン共重合体で代表される、エチレン、プロピレン、１−ブテン、３−メチル−１−ブテン、４−メチル−１−ペンテン、３−メチル−１−ペンテン、１−ヘプテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン等のα−オレフィンの単独または２種類以上の共重合体の熱可塑性エラストマ−が挙げられる。 上記の中でも、エチレン−ブテン共重合体、エチレン−プロピレン共重合体、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、プロピレン−ブテン共重合体、プロピレン−オクテン共重合体が好ましく、これらは単独又は２種類以上を組み合わせて用いられる。 Examples of the thermoplastic elastomer (A) used in the present invention include polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl- 1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, represented by propylene / 1-butene copolymer, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4 Of α-olefin such as methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene and 1-dodecene, or a copolymer of two or more kinds thereof A thermoplastic elastomer is mentioned. Among these, an ethylene-butene copolymer, an ethylene-propylene copolymer, an ethylene-octene copolymer, an ethylene-propylene-butene copolymer, a propylene-butene copolymer, and a propylene-octene copolymer are preferable. These may be used alone or in combination of two or more.
また、その重量平均分子量（以下、Ｍｗと略記する。重量平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準として測定される。）は通常、５，０００〜７００，０００の範囲、好ましくは１０，０００〜５００，０００、さらに好ましくは４０，０００〜４００，０００である。 The weight average molecular weight (hereinafter abbreviated as Mw. The weight average molecular weight is measured by, for example, gel permeation chromatography (GPC) using polystyrene as a standard) is usually 5,000 to 700,000. The range is preferably 10,000 to 500,000, more preferably 40,000 to 400,000.
その他、熱可塑性エラストマー（Ａ）としては、スチレン−共役ジエンブロック共重合体の水素添加物、スチレン−共役ジエンランダム共重合体の水素添加物等が挙げられ、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の水素添加物、スチレン−共役ジエン−スチレンのトリブロック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。上記の中でも、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−ブタジエンのランダム共重合体の水素添加物が好ましい。ここで用いられる熱可塑性エラストマーは、そのスチレンの含有量が通常２〜６０重量％、より好ましくは３〜４５重量％の範囲のものである。 Other examples of the thermoplastic elastomer (A) include hydrogenated styrene-conjugated diene block copolymers, hydrogenated styrene-conjugated diene random copolymers, and the like. Examples of the structure of the hydrogenated product include a hydrogenated product of a styrene-conjugated diene diblock copolymer, a hydrogenated product of a styrene-conjugated diene-styrene triblock copolymer, and the like. Examples of the conjugated diene used here include butadiene and isoprene. Among these, a hydrogenated product of a styrene-isoprene-styrene triblock copolymer and a hydrogenated product of a random copolymer of styrene-butadiene are preferable. The thermoplastic elastomer used here has a styrene content of usually 2 to 60% by weight, more preferably 3 to 45% by weight.
また、その重量平均分子量（以下、Ｍｗと略記する）が５，０００〜７００，０００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５，０００〜５００，０００、さらには１０，０００〜４００，０００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。 The weight average molecular weight (hereinafter abbreviated as Mw) is preferably in the range of 5,000 to 700,000, and in the case of hydrogenated styrene-isoprene-styrene copolymer, 5,000 to 500,000, 10,000 to 400,000 are preferred. Moreover, in the hydrogenated product of a styrene-butadiene copolymer, 10,000-700,000, Furthermore, 50,000-500,000 are preferable.
上記の熱可塑性エラストマーは、単独或いは２種以上併用して用いることができる。 Said thermoplastic elastomer can be used individually or in combination of 2 or more types.
さらに、熱可塑性エラストマー（Ａ）の少なくとも一部が官能基で変性されたものは、上記記載の熱可塑性エラストマー、またはこれら２種以上の混合物に、以下記載の官能基を含有した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を反応させて得られるが、一部に反応しないものを含んでも何ら問題ない。 Furthermore, the thermoplastic elastomer (A) at least partially modified with a functional group is an α, β- containing the functional group described below in the thermoplastic elastomer described above or a mixture of two or more thereof. Although it can be obtained by reacting a monomer having a monoethylenically unsaturated group and another copolymerizable monomer comprising a copolymerizable monomer, there is no problem even if some of them do not react.
