JPH02252778A - Method for curing tacky agent - Google Patents
Method for curing tacky agentInfo
- Publication number
- JPH02252778A JPH02252778A JP7446089A JP7446089A JPH02252778A JP H02252778 A JPH02252778 A JP H02252778A JP 7446089 A JP7446089 A JP 7446089A JP 7446089 A JP7446089 A JP 7446089A JP H02252778 A JPH02252778 A JP H02252778A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- curing
- acrylic polymer
- diisocyanate
- parts
- 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
- 238000000034 method Methods 0.000 title claims description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 claims abstract description 57
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 13
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 4
- -1 polyethylene Polymers 0.000 abstract 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 9
- 239000004698 Polyethylene Substances 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 27
- 238000002156 mixing Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 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 5
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 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
- 238000000465 moulding Methods 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
- 150000008064 anhydrides Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-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
- 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
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000006243 chemical reaction Methods 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
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 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 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
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-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
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-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
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-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
- 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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 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
- 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
- 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
- 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
- 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
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 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
- 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
- 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
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
Abstract
Description
［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。
［従来の技術］
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。
［発明が解決しようとする課題］
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１ｍ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。
本発明の目的は、粘着力が大きく、硬化温度が低く、し
かも硬化時間の短い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。[Industrial Field of Application] The present invention relates to a method of curing an adhesive used for adhering automotive parts such as side protection moldings (hereinafter referred to as moldings). [Prior art] Conventionally, synthetic rubber-based adhesives, polyvinyl acetate-based adhesives, etc. have been used as adhesives generally used in various adhesive products, but they have poor moisture resistance, hot water resistance, heat resistance, etc. was insufficient. 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. [Problems to be Solved by the Invention] However, in the pressure-sensitive adhesive made of an acrylic polymer containing a carboxyl group and a polyisocyanate, the reaction between the carboxyl group and the polyisocyanate does not proceed sufficiently when heated to the extent that the solvent is evaporated. Therefore, there was a problem that adhesive strength was low. In addition, 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 isocyanate 1m,
There were problems in that the curing temperature had to be raised and the curing time had to be lengthened. An object of the present invention is to provide a method for curing an adhesive that has high adhesive strength, low curing temperature, short curing time, and 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
有するアクリルポリマー１００重量部に対しポリイソシ
アネート０．００１〜２０重量部を配合した混合物から
なる粘着剤を剥離紙又は基材に塗布し、硬化触媒の沸点
以上でかつ２００℃以下の硬化触媒雰囲気中で硬化させ
るという手段を採用している。
［手段の詳細な説明］
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。
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！ｉ量％の範囲が好適である
。１重量％未満では粘着剤の粘着力が低下しやすく、１
０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。
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−）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、８０／２０ト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）（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
ート（ＭＤＩ）、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−）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）リレンジイソシアネート
、イソホロンジイソシアネート（ＩＰＤＩ）等を使用す
ることができる。
このポリイソシアネートの使用割合は、前記アクリルポ
リマー１００重量部に対して０．００１〜２０重量部の
範囲である。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。
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（ＰＰ）、ポリエチレン
テレフタレート（ＰＥＴ） 、ｉＥ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。
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、シア★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、ビロリン、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。
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
に塗布する０次に、この粘着剤を塗布した剥離紙又は基
材を硬化触媒の沸点以上２００℃以下の温度の硬化触媒
雰囲気中に置く。この雰囲気温度は、下限は硬化触媒の
沸点で定められ、上限は使用する剥離紙又は基材の種類
によって剥離紙又は基材が損傷しない範囲で定められる
。
例えば、硬化触媒としてジエチルアミンを使用し、基材
として発泡ポリエチレンを使用した場合、約７０℃程度
である。また、加熱時間は２００℃の場合５秒程度、室
温の場合でも５分程度で十分である。このようにして剥
離紙又は基材表面の粘着剤を硬化させることができる。
［作用］
前記手段を採用したことにより、所定温度の硬化触媒雰
囲気中で粘着剤中におけるアクリル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、アクリルポリマーが有す
る粘着性と粘着剤の分子量の増大によって粘着剤層と基
材との界面の強度が上がり、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。In order to achieve the above object, in the present invention, a pressure-sensitive adhesive consisting of a mixture of 100 parts by weight of an acrylic polymer having a carboxyl group and 0.001 to 20 parts by weight of polyisocyanate is applied to a release paper or a base material, and a curing catalyst is applied. A method of curing in a curing catalyst atmosphere at a temperature higher than the boiling point of and lower than 200° C. is adopted. [Detailed Description of Means] 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. The proportion of this unsaturated carboxylic acid or its anhydride used in the acrylic polymer is 1-10! A range of i amount% is suitable. If it is less than 1% by weight, the adhesive strength of the adhesive tends to decrease;
If it exceeds 0% by weight, the adhesive will become hard and will not exhibit sufficient adhesive strength. As the polyisocyanate, 2,4-tolylene diisocyanate (TD I), 65/35 (2°4-
Ratio of tolylene diisocyanate and 2.6-)lylene diisocyanate, hereinafter the same) tolylene diisocyanate, 80/20 tolylene diisocyanate, 1.5-naphthalene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate) ( MDI), dianisidine diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate (MDI), metaxylene diisocyanate, 1.
