JPH0786191B2 - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPH0786191B2 JPH0786191B2 JP61289598A JP28959886A JPH0786191B2 JP H0786191 B2 JPH0786191 B2 JP H0786191B2 JP 61289598 A JP61289598 A JP 61289598A JP 28959886 A JP28959886 A JP 28959886A JP H0786191 B2 JPH0786191 B2 JP H0786191B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- hydrogen atom
- group
- compound represented
- methyl group
- 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
- 239000000203 mixture Substances 0.000 title claims description 23
- 239000000853 adhesive Substances 0.000 title claims description 15
- 230000001070 adhesive effect Effects 0.000 title claims description 15
- -1 acrylamidomethyl group Chemical group 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical class OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical class CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- OHBCEHHJPNBVME-UHFFFAOYSA-N n-[[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]methyl]prop-2-enamide Chemical compound CC1=CC(CNC(=O)C=C)=CC(C)=C1OCC1OC1 OHBCEHHJPNBVME-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、高温での接着強度が高く、耐薬品性に優れる
接着剤組成物に関するものである。TECHNICAL FIELD The present invention relates to an adhesive composition having high adhesive strength at high temperature and excellent chemical resistance.
「従来技術と問題点」 従来、接着剤としては、エポキシ樹脂が接着性が優れて
いるために広く用いられている。また、近年、アクリル
系の接着剤が接着性が優れ、速硬化性があるために用い
られている。しかし乍ら、これらの接着剤は高温での使
用には耐熱性が十分ではなく、また、アクリル系の接着
剤は耐薬品性が悪いという欠点を有する。“Conventional Technology and Problems” Conventionally, epoxy resins have been widely used as adhesives because of their excellent adhesiveness. Further, in recent years, acrylic adhesives have been used because of their excellent adhesiveness and rapid curing. However, these adhesives have the drawbacks that they have insufficient heat resistance for use at high temperatures, and that acrylic adhesives have poor chemical resistance.
「問題点を解決するための手段」 本発明者らは、かかる問題点を解決するべく鋭意検討し
た結果、特定の化合物を用いることによりこれらの問題
点が解決出来ることを見出し、本発明に到達した。“Means for Solving Problems” As a result of intensive studies to solve the problems, the present inventors have found that these problems can be solved by using a specific compound, and arrived at the present invention. did.
即ち、本発明は下記の成分（イ）、（ロ）及び（ハ）を
必須成分として含有することを特徴とする接着剤組成
物； （イ）少なくとも１個のアクリルアミドメチル基または
メタクリルアミドメチル基と少なくとも１個のエポキシ
基を同一分子内に有する化合物、 （ロ）酸無水物、芳香族ジアミン又はイミダゾールから
なるエポキシ樹脂硬化剤、 （ハ）ラジカル重合開始剤、 を内容とするものである。That is, the present invention comprises an adhesive composition containing the following components (a), (b) and (c) as essential components; (a) at least one acrylamidomethyl group or methacrylamidomethyl group. And (b) a compound having at least one epoxy group in the same molecule, (b) an epoxy resin curing agent composed of an acid anhydride, an aromatic diamine or imidazole, and (c) a radical polymerization initiator.
本発明に用いられる少なくとも１個のアクリルアミドメ
チル基またはメタクリルアミドメチル基と少なくとも１
個のエポキシ基を同一分子内に有する化合物としては、
特に限定されないが下記一般式（Ｉ）または（II）で表
されるグリシジル化合物が本発明の目的に特に好適であ
る。At least one acrylamidomethyl group or methacrylamidemethyl group used in the present invention and at least one
As a compound having a single epoxy group in the same molecule,
Although not particularly limited, a glycidyl compound represented by the following general formula (I) or (II) is particularly suitable for the purpose of the present invention.