ここで用いられる、官能基を含有した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、メタクリル酸、マレイン酸、イタコン酸、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、アクリルアミド、メタクリルアミド、メチロールアクリルアミド、メチロールメタクリルアミド等の窒素化合物、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が挙げられ、これらは単独でも、２種以上でも使用できる。 As the copolymerizable monomer composed of a monomer having an α, β-monoethylenically unsaturated group containing a functional group and other copolymerizable monomers used here, hydroxyethyl acrylate, 2-hydroxy Hydroxyl-containing vinyls such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, methacrylic acid Carboxyl group-containing vinyls such as acid, maleic acid, itaconic acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylamide, methacrylamide, methylolacrylamide, methylolmethacrylate Nitrogen compounds such as bromide, maleic anhydride, include carboxylic anhydrides such as citraconic anhydride, it alone, can be used even more.
上記官能基を含有した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の添加量は通常、熱可塑性エラストマーの重量に対し０．５〜２０重量％の範囲、より好ましくは１〜１５重量％である。 The addition amount of the copolymerizable monomer composed of the above-mentioned functional group-containing monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers is usually 0 with respect to the weight of the thermoplastic elastomer. The range is from 5 to 20% by weight, more preferably from 1 to 15% by weight.
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。 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、２−エチルヘキシル（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、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、メタクリル酸、マレイン酸、イタコン酸、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及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、その他アクリロニトリル、メタクリルニトリル、酢酸ビニル、プロピオン酸ビニル、アクリルアミド、メタクリルアミド、メチロールアクリルアミド、及びメチロールメタクリルアミド、エチレン、プロピレン、Ｃ４〜Ｃ２０のα−オレフィン等が挙げられる。また、上記単量体、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, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth ) Acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid esters such as diethylaminoethyl (meth) acrylate, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydride Hydroxyl-containing vinyls such as loxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, Carboxyl group-containing vinyls such as ω-carboxy-polycaprolactone monoacrylate and phthalic acid monohydroxyethyl acrylate, and monoesters thereof, epoxy group-containing vinyls such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate, vinyl Isocyanate group-containing vinyls such as isocyanate and isopropenyl isocyanate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and t-butylstyrene, and other acetates Examples include acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide, ethylene, propylene, C 4 to C 20 α-olefins, and the like. 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.
また、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。これらは、α，β−モノエチレン性不飽和基を有する単量体を主成分として用いることが好ましい。また、α，β−モノエチレン性不飽和基を有する単量体を主成分に、その他共重合可能な単量体を併用することもできる。 Examples of the copolymerizable monomer comprising 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. It is preferable to use a monomer having an α, β-monoethylenically unsaturated group as a main component. Further, a monomer having an α, β-monoethylenically unsaturated group as a main component and other copolymerizable monomers can be used in combination.
本発明で用いられる重合体（Ｃ）は、上記記載の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、熱可塑性エラストマー（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）の比率は、重量比で（Ａ）／（Ｂ）＝１／９〜９／１、或いは（Ａ）／（Ｃ）＝１／９〜９／１、好ましくは（Ａ）／（Ｂ）＝２／８〜８／２、或いは（Ａ）／（Ｃ）＝２／８〜５．５／４．５である。熱可塑性エラストマー（Ａ）の含有量が少なくなると各種ポリオレフィン系基材への密着が低下し、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）の含有量が少なくなると接着剤に対する密着性が低くなるため、上記範囲が好ましい。 The polymer (C) used in the present invention is composed of a copolymerizable monomer (B) comprising the above-described monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers. Is done. In the present invention, a copolymerizable monomer (B) comprising a thermoplastic 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) = 1/9 to 9/1 by weight ratio, or (A) / (C) = 1/9 to 9/1, preferably (A) / ( B) = 2/8 to 8/2, or (A) / (C) = 2/8 to 5.5 / 4.5. When the content of the thermoplastic elastomer (A) decreases, the adhesion to various polyolefin-based substrates decreases, and it is composed of a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers. Since the adhesiveness to the adhesive is lowered when the content of the copolymerizable monomer (B) or the polymer (C) is decreased, the above range is preferable.