6-hexamethylene diisocyanate (1°6HMDI
), hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated 2.4-)lylene diisocyanate, hydrogenated 65/35) lylene diisocyanate, hydrogenated 80/20) lylene diisocyanate, isophorone diisocyanate (IPDI) etc. can be used. The proportion of this polyisocyanate used is 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 part by weight, the adhesive strength tends to decrease, and if it exceeds 20 parts by weight, the adhesive becomes hard and brittle, and the adhesive strength tends to decrease. Next, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), iE, etc. can be used as the base material for applying the adhesive, and the release paper is used to protect the adhesive. Those commonly used can be used. 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, thiamine, diisopropylamine, cyclohexylamine, dipropylamine, dimethylhydrazine, pyrazoline, pyridine, pyrrolidine, viroline, 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. Next, a method of curing the adhesive will be explained. First, the above adhesive is applied to a release paper or base material to a thickness of about 80 to 150 μm. Next, the release paper or base material coated with this adhesive is cured at a temperature above the boiling point of the curing catalyst and below 200°C. Place in a catalytic atmosphere. The lower limit of this atmospheric temperature is determined by the boiling point of the curing catalyst, and the upper limit is determined by the type of release paper or base material used within a range that does not damage the release paper or base material. For example, when diethylamine is used as the curing catalyst and foamed polyethylene is used as the base material, the temperature is about 70°C. Moreover, the heating time is about 5 seconds at 200° C., and about 5 minutes at room temperature. In this way, the adhesive on the surface of the release paper or base material can be cured. [Function] By employing the above means, the carboxyl groups in the acrylic polymer and the isocyanate groups in the polyisocyanate in the adhesive react with each other in a curing catalyst atmosphere at a predetermined temperature, resulting in curing, and the cohesive force of the adhesive is reduced. In addition to preventing peeling at the adhesive layer, the strength of the interface between the adhesive layer and the base material increases due to the tackiness of the acrylic polymer and the increase in the molecular weight of the adhesive. It is estimated that the adhesive strength of
【実施例１〜７及び比較例１〜３】
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、各別における部は
重量部を表す。
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−１に示す割合で使用してトルエン／酢酸エチル＝
１１（重量比）の混合溶剤中で溶液重合法によって固形
分３５％のアクリルポリマーを合成した。
表−１
表−１中の略号は次の意味を表す。
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
（実施例１）
前記アクリルポリマー■の固形分１００部と４゜４′−
ジフェニルメタンジイソシアネート１部を混合して粘着
剤を調製し、これを基材としての８倍発泡のポリエチレ
ンに約１００μｍの厚さに塗布した。次いで、７０℃の
ジエチルアミンの蒸気中で３０秒加熱して粘着剤を硬化
させた。これに別の８倍発泡のポリエチレンを２５ｍｍ
Ｘ ２５ｍｍの接着面積で５ ｋｇ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
剪断強度を測定した。その結果を後記表−２に示す。な
お、引張剪断強度の測定における引張スピードは３゜ｌ
ｌｌ１／ｌ１ｌｉｎである。
（実施例２）
前記アクリルポリマー■の固形分１００部と４゜４１−
ジフェニルエーテルジイソシアネート２部を混合して粘
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℃のイソプロピルアミンの
蒸気中で１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。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。
（実施例３）
前記アクリルポリマー〇の固形分１００部と１゜５−ナ
