JPH034266B2 - - Google Patents
Info
- Publication number
- JPH034266B2 JPH034266B2 JP60147288A JP14728885A JPH034266B2 JP H034266 B2 JPH034266 B2 JP H034266B2 JP 60147288 A JP60147288 A JP 60147288A JP 14728885 A JP14728885 A JP 14728885A JP H034266 B2 JPH034266 B2 JP H034266B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- pattern
- paint
- acid derivative
- silicone
- 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.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 claims description 43
- 239000005060 rubber Substances 0.000 claims description 43
- 239000003973 paint Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 12
- 229920002379 silicone rubber Polymers 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 238000009415 formwork Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000004945 silicone rubber Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004447 silicone coating Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- -1 chloroprene compound Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Description
発明の目的
(産業上の利用分野)
本発明は各種ゴムからなる成形品の表面に模様
を形成する方法に関するものである。
(従来の技術)
ゴム成形品の表面に装飾などの目的で種々の模
様を形成するには、ゴムの成形時、すなわちゴム
の練生地を圧縮成形あるいは射出成形する際の金
型面に所望する模様を形成して行うのが通例であ
る。しかし、成形時に模様を形成する上記方法は
大量生産には適しているが、多種の模様を少量の
成形品に形成しようとする場合には金型の製造コ
ストが高価になるため採用することが困難であ
り、成形後の製品に別途、模様を形成する方法を
採用する必要がある。
(発明が解決しようとする問題点)
成形後の製品に模様を形成する方法としては、
ゴム成形品の表面に別途、予め模様の形成された
ゴム製薄膜層を接着したり、あるいは、ゴム成形
品の表面に塗料または接着剤を塗布して塗膜層を
形成し、その塗膜層に所定の模様が形成された型
枠を押圧して塗膜層を硬化させた後、この型枠を
除去することにより前記塗膜層に模様を転写する
方法が考えられる。
ところが、ゴム成形品は合成樹脂成形品と異な
り、使用に際しての形状の変形が極極めて大き
い。
そのため、従来各種のゴム基材の表面に塗布さ
れている塗料や接着剤、すなわちスチレン−ブタ
ジエン共重合ゴム(SBR)系や天然ゴム(NR)
系の塗料、接着剤を用いた場合、密着力の不足か
らゴム成形品の変形時に上記ゴム製薄膜層や塗膜
層が同ゴム成形品から剥離するのを防止できない
ため、上記いずれの方法も現実には、未だ採用さ
れるに至つていないのが現状である。
上記問題点に鑑み、本発明者らは長年研究を行
つた結果、ゴム成形品が変形を繰り返しても密着
力の低下し難い塗料を見出し、これをゴム成形品
の表面に塗布することにより簡単にその表面に模
様を形成する方法を案出し、本発明に到達するに
至つたものである。
発明の構成
(問題点を解決するための手段)
上記問題点を解決するため、本発明はゴム成形
品の表面にゴム系塗料を塗布し、次いで前記塗料
の塗布された面に型枠を押圧した後、前記塗料を
硬化させ、しかる後前記型枠を除去することによ
りゴム成形品の表面に模様を形成する方法におい
て、前記ゴム系塗料には、
(a) ポリメタクリル酸誘導体またはポリアクリル
酸誘導体の少なくとも一種と、クロロプレンゴ
ムと、フエノール樹脂との混合物、または
(b) メタクリル酸誘導体またはアクリル酸誘導体
の少なくとも一種とクロロプレンゴムとの重合
体と、フエノール樹脂との混合物、
より選ばれたいずれか一種を用いることを特徴と
するゴム成形品の模様形成法を採用したものであ
る。
(作用)
ゴム成形品の表面に前記ゴム系塗料を塗布後、
各種模様の形成された型枠を前記塗料の未硬化時
にその塗膜面に押圧して塗料を硬化させ、次いで
上記型枠を除去することにより、予め型枠に形成
された各種模様が上記塗膜面に転写される。
さらに、前記ゴム系塗料はいずれも上記ゴム成
形品に対し強固な密着力と追従性を備えているた
め、このような凹凸模様の形成された塗膜層は長
期間の使用においても剥離の虞れがない。
(実施例)
本発明の模様形成法を説明するに先立つて、前
記ゴム系塗料の組成および型枠素材につき説明す
る。前記ゴム系塗料とは具体的には、
(a) ポリメタクリル酸誘導体またはポリアクリル
酸誘導体の少なくとも一種と、クロロプレンゴ
ムと、フエノール樹脂との混合物、または
(b) メタクリル酸誘導体またはアクリル酸誘導体
の少なくとも一種とクロロプレンゴムとの重合
体と、フエノール樹脂との混合物、
より選ばれたいずれか一種からなるゴム系塗料で
あり、以下、(a)〜(b)のそれぞれの組成につき詳述
する。
(a) まず、(a)のゴム系塗料を構成するポリメタク
リル酸誘導体とは、メチルメタクリレート、エ
チルメタクリレート、n−ブチルメタクリレー
ト、iso−ブチルメタクリレート、2−エチル
ヘキシルメタクリレート、イソデシルメタクリ
レート、2−ヒドロキシエチルメタクリレー
ト、2−ヒドロキシプロピルメタクリレート、
グリシジルメタクリレート、ジメチルアミノエ
チルメタクリレートの各ポリマーを例示するこ
とができる。
また、ポリアクリル酸誘導体とは、エチルア
クリレート、n−ブチルアクリレート、iso−
ブチルアクリレート、2−エチルヘキシルアク
リレート、イソデシルアクリレート、2−ヒド
ロキシエチルアクリレート、2−ヒドロキシプ
ロピルアクリレート、ジメチルアミノエチルア
クリレートの各ポリマーを例示することができ
る。
なお、上記ポリメタクリル酸誘導体やポリア
クリル酸誘導体は数種を混合して使用すること
も可能であり、さらにこれらの外、ポリアクリ
ル酸やポリメタクリル酸を使用してもよい。
また、ポリアクリル酸誘導体および/または
ポリメタクリル酸誘導体とクロロプレンゴムと
の混合割合は、クロロプレンゴム100重量部に