本発明のプライマーを得る際に用いる溶剤としては、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、熱可塑性エラストマー（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。 Solvents used in obtaining the primer of 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, Alicyclic hydrocarbons such as ethylcyclohexane, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ester systems such as 3 methoxybutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. Organic solvents such as ketone solvents 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 thermoplastic 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、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 cumene hydroperoxide, azobisisobutyronitrile, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-methyl-N- (2-hydroxy) And azo compounds such as ethyl) propioamide). 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。光重合開始剤としては、例えば、ベンゾフェノン、ジアセチル、ベンジル、ベンゾイン、２−メチルベンゾイン、ω−ブロモアセトフェノン、クロロアセトン、アセトフェノン、２，２−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、２−ヒドロキシ−２−メチルプロピオフェノン、２−クロロベンゾフェノン、ｐ−ジメチルアミノプロピオフェノン、ｐ−ジメチルアミノアセトフェノン、ｐ，ｐ’−ビスジエチルアミノベンゾフェノン、３，３’−４，４’−テトラ−ベンゾフェノン、ミヒラーケトン、ベンゾインメチルエーテル、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、ベンゾイン−ｎ−ブチルエーテル、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド、ベンジルジメチルケタール、メチルベンゾイルホルメート等のカルボニル類、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モノスルフィド等のスルフィド類、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、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が挙げられるが、これらは単独或いは２種以上併用して用いても良い。又、これらの光重合開始剤には、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用いても良い。 Further, the radical generation method in the case of performing the reaction by further generating radicals uses a known method such as a method of irradiating light in the presence of a photopolymerization initiator or a method of adding an organic peroxide. can do. Examples of the photopolymerization initiator include benzophenone, diacetyl, benzyl, benzoin, 2-methylbenzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone. 2-hydroxy-2-methylpropiophenone, 2-chlorobenzophenone, p-dimethylaminopropiophenone, p-dimethylaminoacetophenone, p, p'-bisdiethylaminobenzophenone, 3,3'-4,4'- Tetra-benzophenone, Michler's ketone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 2,4,6-trimethylbenzoyldiphenylphosphineoxy Carbonyls such as benzyl dimethyl ketal and methyl benzoyl formate, sulfides such as diphenyl disulfide, dibenzyl disulfide, tetramethyl thiuram monosulfide, quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethyl anthraquinone, butyl anthraquinone, thioxanthone, Examples thereof include thioxanthones such as 2-methylthioxanthone and 2-chlorothioxanthone, but these may be used alone or in combination of two or more. These photopolymerization initiators include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline and trimethylbenzylammonium chloride, allylphosphines such as triphenylphosphine, and β-thiodiglycol. A thiol ether such as the above may be used in combination.
上記光重合開始剤の使用量は、前記熱可塑性エラストマー（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。 The amount of the photopolymerization initiator used is usually 0.01 to 10% by weight based on the total weight of the thermoplastic elastomer (A) and the copolymerizable monomer (B) or polymer (C). Preferably, a great effect on the stability appears when used in the range of 0.1 to 5% by weight.
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、上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、熱可塑性エラストマーとのグラフト率を向上させる効果がある。 上記有機過酸化物の使用量は、熱可塑性エラストマー（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。上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。 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-mentioned organic peroxides, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are more preferably used. That is, the 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 thermoplastic elastomer. The amount of the organic peroxide used is usually 2 to 50% by weight, more preferably 3 to the total weight of the thermoplastic 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 to add this little by little.