（式中、Arはグリシジルオキシ基を少なくとも１つ有す
る炭素数６−20の芳香族炭化水素を、Ｒは水素原子また
はメチル基を表し、ｎは１−４の整数である） （式中、Ar2はN,N−ジグリシジルアミノ基を少なくとも
１つ有する炭素数６−14の芳香族炭化水素を、Ｒは水素
原子またはメチル基を表し、ｎは１−３の整数である） 本発明のグリシジル化合物（Ｉ）は、下記一般式（VI
I） （式中、Ar′は水酸基を少なくとも１つ有する炭素数６
−20の芳香族炭化水素を、Ｒは水素原子またはメチル基
を表し、ｎは１−４の整数である）で表される化合物と
エピハロヒドリンを付加させたのち、アルカリで脱ハロ
ゲン化水素反応を行うことにより製造される。 (In the formula, Ar represents an aromatic hydrocarbon having at least one glycidyloxy group and having 6 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and n is an integer of 1-4). (In the formula, Ar 2 is a C 6-14 aromatic hydrocarbon having at least one N, N-diglycidylamino group, R is a hydrogen atom or a methyl group, and n is an integer of 1-3. The glycidyl compound (I) of the present invention has the following general formula (VI
I) (In the formula, Ar ′ has 6 carbon atoms having at least one hydroxyl group.
-20 aromatic hydrocarbon, R represents a hydrogen atom or a methyl group, and n is an integer of 1-4) and epihalohydrin are added, and then dehydrohalogenation reaction is carried out with alkali. It is manufactured by carrying out.
一般式（Ｖ）で表される化合物は、例えばフェノール性
水酸基を少なくとも１つ以上有する芳香族炭化水素とＮ
−メチロールアクリルアミドまたはＮ−メチロールメタ
アクリルアミドまたはＮ−メチロール（メタ）アクリル
アミドのアルキルエーテル誘導体（以下、これをＮ−メ
チロールアクリルアミド類という）を酸触媒で縮合させ
ることにより容易に得ることができる。The compound represented by the general formula (V) is, for example, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N
-Methylol acrylamide or N-methylol methacrylamide or an alkyl ether derivative of N-methylol (meth) acrylamide (hereinafter referred to as N-methylol acrylamides) can be easily obtained by condensing with an acid catalyst.
例えば、出発物質として2,6−キシレノールとＮ−メチ
ロールアクリルアミドを用いた場合、下記構造式（II
I） （式中、Ｒは水素原子またはメチル基である）で表され
るグリシジル化合物を得ることが出来る。For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (II
I) A glycidyl compound represented by the formula (wherein R is a hydrogen atom or a methyl group) can be obtained.
また、出発物質としてオルトクレゾールとＮ−メチロー
ルアクリルアミドを用いた場合、下記構造式（IV） （式中、Ｒは水素原子またはメチル基を表し、ｎは１ま
たは２である）で表されるグリシジル化合物を得ること
が出来る。When orthocresol and N-methylolacrylamide are used as starting materials, the following structural formula (IV) (In the formula, R represents a hydrogen atom or a methyl group, and n is 1 or 2) to obtain a glycidyl compound.
更に出発物質としてビスフェノールＡとＮ−メチロール
アクリルアミド類を用いた場合、下記構造式（Ｖ） （式中、Ｒは水素原子またはメチル基を表し、ｎ、ｎ′
の少なくとも１つは１以上である）で表されるグリシジ
ル化合物を得ることが出来る。Furthermore, when bisphenol A and N-methylol acrylamides are used as starting materials, the following structural formula (V) (In the formula, R represents a hydrogen atom or a methyl group, and n, n '
At least one of which is 1 or more) can be obtained.
