JPH0657213A - Heat-resistant acrylic adhesive composition - Google Patents
Heat-resistant acrylic adhesive compositionInfo
- Publication number
- JPH0657213A JPH0657213A JP23528292A JP23528292A JPH0657213A JP H0657213 A JPH0657213 A JP H0657213A JP 23528292 A JP23528292 A JP 23528292A JP 23528292 A JP23528292 A JP 23528292A JP H0657213 A JPH0657213 A JP H0657213A
- Authority
- JP
- Japan
- Prior art keywords
- maleimide
- acrylic
- adhesive
- meth
- heat
- 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.)
- Granted
Links
- 239000003522 acrylic cement Substances 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 title claims description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 44
- 239000000853 adhesive Substances 0.000 claims abstract description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- -1 phosphorus compound Chemical class 0.000 claims description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 9
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 3
- 230000032798 delamination Effects 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XPUJOEOXHUYRPJ-UHFFFAOYSA-N 2,4-ditert-butyl-4-methylcyclohexa-1,5-dien-1-ol Chemical compound CC(C)(C)C1=C(O)C=CC(C)(C(C)(C)C)C1 XPUJOEOXHUYRPJ-UHFFFAOYSA-N 0.000 description 1
- MHUFITQZKOMYKX-UHFFFAOYSA-N 2,5-dioxo-4-phenylpyrrole-3-carboxylic acid Chemical compound O=C1NC(=O)C(C(=O)O)=C1C1=CC=CC=C1 MHUFITQZKOMYKX-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-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
- VXPSQDAMFATNNG-UHFFFAOYSA-N 3-[2-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=CC=CC=2)C=2C(NC(=O)C=2)=O)=C1 VXPSQDAMFATNNG-UHFFFAOYSA-N 0.000 description 1
- JXYBPWLCIBLVRB-UHFFFAOYSA-N 3-[hydroxy-[3-(2-methylprop-2-enoyloxy)propoxy]phosphoryl]oxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOP(O)(=O)OCCCOC(=O)C(C)=C JXYBPWLCIBLVRB-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- VISOTGQYFFULBK-UHFFFAOYSA-N 3-hydroxy-4-phenylpyrrole-2,5-dione Chemical compound O=C1C(=O)NC(O)=C1C1=CC=CC=C1 VISOTGQYFFULBK-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- CIIWMXSMCCRQEQ-UHFFFAOYSA-N 3-phosphonooxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOP(O)(O)=O CIIWMXSMCCRQEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- WIDLYFZFVAGYAJ-UHFFFAOYSA-N 4-(2,5-dioxopyrrol-3-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(=O)NC1=O WIDLYFZFVAGYAJ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高温下での接着強度お
よび耐熱老化性に優れたアクリル系の接着剤組成物に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic adhesive composition having excellent adhesive strength at high temperatures and heat aging resistance.
【０００２】[0002]
【従来の技術】（メタ）アクリル系重合性モノマーとラ
ジカル重合開始剤を主成分とするアクリル系接着剤はネ
ジ部の緩み止や、篏合部のシール、金属板の接合等工業
分野で幅広く使用されている。（メタ）アクリル系重合
性モノマーを主成分とするため特に金属に対して優れた
接着性を有するが、連続使用できる温度の上限は１５０
℃程度であり、しかも高温での接着強度はかなり低い。
これらのアクリル系接着剤の耐熱性の改善に関してはマ
レイミド化合物を配合する方法が一般的であり、特開昭
５１−１１２８９５、同５１−１２５１８５、同６２−
１０１７９号公報等において開示されている。これらは
高温で加熱硬化すると高温での接着強度や耐熱老化性が
かなり良好になっているが、用途によってはまだ不十分
である。2. Description of the Related Art Acrylic adhesives containing (meth) acrylic polymerizable monomers and radical polymerization initiators as main components are widely used in industrial fields such as preventing loosening of screw parts, sealing of mating parts, and joining of metal plates. It is used. Since it has a (meth) acrylic polymerizable monomer as a main component, it has excellent adhesiveness to a metal, but the upper limit of the temperature at which it can be continuously used is 150.
The adhesive strength at high temperature is considerably low.