本発明で用いられる光重合開始剤（Ｄ）としては紫外線照射によりラジカルを発生するものであればいずれも使用できる。たとえば、ベンゾフェノン、ジアセチル、ベンジル、ベンゾイン、２−メチルベンゾイン、ω−ブロモアセトフェノン、クロロアセトン、アセトフェノン、２，２−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、２−ヒドロキシ−２−メチルプロピオフェノン、２−クロロベンゾフェノン、ｐ−ジメチルアミノプロピオフェノン、ｐ−ジメチルアミノアセトフェノン、ｐ，ｐ’−ビスジエチルアミノベンゾフェノン、３，３’−４，４’−テトラ−ベンゾフェノン、ミヒラーケトン、ベンゾインメチルエーテル、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、ベンゾイン−ｎ−ブチルエーテル、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド、ベンジルジメチルケタール、メチルベンゾイルホルメート等のカルボニル類、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モノスルフィド等のスルフィド類、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、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が挙げられるが、これらは単独或いは２種以上併用して用いても良い。又、これらの光重合開始剤には、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用いても良い。上記した光重合開始剤のうちでも、ベンゾフェノン、３，３’−４，４’−テトラ−ベンゾフェノン等水素引抜能力が比較的高く、基材との密着性を向上させる効果がある、分子内にベンジル基を有するものがより好適に用いられる。 As the photopolymerization initiator (D) used in the present invention, any photopolymerization initiator (D) may be used as long as it generates radicals upon irradiation with ultraviolet rays. For example, benzophenone, diacetyl, benzyl, benzoin, 2-methylbenzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- Methylpropiophenone, 2-chlorobenzophenone, p-dimethylaminopropiophenone, p-dimethylaminoacetophenone, p, p'-bisdiethylaminobenzophenone, 3,3'-4,4'-tetra-benzophenone, Michler's ketone, benzoin Methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethyl Tars, carbonyls such as methylbenzoyl formate, sulfides such as diphenyl disulfide, dibenzyl disulfide, tetramethylthiuram monosulfide, quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethylanthraquinone, butylanthraquinone, thioxanthone, 2-methyl Examples include thioxanthones such as thioxanthone and 2-chlorothioxanthone, but these may be used alone or in combination of two or more. These photopolymerization initiators include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline and trimethylbenzylammonium chloride, allylphosphines such as triphenylphosphine, and β-thiodiglycol. A thiol ether such as the above may be used in combination. Among the above-mentioned photopolymerization initiators, benzophenone, 3,3′-4,4′-tetra-benzophenone and the like have a relatively high hydrogen abstraction ability, and have an effect of improving the adhesion to the substrate. Those having a benzyl group are more preferably used.
上記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 manufacturing the primer, 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、水酸基を有する上記ポリエステルに、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。上記、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プライマーは、とりわけ各種オレフィン系樹脂との相溶性が良く、接着剤との密着が良好で、特にヒマシ油を含むものは効果が大きい。 Also, a resin containing a polymerizable unsaturated bond in the molecule obtained by adding a carboxylic anhydride having a polymerizable unsaturated bond in the molecule to the polyester having a hydroxyl group can 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, primers obtained using oils and fats and derivatives of oils and fats as the third component are particularly compatible with various olefinic resins, have good adhesion to adhesives, and particularly those containing castor oil. Great effect.
以上説明したような有機溶媒中における反応により得た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。 For the primer obtained by the reaction in the organic solvent as described above, for example, after removing the solvent during the reaction, a method of adding a desired solvent to dissolve and disperse the resin, or adding a desired solvent Then, it can be changed to a resin solution having a desired solvent composition by, for example, a method of removing the solvent during the reaction.
