JPH03259983A - Method for curing self-adhesive - Google Patents
Method for curing self-adhesiveInfo
- Publication number
- JPH03259983A JPH03259983A JP5879690A JP5879690A JPH03259983A JP H03259983 A JPH03259983 A JP H03259983A JP 5879690 A JP5879690 A JP 5879690A JP 5879690 A JP5879690 A JP 5879690A JP H03259983 A JPH03259983 A JP H03259983A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- self
- acrylic polymer
- curing
- polyisocyanate
- 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
- 239000000853 adhesive Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title description 11
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000001070 adhesive effect Effects 0.000 claims description 54
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 abstract 1
- BPOZNMOEPOHHSC-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCOC(=O)C=C BPOZNMOEPOHHSC-UHFFFAOYSA-N 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 13
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- -1 polyethylene Polymers 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- CQTRUFMMCCOKTA-UHFFFAOYSA-N 4-amino-4-methylpentan-2-one Chemical compound CC(=O)CC(C)(C)N CQTRUFMMCCOKTA-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NNWUEBIEOFQMSS-UHFFFAOYSA-N 2-Methylpiperidine Chemical compound CC1CCCCN1 NNWUEBIEOFQMSS-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KAOHYMHKNXJUFY-HYXAFXHYSA-N ethyl (z)-2-aminobut-2-enoate Chemical compound CCOC(=O)C(\N)=C\C KAOHYMHKNXJUFY-HYXAFXHYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical group CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、例えばサイドプロテクションモール（以下モ
ールという）等の自動車用部品を自動車ボディに接着す
るために使用される粘着剤の硬化方法に関するものであ
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for curing an adhesive used for adhering automobile parts such as side protection moldings (hereinafter referred to as moldings) to an automobile body. It is.
従来、各種粘着製品に一般的に使用される粘着剤として
は、合成ゴム系、ポリ酢酸ビニル系等のものが使用され
ているが、耐湿性、耐温水性、耐熱性等が不十分であっ
た。また、自動車のモール等の装着に使用される粘着剤
として、カルボキシル基を有するアクリルポリマーとポ
リイソシアネートとからなるものが提案されている。こ
の粘着剤は加熱によって含有されている溶剤を蒸発させ
た後、使用に供されている。Traditionally, adhesives commonly used in various adhesive products include synthetic rubber and polyvinyl acetate, but these have insufficient moisture resistance, hot water resistance, heat resistance, etc. Ta. Furthermore, an adhesive made of an acrylic polymer having a carboxyl group and a polyisocyanate has been proposed as an adhesive used for mounting on automobile moldings and the like. This pressure-sensitive adhesive is heated to evaporate the solvent contained therein before being used.
ところが、上記カルボキシル基を含有するアクリルポリ
マーとポリイソシアネートとからなる粘着剤は、溶剤を
蒸発除去する程度の加熱ではカルボキシル基とポリイソ
シアネートとの反応が十分進まないため、粘着力が低い
という問題点があった。また、粘着力を高めるため、例
えばカルボキシル基を含有するアクリルポリマーとトリ
メチロールプロパンのトリレンジイソシアネート付加体
又はイソシアネート類との混合物を硬化させる場合、硬
化温度を高くしたり、硬化時間を長くしなければならな
いという問題点があった。However, the above adhesive made of an acrylic polymer containing a carboxyl group and a polyisocyanate has a problem of low adhesive strength because the reaction between the carboxyl group and the polyisocyanate does not proceed sufficiently when heated to the extent that the solvent is evaporated and removed. was there. Furthermore, in order to increase adhesive strength, for example, when curing a mixture of an acrylic polymer containing a carboxyl group and a tolylene diisocyanate adduct of trimethylolpropane or isocyanates, it is necessary to increase the curing temperature or lengthen the curing time. There was a problem that it had to be done.
本発明の目的は、粘着力が大きく、しかも硬化が容易で
作業性の優れた粘着剤の硬化方法を提供することにある
。An object of the present invention is to provide a method for curing an adhesive that has high adhesive strength, is easy to cure, and has excellent workability.