本発明のグリシジル化合物（II）は、下記一般式（VII
I） （NH2 nAr′ （VIII） （式中、Ar′は炭素数６〜14の芳香族炭化水素を表し、
ｎは１〜３の整数である）で表される化合物とエピクロ
ルヒドリンを付加せしめたものに下記一般式（IX） （式中、R1は水素原子またはメチル基を、R2は水素原子
または炭素数１〜４の炭化水素を表す）で示されるＮ−
メチロール（メタ）アクリルアミドまたはＮ−アルコキ
シメチル（メタ）アクリルアミドを縮合させたのち、苛
性アルカリで脱ハロゲン化水素反応を行うことにより容
易に得られる。特に原料のアミン類として （ｍは０〜２の整数）で表される化合物を用いると、下
記一般式（VI） （式中、R1は水素原子またはメチル基を表し、ｍは０〜
２の整数である）で表されるグリシジル化合物を得るこ
とができる。The glycidyl compound (II) of the present invention has the following general formula (VII
I) (NH 2 n Ar ′ (VIII) (wherein Ar ′ represents an aromatic hydrocarbon having 6 to 14 carbon atoms,
n is an integer from 1 to 3) and epichlorohydrin is added to the compound represented by the following general formula (IX) (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms).
It can be easily obtained by condensing methylol (meth) acrylamide or N-alkoxymethyl (meth) acrylamide and then performing a dehydrohalogenation reaction with caustic. Especially as the raw material amines When a compound represented by (m is an integer of 0 to 2) is used, the following general formula (VI) is used. (In the formula, R 1 represents a hydrogen atom or a methyl group, and m is 0 to
It is possible to obtain a glycidyl compound represented by (an integer of 2).
本発明に使用されるエポキシ樹脂硬化剤としては、酸無
水物，芳香族ジアミン又はイミダゾール類が用いられ
る。例示すれば無水フタル酸、無水テトラヒドロフタル
酸、無水ヘキサヒドロフタル酸、無水トリメリット類、
無水ピロメリット類、無水クロレンディック酸、無水ベ
ンゾフェノンテトラカルボン酸等の酸無水物、4,4′−
ジアミノジフェニルメタン、4,4′−ジアミノジフェニ
ルスルホン、メタフェニレンジアミン、パラフェニレン
ジアミン等の芳香族ジアミン、イミダゾール、２−エチ
ル−４−メチルイミダゾール、２−フェニルイミダゾー
ル、１−ベンジル−２−メチルイミダゾール、２−ウン
デシルイミダゾール等のイミダゾール類があげられる。As the epoxy resin curing agent used in the present invention, acid anhydride, aromatic diamine or imidazole is used. For example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride,
Acid anhydrides such as pyromellitic dianhydride, chlorendic anhydride, benzophenone tetracarboxylic anhydride, 4,4'-
Aromatic diamines such as diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, metaphenylenediamine and paraphenylenediamine, imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, Examples include imidazoles such as 2-undecylimidazole.
硬化剤の使用量は、硬化剤の種類によって異なるが、例
えば酸無水物ではエポキシ基に対して0.5−1.5当量が望
ましい。The amount of the curing agent used varies depending on the type of the curing agent, but in the case of an acid anhydride, it is preferably 0.5 to 1.5 equivalents based on the epoxy groups.
本発明においては、必要に応じてエポキシ樹脂の硬化促
進剤を添加しても良い。硬化促進剤としては、一般に知
られているものが任意に使用できる。例示すれば、ベン
ジルジメチルアミン、２、４、６−トリス（ジメチルア
ミノメチル）フェノール等の第三級アミン類、２−エチ
ル−４−メチルイミダゾール、Ｎ−ベンジルイミダゾー
ル等のイミダゾール類、三フッ化ホウ素−アミン錯体、
尿素類、ホスフィン類、金属塩類等があげられる。In the present invention, a curing accelerator for the epoxy resin may be added if necessary. As the curing accelerator, any generally known one can be arbitrarily used. For example, benzyldimethylamine, tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, imidazoles such as N-benzylimidazole, trifluoride, etc. Boron-amine complex,
Examples thereof include ureas, phosphines, metal salts and the like.