本発明のプライマーがとる構造としては、相分離構造がある。具体的には、熱可塑性エラストマー（Ａ）、熱可塑性エラストマー（Ａ）の少なくとも一部が官能基で変性された樹脂を中心とした成分と、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）の重合体を中心とした成分がそれぞれ相を形成する。その構造は、一方がマトリックスを形成し、他方が球状、楕円等の独立相を有する海島構造や、両方の樹脂がそれぞれ相構造を持ち、その相構造が３次元的に連続している相分離構造、即ち共連続構造をとるものがある。海島構造をとるものは部分的に島同士がつながったものを有していても良く、また共連続構造を有するものは部分的に途切れた箇所や海島構造を含有していても良い。 The structure of the primer of the present invention includes a phase separation structure. Specifically, a thermoplastic elastomer (A), a component centered on a resin in which at least a part of the thermoplastic elastomer (A) is modified with a functional group, and a single monomer having an α, β-monoethylenically unsaturated group. Components centering on the polymer of the copolymerizable monomer (B) composed of the monomer and other copolymerizable monomers each form a phase. The structure is a sea-island structure in which one side forms a matrix and the other side has an independent phase such as a sphere or ellipse, and both resins have a phase structure, and the phase structure is three-dimensionally continuous. Some have a structure, that is, a co-continuous structure. Those having a sea-island structure may have a part in which islands are partially connected, and those having a co-continuous structure may contain a partly discontinuous portion or a sea-island structure.
これらの構造において、海島構造を有するものは、その平均粒子径が０．０００１〜１０μｍの範囲が好ましく、０．０００５〜５μｍの範囲がさらに好ましい。また、共連続構造を有するものは、その網目の寸法は、厚さ方向に０．０００１〜１０μｍの範囲が好ましく、０．０００５〜５μｍの範囲がさらに好ましい。 Among these structures, those having a sea-island structure preferably have an average particle size in the range of 0.0001 to 10 μm, and more preferably in the range of 0.0005 to 5 μm. Moreover, what has a co-continuous structure has the mesh | network dimension in the range of 0.0001-10 micrometers in the thickness direction, and the range of 0.0005-5 micrometers is further more preferable.
また、本発明のプライマーは、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、酸化防止剤、耐候安定剤、耐熱防止剤等の各種安定剤、添加剤等の成分を本発明の目的を損なわない範囲で含有させることができる。 In addition, the primer of the present invention may be prepared by using an organic pigment such as an azo pigment or phthalocyanine blue, a dye such as an azo dye or an anthraquinone dye, a colorant such as an inorganic pigment such as titanium oxide, molybdenum, or carbon black, an oxidation pigment, if necessary. Components such as various stabilizers such as an inhibitor, a weather resistance stabilizer, and a heat resistance inhibitor, and additives can be contained within a range that does not impair the object of the present invention.
本発明のプライマーの塗布方法は特に限定するものではなく、たとえば、噴霧塗布、刷毛塗り等により塗布を行うことができる。塗布は通常、常温にて容易に行うことができ、光重合開始剤（Ｄ）を含有するものについては塗布後に紫外線を照射するのが好適である。紫外線を照射する方法については、特に限定されることはなく、被塗物が変形したり、変色したりしない程度の強度で紫外線を照射する。また塗布後の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。
本発明のプライマーはポリオレフィン系樹脂からなる履物用部品接着用プライマーとして広く使用することができる。たとえばポリオレフィン系発泡体からなるミッドソールとインソール（ポリウレタン製等）およびアウトソール（ゴム製等）の接着を行う際のポリオレフィン用プライマーとして使用する事ができる。
The primer application method of the present invention is not particularly limited, and for example, application can be performed by spray application, brush application, or the like. Application can usually be performed easily at room temperature, and those containing a photopolymerization initiator (D) are preferably irradiated with ultraviolet rays after application. The method of irradiating the ultraviolet rays is not particularly limited, and the ultraviolet rays are irradiated with an intensity that does not cause the object to be coated to be deformed or discolored. Moreover, there is no limitation in particular also about the drying method after application | coating, It can dry by appropriate methods, such as natural drying and heat forced drying.
The primer of the present invention can be widely used as a primer for footwear parts made of polyolefin resin. For example, it can be used as a polyolefin primer for bonding a midsole made of a polyolefin-based foam, an insole (made of polyurethane, etc.) and an outsole (made of rubber, etc.).
