JPS6335679B2 - - Google Patents
Info
- Publication number
- JPS6335679B2 JPS6335679B2 JP54016731A JP1673179A JPS6335679B2 JP S6335679 B2 JPS6335679 B2 JP S6335679B2 JP 54016731 A JP54016731 A JP 54016731A JP 1673179 A JP1673179 A JP 1673179A JP S6335679 B2 JPS6335679 B2 JP S6335679B2
- Authority
- JP
- Japan
- Prior art keywords
- methacryloxyethyl trimellitic
- anhydride
- trimellitic acid
- vinyl
- acid
- 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
Links
- -1 vinyl compound Chemical class 0.000 claims description 36
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 21
- GOGCLLMDQOJKHB-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]phthalic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GOGCLLMDQOJKHB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 5
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RMCCONIRBZIDTH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 1,3-dioxo-2-benzofuran-5-carboxylate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 RMCCONIRBZIDTH-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-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
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-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
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、４―メタクリロキシエチルトリメリ
ツト酸、またはその酸無水物とメタクリロイル基
を有するビニル化合物および反応性有機シラン系
化合物を主構成成分とする接着剤組成物に関す
る。
４―メタクリロキシエチルトリメリツト酸また
はその酸無水物とビニル化合物とからなる接着剤
組成物については、本願と同一の出願人により既
に特願昭52−121858号として出願されている。４
―メタクリロキシエチルトリメリツト酸またはそ
の酸無水物を含む接着剤は、接着力が優れた接着
剤として歯牙用、金属用途に用いることができる
が、該接着剤組成物は被着体を80℃程度の温水に
浸漬すると接着強度が著しく低下するという欠点
があり、改良を求められていた。
本発明は、上記の欠点を解決するためになされ
たものであり、(A)４―メタクリロキシエチルトリ
メリツト酸および、またはその酸無水物、(B)メタ
クリロイル基を有するビニル化合物、(C)遊離基発
生剤および、または光増感剤および(D)反応性有機
シラン系化合物を含有する接着剤組成物である。
本発明で使用される(A)４―メタクリロキシエチ
ルトリメリツト酸は次の構造式（）で示される
化合物であり、融点は119.5℃ないし120.0℃であ
る。
また、４―メタクリロキシエチルトリメリツト
酸無水物は次の構造式（）で示される化合物で
あり、融点は95.0℃ないし95.8℃である。
４―メタクリロキシエチルトリメリツト酸また
はその酸無水物は新規な化合物であり、例えば同
一出願人の出願に係る特願昭52−76190号明細書
に記載している方法などで調製できるが、好まし
くは、ヒドロキシエチルメタクリレートと無水ト
リメリツト酸クロリドの脱塩化水素反応、あるい
はヒドロキシエチルメタクリレートと無水トリメ
リツト酸との脱水反応により製造することができ
る。また、４―メタクリロキシエチルトリメリツ
ト酸は、４―メタクリロキシエチルトリメリツト
酸無水物の水和により容易に製造できる。勿論、
本発明において、４―メタクリロキシエチルトリ
メリツト酸と、その酸無水物とは混合して使用す
ることもできる。
(A)４―メタクリロキシエチルトリメリツト酸ま
たはその酸無水物と(B)各種メタクリロイル基を有
するビニル化合物とは(C)遊離基発生剤および、ま
たは光増感剤の存在により接着剤層を生成する。
(A)４―メタクリロキシエチルトリメリツト酸ま
たはその酸無水物と併用される(B)各種メタクリロ
イル基を有するビニル化合物としては、メチルア
クリレート、メチルメタクリレート、エチルメタ