硬化促進剤の使用量は所望の硬化速度が得られるように
調節されるべきであるが、通常、組成物中に1.01〜５重
量％添加される。The amount of the curing accelerator used should be adjusted so as to obtain a desired curing rate, but usually 1.01 to 5% by weight is added to the composition.
ラジカル重合開始剤としては、一般にラジカル重合の開
始剤として知られているものが任意に使用できるが、そ
の中でも有機過酸化物が特に適している。例示すればｔ
−ブチルハイドロパーオキサイド、キュメンハイドロパ
ーオキサイド、ジ−ｔ−ブチルパーオキサイド、ジクミ
ルパーオキサイド、ベンゾイルパーオキサイド、ｔ−ブ
チルパーオキシベンゾエート等があげられる。ラジカル
重合開始剤の使用量としては、特に限定されないが、通
常、組成物に対して0.1〜20重量％の範囲で使用され
る。As the radical polymerization initiator, any one generally known as a radical polymerization initiator can be arbitrarily used, and among them, an organic peroxide is particularly suitable. For example, t
-Butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate and the like can be mentioned. The amount of the radical polymerization initiator used is not particularly limited, but it is usually used in the range of 0.1 to 20% by weight based on the composition.
本発明の組成物には、必要に応じてアクリル系のモノマ
ーまたはオリゴマー、その他のビニル化合物を添加して
もよい。また、本発明の目的が失われない範囲で、エポ
キシ樹脂、エポキシ系反応性希釈剤を添加してもよい。Acrylic monomers or oligomers and other vinyl compounds may be added to the composition of the present invention, if necessary. Moreover, you may add an epoxy resin and an epoxy type reactive diluent in the range which does not lose the objective of this invention.
本発明による組成物の製造方法は特に限定されないが、
ロールによる混練、らいかい機による混合、ミキサーに
よる混合が推奨される。The method for producing the composition according to the present invention is not particularly limited,
Kneading with rolls, mixing with a raker, mixing with a mixer is recommended.
「作用・効果」 本発明による接着剤組成物は、各種の被着体に対する接
着性に優れており、特に、高温における接着性が高い特
徴である。また、本発明の組成物は、アクリル系の接着
剤に比較して、耐薬品性に優れている。"Operation / Effect" The adhesive composition according to the present invention has excellent adhesiveness to various adherends, and is particularly characterized by high adhesiveness at high temperatures. Further, the composition of the present invention has excellent chemical resistance as compared with an acrylic adhesive.
「実施例」 以下、本発明を実施例にて説明するが、本発明は、これ
ら実施例のみに限定されるものではない。"Examples" Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.
実施例１ Ｎ−（４−グリシジルオキシ−３、５−ジメチルフェニ
ルメチル）アクリルアミド（前記構造式（III）でＲが
水素原子であるもの）100部（重量部、以下同様）、無
水メチルナジック酸58部、１−ベンジル−２−メチルイ
ミダゾール１部、ｔ−ブチルパーベンゾエート1.5部を
３本ロールで混練し、接着剤組成物を得た。Example 1 N- (4-glycidyloxy-3,5-dimethylphenylmethyl) acrylamide (R in the structural formula (III) in which R is a hydrogen atom) 100 parts (parts by weight, the same applies hereinafter), methyl nadic acid anhydride 58 parts, 1-benzyl-2-methylimidazole 1 part, and t-butyl perbenzoate 1.5 parts were kneaded with a three-roll mill to obtain an adhesive composition.
上記組成物を軟鋼板に塗布、圧着し150℃30分間加熱し
硬化させた。JISK6850に基づいて引張剪断強度は23℃で
95kg/cm2であり、200℃で105kg/cm2であった。また硬化
物のガラス転移温度は230℃であった。The above composition was applied to a mild steel plate, pressure-bonded, and heated at 150 ° C. for 30 minutes to be cured. Tensile shear strength at 23 ° C based on JIS K6850
It was 95 kg / cm 2 and 105 kg / cm 2 at 200 ° C. The glass transition temperature of the cured product was 230 ° C.