以下、本発明の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。また、以下において、部および％は特記していない限り重量基準である。
［実施例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、熱可塑性エラストマーとしてダイナロン１３２０Ｐを１００部とメチルシクロヘキサン（以下ＭＣＨと略す）を３５０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、官能基を有する重合性モノマーとしてプラクセルＦＭ−３を６部添加、分散させた後、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）を６部添加して１時間反応させた。その後ＭＣＨを２００部添加して、熱可塑性エラストマーの少なくとも一部が官能基で変性された樹脂を得た。次いで、反応器内を９５℃に保持したまま、重合可能な単量体としてメチルメタアクリレート４５．５部とエチルアクリレート３６．８部と２−ヒドロキシエチルメタアクリレート１０部とプラクセルＦＭ−３を６．７部とメタクリル酸１部とＰＢＯ１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時間後に、ＰＢＯを０．５部添加し、更に１時間後にＰＢＯを０．５部添加した。このＰＢＯ添加より２時間放置して反応させプライマーを得た。なお、上記で熱可塑性エラストマーとして用いたダイナロン１３２０ＰはＪＳＲ（株）製の水素添加スチレン−ブタジエン共重合体で、官能基を有する重合性モノマーとして用いたプラクセルＦＭ−３はダイセル化学工業（株）製の不飽和脂肪酸ヒドロキシアルキルエーテル修飾ε−カプロラクトンである。
ある。
［実施例２］
実施例１で得られたプライマーに光重合開始剤（Ｄ）であるイルガキュア５００（商品名；チバ・スペシャリティ・ケミカルズ（株）製、１−ヒドロキシ−シクロヘキシルフェニルケトンとベンゾフェノンの共融混合物）を樹脂成分１００部に対して２部添加し、プライマーを得た。
［実施例３]
実施例１で得られたプライマーに光重合開始剤（Ｄ）であるイルガキュア１８４（商品名；チバ・スペシャリティ・ケミカルズ（株）製、１−ヒドロキシ−シクロヘキシルフェニルケトン）を樹脂成分１００部に対して２部添加し、プライマーを得た。
［比較例１］
上記プライマーを使用せず以下の接着評価を行った。
＜＜接着評価＞＞
上記で得られたプライマーを、実施例に用いたものと同一の溶剤を添加し、不揮発分が１０％になるように調整した。次いで、特開２０００−３４４９２４号公報の実施例１に記載された方法によって作製された発泡体を混合溶剤（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部／２０部／１５部）に１分間浸漬した後、乾燥後の膜厚が３μｍとなるように上記プライマーを刷毛で塗布して乾燥させた。
Hereinafter, although the manufacturing method of the primer of this invention and various test examples are given and demonstrated further, this invention is not limited to these Examples. In the following, parts and% are based on weight unless otherwise specified.
[Example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was charged with 100 parts of Dynalon 1320P and 350 parts of methylcyclohexane (hereinafter abbreviated as MCH) as a thermoplastic elastomer, and 95 while replacing with nitrogen. The temperature was raised to ° C. Next, 6 parts of Plaxel FM-3 as a polymerizable monomer having a functional group was added and dispersed therein, followed by 6 parts of tert-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as PBO). The mixture was added and allowed to react for 1 hour. Thereafter, 200 parts of MCH was added to obtain a resin in which at least a part of the thermoplastic elastomer was modified with a functional group. Subsequently, while maintaining the inside of the reactor at 95 ° C., 45.5 parts of methyl methacrylate, 36.8 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, and 6 parts of Plaxel FM-3 were obtained as polymerizable monomers. A mixed solution of 7 parts, 1 part of methacrylic acid and 1 part of PBO was fed over 4 hours. One hour after the end of the feed, 0.5 part of PBO was added, and after another hour, 0.5 part of PBO was added. A primer was obtained by allowing to react for 2 hours after the addition of PBO. Incidentally, Dynalon 1320P used as the thermoplastic elastomer above is a hydrogenated styrene-butadiene copolymer manufactured by JSR Corporation, and Plaxel FM-3 used as a polymerizable monomer having a functional group is Daicel Chemical Industries, Ltd. Unsaturated fatty acid hydroxyalkyl ether modified ε-caprolactone.
is there.