クリレート、ブチルメタクリレート、ポリエチレ
ングリコールジメタクリレート類、２，２―ビス
（ｐ―2′―ヒドロキシ―3′―メタクリロキシプロ
ポキシフエニル）プロパン、アクリロニトリル、
酢酸ビニル、２―シアノアクリル酸エステル、ス
チレン、ジビニルベンゼンなどがあげられ、それ
らは単独あるいは組合せて用いられる。中でもメ
チルメタクリレートとスチレンが好ましく使用さ
れる。
本発明において(A)４―メタクリロキシエチルト
リメリツト酸またはその酸無水物と(B)各種メタク
リロイル基を有するビニル化合物との使用割合
は、接着剤の使用目的により変化させられるが、
一般的には(A)４―メタクリロキシエチルトリメリ
ツト酸またはその酸無水物が(B)メタクリロイル基
を有するビニル化合物との合計量に対し0.1ない
し10モル％を占めるものが好ましい。
使用される(C)遊離基発生剤としては、ベンゾイ
ルペルオキシド、ジクミルペルオキシド、アゾビ
スイソブチロニトリルなどの各種過酸化物があげ
られるが、室温で接着させる場合にはトリ―ｎ―
ブチルボラン酸化物、ナフテン酸コバルト、メチ
ルエチルケトンペルオキシドが特に好ましく使用
される。
さらに、紫外線照射下に接着させる場合に使用
される(C)光増感剤としては、ベンゾインメチルエ
ーテル、ベンゾインエチルエーテル、ベンゾイン
イソプロピルエーテルなどがあげられる。
これらの使用量は(A)４―メタクリロキシエチル
トリメリツト酸またはその酸無水物と(B)メタクリ
ロイル基を有するビニル化合物の合計量に対して
0.1ないし５重量％程度である。
本発明の接着剤組成物は更に(D)反応性有機シラ
ン系化合物が含有される。本発明で使用しうる反
応性有機シラン系化合物としては、例えばγ―ク
ロロプロピルトリメトキシシラン、ビニルトリク
ロロシラン、ビニルトリアセトキシシラン、ビニ
ルトリエトキシシラン、ビニルトリス（β―メト
キシエトキシ）シラン、γ―メタクリロキシプロ
ピルトリメトキシシラン、メタクリロキシプロピ
ルトリアルコキシシラン、β―（３，４―エポキ
シシクロヘキシル）エチルトリメトキシシラン、
γ―グリシドキシプロピルトリメトキシシラン、
メルカプトプロピルトリメトキシシラン、γ―メ
ルカプトプロピルトリメトキシシラン、Ｎ―（ト
リメトキシシリルプロピル）―エチレンジアミ
ン、アミノプロピルトリエトキシシラン、Ｎ―β
―（アミノエチル）―γ―アミノプロピルメチル
ジメトキシシラン、γ―（ポリエチレンアミノ）
プロピルトリメトキシシラン、Ｎ―β―（アミノ
エチル）―γ―アミノプロピルメトキシシラン、
Ｎ―β―（アミノエチル）―γ―オキシプロピル
メチルジアルコキシシラン、γ―ウレイドプロピ
ルトリエトキシシラン、γ―アミノジチオプロピ
ルトリヒドロキシシラン、Ｎ―ビニルベンジル―
Ｎ―トリメトキシシリルプロピルエチレンジアミ
ン塩、γ―アミノプロピルトリエトキシシラン等
を挙げることができる。
本発明の接着剤組成物において、(D)反応性有機
シラン系化合物の配合量は、(A)４―メタクリロキ
シエチルトリメリツト酸またはその無水物と(B)メ
タクリロイル基を有するビニル化合物の合計量に
対し、0.1ないし30重量％、とくに１ないし10重
量％の範囲とすることが好ましい。
本発明の接着剤組成物は、必要に応じて(E)ビニ
ル重合体粉末を配合することもできる。かかるビ
ニル重合体は、(B)のメタクリロイル基を有するビ
ニル化合物と同種類であることが好ましく、(A)４
―メタクリロキシエチルトリメリツト酸またはそ
の無水物および(B)メタクリロイル基を有するビニ
ル化合物の混合液に溶解して組成物全体の粘度を
増加させ、被着体への塗布工程における粘度調節
剤としての働きとともに、有機充填剤として接着
剤の強度を上する働きを持つ。
本発明で用いることのできる(E)ビニル重合体の
粉体としては、ポリメチルアクリレート、ポリメ
チルメタクリレート、ポリエチルメタクリレー
ト、ポリブチルメタクリレート、ポリスチレン、
ポリ酢酸ビニル、アクリロニトリル―スチレン共
重合体などの各種ビニル単独重合体もしくは共重
合体の粉体を挙げることができる。これらのうち
では、ポリメチルメタアクリレートとポリスチレ
ンの粉末が好ましい。
本発明の接着剤用組成物には、さらに他の添加
剤、例えばカオリン、タルク、クレー、炭酸カル
シウム、シリカ、アルミナ、シリカ・アルミナ、
リン酸カルシウム、ガラスなどの無機質系粉末の
充填剤、ワツクス、エチレン―酢酸ビニル共重合
体および粘着性付与剤、重合促進剤、重合調節
剤、重合抑制剤などを配合することもできる。
本発明の接着剤は一般には溶剤を特に必要とせ
ずに、(A)４―メタクリロキシエチルトリメリツト
酸またはその酸無水物を(B)メタクリロイル基を有
するビニル化合物に均一に溶解させ、かかる混合
物中に(D)反応性有機シラン系化合物を更に混合し
た状態で使用する方法によるのが好ましい方法で
ある。
好ましい実施態様としては、例えば(A)４―メタ
クリロキシエチルトリメリツト酸無水物を(B)メチ
ルメタクリレートと(C)トリ―ｎ―ブチルボラン酸
化物の存在下に室温で混合し、更に該混合液に(E)
ポリメチルメタクリレートの粉末および(D)反応性
有機シラン系化合物をへら等で混合し、接着剤層
を生成させる方法である。
本発明の(A)４―メタクリロキシエチルトリメリ
ツト酸またはその無水物、(B)メタクリロイル基を
有するビニル化合物および(D)反応性有機シラン系
化合物を含む接着剤は極めて接着性に富み、特に