上記目的を達成するため、本発明ではカルボキシル基を
有するアクリル系ポリマーにポリイソシアネートを配合
してなる粘着剤を剥離紙又は基材に塗布した後、硬化触
媒を塗布し、次いで空気中又は水蒸気中で加熱硬化させ
るという手段を採用している。なお、補助的に粘着剤中
に硬化触媒を含有させておいてもよい。In order to achieve the above object, in the present invention, a pressure-sensitive adhesive made of an acrylic polymer having a carboxyl group and a polyisocyanate is applied to a release paper or a base material, and then a curing catalyst is applied, and then the adhesive is exposed to air or water vapor. A method of heating and curing is used. Note that a curing catalyst may be supplementarily contained in the adhesive.
まず、粘着剤について説明する。カルボキシル基を有す
るアクリルポリマーは、通常アクリル酸エステルと不飽
和カルボン酸又はその無水物を溶液重合法により共重合
させることによって得られる。アクリル酸エステルとし
ては、ブチルアクリレート、イソブチルアクリレート、
２−エチルへキシルアクリレート等が使用できる。不飽
和カルボン酸としては、アクリル酸、メタクリル酸、マ
レイン酸、イタコン酸等が使用でき、不飽和カルボン酸
の無水物としては、無水マレイン酸、無水イタコン酸等
を使用することができる。First, the adhesive will be explained. Acrylic polymers having carboxyl groups are usually obtained by copolymerizing acrylic esters and unsaturated carboxylic acids or their anhydrides by solution polymerization. As acrylic esters, butyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate and the like can be used. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc. can be used, and as the anhydride of the unsaturated carboxylic acid, maleic anhydride, itaconic anhydride, etc. can be used.
この不飽和カルボン酸又はその無水物の使用割合は、ア
クリルポリマー中１〜１０重量％の範囲が好適である。The proportion of this unsaturated carboxylic acid or its anhydride used is preferably in the range of 1 to 10% by weight in the acrylic polymer.
１重量％未満では粘着剤の粘着力か低下しやすく、１０
重量％を超えると粘着剤が硬くなって十分な粘着力が発
揮されない。If it is less than 1% by weight, the adhesive strength of the adhesive tends to decrease;
If it exceeds % by weight, the adhesive will become hard and will not exhibit sufficient adhesive strength.
ポリイソシアネートとしては、２．４−トリレンジイソ
シアネート（ＴＤ Ｉ） 、６５／３５ （２゜４−ト
リレンジイソシアネートと２，６−トリレンジイソシア
ネートとの割合、以下同様）トリレンジイソシアネート
、８０／２０１−リレンジイソシアネート、１，５−ナ
フタレンジイソシアネート（ＮＤＩ） 、４．４’−ジ
フェニルメタンジイソシアネート（ＭＤＩ）、ジアニシ
ジンジイソシアネート、トリデンジイソシアネート、ヘ
キサメチレンジイソシアネート、キシレンジイソシアネ
−）（ＸＤＩ）、メタキシレンジイソシアネート、１．
６−へキサメチレンジイソシアネート（１゜６ＨＭＤＩ
）、水添４，４′−ジフェニルメタンジイソシアネート
、水添キシレンジイソシアネート、水添２，４−トリレ
ンジイソシアネート、水添６５／３５ ）リレンジイソ
シアネート、水添８０／２０トリレンジイソシアネート
、イソホロンジイソシアネー１−（ＩＰＤＩ）等を使用
することができる。As the polyisocyanate, 2.4-tolylene diisocyanate (TD I), 65/35 (ratio of 2° 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, the same applies hereinafter) tolylene diisocyanate, 80/201 -lylene diisocyanate, 1,5-naphthalene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate (XDI), metaxylene diisocyanate , 1.
6-hexamethylene diisocyanate (1°6HMDI
), hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, hydrogenated 65/35) lylene diisocyanate, hydrogenated 80/20 tolylene diisocyanate, isophorone diisocyanate 1 -(IPDI) etc. can be used.