[Example 2]
Irgacure 500 (trade name; manufactured by Ciba Specialty Chemicals Co., Ltd., eutectic mixture of 1-hydroxy-cyclohexyl phenyl ketone and benzophenone), which is a photopolymerization initiator (D), is used as a primer for the primer obtained in Example 1. 2 parts were added to 100 parts of the component to obtain a primer.
[Example 3]
Irgacure 184 (trade name; manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl phenyl ketone) as a photopolymerization initiator (D) is added to the primer obtained in Example 1 with respect to 100 parts of the resin component. 2 parts were added to obtain a primer.
[Comparative Example 1]
The following adhesion evaluation was performed without using the primer.
<< Adhesion evaluation >>
The primer obtained above was adjusted to have a non-volatile content of 10% by adding the same solvent as used in the examples. Next, the foam produced by the method described in Example 1 of JP-A-2000-344924 was immersed in a mixed solvent (methylcyclohexane / isopropyl alcohol / methyl ethyl ketone = 65 parts / 20 parts / 15 parts) for 1 minute. Thereafter, the primer was applied with a brush so that the film thickness after drying was 3 μm and dried.
実施例２および３に記載のプライマーについては、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紫外線照射装置（日本電池（株）製、ＥＰＳＨ−６００−３Ｓ型）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。また、比較例については、上記の溶剤浸漬を行った発泡体をそのまま使用し、下記の２方法で接着評価を行った。
＜評価１＞
上記の処理を施した発泡体表面に、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：ＮＩＰＯＬＢＲ１２２１）に乾燥後の膜厚が１μｍとなるようにプライマー（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。
For the primers described in Examples 2 and 3, an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd., EPSH-600-3S type) in which one 80 W / cm high-pressure mercury lamp was installed perpendicularly to the passing direction was used. Placed at a position 15 cm under the light source, the conveyor speed was moved at a speed of 10 m / min, and ultraviolet rays were irradiated. Moreover, about the comparative example, the foam which performed said solvent immersion was used as it was, and adhesive evaluation was performed by the following two methods.
<Evaluation 1>
A water-based urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) is applied to the surface of the foam subjected to the above treatment with a brush so that the film thickness after drying is 5 μm and dried. A primer (manufactured by Tosei Chemical Co., Ltd., trade name: D-PLY 007) so that the film thickness after drying on a synthetic rubber sheet (JSR Co., Ltd., trade name: NIPOLBR1221) wiped with acetone is 1 μm. ), And after applying an aqueous urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) with a brush so that the film thickness after drying is 5 μm. The pressure was applied at 60 ° C. with a force of 40 kg / m 2 for 10 seconds and left for 48 hours.
上記のようにして得られたものを２ｃｍ×１０ｃｍに切断し試験片を得た。上記試験片の一端を固定し、中央部付近から９０°に折り曲げ、次いで反対方向に９０°折り曲げ、これを１回として、１００００回屈曲を行った後プライマーと発泡体の界面の状態を観察し剥離がみられるものを×とし、剥離のみられないものについて、強制剥離を行い、発泡体との界面で剥離したものを○、発泡体の材料破壊をおこしたものを◎とし、その結果を表１に示した。
＜評価２＞
上記の処理を施した発泡体表面に、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（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。
What was obtained as described above was cut into 2 cm × 10 cm to obtain test pieces. One end of the above test piece is fixed, bent at 90 ° from the vicinity of the center, and then bent at 90 ° in the opposite direction. This is taken as one time, and after bending 10,000 times, the state of the interface between the primer and the foam is observed. The case where peeling was observed was marked as x, and for those where peeling was not possible, forced peeling was carried out, where ○ was peeled off at the interface with the foam, and ◎ was caused when the foam material was destroyed. It was shown in 1.
<Evaluation 2>
A water-based urethane resin (manufactured by Tosei Chemical Co., Ltd., product name: BOND ACE W-01) is applied to the surface of the foam subjected to the above treatment with a brush so that the film thickness after drying is 5 μm and dried. And a primer (manufactured by Tosei Chemical Co., Ltd., trade name: BOND ACE 232H) on a urethane sheet (Dae Jin Synthesis Chemical, polyurethane sheet for DRY-type shoes) so that the film thickness after drying becomes 1 μm. After coating, a 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. For 10 seconds with a force of 40 kg / m 2 and left for 48 hours.