対し500重量部以下が好ましく、500重量部を超
えると次第に密着力が低下する。
次に、フエノール樹脂としては、タマノル
520S、タマノル521、タマノル526、タマノル
586(以上、いずれも荒川化学製フエノール樹
脂)などが例示できる。あるいは、同社製のテ
ルペンフエノール樹脂であるタマノル803や同
じく同社製ロジン変性フエノール樹脂であるタ
マノル135、タマノル340、タマノル350なども
例示することができる。なお、これらのフエノ
ール樹脂の場合も、数種を混合して使用するこ
とが可能である。
上記フエノール樹脂の混合割合は、クロロプ
レンゴム100重量部に対し1〜50重量部が好ま
しく、1部未満では効果がない。また、50重量
部以上では塗料の硬度が高く、塗膜が硬くなる
ためにゴム成形品に歪をかけた場合、剥離が生
じやすくなる。なお、これらの混合の際用いる
溶剤としてはベンゼン、トルエン、キシレンな
どの芳香炭化水素;ジオキサン、テトラヒドロ
フランなどのエーテル類;酢酸メチル、酢酸イ
ソプロピルなどの酢酸エステル類;メチルエチ
ルケトン、アセトン、シクロヘキサノンなどの
ケトン類;塩化エチル、クロロホルム、四塩化
炭素などの塩素系炭化水素などから適宜選択さ
れた溶剤、もしくは二種以上の混合溶剤であ
る。
(b) 次に、メタクリル酸誘導体またはアクリル酸
誘導体の少なくとも一種とクロロプレンゴムと
の重合体と、フエノール樹脂との混合物からな
るゴム系塗料とは、クロロプレンゴム100重量
部に対し、上記例示のメタクリル酸誘導体およ
び/またはアクリル酸誘導体を10重量部〜500
重量部加え、これを重合開始剤とともに上記例
示の溶剤中で常法に従つて反応させて得た重合
体および上記例示にフエノール樹脂の混合物で
ある。
次に、型枠に用いる素材とは通常、シリコーン
ゴムであつて、(1)室温硬化型シリコーン、(2)熱加
硫型シリコーン、(3)低温硬化型シリコーンを例示
することができる。
室温硬化型シリコーンの例としては、信越化学
工業製KE41RTV、KE42RTV、KE42S−RTV、
KE441RTV、KE44RTV、KE45RTV、KE45S
−RTVあるいは東芝シリコーン製TSF−
350RTVを例示することができる。
また、熱加硫型シリコーンとしては、東芝シリ
コーン製TSE−221、TSE−260、TSE−261、
TSE−2323を、さらに低温硬化型シリコーンと
しては、信越化学工業製KE1021LTV、
KE1202LTV、KE1204LTVを例示することがで
きる。
上記例示の各種シリコーンゴムを用いて型枠を
製造するには、予め離型剤を塗布した凹型に硬化
型シリコーンゴムを充填してこれを硬化させた
後、前記凹型より取り出す方法や、凹型に硬化型
シリコーンゴムを充填し、これを硬化させた後、
シリコーンゴムが充填された凹型全体を有機溶剤
中に浸漬させ、溶剤によるシリコーンゴムの膨潤
力を利用して凹型より取り出す方法などを用いれ
ばよい。なお、型枠は上記シリコーンゴムの他、
各種合成樹脂、合成ゴムまたは金属など、用途に
応じて各種の材質からなるものを使用することが
できる。
次に、本発明の対象となるゴム成形品としては
天然ゴム、クロロプレンゴム、アクリロニトリル
−ブタジエンゴム、スチレン−ブタジエンゴム、
エチレン−ブタジエンゴム、クロロスルホン化ポ
リエチレン、エピクロルヒドリンゴムあるいは塩
素化ブチルゴムなど、各種のゴムを使用対象とす
ることができる。
実施例 1
以下、本発明を自動車用補助バンパーの網目模
様の形成法に具体化した一実施例を第1〜3図に
より説明する。
第3図に示すように、自動車用フロントバンパ
ー1には表−1の組成からなるクロロプレン配合
物を160℃、15分間加硫して得られたクロロプレ
ンゴム製補助バンパー2が取着され、また、その
表面には、装飾用の網目模様3が以下に詳述する
方法により形成されている。
すなわち、上記補助バンパー2の表面を常法に
従つて脱脂した後、表−2の組成のクロロプレン
系塗料をスプレー塗布して膜厚約200μの塗膜層
5を形成し、その後、第1図に示すように、網目
模様が形成された室温硬化型シリコーンゴム製の
型枠4を上記塗膜層5の所定位置に置いた。
次いで第2図に示すように、そのままの状態で
24時間室温で放置して上記塗料を硬化させた後、
型枠4を取り外して塗膜層5に網目模様3を形成
した。
Object of the Invention (Field of Industrial Application) The present invention relates to a method of forming a pattern on the surface of a molded article made of various rubbers. (Prior Art) In order to form various patterns on the surface of rubber molded products for purposes such as decoration, desired patterns are formed on the mold surface during rubber molding, that is, when compression molding or injection molding of rubber dough. It is customary to form a pattern. However, although the above method of forming a pattern during molding is suitable for mass production, it cannot be used when trying to form a variety of patterns on a small amount of molded products because the manufacturing cost of the mold becomes high. This is difficult and requires a separate method to form a pattern on the molded product. (Problem to be solved by the invention) As a method for forming a pattern on a product after molding,