このポリイソシアネートの使用割合は、前記アクリル系
ポリマー１００重量部に対して０．００１〜２０重量部
の範囲が好適である。０．００１重量部未満では粘着力
が低下しやすく、２０重量部を超えると粘着剤が硬く、
脆くなって粘着力が低下しやすい。The proportion of this polyisocyanate used is preferably in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the acrylic polymer. If it is less than 0.001 parts by weight, the adhesive strength tends to decrease, and if it exceeds 20 parts by weight, the adhesive becomes hard.
It becomes brittle and tends to lose its adhesive strength.
次に、粘着剤を塗布するための基材としては、ポリエチ
レン（ＰＥ）、ポリプロピレン（Ｐ Ｐ）、ポリエチレ
ンテレフタレート（ＰＥＴ）、紙等を使用することがで
き、剥離紙としては粘着剤を保護するために一般的に用
いられているものを使用することができる。Next, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), paper, etc. can be used as the base material for applying the adhesive, and the release paper protects the adhesive. Those commonly used for this purpose can be used.
硬化触媒としては、アミン系化合物例えばモノエチルア
ミン、ジエチルアミン、トリエチルアミン、プロピルア
ミン、アミノクロトン酸エチル、ｐ−アミノチオフェノ
ール、２−アミノチオフェン、第２アミルアミン、第３
７ミルアミン、アルデヒドアンモニア、イソアミルアミ
ン、イソブチルアミン、イソプロピルアミン、ジアセト
ンアミン、ジイソプロピルアミン、シクロヘキシルアミ
ン、ジプロピルアミン、ジメチルヒドラジン、ピラゾリ
ン、ピリジン、ピロリジン、ピロリン、ブチルアミン、
第２ブチルアミン、第３ブチルアミン、２−メチルピペ
リジン、３−メチルピペリジン、４−メチルピペリジン
、Ｎ−メチルピペリジン、２−メチルピリジン、３−メ
チルピリジン、４−メチルピリジン、有機金属化合物例
えばテトラメチルスズ、テトラメチル鉛等の１種又は２
種以上を使用することができる。As the curing catalyst, amine compounds such as monoethylamine, diethylamine, triethylamine, propylamine, ethyl aminocrotonate, p-aminothiophenol, 2-aminothiophene, secondary amylamine, tertiary
7-mylamine, aldehyde ammonia, isoamylamine, isobutylamine, isopropylamine, diacetonamine, diisopropylamine, cyclohexylamine, dipropylamine, dimethylhydrazine, pyrazoline, pyridine, pyrrolidine, pyrroline, butylamine,
Secondary butylamine, tertiary butylamine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, N-methylpiperidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, organometallic compounds such as tetramethyltin , tetramethyl lead, etc. 1 or 2
More than one species can be used.
この硬化触媒は、通常ポリエーテル系ポリオール等に分
散又は溶解したもの又は有機溶剤に溶解したものを使用
でき、通常その濃度は１〜５０％の範囲である。塗布量
は、少ないと十分な効果か発揮されず、多過ぎると分解
触媒として作用するおそれがあるので、粘着剤の組成に
応じて適宜設定される。また、塗布方法としては、はけ
塗り法、スプレー塗布法、ロールコータ塗布法等か採用
される。This curing catalyst can be normally dispersed or dissolved in polyether polyol or the like, or dissolved in an organic solvent, and its concentration is usually in the range of 1 to 50%. The coating amount is appropriately set depending on the composition of the adhesive, since if the coating amount is too small, sufficient effect will not be exhibited, and if it is too large, it may act as a decomposition catalyst. Further, as a coating method, a brush coating method, a spray coating method, a roll coater coating method, etc. are employed.