In order to improve the heat resistance of these acrylic adhesives, a method of blending a maleimide compound is generally used, and JP-A-51-112895, 51-125185 and 62-
It is disclosed in Japanese Patent No. 10179. When these are heat-cured at a high temperature, their adhesive strength and heat aging resistance at a high temperature are considerably improved, but they are still insufficient depending on the application.
【０００３】一方、接着強度の改善に関しては重合性酸
性リン化合物を添加したアクリル系接着剤が知られてい
る（特開昭５１−１３２２３４、同５４−１４１８２６
号公報等）が、これらは低温での接着強度は改善されて
いるものの、耐熱性の点では殆ど効果は認められない。On the other hand, acrylic adhesives containing a polymerizable acidic phosphorus compound are known for improving the adhesive strength (Japanese Patent Laid-Open Nos. 51-132234 and 54-141826).
However, although the adhesive strength at low temperatures is improved, almost no effect is recognized in terms of heat resistance.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来のマレ
イミド化合物を含有するアクリル系接着剤の耐熱性、す
なわち１５０℃以上における熱時強度と耐熱老化性を大
幅に向上させたアクリル系耐熱性接着剤組成物を提供す
ることを目的とする。DISCLOSURE OF THE INVENTION The present invention is directed to the heat resistance of an acrylic adhesive containing a conventional maleimide compound, that is, an acrylic heat resistance in which the strength under heat at 150 ° C. or higher and the heat aging resistance are greatly improved. It is an object to provide an adhesive composition.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、（メ
タ）アクリル系重合性モノマー、マレイミド化合物およ
びラジカル重合開始剤を主成分とするアクリル系接着剤
組成物に対して、重合性酸性リン化合物を０．０１〜１
０重量％添加したことを特徴とするアクリル系耐熱性接
着剤組成物が提供され、また前記マレイミド化合物が分
子中にカルボキシル基または水酸基を有するマレイミド
であることを特徴とする前記アクリル系耐熱性接着剤組
成物が提供され、さらに、該接着剤組成物に対して無機
質充填剤を１０〜５０重量％添加したことを特徴とする
アクリル系耐熱性接着剤組成物が提供される。According to the present invention, a polymerizable acidic phosphorus composition is added to an acrylic adhesive composition containing a (meth) acrylic polymerizable monomer, a maleimide compound and a radical polymerization initiator as main components. 0.01 to 1 compound
Provided is an acrylic heat-resistant adhesive composition characterized by being added at 0% by weight, and the above-mentioned acrylic heat-resistant adhesive characterized in that the maleimide compound is a maleimide having a carboxyl group or a hydroxyl group in the molecule. There is provided an agent composition, and further, there is provided an acrylic heat-resistant adhesive composition characterized by adding 10 to 50% by weight of an inorganic filler to the adhesive composition.
【０００６】すなわち、マレイミド化合物を含有するア
クリル系接着剤に少量の重合性酸性リン化合物の添加が
耐熱性の向上に非常に効果的であり、またマレイミド化
合物として分子中にカルボキシル基または水酸基を持つ
マレイミドを用いた場合にさらに重合性酸性リン化合物
の添加効果が顕著になること、さらには無機質充填剤の
添加が硬化収縮防止、耐熱性向上等の点で効果があるこ
とを見出し、本発明を完成するに至った。That is, the addition of a small amount of a polymerizable acidic phosphorus compound to an acrylic adhesive containing a maleimide compound is very effective for improving heat resistance, and the maleimide compound has a carboxyl group or a hydroxyl group in the molecule. It was found that the effect of addition of the polymerizable acidic phosphorus compound becomes more remarkable when maleimide is used, and further that the addition of the inorganic filler is effective in preventing curing shrinkage, improving heat resistance, etc. It came to completion.