Separately, a thin rubber film layer with a pattern formed in advance is adhered to the surface of the rubber molded product, or a paint or adhesive is applied to the surface of the rubber molded product to form a coating layer. A possible method is to press a mold on which a predetermined pattern is formed to harden the coating layer, and then remove the mold to transfer the pattern to the coating layer. However, unlike synthetic resin molded products, rubber molded products undergo extremely large deformations in shape during use. For this reason, the paints and adhesives conventionally applied to the surface of various rubber substrates, such as styrene-butadiene copolymer rubber (SBR) and natural rubber (NR),
If a type of paint or adhesive is used, it is impossible to prevent the thin rubber film layer or coating layer from peeling off from the rubber molded product when the rubber molded product is deformed due to insufficient adhesion, so none of the above methods can be used. In reality, the current situation is that it has not yet been adopted. In view of the above problems, the present inventors have conducted research for many years and found a paint that does not easily lose its adhesion even when the rubber molded product is repeatedly deformed. They devised a method for forming a pattern on the surface of the material, and arrived at the present invention. Structure of the Invention (Means for Solving the Problems) In order to solve the above problems, the present invention applies a rubber paint to the surface of a rubber molded product, and then presses a formwork onto the surface coated with the paint. In the method of forming a pattern on the surface of a rubber molded article by curing the paint and then removing the mold, the rubber paint contains (a) a polymethacrylic acid derivative or a polyacrylic acid; A mixture of at least one derivative, chloroprene rubber, and a phenolic resin, or (b) a mixture of a polymer of at least one methacrylic acid derivative or acrylic acid derivative and chloroprene rubber, and a phenolic resin. This method employs a pattern forming method for rubber molded products, which is characterized by using one of the following methods. (Function) After applying the rubber paint to the surface of the rubber molded product,
By pressing the formwork with various patterns formed on the coating surface of the uncured paint to harden the paint, and then removing the formwork, the various patterns previously formed on the formwork are applied to the coating surface. Transferred to the membrane surface. Furthermore, since all of the above-mentioned rubber-based paints have strong adhesion and followability to the above-mentioned rubber molded products, there is a risk that the coating layer with such an uneven pattern will peel off even after long-term use. There is no such thing. (Example) Before explaining the pattern forming method of the present invention, the composition of the rubber paint and the mold material will be explained. Specifically, the rubber-based paint is (a) a mixture of at least one of a polymethacrylic acid derivative or a polyacrylic acid derivative, chloroprene rubber, and a phenolic resin, or (b) a mixture of a methacrylic acid derivative or an acrylic acid derivative. This is a rubber-based paint consisting of any one selected from a mixture of a polymer of at least one type of rubber, chloroprene rubber, and a phenol resin, and each composition of (a) to (b) will be described in detail below. (a) First, the polymethacrylic acid derivatives constituting the rubber paint in (a) are methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, 2-hydroxy Ethyl methacrylate, 2-hydroxypropyl methacrylate,