次に、粘着剤の硬化方法について説明する。まず、上記
粘着剤を剥離紙又は基材に８０〜１５０μｍ程度の厚さ
に塗布した後、硬化触媒を塗布する。次いで、これを空
気中又は水蒸気中で加熱することにより、粘着剤を硬化
させる。加熱温度は剥離紙又は基材が損傷しない温度以
下で適宜設定される。さらに、粘着剤中に予め硬化触媒
を含有させることにより、上記作用が一層確実に発揮さ
れる。Next, a method of curing the adhesive will be explained. First, the adhesive is applied to a release paper or a base material to a thickness of about 80 to 150 μm, and then a curing catalyst is applied. Next, the adhesive is cured by heating it in air or steam. The heating temperature is appropriately set at a temperature below which the release paper or base material is not damaged. Furthermore, by including a curing catalyst in the adhesive in advance, the above-mentioned effect can be exhibited more reliably.
前記手段を採用したことにより、硬化触媒を塗布後、空
気中又は水蒸気中で所定温度に加熱された粘着剤中にお
けるアクリル系ポリマー中のカルボキシル基とポリイソ
シアネート中のイソシアネート基とが反応して硬化し、
粘着剤の凝集力が向上し粘着剤層で剥離することがない
とともに、カルボキシル基を有するアクリル系ポリマー
とポリイソシアネートとの反応生成物を含む粘着剤層と
基材との間の分子間力やカルボキシル基、イソシアネー
ト基に基づく水素結合等により、粘着剤層と基材との間
の接着力が向上するものと推定される。By adopting the above method, after applying the curing catalyst, the carboxyl groups in the acrylic polymer and the isocyanate groups in the polyisocyanate react with each other in the adhesive, which is heated to a predetermined temperature in air or water vapor, resulting in curing. death,
The cohesive force of the adhesive is improved and the adhesive layer does not peel off, and the intermolecular force between the adhesive layer containing the reaction product of the acrylic polymer having a carboxyl group and the polyisocyanate and the base material is reduced. It is presumed that hydrogen bonding based on carboxyl groups and isocyanate groups improves the adhesive force between the adhesive layer and the base material.
〔実施例１〜８及び比較例１，２〕
以下、本発明を具体化した粘着剤の硬化方法にについて
、比較例と対比して説明する。なお、各側における部は
重量部を表す。[Examples 1 to 8 and Comparative Examples 1 and 2] Hereinafter, a method for curing an adhesive embodying the present invention will be described in comparison with a comparative example. Note that parts on each side represent parts by weight.
（１）アクリル系ポリマーの合成
まず、アクリル酸エステルと不飽和カルボン酸とを下記
の表−■に示す割合で使用してトルエン／酢酸エチル＝
２：１（重量比）の混合溶剤中で溶液重合法によって固
形分３５％のアクリル系ポリマーを合成した。(1) Synthesis of acrylic polymer First, acrylic ester and unsaturated carboxylic acid were used in the ratio shown in the table below (■) toluene/ethyl acetate=
An acrylic polymer with a solid content of 35% was synthesized by a solution polymerization method in a mixed solvent of 2:1 (weight ratio).
表−１ 表−１中の略号は次の意味を表す。Table-1 The abbreviations in Table-1 represent the following meanings.
ＢｕＡニブチルアクリレート
ＡＡニアクリル酸
２−ＥＨＡ：２−エチルへキシルアクリレートＡＭＡ
：無水マレイン酸
ＡＩＡ：無水イタコン酸
（２）試験片の作製及び引張剪断強度の測定基材として
２枚の８倍発泡のポリエチレンに粘着剤を２５ｍｍＸ
２５ｍｍの接着面積で塗布した後、所定の処理をし、次
いで５ｋｇの圧力を１分間かけて貼り合わせ、試験片を
作製した。これについて、引張スピーｔ” ５０ ｍｍ
／ ｍｉｎの条件で引張剪断強度を測定した。BuA Nibutyl acrylate AA Niacrylic acid 2-EHA: 2-Ethylhexyl acrylate AMA
:Maleic anhydride AIA:Itaconic anhydride (2) Preparation of test piece and measurement of tensile shear strength As a base material, adhesive was applied to two sheets of 8x foamed polyethylene at a thickness of 25 mm.