【０００７】重合性酸性リン化合物はマレイミド化合物
との共存下において、高温での接着剤が被着体の界面で
剥離するのを防止する役目を果しているものと思われ
る。すなわち、本発明のアクリル系耐熱性接着剤組成物
は、密着性の向上によって優れた接着強度が付与される
と共に、１５０℃以上の高温に曝された時、界面剥離を
防止し、硬化した接着剤が高温の空気で酸化劣化される
のを防ぐことによって、従来には見られなかった非常に
優れた接着特性を奏するものと思われる。特にマレイミ
ド化合物が分子中にカルボキシル基や水酸基のような極
性基を有するものを使用した場合、さらに密着性が良好
となって耐熱老化性が向上することが明らかとなった。It is considered that the polymerizable acidic phosphorus compound, in the coexistence with the maleimide compound, serves to prevent the adhesive at high temperature from peeling off at the interface of the adherend. That is, the acrylic heat-resistant adhesive composition of the present invention is provided with excellent adhesive strength due to improved adhesion and, at the time of being exposed to a high temperature of 150 ° C. or higher, prevents interfacial peeling and provides a cured adhesive. By preventing the agent from being oxidatively deteriorated by high temperature air, it is believed that the agent exhibits very excellent adhesive properties which have never been seen before. In particular, it was revealed that when a maleimide compound having a polar group such as a carboxyl group or a hydroxyl group in the molecule was used, the adhesion was further improved and the heat aging resistance was improved.
【０００８】重合性酸性リン化合物単独の添加でも密着
性の向上によって低温ではある程度の接着強度の改善効
果が見られるが、本発明が目的とする１５０℃以上の高
温では殆どその効果はなくなり、マレイミド化合物と併
用した時はじめて、極めて優れた耐熱性が発現する。す
なわち、重合性酸性リン化合物とマレイミド化合物の相
乗効果によることが明白となった。Even if the polymerizable acidic phosphorus compound is added alone, the adhesiveness is improved and the adhesive strength is improved to some extent at a low temperature, but the effect is almost eliminated at a high temperature of 150 ° C. or higher, which is the object of the present invention, and maleimide. Only when used in combination with a compound, extremely excellent heat resistance is exhibited. That is, it was clarified that it was due to the synergistic effect of the polymerizable acidic phosphorus compound and the maleimide compound.
【０００９】本発明に用いられる（メタ）アクリル系重
合性モノマーとしては特に制限はないが、例えば次のよ
うな化合物が挙げられる。メチル（メタ）アクリレー
ト、エチル（メタ）アクリレート、フェノキシエチル
（メタ）アクリレートなどのアルコールのモノ（メタ）
アクリレート、ヒドロキシエチル（メタ）アクリレー
ト、ヒドロキシプロピル（メタ）アクリレート、ヒドロ
キシブチル（メタ）アクリレートなどのヒドロキシアル
キル（メタ）アクリレート、ジエチレングリコールジ
（メタ）アクリレート、ポリエチレングリコールジ（メ
タ）アクリレート、トリメチロールプロパントリ（メ
タ）アクリレート、グリセリンジ（メタ）アクリレー
ト、グリセリントリ（メタ）アクリレート、ビスフェノ
ールＡまたはビスフェノールＳのアルキレンオキサイド
付加物のジ（メタ）アクリレート等の多価アルコールの
ポリ（メタ）アクリレート、エポキシ樹脂に（メタ）ア
クリル酸を付加して得られるエポキシ（メタ）アクリレ
ート、イソシアネート基含有（メタ）アクリレートと多
価アルコールとの反応生成物、または多価イソシアネー
トと活性水素原子を有する（メタ）アクリレートとの反
応生成物であるウレタン（メタ）アクリレート、多価ア
ルコールと多塩基酸（または多塩基酸無水物）および
（メタ）アクリル酸を反応して得られるポリエステル
（メタ）アクリレート、末端（メタ）アクリレートの液
状ゴム等である。また必要に応じてビニルエステル、フ
マル酸エステル等のモノマーを共存させることも可能で
ある。The (meth) acrylic polymerizable monomer used in the present invention is not particularly limited, but examples thereof include the following compounds. Alcohol mono (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, phenoxyethyl (meth) acrylate
Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and other hydroxyalkyl (meth) acrylates, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, poly (meth) acrylate of polyhydric alcohol such as di (meth) acrylate of alkylene oxide adduct of bisphenol A or bisphenol S, epoxy resin Epoxy (meth) acrylate obtained by adding (meth) acrylic acid, reaction formation of isocyanate group-containing (meth) acrylate and polyhydric alcohol Or a reaction product of a polyvalent isocyanate with a (meth) acrylate having an active hydrogen atom, a urethane (meth) acrylate, a polyhydric alcohol and a polybasic acid (or polybasic acid anhydride) and (meth) acrylic acid Examples include polyester (meth) acrylate obtained by the reaction and liquid rubber having a terminal (meth) acrylate. If necessary, monomers such as vinyl ester and fumaric acid ester can be allowed to coexist.