Examples include glycidyl methacrylate and dimethylaminoethyl methacrylate. In addition, polyacrylic acid derivatives include ethyl acrylate, n-butyl acrylate, iso-
Examples include butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and dimethylaminoethyl acrylate. In addition, it is also possible to use a mixture of several types of the above-mentioned polymethacrylic acid derivatives and polyacrylic acid derivatives, and furthermore, in addition to these, polyacrylic acid and polymethacrylic acid may be used. Further, the mixing ratio of the polyacrylic acid derivative and/or polymethacrylic acid derivative and chloroprene rubber is preferably 500 parts by weight or less per 100 parts by weight of chloroprene rubber, and if it exceeds 500 parts by weight, the adhesion gradually decreases. Next, as a phenolic resin, Tamanol
520S, Tamanol 521, Tamanol 526, Tamanol
586 (all of the above are phenolic resins manufactured by Arakawa Chemical), etc. Alternatively, Tamanol 803, a terpene phenol resin manufactured by the same company, and Tamanol 135, Tamanol 340, Tamanol 350, which are rosin-modified phenol resins also manufactured by the same company, can also be used. In addition, also in the case of these phenolic resins, it is possible to use a mixture of several types. The mixing ratio of the phenolic resin is preferably 1 to 50 parts by weight per 100 parts by weight of chloroprene rubber, and less than 1 part has no effect. Further, if the amount is 50 parts by weight or more, the hardness of the paint is high, and the coating film becomes hard, so that when a rubber molded product is strained, peeling is likely to occur. The solvents used for mixing these include aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as dioxane and tetrahydrofuran; acetate esters such as methyl acetate and isopropyl acetate; ketones such as methyl ethyl ketone, acetone, and cyclohexanone. ; A solvent appropriately selected from chlorinated hydrocarbons such as ethyl chloride, chloroform, and carbon tetrachloride, or a mixed solvent of two or more. (b) Next, a rubber-based paint consisting of a mixture of a polymer of at least one methacrylic acid derivative or an acrylic acid derivative and chloroprene rubber, and a phenol resin is a mixture of 100 parts by weight of chloroprene rubber and the above-mentioned methacrylate. 10 parts by weight to 500 parts by weight of acid derivatives and/or acrylic acid derivatives
This is a mixture of a polymer obtained by adding parts by weight and reacting it together with a polymerization initiator in the above-mentioned solvent in a conventional manner, and a phenol resin as above-mentioned. Next, the material used for the mold is usually silicone rubber, and examples thereof include (1) room temperature curable silicone, (2) heat vulcanizable silicone, and (3) low temperature curable silicone. Examples of room temperature curing silicones include Shin-Etsu Chemical's KE41RTV, KE42RTV, KE42S-RTV,
KE441RTV, KE44RTV, KE45RTV, KE45S