上記のようにして得られたものを２ｃｍ×１０ｃｍに切断し試験片を得た。上記試験片の一端を固定し、中央部付近から９０°に折り曲げ、次いで反対方向に９０°折り曲げ、これを１回として、１００００回屈曲を行った後プライマーと発泡体の界面の状態を観察し剥離がみられるものを×とし、剥離のみられないものについて、強制剥離を行い、発泡体との界面で剥離したものを○、発泡体の材料破壊をおこしたものを◎とし、その結果を表１に示した。 What was obtained as described above was cut into 2 cm × 10 cm to obtain test pieces. One end of the above test piece is fixed, bent at 90 ° from the vicinity of the center, and then bent at 90 ° in the opposite direction. This is taken as one time, and after bending 10,000 times, the state of the interface between the primer and the foam is observed. The case where peeling was observed was marked as x, and for those where peeling was not possible, forced peeling was carried out, where ○ was peeled off at the interface with the foam, and ◎ was caused when the foam material was destroyed. It was shown in 1.
本発明の履物用部品接着用プライマーは、履物用部品、たとえばポリオレフィン系発泡体からなるミッドソールと、インソール（ポリウレタン製等）およびアウトソール（ゴム製等）の接着を行う際のポリオレフィン用プライマーとして使用する事ができる。
The primer for adhering footwear parts of the present invention is used as a primer for polyolefin when adhering footwear parts, for example, a midsole made of a polyolefin-based foam, an insole (made of polyurethane, etc.) and an outsole (made of rubber, etc.). Can be used.
Claims (6)
The primer for bonding footwear parts according to claim 1 or 2, wherein the footwear parts are made of an olefin resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004110852A JP2005290313A (en) | 2004-04-05 | 2004-04-05 | Primer for bonding footwear part |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004110852A JP2005290313A (en) | 2004-04-05 | 2004-04-05 | Primer for bonding footwear part |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005290313A true JP2005290313A (en) | 2005-10-20 |
Family
ID=35323604
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004110852A Pending JP2005290313A (en) | 2004-04-05 | 2004-04-05 | Primer for bonding footwear part |
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| Country | Link |
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| JP (1) | JP2005290313A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302735A (en) * | 2006-05-09 | 2007-11-22 | Mitsui Chemicals Inc | Optical coating material |
| KR20230164114A (en) | 2021-03-29 | 2023-12-01 | 도요보 엠씨 가부시키가이샤 | Polyolefin-based adhesive composition and laminate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000502964A (en) * | 1995-12-21 | 2000-03-14 | ザ・ダウ・ケミカル・カンパニー | Manufacturing method of laminate |
| WO2002057357A1 (en) * | 2001-01-17 | 2002-07-25 | Mitsui Chemicals, Inc. | Resin composition, coating materials containing the same, coating film and process for forming the film |
| JP2003521547A (en) * | 1997-07-18 | 2003-07-15 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Adhesion of primer composition and organic polymer substrate |
-
2004
- 2004-04-05 JP JP2004110852A patent/JP2005290313A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000502964A (en) * | 1995-12-21 | 2000-03-14 | ザ・ダウ・ケミカル・カンパニー | Manufacturing method of laminate |
| JP2003521547A (en) * | 1997-07-18 | 2003-07-15 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Adhesion of primer composition and organic polymer substrate |
| WO2002057357A1 (en) * | 2001-01-17 | 2002-07-25 | Mitsui Chemicals, Inc. | Resin composition, coating materials containing the same, coating film and process for forming the film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007302735A (en) * | 2006-05-09 | 2007-11-22 | Mitsui Chemicals Inc | Optical coating material |
| KR20230164114A (en) | 2021-03-29 | 2023-12-01 | 도요보 엠씨 가부시키가이샤 | Polyolefin-based adhesive composition and laminate |
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