【００１０】マレイミド化合物は、分子中に下記化１で
表わされる基を１個以上有する化合物である。The maleimide compound is a compound having at least one group represented by the following chemical formula 1 in the molecule.
【化１】 例えば、マレイミド、フェニルマレイミド、ヒドロキシ
フェニルマレイミド、カルボキシフェニルマレイミド、
シクロヘキシルマレイミド、エチルマレイミド、フェニ
レンビスマレイミド等が挙げられる。また、ビスマレイ
ミド化合物と、ジアミンを末端がマレイミド基になるよ
うにマイケル付加反応させて得られるプレポリマーをマ
レイミド化合物として用いることもできる。これらのマ
レイミド化合物は（メタ）アクリル系重合性モノマーと
マレイミド化合物の合計量に対して５〜５０重量％使用
するのが耐熱性を発揮させる上で好ましい。[Chemical 1] For example, maleimide, phenylmaleimide, hydroxyphenylmaleimide, carboxyphenylmaleimide,
Cyclohexyl maleimide, ethyl maleimide, phenylene bismaleimide, etc. are mentioned. Further, a prepolymer obtained by subjecting a bismaleimide compound and a diamine to a Michael addition reaction so that the terminal becomes a maleimide group can also be used as a maleimide compound. These maleimide compounds are preferably used in an amount of 5 to 50% by weight based on the total amount of the (meth) acrylic polymerizable monomer and the maleimide compound in order to exert heat resistance.
【００１１】重合性酸性リン化合物は分子中にリン酸基
とエチレン性二重結合を有する化合物であり、例えば、
下記化２で表される化合物である。The polymerizable acidic phosphorus compound is a compound having a phosphoric acid group and an ethylenic double bond in the molecule.
It is a compound represented by the following chemical formula 2.
【化２】 （但し、Ｒ1、Ｒ2は水素又はエチレン性二重結合を有す
る官能基であり、Ｒ1、Ｒ2の少なくとも一方はエチレン
性二重結合を有する官能基である。）代表的なものに、
モノ（メタクリロイルオキシエチル）フォスフェート、
ジ（メタクリロイルオキシエチル）フォスフェート、モ
ノ（メタクリロイルオキシプロピル）フォスフェート、
ジ（メタクリロイルオキシプロピル）フォスフェート等
が挙げられる。添加量は接着剤組成物中の０．０１〜１
０重量％、好ましくは０．１〜３重量％である。[Chemical 2] (However, R 1 and R 2 are functional groups having hydrogen or an ethylenic double bond, and at least one of R 1 and R 2 is a functional group having an ethylenic double bond.) Representative Examples ,
Mono (methacryloyloxyethyl) phosphate,
Di (methacryloyloxyethyl) phosphate, mono (methacryloyloxypropyl) phosphate,
Examples thereof include di (methacryloyloxypropyl) phosphate. The addition amount is 0.01 to 1 in the adhesive composition.
It is 0% by weight, preferably 0.1 to 3% by weight.
【００１２】ラジカル重合開始剤としては、ハイドロパ
ーオキサイド類、ジアルキルパーオキサイド類、ケトン
パーオキサイド類、ジアシルパーオキサイド類、および
パーオキシエステル類等の有機過酸化物、２，２’−ア
ゾビス（２−メチルブチロニトリル）、２，２’−アゾ
ビス（４−メトキシ−２，４−ジメチルバレロニトリ
ル）等のアゾ化合物等が挙げられ、（メタ）アクリル系
モノマー１００重量部に対して０．０５〜１０重量％用
いられる。As the radical polymerization initiator, organic peroxides such as hydroperoxides, dialkyl peroxides, ketone peroxides, diacyl peroxides and peroxyesters, 2,2'-azobis (2 -Methyl butyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and other azo compounds, and the like, and is 0.05 per 100 parts by weight of the (meth) acrylic monomer. It is used in an amount of 10% by weight.