−RTV or Toshiba Silicone TSF−
An example is 350RTV. In addition, as heat-curable silicones, Toshiba Silicone TSE-221, TSE-260, TSE-261,
In addition to TSE-2323, low-temperature curing silicones include Shin-Etsu Chemical's KE1021LTV,
Examples include KE1202LTV and KE1204LTV. In order to manufacture molds using the various silicone rubbers listed above, there are two methods: filling a concave mold coated with a release agent in advance with a curable silicone rubber, curing the silicone rubber, and then removing it from the concave mold; After filling with curable silicone rubber and curing it,
A method may be used in which the entire concave mold filled with silicone rubber is immersed in an organic solvent and taken out from the concave mold using the swelling power of the silicone rubber by the solvent. In addition to the silicone rubber mentioned above, the formwork is made of
It is possible to use materials made of various materials depending on the purpose, such as various synthetic resins, synthetic rubbers, or metals. Next, the rubber molded products to which the present invention applies include natural rubber, chloroprene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber,
Various rubbers can be used, such as ethylene-butadiene rubber, chlorosulfonated polyethylene, epichlorohydrin rubber or chlorinated butyl rubber. Example 1 Hereinafter, an example in which the present invention is applied to a method of forming a mesh pattern on an auxiliary bumper for an automobile will be described with reference to FIGS. 1 to 3. As shown in FIG. 3, an auxiliary bumper 2 made of chloroprene rubber obtained by vulcanizing a chloroprene compound having the composition shown in Table 1 at 160°C for 15 minutes is attached to a front bumper 1 for an automobile. A decorative mesh pattern 3 is formed on its surface by a method described in detail below. That is, after degreasing the surface of the auxiliary bumper 2 according to a conventional method, a chloroprene-based paint having the composition shown in Table 2 is spray-coated to form a coating layer 5 with a thickness of about 200 μm. As shown in FIG. 2, a mold 4 made of room temperature curing silicone rubber and having a mesh pattern formed thereon was placed at a predetermined position on the coating layer 5. Then, as shown in Figure 2, leave it as it is.
After curing the above paint by leaving it at room temperature for 24 hours,
The formwork 4 was removed and a mesh pattern 3 was formed on the coating layer 5.
【表】【table】
【表】【table】
【表】
次に、上記網目模様3の形成された塗膜層5
の、クロロプレンゴム製補助バンパー2に対する
密着力をゴバン目試験により調べた結果、良好な
密着性(100/100)を示した。一方、比較例とし
て表−3、4にそれぞれ示す組成の塗料を用いて
同様の凹凸模様を形成した塗膜層の密着力をゴバ
ン目試験により調べた結果、簡単に剥離してしま
つた(0/100)。[Table] Next, the coating layer 5 on which the mesh pattern 3 is formed is shown.
The adhesion to the chloroprene rubber auxiliary bumper 2 was examined by a goblin test, and the results showed good adhesion (100/100). On the other hand, as a comparative example, we investigated the adhesion of a paint film layer with a similar uneven pattern using paints with the compositions shown in Tables 3 and 4, respectively, using a goblin test. As a result, the paints peeled off easily (0 /100).