耐水耐久性にすぐれており、各種用途に使用でき
る。中でも歯牙用、金属用および塗料の下塗りに
好適なものである。とくに本発明の接着剤組成物
は、(A)４―メタクリロキシエチルトリメリツト酸
またはその無水物および(B)ビニル化合物のみから
なる接着剤に比して高温の湯水中での耐久密着性
に優れているため、高温の湯水に長時間接触する
構造材等の用途に好適である。
実施例 １
長さ100mm、巾10mm、厚さ１mmのステンレス鋼
板（SUS304、2B仕上げ、脱脂処理）の片面先端
部に遊離基発生剤として混合物に対して４重量％
のトリ―ｎ―ブチルボラン酸化物を含むメチルメ
タクリレート95重量％と４―メタクリロキシエチ
ルトリメリツト酸無水物５重量％との混合物約
250mgを滴下した。次に該混合物にポリメチルメ
タアクリレート粉末100mgおよびビニルトリス
（β―メトキシエトキシ）シラン7.5mgを加えてよ
く混合後、他方のステンレス板を重ね、そのまま
保持固定して室温で硬化接着させた。次に24時間
経過後、上記試験片を取出し、引張り速度50mm／
minで試験片を引張り剪断すことにより接着強度
を測定した。また、室温24時間経過後の試験片を
80℃の温水中に７日間浸漬後取出し、上記したと
同様の方法で接着強度を測定した。結果を第１表
に示す。
実施例 ２
ビニルトリス（β―メトキシエトキシ）シラン
の代りにγ―メタクリロキシプロピルトリメトキ
シシランを用いる以外は実施例１と同様に行つ
た。結果を第１表に示す。
比較例 １
実施例１において、ビニルトリス（β―メトキ
シエトキシ）シランを配合しない以外は実施例１
と同様に行つた。結果を第１表に示す。
実施例 ３
ビニルトリス（β―メトキシエトキシ）シラン
の代りにγ―アミノプロピルトリエトキシシラン
を用いる以外は実施例１と同様に行つた。結果を
第１表に示す。
The present invention relates to an adhesive composition whose main components are 4-methacryloxyethyl trimellitic acid or its acid anhydride, a vinyl compound having a methacryloyl group, and a reactive organic silane compound. An adhesive composition comprising 4-methacryloxyethyl trimellitic acid or its acid anhydride and a vinyl compound has already been filed as Japanese Patent Application No. 121858/1985 by the same applicant as the present application. 4
- Adhesives containing methacryloxyethyl trimellitic acid or its acid anhydride can be used for teeth and metal applications as adhesives with excellent adhesive strength, but the adhesive composition is suitable for bonding to adherends at 80°C. It has the disadvantage that the adhesive strength significantly decreases when immersed in warm water, and improvements have been sought. The present invention was made to solve the above-mentioned drawbacks, and consists of (A) 4-methacryloxyethyl trimellitic acid and/or its acid anhydride, (B) a vinyl compound having a methacryloyl group, (C) This is an adhesive composition containing a free radical generator and/or a photosensitizer and (D) a reactive organosilane compound. 4-Methacryloxyethyl trimellitic acid (A) used in the present invention is a compound represented by the following structural formula (), and has a melting point of 119.5°C to 120.0°C. Further, 4-methacryloxyethyl trimellitic anhydride is a compound represented by the following structural formula (), and has a melting point of 95.0°C to 95.8°C. 4-Methacryloxyethyl trimellitic acid or its acid anhydride