【００１３】本発明の接着剤にはさらに、接着剤におい
て公知の各種添加剤を加えることができる。すなわち、
長期保存安定性を付与する目的で２，４−ジ−ｔ−ブチ
ル−４−メチルフェノール、ベンゾキノン、ハイドロキ
ノンモノメチルエーテル、シュウ酸、エチレンジアミン
テトラキス（メチレンフォスフォン酸）等の重合禁止
剤、硬化性を高める目的で０・ベンゾイックスルフィミ
ド、複素環第２級アミン、芳香族第３級アミン等の促進
剤、光硬化性を付与する目的でベンジル、ベンゾインア
ルキルエーテル、１−ハイドロキシシクロヘキシルフェ
ニルケトン等の光重合開始剤、粘度を調整する目的でポ
リメチルメタクリレート、ポリブチルメタクリレート、
ポリビニルブチラール等の増粘剤、シリカ、アルミナ、
酸化チタン等の充填剤等が使用できる。特に無機質充填
剤を１０〜５０重量％添加した場合には接着剤組成物中
で不溶のマレイミド化合物が均一に安定に分散されると
ともに、接着剤の硬化収縮率が低下して耐熱性がさらに
良好となる。中でも、酸化チタンはそのような効果に優
れた充填剤である。Various additives known in the adhesive can be further added to the adhesive of the present invention. That is,
For the purpose of imparting long-term storage stability, polymerization inhibitors such as 2,4-di-t-butyl-4-methylphenol, benzoquinone, hydroquinone monomethyl ether, oxalic acid, ethylenediamine tetrakis (methylene phosphonic acid), curability 0. Benzoxulfimide, heterocyclic secondary amines, accelerators such as aromatic tertiary amines for the purpose of increasing, benzyl, benzoin alkyl ether, 1-hydroxycyclohexyl phenyl ketone, etc. for imparting photocurability Photopolymerization initiator, polymethylmethacrylate, polybutylmethacrylate for the purpose of adjusting viscosity,
Thickeners such as polyvinyl butyral, silica, alumina,
A filler such as titanium oxide can be used. In particular, when the inorganic filler is added in an amount of 10 to 50% by weight, the insoluble maleimide compound is uniformly and stably dispersed in the adhesive composition, and the curing shrinkage rate of the adhesive is lowered to further improve the heat resistance. Becomes Among them, titanium oxide is a filler excellent in such an effect.
【００１４】[0014]
【実施例】次に本発明を実施例、比較例によってさらに
詳しく説明する。なお、これらの例において部はすべて
重量部を表し、％は重量％を表すものとする。また接着
強度の測定は以下の通りである。 ・接着強度の測定 ＭＩＯ鉄ボルト・ナットを２３℃で接着し、４８時間後
にトルクレンチにて破壊トルク強度を測定して室温強度
とした。また、同様に接着して４８時間養生した鉄ボル
ト・ナットを８０〜２４０℃のオーブンに入れ２時間加
熱して、加熱状態で破壊トルク強度を測定し熱時接着強
度とした。さらに、４８時間接着養生した鉄ボルト・ナ
ットを２００℃のオーブンに入れ所定時間毎に取り出し
て室温に戻した後、破壊トルク強度を測定し熱劣化後の
接着強度とした。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In these examples, all parts represent parts by weight, and% represents% by weight. The measurement of the adhesive strength is as follows. -Measurement of adhesive strength MIO iron bolts and nuts were adhered at 23 ° C, and after 48 hours, the breaking torque strength was measured with a torque wrench to obtain room temperature strength. Further, the iron bolts and nuts that had been similarly bonded and cured for 48 hours were placed in an oven at 80 to 240 ° C. and heated for 2 hours, and the breaking torque strength was measured in the heated state to obtain the hot bonding strength. Further, the iron bolts and nuts that had been adhesive-cured for 48 hours were put in an oven at 200 ° C., taken out at predetermined intervals and returned to room temperature, and then the breaking torque strength was measured to obtain the adhesive strength after heat deterioration.