After coating with an adhesion area of 25 mm, a predetermined treatment was performed, and then a pressure of 5 kg was applied for 1 minute to bond them together to prepare a test piece. Regarding this, the tensile speed t” 50 mm
The tensile shear strength was measured under the condition of /min.
（実施例１）
前記アクリル系ポリマー■の固形分１００部とＭＤＩを
１部及びジエチルアミン０．１部を混合して粘着剤を調
製し、これを基材に約１００μｍの厚さに塗布した後、
さらに硬化触媒として１０％のジエチルアミン溶液をス
プレー塗布した（以下の各側でも同様の塗布方法を採用
した）。次いで、１５０°Ｃの水蒸気中で加熱して粘着
剤を硬化させた。これについて、引張剪断強度を測定し
た。その結果を後記表−２に示す。(Example 1) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer (1), 1 part of MDI, and 0.1 part of diethylamine, and this was applied to a base material to a thickness of about 100 μm. ,
Furthermore, a 10% diethylamine solution was spray applied as a curing catalyst (the same application method was adopted on each side below). The adhesive was then cured by heating in steam at 150°C. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例２）
前記アクリル系ポリマー■の固形分１００部とＴＤＩを
０．５部混合して粘着剤を調製し、これを実施例１と同
様の基材に同じ厚さで塗布した後、硬化触媒として１０
％のイソプロピルアミン溶液を塗布した。次いで、１５
０’Ｃの水蒸気中で加熱して粘着剤を硬化させた。これ
について、引張剪断強度を測定した。その結果を後記表
−２に示す。(Example 2) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① and 0.5 part of TDI, and this was applied to the same substrate as in Example 1 to the same thickness. 10 as a curing catalyst
% isopropylamine solution was applied. Then 15
The adhesive was cured by heating in steam at 0'C. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例３）
前記アクリル系ポリマー■の固形分１００部とＸＤＩを
１．５部混合して粘着剤を調製し、これを実施例１と同
様の基材に同じ厚さで塗布した後、硬化触媒として１０
％のブチルアミン溶液を塗布した。次いで、１５０°Ｃ
の水蒸気中で加熱して粘着剤を硬化させた。これについ
て、引張剪断強度を測定した。その結果を後記表−２に
示す。(Example 3) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer (1) and 1.5 parts of XDI, and this was applied to the same substrate as in Example 1 to the same thickness. 10 as a curing catalyst
% butylamine solution was applied. Then 150°C
The adhesive was cured by heating in water vapor. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例４）
前記アクリル系ポリマー■の固形分１００部とＴＤＩを
１部混合して粘着剤を調製し、これを実施例１と同様の
基材に同じ厚さで塗布した後、硬化触媒として１０％の
第３級アミン溶液を塗布した。次いで、１５０℃の水蒸
気中で加熱して粘着剤を硬化させた。これについて、引
張剪断強度を測定した。その結果を後記表−２に示す。(Example 4) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① and 1 part of TDI, and this was applied to the same substrate as in Example 1 to the same thickness, and then a curing catalyst was applied. A 10% tertiary amine solution was applied as a solution. Next, the adhesive was cured by heating in steam at 150°C. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例５）
前記アクリル系ポリマー■の固形分１００部とＭＤＩを
２部混合して粘着剤を調製し、これを実施例１と同様の
基材に同じ厚さで塗布した後、硬化触媒として５％の２
−メチルピペラジン溶液を塗布した。次いで、１５０℃
の水蒸気中で加熱して粘着剤を硬化させた。これについ
て、引張剪断強度を測定した。その結果を後記表−２に
示す。(Example 5) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① and 2 parts of MDI, and this was applied to the same substrate as in Example 1 to the same thickness, and then a curing catalyst was applied. as 5% 2
-A methylpiperazine solution was applied. Then, 150℃
The adhesive was cured by heating in water vapor. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例６）
前記アクリル系ポリマー■の固形分１００部とＮＤＩを
１部混合して粘着剤を調製し、これを実施例１と同様の
基材に同じ厚さで塗布した後、硬化触媒として１％のテ
トラメチルスズ溶液を塗布した。次いで、１５０°Ｃの
水蒸気中で加熱して粘着剤を硬化させた。これについて
、引張剪断強度を測定した。その結果を後記表−２に示
す。(Example 6) A pressure-sensitive adhesive was prepared by mixing 100 parts of solid content of the acrylic polymer ① and 1 part of NDI, and this was applied to the same base material as in Example 1 to the same thickness, and then a curing catalyst was applied. A 1% tetramethyltin solution was applied as a solution. The adhesive was then cured by heating in steam at 150°C. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例７）
前記アクリル系ポリマー■の固形分１００部とＭＤＩを
１部混合して粘着剤を調製し、これを基材に約１００μ
ｍの厚さに塗布した後、硬化触媒として１０％のジエチ
ルアミン溶液を塗布した。(Example 7) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① and 1 part of MDI, and this was applied to a base material of approximately 100 μm.