実施例２ Ｎ−（４−Ｎ、Ｎ′−ジグリシジルアミノフェニルメチ
ル）アクリルアミド（前記構造式（VI）でR1が水素原
子、ｍ＝０であるもの）100部、無水メチルナジック酸9
8部、２−エチル−４−メチルイミダゾール1.5部及びｔ
−ブチルパーベンゾエート1.5部を混合し接着剤組成物
を得た。Example 2 100 parts of N- (4-N, N'-diglycidylaminophenylmethyl) acrylamide (the structural formula (VI) wherein R 1 is a hydrogen atom and m = 0) 100 parts, methyl nadic acid anhydride 9
8 parts, 2-ethyl-4-methylimidazole 1.5 parts and t
An adhesive composition was obtained by mixing 1.5 parts of butyl perbenzoate.
上記組成物を軟鋼板に塗布、圧着し、150℃30分間加熱
し硬化させた。JISK6850に基づいて引張剪断強度は23℃
で110kg/cm2、200℃で115kg/cmであった。また、硬化物
のガラス転移温度は250℃であった。The above composition was applied to a mild steel plate, pressure-bonded, and heated at 150 ° C. for 30 minutes to be cured. Tensile shear strength is 23 ° C based on JIS K6850
It was 110 kg / cm 2 and 115 kg / cm at 200 ° C. The glass transition temperature of the cured product was 250 ° C.
“実施例３ 無水メチルナジック酸58部、１−ベンジル−２−メチル
イミダゾール１部に代えて、4,4′−ジアミノジフェニ
ルスルホン59部を用いた他は実施例１と同様にして接着
剤組成物を得、硬化させた。Example 3 Adhesive composition in the same manner as in Example 1 except that 58 parts of methyl nadic acid anhydride and 1 part of 1-benzyl-2-methylimidazole were used, and 59 parts of 4,4′-diaminodiphenyl sulfone was used. The product was obtained and cured.
硬化物のガラス転移温度は240℃であった。The glass transition temperature of the cured product was 240 ° C.
実施例４ 無水メチルナジック酸58部、１−ベンジル−２−メチル
イミダゾール１部に代えて、イミダゾール59部を用いた
他は実施例１と同様にして接着剤組成物を得、硬化させ
た。Example 4 An adhesive composition was obtained and cured in the same manner as in Example 1 except that 59 parts of imidazole was used instead of 58 parts of methyl nadic acid anhydride and 1 part of 1-benzyl-2-methylimidazole.
硬化物のガラス転移温度は240℃であった。The glass transition temperature of the cured product was 240 ° C.
比較例１ 無水メチルナジック酸58部、１−ベンジル−２−メチル
イミダゾール１部に代えて、イソホロジアミン59部を用
いた他は実施例１と同様にして接着剤組成物を得、硬化
させた。Comparative Example 1 An adhesive composition was obtained and cured in the same manner as in Example 1 except that 58 parts of methyl nadic acid anhydride and 1 part of 1-benzyl-2-methylimidazole were used instead of 59 parts of isophorodiamine. It was
硬化物のガラス転移温度は190℃であった。”The glass transition temperature of the cured product was 190 ° C. ”
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−252624（ＪＰ，Ａ) 特開 昭60−258225（ＪＰ，Ａ) 特開 昭60−195119（ＪＰ，Ａ) 垣内弘編「新エポキシ樹脂」昭晃堂 昭 和60年発行 第164ー171頁第175ー179頁 第191ー203頁 第221ー233頁 ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-60-252624 (JP, A) JP-A-60-258225 (JP, A) JP-A-60-195119 (JP, A) Edited by Hiroshi Kakiuchi "New "Epoxy resin" Shokōdou Showa 60 years issue 164-171 pages 175-179 pages 191-203 pages 221-233
Claims (7)
須成分として含有することを特徴とする接着剤組成物； （イ）少なくとも１個のアクリルアミドメチル基または
メタクリルアミドメチル基と少なくとも１個のエポキシ
基を同一分子内に有する化合物、 （ロ）酸無水物、芳香族ジアミン又はイミダゾール類か
らなるエポキシ樹脂硬化剤、 （ハ）ラジカル重合開始剤。1. An adhesive composition containing the following components (a), (b) and (c) as essential components; (a) at least one acrylamidomethyl group or methacrylamidomethyl group. And a compound having at least one epoxy group in the same molecule, (b) an epoxy resin curing agent consisting of an acid anhydride, an aromatic diamine or an imidazole, and (c) a radical polymerization initiator.