【００１５】実施例１、比較例１，２ トリエチレングリコールジメタクリレート５０部、２−
ヒドロキシプロピルメタクリレート２０部、４−カルボ
キシフェニルマレイミド３０部からなるモノマー混合物
の１００部に対して増粘剤としてアクリルポリマー（三
菱レーヨン社製：ダイヤナールＢＲ−７５）１０％、分
散安定剤として微粉末ケイ酸（日本アエロジル社製：ア
エロジル２００）１．５％、ラジカル重合開始剤として
クメンハイドロパーオキサイド１．０％、保存安定剤と
してｐ−ベンゾキノン０．０５％、硬化促進剤としてＯ
・ベンゾイックスルフィミド０．８７％、１，２，３，
４−テトラヒドロキノリン０．６３％を添加溶解または
分散して一液性のアクリル系接着剤を得た。これに対し
て重合性酸性リン化合物としてモノ（メタクリロイルオ
キシエチル）フォスフェートを０．３％添加し、各種接
着強度を測定した。結果を表１に示す。比較のために他
の重合性酸性化合物を１％添加した系についても行っ
た。表１より他の重合性酸性化合物を添加した系と比較
して極めて優れた耐熱性を示していることが明らかであ
る。Example 1, Comparative Example 1, 50 parts of triethylene glycol dimethacrylate, 2-
Acrylic polymer (manufactured by Mitsubishi Rayon Co., Ltd .: Dianal BR-75) 10% as a thickening agent and 100% fine powder as a dispersion stabilizer with respect to 100 parts of a monomer mixture consisting of 20 parts of hydroxypropyl methacrylate and 30 parts of 4-carboxyphenylmaleimide. Silicic acid (manufactured by Nippon Aerosil Co., Ltd .: Aerosil 200) 1.5%, cumene hydroperoxide 1.0% as a radical polymerization initiator, p-benzoquinone 0.05% as a storage stabilizer, and O as a curing accelerator.
・ Benzoxulfimide 0.87%, 1,2,3
0.63% of 4-tetrahydroquinoline was added and dissolved or dispersed to obtain a one-component acrylic adhesive. On the other hand, 0.3% of mono (methacryloyloxyethyl) phosphate was added as a polymerizable acidic phosphorus compound, and various adhesive strengths were measured. The results are shown in Table 1. For comparison, a system containing 1% of another polymerizable acidic compound was also added. It is clear from Table 1 that it shows extremely excellent heat resistance as compared with the system to which another polymerizable acidic compound was added.
【００１６】[0016]
【表１】 [Table 1]
【００１７】比較例３〜５ 実施例１の組成から一部の成分を除いた系の接着剤を調
製し、物性を測定した結果を表２に示す。表２より、比
較例３は重合性酸性リン化合物を除いた系であるが、実
施例１と比較して明らかなようにマレイミド化合物を含
有しているにもかかわらず、熱時接着強度、熱劣化後の
接着強度ともあまり良好といえない。比較例４は重合性
酸性リン化合物は含有しているが、マレイミド化合物を
含有していない系であり、明らかに耐熱性不良である。
比較例５はマレイミド化合物も重合性酸性リン化合物も
含んでいない通常のアクリル系接着剤であるが、もっと
も耐熱性不良である。以上のことから、マレイミド化合
物と重合性酸性リン化合物が共存した時にはじめて極め
て優れた耐熱性が発現している。Comparative Examples 3 to 5 Table 2 shows the results of measuring the physical properties of an adhesive of the system prepared by removing some components from the composition of Example 1. From Table 2, Comparative Example 3 is a system in which the polymerizable acidic phosphorus compound is removed, but as is clear from the comparison with Example 1, the adhesive strength under heat, the heat The adhesive strength after deterioration is not so good. Comparative Example 4 is a system that contains a polymerizable acidic phosphorus compound but does not contain a maleimide compound, and clearly has poor heat resistance.
Comparative Example 5 is a normal acrylic adhesive containing neither a maleimide compound nor a polymerizable acidic phosphorus compound, but has the poorest heat resistance. From the above, extremely excellent heat resistance is exhibited only when the maleimide compound and the polymerizable acidic phosphorus compound coexist.