is a new compound, and can be prepared, for example, by the method described in Japanese Patent Application No. 76190/1985 filed by the same applicant. can be produced by a dehydrochlorination reaction between hydroxyethyl methacrylate and trimellitic anhydride chloride, or a dehydration reaction between hydroxyethyl methacrylate and trimellitic anhydride. Furthermore, 4-methacryloxyethyl trimellitic acid can be easily produced by hydration of 4-methacryloxyethyl trimellitic anhydride. Of course,
In the present invention, 4-methacryloxyethyl trimellitic acid and its acid anhydride can also be used in combination. (A) 4-methacryloxyethyl trimellitic acid or its acid anhydride; (B) vinyl compounds having various methacryloyl groups; and (C) the adhesive layer due to the presence of a free radical generator and/or photosensitizer. generate. (A) Used in combination with 4-methacryloxyethyl trimellitic acid or its acid anhydride. (B) Vinyl compounds having various methacryloyl groups include methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and polyethylene glycol dimethacrylate. , 2,2-bis(p-2′-hydroxy-3′-methacryloxypropoxyphenyl)propane, acrylonitrile,
Vinyl acetate, 2-cyanoacrylic acid ester, styrene, divinylbenzene and the like are used alone or in combination. Among them, methyl methacrylate and styrene are preferably used. In the present invention, the ratio of (A) 4-methacryloxyethyl trimellitic acid or its acid anhydride to (B) vinyl compounds having various methacryloyl groups can be changed depending on the intended use of the adhesive.
Generally, it is preferable that (A) 4-methacryloxyethyl trimellitic acid or its acid anhydride accounts for 0.1 to 10 mol % based on the total amount of (B) vinyl compound having a methacryloyl group. Examples of the free radical generator (C) used include various peroxides such as benzoyl peroxide, dicumyl peroxide, and azobisisobutyronitrile, but when adhering at room temperature, tri-n-
Butyl borane oxide, cobalt naphthenate, and methyl ethyl ketone peroxide are particularly preferably used. Furthermore, examples of the photosensitizer (C) used when adhering under ultraviolet irradiation include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. These usage amounts are based on the total amount of (A) 4-methacryloxyethyl trimellitic acid or its acid anhydride and (B) vinyl compound having a methacryloyl group.