る炭素数６−20の芳香族炭化水素を、Ｒは水素原子また
はメチル基を表し、ｎは１−４の整数である）で表され
るグリシジル化合物である特許請求の範囲第１項記載の
組成物。2. The component (a) is represented by the following general formula (I): (Wherein Ar represents an aromatic hydrocarbon having at least one glycidyloxy group and having 6 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and n is an integer of 1-4). The composition according to claim 1, which is a glycidyl compound.
１つ有する炭素数６−14の芳香族炭化水素を、Ｒは水素
原子またはメチル基を表し、ｎは１−３の整数である）
で表されるグリシジル化合物である特許請求の範囲第１
項及び第２項記載の組成物。3. The component (a) is represented by the following general formula (II). (In the formula, Ar 2 is a C 6-14 aromatic hydrocarbon having at least one N, N-diglycidylamino group, R is a hydrogen atom or a methyl group, and n is an integer of 1-3. is there)
Claim 1 which is a glycidyl compound represented by:
The composition according to the items 2 and 3.
る化合物である特許請求の範囲第４項記載の組成物。4. A glycidyl compound represented by the following structural formula (III) The composition according to claim 4, which is a compound represented by the formula (wherein R represents a hydrogen atom or a methyl group).
たは２である）で表される化合物である特許請求の範囲
第２項記載の組成物。5. A glycidyl compound represented by the following structural formula (IV) The composition according to claim 2, which is a compound represented by the formula (wherein R represents a hydrogen atom or a methyl group, and n is 1 or 2).
の少なくとも１つは１以上である）で表される化合物で
ある特許請求の範囲第２項記載の組成物。6. A glycidyl compound having the following structural formula (V) (In the formula, R represents a hydrogen atom or a methyl group, and n, n '
The composition according to claim 2, which is a compound represented by at least one of 1 or more).
２の整数である）で表されるグリシジル化合物である特
許請求の範囲第３項記載の組成物。7. A glycidyl compound having the following structural formula (VI) (In the formula, R 1 represents a hydrogen atom or a methyl group, and m is 0 to
The composition according to claim 3, which is a glycidyl compound represented by the formula (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61289598A JPH0786191B2 (en) | 1986-12-04 | 1986-12-04 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61289598A JPH0786191B2 (en) | 1986-12-04 | 1986-12-04 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63142082A JPS63142082A (en) | 1988-06-14 |
| JPH0786191B2 true JPH0786191B2 (en) | 1995-09-20 |
Family
ID=17745306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61289598A Expired - Lifetime JPH0786191B2 (en) | 1986-12-04 | 1986-12-04 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0786191B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60252624A (en) * | 1984-05-30 | 1985-12-13 | Kanegafuchi Chem Ind Co Ltd | reactive resin composition |
| JPS60258225A (en) * | 1984-06-04 | 1985-12-20 | Kanegafuchi Chem Ind Co Ltd | Reactive resin composition |
-
1986
- 1986-12-04 JP JP61289598A patent/JPH0786191B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 垣内弘編「新エポキシ樹脂」昭晃堂昭和６０年発行第１６４ー１７１頁第１７５ー１７９頁第１９１ー２０３頁第２２１ー２３３頁 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63142082A (en) | 1988-06-14 |
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