【００１８】[0018]
【表２】 [Table 2]
【００１９】実施例２〜５ 重合性酸性リン化合物としてモノ（メタクリロイルオキ
シエチル）フォスフェートとジ（メタクリロイルオキシ
エチル）フォスフェートの当モル混合物を１％用い、無
水ケイ酸のかわりに酸化チタンを３０％用い、更にマレ
イミド化合物を表３のものに変えた以外は実施例１と同
じ組成で接着剤を調製した。マレイミド化合物の種類と
接着強度の関係を表３に示す。これらの接着剤は酸化チ
タンによってマレイミド化合物が均一に安定に分散され
ており、ボルト・ナットに対する濡れも非常に良好であ
った。またマレイミド化合物間の比較ではカルボキシル
基および水酸基を有するマレイミド化合物含有系が特に
優れた耐熱劣化性を示している。Examples 2 to 5 An equimolar mixture of mono (methacryloyloxyethyl) phosphate and di (methacryloyloxyethyl) phosphate was used as the polymerizable acidic phosphorus compound in an amount of 1%, and titanium oxide was used in place of silicic acid anhydride. %, And an adhesive having the same composition as in Example 1 except that the maleimide compound was changed to that shown in Table 3. Table 3 shows the relationship between the type of maleimide compound and the adhesive strength. In these adhesives, the maleimide compound was uniformly dispersed by titanium oxide, and the wetting of bolts and nuts was also very good. Further, in comparison between maleimide compounds, the maleimide compound-containing system having a carboxyl group and a hydroxyl group shows particularly excellent heat deterioration resistance.
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【発明の効果】以上のごとく、本発明のアクリル系耐熱
性接着剤組成物はマレイミド化合物と重合性酸性リン化
合物の相乗効果によって室温から高温まで高い接着強度
を有するとともに、耐熱老化性にも極めて優れているた
め、機械、電気、自動車、その他の工業分野において、
高度の耐熱性が要求される接着分野に極めて有効に使用
出来る。As described above, the acrylic heat-resistant adhesive composition of the present invention has a high adhesive strength from room temperature to a high temperature due to the synergistic effect of the maleimide compound and the polymerizable acidic phosphorus compound, and is extremely resistant to heat aging. Because of its superiority, in mechanical, electrical, automotive and other industrial fields,
It can be used very effectively in the adhesive field where high heat resistance is required.
Claims (3)
レイミド化合物およびラジカル重合開始剤を主成分とす
るアクリル系接着剤組成物に対して、重合性酸性リン化
合物を０．０１〜１０重量％添加したことを特徴とする
アクリル系耐熱性接着剤組成物。1. A polymerizable acidic phosphorus compound is added in an amount of 0.01 to 10% by weight to an acrylic adhesive composition containing a (meth) acrylic polymerizable monomer, a maleimide compound and a radical polymerization initiator as main components. An acrylic heat-resistant adhesive composition characterized by the above.
キシル基または水酸基を有するマレイミドであることを
特徴とする請求項１記載のアクリル系耐熱性接着剤組成
物。2. The acrylic heat-resistant adhesive composition according to claim 1, wherein the maleimide compound is a maleimide having a carboxyl group or a hydroxyl group in the molecule.
加したことを特徴とする請求項１または２記載のアクリ
ル系耐熱性接着剤組成物。3. The acrylic heat-resistant adhesive composition according to claim 1, further comprising 10 to 50% by weight of an inorganic filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23528292A JP3345785B2 (en) | 1992-08-11 | 1992-08-11 | Acrylic heat-resistant adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23528292A JP3345785B2 (en) | 1992-08-11 | 1992-08-11 | Acrylic heat-resistant adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0657213A true JPH0657213A (en) | 1994-03-01 |
| JP3345785B2 JP3345785B2 (en) | 2002-11-18 |
Family
ID=16983796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23528292A Expired - Fee Related JP3345785B2 (en) | 1992-08-11 | 1992-08-11 | Acrylic heat-resistant adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3345785B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09183950A (en) * | 1995-12-28 | 1997-07-15 | Koatsu Gas Kogyo Co Ltd | Two-pack acrylic adhesive composition |
| WO2006082672A1 (en) * | 2005-02-03 | 2006-08-10 | Sony Chemical & Information Device Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
-
1992
- 1992-08-11 JP JP23528292A patent/JP3345785B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09183950A (en) * | 1995-12-28 | 1997-07-15 | Koatsu Gas Kogyo Co Ltd | Two-pack acrylic adhesive composition |
| WO2006082672A1 (en) * | 2005-02-03 | 2006-08-10 | Sony Chemical & Information Device Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| US8034849B2 (en) * | 2005-02-03 | 2011-10-11 | Sony Corporation | Adhesive composition and adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3345785B2 (en) | 2002-11-18 |
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