After coating to a thickness of m, a 10% diethylamine solution was applied as a curing catalyst.
次いで、１５０℃の空気中で加熱して粘着剤を硬化させ
た。これについて、引張剪断強度を測定した。その結果
を後記表−２に示す。Next, the adhesive was cured by heating in air at 150°C. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below.
（実施例８）
前記アクリル系ポリマー■の固形分１００部とＮＤＩを
１部混合して粘着剤を調製し、これを実施例１と同様の
基材に同じ厚さで塗布した後、硬化触媒として１％のテ
トラメチルスズ溶液を塗布した。次いで、１５０°Ｃの
空気中で加熱して粘着剤を硬化させた。これについて、
引張剪断強度を測定した。その結果を後記表−２に示す
。(Example 8) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① and 1 part of NDI, and this was applied to the same substrate as in Example 1 to the same thickness, and then a curing catalyst was applied. A 1% tetramethyltin solution was applied as a solution. Next, the adhesive was cured by heating in air at 150°C. about this,
Tensile shear strength was measured. The results are shown in Table 2 below.
（比較例１）
前記アクリル系ポリマー■の固形分１００部とＭＤＩを
１部混合して粘着剤を調製し、これを実施例１と同様の
基材に同じ厚さで塗布した。そして、加熱することなく
そのままの状態で実施例１と同様にして試験片を作製し
た。これについて、引張剪断強度を測定した。その結果
を併せて後記表−２に示す。(Comparative Example 1) A pressure-sensitive adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① with 1 part of MDI, and this was applied to the same substrate as in Example 1 to the same thickness. Then, a test piece was produced in the same manner as in Example 1 without heating. Regarding this, the tensile shear strength was measured. The results are also shown in Table 2 below.
（比較例２）
前記アクリル系ポリマー■の固形分１００部とＴＤＩを
１部混合して粘着剤を調製し、これを実施例１と同様の
基材に同じ厚さで塗布した。次いで、１００°Ｃ，２分
間加熱して粘着剤を硬化させた。以下実施例１と同様に
して試験片を作製した。(Comparative Example 2) An adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① with 1 part of TDI, and this was applied to the same substrate as in Example 1 to the same thickness. Next, the adhesive was cured by heating at 100°C for 2 minutes. Thereafter, test pieces were prepared in the same manner as in Example 1.
これについて、引張剪断強度を測定した。その結果を併
せて後記表−２に示す。Regarding this, the tensile shear strength was measured. The results are also shown in Table 2 below.
表−２
表−２中の＊はポリエチレンの発泡体が破壊したことを
示す。Table 2 * in Table 2 indicates that the polyethylene foam was destroyed.
表−２かられかるように、本発明の実施例１〜８におい
ては引張剪断強度が１．９〜２．１ ｋｇ ／ ｃｒｌ
という高い値を示す。一方、アクリル系ポリマーとポリ
イソシアネートの混合物をそのまま使用した場合（比較
例１）、硬化触媒を塗布しなかった場合（比較例２）に
は、引張剪断強度か０．３〜０．５ｋｇ ／ ｃｄとい
う低い値であった。As can be seen from Table 2, in Examples 1 to 8 of the present invention, the tensile shear strength was 1.9 to 2.1 kg/crl.