フタレンジイソシアネート５部を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、１５０”Ｃのブチルアミンの蒸気中で１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。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。
（実施例４）
前記アクリルポリマー〇の固形分１００部とキシレンジ
イソシアネート１部を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０次いで、
１５０℃の第３級アミンの蒸気中で１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。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。
（実施例５）
前記アクリルポリマー〇の固形分１００部とイソホロン
ジイソシアネート１部を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０次いで
、２００℃の２−メチルピペラジンの蒸気中で１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。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。
（実施例６）
前記アクリルポリマー■の固形分１００部と水添４．４
′ジフ工ニルメタンジイソシアネート１部を混合して粘
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０次いで、２００℃のテトラメチルスズの蒸
気中で１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。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。
（実施例７）
上記実施例６において、水添４．４′ジフエニルメタン
ジイソシアネートの配合割合を２０部とした以外は、同
実施例６と同様にして試験片を作製し、引張剪断強度を
測定した。その結果を後記表−２に示す。
（比較例１）
前記アクリルポリマー■の固形分１００部と水添４．４
′ジフ工ニルメタンジイソシアネート１部を混合して粘
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、硬化触媒雰囲気中で硬化させるこ
となく、その他は実施例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。
（比較例２）
前記アクリルポリマー■の固形分１００部と１゜５−ナ
フタレンジイソシアネート０．０００１部を混合して粘
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℃のイソプロピルアミンの
蒸気中で１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。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。
（比較例３）
上記比較例２において、１．５−ナフタレンジイソシア
ネートの配合割合を１００部とした以外は、同比較例２
と同様にして試験片を作製し、引張剪断強度を測定した
。その結果を併せて下記表−２に示す。
表−２
表−２かられかるように、本発明の実施例１〜７におい
ては引張剪断強度が７．５〜７．９ｋｇ／ｃｎという高
い値を示す。一方、アクリル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）、ポ
リイソシアネートの混合量が過少又は過多の場合（比較
例２．３）には、接着しないか又は引張剪断強度が０．
０１〜２．１ｋｇ／ｃＩ！という低い値しか示さなかっ
た。
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、各実施例において粘着剤を所定温度の硬化剤雰囲気
中で加熱することにより、アクリル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、かつ硬化剤の反応によって粘着剤の凝
集力が高まるとともに、アクリルポリマーの有する粘着
性と粘着剤の分子量の増大とによって、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。
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。
［発明の効果］
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、また硬化温度が低（、しかも硬化時間が短く作
業性に優れているという効果を奏する。[Examples 1 to 7 and Comparative Examples 1 to 3] Hereinafter, a method for curing an adhesive embodying the present invention will be explained in comparison with a comparative example. In addition, each part represents a part by weight. First, using acrylic ester and unsaturated carboxylic acid in the ratio shown in Table 1 below, toluene/ethyl acetate =
An acrylic polymer having a solid content of 35% was synthesized by a solution polymerization method in a mixed solvent of 11 (weight ratio). Table-1 The abbreviations in Table-1 represent the following meanings. BuA Nibutyl acrylate AA Niacrylic acid 2-EHA: 2-Ethylhexyl acrylate AMA
: Maleic anhydride AIA : Itaconic anhydride (Example 1) 100 parts of the solid content of the acrylic polymer (■) and 4°4'-
An adhesive was prepared by mixing 1 part of diphenylmethane diisocyanate, and this was applied to a thickness of about 100 μm on 8 times expanded polyethylene as a base material. Next, the adhesive was cured by heating in diethylamine vapor at 70° C. for 30 seconds. Add another 25mm of 8x foamed polyethylene to this.
A test piece was prepared by applying a pressure of 5 kg for 1 minute to prepare a test piece with an adhesion area of 25 mm x 25 mm. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below. In addition, the tensile speed in measuring the tensile shear strength was 3゜l.