【表】【table】
【表】
なお、本発明は上記実施例−1に限定されず、
前記例示の各種ゴム系塗料や、熱加硫型シリコー
ン、低温硬化型シリコーンなどの各種シリコーン
ゴムを用いて同様に実施することができる。
実施例 2
次に、本発明を自動車用ゴム製品の歪測定方法
に具体化した一実施例を第4、5図を用いて説明
する。
従来、形状の複雑な自動車用ゴム製品、例えば
曲がりホース、ブーツ、ウエザーストリツプなど
の取付けの際に生ずる歪を測定する満足な方法は
存在しなかつたが、本発明の模様形成法を用いる
ことにより、簡単に上記歪を測定することが可能
となつた。
すなわち、クロロプレンゴム製ブーツ9の適宜
箇所に表−5の配合物を80℃で8時間反応させて
得た重合体にフエノール樹脂として前記タマノル
520Sを混合(クロロプレンゴム100部に対し、10
部)してなるクロロプレン系塗料をスプレー塗布
して膜厚約200μの塗膜層5を形成した。次に、
上記ブーツの部分拡大図である第4図に示すよう
に、格子状の模様が形成された室温硬化型シリコ
ーン製型枠4を上記塗膜5の所定位置に置き、さ
らにこの状態のまま室温で4時間乾燥し、上記型
枠4を除去して室温でさらに20時間放置すること
により、前記実施例−1と同様の方法で上記塗膜
層5上に格子模様8を形成した[Table] Note that the present invention is not limited to the above Example-1,
It can be carried out in the same manner using the various rubber-based paints mentioned above, and various silicone rubbers such as heat-vulcanizing silicone and low-temperature curing silicone. Embodiment 2 Next, an embodiment in which the present invention is applied to a strain measuring method for automobile rubber products will be described with reference to FIGS. 4 and 5. Until now, there has been no satisfactory method for measuring the distortion that occurs when installing automotive rubber products with complex shapes, such as bent hoses, boots, weather strips, etc. However, the pattern forming method of the present invention can be used to This made it possible to easily measure the above distortion. That is, the above-mentioned Tamanol was added as a phenolic resin to a polymer obtained by reacting the formulations shown in Table 5 at appropriate locations of the chloroprene rubber boots 9 at 80°C for 8 hours.
Mix 520S (10 parts for 100 parts of chloroprene rubber)
The chloroprene-based paint prepared by Part) was spray-coated to form a coating layer 5 having a thickness of about 200 μm. next,
As shown in FIG. 4, which is a partially enlarged view of the boot, a room-temperature curing silicone mold 4 with a grid-like pattern formed thereon is placed at a predetermined position on the coating film 5, and then left in this state at room temperature. After drying for 4 hours, the formwork 4 was removed and left at room temperature for an additional 20 hours to form a lattice pattern 8 on the coating layer 5 in the same manner as in Example-1.
【表】
次に、上記ブーツ9に歪を加えて変形させた状
態でTSF−350RTV(東芝シリコーン製、室温硬
化型シリコーン)/硬化剤(E−60)=100/3.5
からなる組成の塗料を上記格子模様8の形成され
た塗膜層5の上に塗布し、室温で4時間放置して
このシリコーン塗膜層7を硬化させた後、これを
上記塗膜層5から除去することにより、第5図に
示すように上記シリコーン塗膜層7に歪んだ格子
模様8を転写することができる。
そこで、前記型枠4に形成された格子模様と上
記シリコーン塗膜層7に転写された歪んだ格子模
様とを比較することにより、ブーツ9に加えられ
た歪の量を容易に目視または測定することが可能
となる。
なお、本実施例の歪測定法は上記自動車用ゴム
製品に限定されず、他の工業用各種ゴム製品の歪
測定法として利用することができる。
発明の効果
以上詳述したように、本発明の模様形成法は各
種ゴムからなる成形品の表面に所望する模様を簡
単に形成することができるため、少量の成形品に
多種類の模様を形成するような場合などに極めて
便利であり、しかも長期間の使用においても模様
が剥離し難いという優れた効果を発揮する発明で
ある。[Table] Next, with the boot 9 deformed by applying strain, TSF-350RTV (manufactured by Toshiba Silicone, room temperature curing silicone)/curing agent (E-60) = 100/3.5
A coating composition consisting of the following is applied onto the coating layer 5 on which the lattice pattern 8 is formed, and the silicone coating layer 7 is cured by being left at room temperature for 4 hours. As shown in FIG. 5, a distorted lattice pattern 8 can be transferred to the silicone coating layer 7. Therefore, by comparing the lattice pattern formed on the formwork 4 and the distorted lattice pattern transferred to the silicone coating layer 7, the amount of distortion applied to the boot 9 can be easily observed or measured. becomes possible. Note that the strain measurement method of this example is not limited to the above-mentioned rubber products for automobiles, but can be used as a strain measurement method for various other industrial rubber products. Effects of the Invention As detailed above, the pattern forming method of the present invention can easily form a desired pattern on the surface of a molded product made of various rubbers, and therefore can form many types of patterns on a small amount of molded product. This invention is extremely convenient in cases such as when using a cloth, and has an excellent effect in that the pattern does not easily peel off even after long-term use.