This shows a high value. On the other hand, when the mixture of acrylic polymer and polyisocyanate was used as it was (Comparative Example 1), and when no curing catalyst was applied (Comparative Example 2), the tensile shear strength was 0.3 to 0.5 kg/cd. This was a low value.
各実施例の硬化方法が高い引張剪断強度を発揮する理由
は、各実施例において硬化触媒を塗布後、空気中又は水
蒸気中で粘着剤を所定温度に加熱することにより、また
硬化触媒の作用によりアクリル系ポリマー中のカルボキ
シル基とポリイソシアネート中のイソシアネート基とが
十分に反応し、粘着剤の凝集力が高まるとともに、アク
リル系ポリマーとポリイソシアネートとの反応生成物に
よる分子間力やカルボキシル基、イソシアネート基によ
る水素結合等の作用により、２つの８倍発泡ポリエチレ
ン間の接着力が向上するものと考えられる。なお、特に
実施例１に示したように、粘着剤中に硬化触媒を含有さ
せることにより、粘着層の表面側の未硬化状態を確実に
改善できる。The reason why the curing method of each example exhibits high tensile shear strength is that in each example, after applying the curing catalyst, the adhesive is heated to a predetermined temperature in air or steam, and due to the action of the curing catalyst. The carboxyl groups in the acrylic polymer and the isocyanate groups in the polyisocyanate fully react, increasing the cohesive force of the adhesive, and increasing the intermolecular force due to the reaction product between the acrylic polymer and the polyisocyanate. It is thought that the adhesive force between the two 8 times expanded polyethylenes is improved due to the effects of hydrogen bonding and the like caused by the groups. In particular, as shown in Example 1, by incorporating a curing catalyst into the adhesive, the uncured state on the surface side of the adhesive layer can be reliably improved.
従って、本発明の粘着剤の硬化方法は、例えば自動車の
モール、内装品等の樹脂製品、ゴム製品等に使用される
各種粘着剤の硬化方法として好適である。Therefore, the method for curing adhesives of the present invention is suitable as a method for curing various adhesives used, for example, in resin products such as automobile moldings and interior parts, rubber products, and the like.
本発明の粘着剤の硬化方法によれば、粘着剤の粘着力が
大きく、しかも短時間にかつ容易に粘着剤を硬化させる
ことができ作業性に優れている上に、粘着層の表面側の
未硬化状態を確実に改善できるという効果を奏する。According to the adhesive curing method of the present invention, the adhesive has a high adhesive strength, can be easily cured in a short time, and has excellent workability. This has the effect of reliably improving the uncured state.
Claims (1)
イソシアネートを配合してなる粘着剤を剥離紙又は基材
に塗布した後、硬化触媒を塗布し、次いで空気中又は水
蒸気中で加熱硬化させることを特徴とする粘着剤の硬化
方法。1. After applying an adhesive made of an acrylic polymer having a carboxyl group and a polyisocyanate to a release paper or a base material, a curing catalyst is applied, and the adhesive is then heated and cured in air or steam. How to cure adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5879690A JPH03259983A (en) | 1990-03-09 | 1990-03-09 | Method for curing self-adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5879690A JPH03259983A (en) | 1990-03-09 | 1990-03-09 | Method for curing self-adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03259983A true JPH03259983A (en) | 1991-11-20 |
Family
ID=13094544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5879690A Pending JPH03259983A (en) | 1990-03-09 | 1990-03-09 | Method for curing self-adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03259983A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2568026A1 (en) * | 2011-09-07 | 2013-03-13 | Nitto Denko Corporation | Aqueous dispersion pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
-
1990
- 1990-03-09 JP JP5879690A patent/JPH03259983A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2568026A1 (en) * | 2011-09-07 | 2013-03-13 | Nitto Denko Corporation | Aqueous dispersion pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| CN102994019A (en) * | 2011-09-07 | 2013-03-27 | 日东电工株式会社 | Aqueous dispersion pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
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