ll1/l1lin. (Example 2) 100 parts of the solid content of the acrylic polymer (2) and 4°41-
An adhesive was prepared by mixing 2 parts of diphenyl ether diisocyanate, and this was applied to the same substrate as in Example 1 to the same thickness. Then, the adhesive was cured by heating for 1 minute in isopropylamine vapor at 100°C. Thereafter, test pieces were prepared in the same manner as in Example 1. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below. (Example 3) An adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer 〇 and 5 parts of 1゜5-naphthalene diisocyanate, and this was applied to the same substrate as in Example 1 to the same thickness. . Next, the adhesive was cured by heating in butylamine vapor at 150"C for 1 minute. A test piece was prepared in the same manner as in Example 1. The tensile shear strength of this was measured. The results were It is shown in Table 2 below. (Example 4) An adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer 〇 and 1 part of xylene diisocyanate, and this was applied to the same base material as in Example 1 to the same thickness. 0 applied with
The adhesive was cured by heating for 1 minute in tertiary amine vapor at 150°C. Thereafter, test pieces were prepared in the same manner as in Example 1. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below. (Example 5) An adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer 〇 and 1 part of isophorone diisocyanate, and this was applied to the same substrate as in Example 1 to the same thickness. The adhesive was cured by heating for 1 minute in 2-methylpiperazine vapor at <0>C. Thereafter, test pieces were prepared in the same manner as in Example 1. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below. (Example 6) 100 parts of solid content of the acrylic polymer (1) and hydrogenation of 4.4 parts
' A pressure-sensitive adhesive was prepared by mixing 1 part of diphenylmethane diisocyanate, and this was applied to the same substrate as in Example 1 to the same thickness.Then, it was coated in tetramethyltin vapor at 200°C for 1 minute. The adhesive was cured by heating. Thereafter, test pieces were prepared in the same manner as in Example 1. Regarding this, the tensile shear strength was measured. The results are shown in Table 2 below. (Example 7) A test piece was prepared in the same manner as in Example 6, except that the blending ratio of hydrogenated 4.4' diphenylmethane diisocyanate was changed to 20 parts, and the tensile shear strength was measured. It was measured. The results are shown in Table 2 below. (Comparative Example 1) Hydrogenation with 100 parts of the solid content of the acrylic polymer (■): 4.4
A pressure-sensitive adhesive was prepared by mixing 1 part of diphenylmethane diisocyanate, and this was applied to the same substrate as in Example 1 to the same thickness. Then, a test piece was prepared in the same manner as in Example 1 except that it was not cured in a curing catalyst atmosphere. Regarding this, the tensile shear strength was measured. The results are also shown in Table 2 below. (Comparative Example 2) An adhesive was prepared by mixing 100 parts of the solid content of the acrylic polymer ① and 0.0001 part of 1°5-naphthalene diisocyanate, and this was applied to the same base material as in Example 1 to the same thickness. Coated. Then, the adhesive was cured by heating for 1 minute in isopropylamine vapor at 100°C. Thereafter, test pieces were prepared in the same manner as in Example 1. Regarding this, the tensile shear strength was measured. The results are also shown in Table 2 below. (Comparative Example 3) The same Comparative Example 2 except that the blending ratio of 1.5-naphthalene diisocyanate was 100 parts.
A test piece was prepared in the same manner as above, and the tensile shear strength was measured. The results are also shown in Table 2 below. Table 2 As seen from Table 2, Examples 1 to 7 of the present invention exhibit high tensile shear strengths of 7.5 to 7.9 kg/cn. On the other hand, when the mixture of acrylic polymer and polyisocyanate is used as is (Comparative Example 1), or when the amount of polyisocyanate mixed is too little or too much (Comparative Example 2.3), there is no adhesion or the tensile shear strength is 0. ．．
01~2.1kg/cI! It showed only a low value. The reason why the curing method of each example exhibits high tensile shear strength is that in each example, by heating the adhesive in a curing agent atmosphere at a predetermined temperature, the carboxyl group in the acrylic polymer and the isocyanate group in the polyisocyanate are combined. The cohesive force of the adhesive increases due to the reaction of the curing agent, and the adhesive strength between the two 8x expanded polyethylene is improved due to the adhesiveness of the acrylic polymer and the increase in the molecular weight of the adhesive. It is considered that 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. [Effects of the Invention] According to the adhesive curing method of the present invention, the adhesive has a high adhesive strength, a low curing temperature (and a short curing time, and excellent workability).
Claims (1)
量部に対しポリイソシアネート０．００１〜２０重量部
を配合した混合物からなる粘着剤を剥離紙又は基材に塗
布し、硬化触媒の沸点以上でかつ２００℃以下の硬化触
媒雰囲気中で硬化させることを特徴とする粘着剤の硬化
方法。1. Apply an adhesive consisting of a mixture of 0.001 to 20 parts by weight of polyisocyanate to 100 parts by weight of an acrylic polymer having a carboxyl group on release paper or a base material, and heat the adhesive at a temperature above the boiling point of the curing catalyst and below 200°C. A method for curing an adhesive, characterized by curing in a curing catalyst atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7446089A JPH02252778A (en) | 1989-03-27 | 1989-03-27 | Method for curing tacky agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7446089A JPH02252778A (en) | 1989-03-27 | 1989-03-27 | Method for curing tacky agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02252778A true JPH02252778A (en) | 1990-10-11 |
Family
ID=13547887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7446089A Pending JPH02252778A (en) | 1989-03-27 | 1989-03-27 | Method for curing tacky agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02252778A (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 |
-
1989
- 1989-03-27 JP JP7446089A patent/JPH02252778A/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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