第1、2図はそれぞれ自動車用補助バンパーの
模様形成法に具体化した本発明の一実施例を示す
斜視図、第3図は本発明の方法により形成された
模様を有する補助バンパーの取付状態を示す斜視
図、また第4、5図はそれぞれ自動車用ゴム製品
の歪測定法に具体化した本発明の一実施例を示す
斜視図である。
3……網目模様、4……型枠、5……塗膜層、
7……シリコーン塗膜層、8……格子模様。
Figures 1 and 2 are perspective views showing an embodiment of the present invention as embodied in a pattern forming method for an auxiliary bumper for automobiles, and Figure 3 is an attached state of an auxiliary bumper having a pattern formed by the method of the present invention. FIGS. 4 and 5 are perspective views showing an embodiment of the present invention, which is applied to a strain measurement method for automobile rubber products. 3...Mesh pattern, 4...Formwork, 5...Paint layer,
7... Silicone coating layer, 8... Checkered pattern.
Claims (1)
いで前記塗料の塗布された面に型枠を押圧した
後、前記塗料を硬化させ、しかる後前記型枠を除
去することによりゴム成形品の表面に模様を形成
する方法において、前記ゴム系塗料には、 (a) ポリメタクリル酸誘導体またはポリアクリル
酸誘導体の少なくとも一種と、クロロプレンゴ
ムと、フエノール樹脂との混合物、または (b) メタクリル酸誘導体またはアクリル酸誘導体
の少なくとも一種とクロロプレンゴムとの重合
体と、フエノール樹脂との混合物、 より選ばれたいずれか一種を用いることを特徴と
するゴム成形品の模様形成法。[Scope of Claims] 1. A rubber-based paint is applied to the surface of a rubber molded product, and then a mold is pressed against the surface coated with the paint, the paint is cured, and then the mold is removed. In the method of forming a pattern on the surface of a rubber molded article, the rubber paint includes (a) a mixture of at least one of a polymethacrylic acid derivative or a polyacrylic acid derivative, chloroprene rubber, and a phenolic resin; (b) A method for forming a pattern on a rubber molded article, characterized by using one selected from the following: a polymer of at least one methacrylic acid derivative or an acrylic acid derivative and chloroprene rubber, and a mixture of a phenol resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14728885A JPS627477A (en) | 1985-07-04 | 1985-07-04 | Method for forming pattern to rubber molded product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14728885A JPS627477A (en) | 1985-07-04 | 1985-07-04 | Method for forming pattern to rubber molded product |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS627477A JPS627477A (en) | 1987-01-14 |
JPH034266B2 true JPH034266B2 (en) | 1991-01-22 |
Family
ID=15426811
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14728885A Granted JPS627477A (en) | 1985-07-04 | 1985-07-04 | Method for forming pattern to rubber molded product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS627477A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130018134A1 (en) * | 2011-07-11 | 2013-01-17 | E I Du Pont De Nemours And Company | Polychloroprene compositions with improved adhesion properties |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5233478A (en) * | 1975-09-10 | 1977-03-14 | Nec Corp | Gaseous epitaxial growth process |
JPS55140799A (en) * | 1979-04-13 | 1980-11-04 | Matsushita Electric Ind Co Ltd | Gallium nitride crystal growing method |
JPS5965434A (en) * | 1982-10-05 | 1984-04-13 | Nec Corp | Vapor phase etching of compound semiconductor |
-
1985
- 1985-07-04 JP JP14728885A patent/JPS627477A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5233478A (en) * | 1975-09-10 | 1977-03-14 | Nec Corp | Gaseous epitaxial growth process |
JPS55140799A (en) * | 1979-04-13 | 1980-11-04 | Matsushita Electric Ind Co Ltd | Gallium nitride crystal growing method |
JPS5965434A (en) * | 1982-10-05 | 1984-04-13 | Nec Corp | Vapor phase etching of compound semiconductor |
Also Published As
Publication number | Publication date |
---|---|
JPS627477A (en) | 1987-01-14 |
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