It is about 0.1 to 5% by weight. The adhesive composition of the present invention further contains (D) a reactive organosilane compound. Examples of reactive organic silane compounds that can be used in the present invention include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and γ-methacrylate. Roxypropyltrimethoxysilane, methacryloxypropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane,
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-(trimethoxysilylpropyl)-ethylenediamine, aminopropyltriethoxysilane, N-β
-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(polyethyleneamino)
Propyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethoxysilane,
N-β-(aminoethyl)-γ-oxypropylmethyldialkoxysilane, γ-ureidopropyltriethoxysilane, γ-aminodithiopropyltrihydroxysilane, N-vinylbenzyl-
Examples include N-trimethoxysilylpropylethylenediamine salt and γ-aminopropyltriethoxysilane. In the adhesive composition of the present invention, the amount of (D) the reactive organosilane compound is the sum of (A) 4-methacryloxyethyl trimellitic acid or its anhydride and (B) the vinyl compound having a methacryloyl group. The amount is preferably in the range of 0.1 to 30% by weight, particularly 1 to 10% by weight. The adhesive composition of the present invention may also contain (E) vinyl polymer powder, if necessary. The vinyl polymer is preferably of the same type as the vinyl compound having a methacryloyl group (B), and (A) 4
-Dissolved in a mixture of methacryloxyethyl trimellitic acid or its anhydride and (B) a vinyl compound having a methacryloyl group to increase the viscosity of the entire composition, and used as a viscosity modifier in the coating process to adherends. Along with its function, it also acts as an organic filler to increase the strength of adhesives. (E) Vinyl polymer powder that can be used in the present invention includes polymethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polystyrene,
Examples include powders of various vinyl homopolymers or copolymers such as polyvinyl acetate and acrylonitrile-styrene copolymers. Among these, polymethyl methacrylate and polystyrene powders are preferred. The adhesive composition of the present invention further includes other additives such as kaolin, talc, clay, calcium carbonate, silica, alumina, silica/alumina,
Inorganic powder fillers such as calcium phosphate and glass, wax, ethylene-vinyl acetate copolymers, tackifiers, polymerization accelerators, polymerization regulators, polymerization inhibitors, and the like can also be blended. Generally, the adhesive of the present invention does not particularly require a solvent, and is produced by uniformly dissolving (A) 4-methacryloxyethyl trimellitic acid or its acid anhydride in (B) a vinyl compound having a methacryloyl group, and then dissolving such a mixture. A preferred method is to use the reactive organosilane compound (D) in the mixture. In a preferred embodiment, for example, (A) 4-methacryloxyethyl trimellitic anhydride is mixed at room temperature in the presence of (B) methyl methacrylate and (C) tri-n-butylborane oxide; ni(E)
In this method, polymethyl methacrylate powder and (D) a reactive organic silane compound are mixed using a spatula or the like to form an adhesive layer. The adhesive of the present invention containing (A) 4-methacryloxyethyl trimellitic acid or its anhydride, (B) a vinyl compound having a methacryloyl group, and (D) a reactive organosilane compound has extremely high adhesive properties, especially It has excellent water resistance and durability and can be used for various purposes. Among these, it is suitable for use in teeth, metals, and as an undercoat for paints. In particular, the adhesive composition of the present invention has better durable adhesion in hot water than an adhesive consisting only of (A) 4-methacryloxyethyl trimellitic acid or its anhydride and (B) a vinyl compound. Due to its excellent properties, it is suitable for applications such as structural materials that come into contact with hot water for a long time. Example 1 4% by weight of the mixture as a free radical generator was added to the tip of one side of a stainless steel plate (SUS304, 2B finish, degreased) with a length of 100 mm, width of 10 mm, and thickness of 1 mm.
A mixture of 95% by weight of methyl methacrylate and 5% by weight of 4-methacryloxyethyl trimellitic anhydride containing tri-n-butylborane oxide of about
250mg was added dropwise. Next, 100 mg of polymethyl methacrylate powder and 7.5 mg of vinyl tris (β-methoxyethoxy) silane were added to the mixture and mixed well, and then the other stainless steel plate was placed on top of the other plate and held and fixed as it was to cure and bond at room temperature. Next, after 24 hours, the above test piece was taken out and the tensile speed was 50mm/
Adhesive strength was measured by tensile shearing the specimens at min. In addition, the test piece after 24 hours at room temperature
After being immersed in warm water at 80°C for 7 days, it was taken out and the adhesive strength was measured in the same manner as described above. The results are shown in Table 1. Example 2 Example 1 was repeated except that γ-methacryloxypropyltrimethoxysilane was used instead of vinyltris(β-methoxyethoxy)silane. The results are shown in Table 1. Comparative Example 1 Example 1 except that vinyltris(β-methoxyethoxy)silane was not blended in Example 1.
I went in the same way. The results are shown in Table 1. Example 3 Example 1 was repeated except that γ-aminopropyltriethoxysilane was used instead of vinyltris(β-methoxyethoxy)silane. The results are shown in Table 1.
【表】
実施例４、比較例２
ステンレス板の代りに銅板を用いる以外は、実
施例３、比較例１と同様に行つた。結果を第２表
に示す。
実施例５、比較例３
ステンレス板の代りに鉄板を用いるる以外は、
実施例３、比較例１と同様に行つた。結果を第２
表に示す。[Table] Example 4, Comparative Example 2 The same procedure as Example 3 and Comparative Example 1 was performed except that a copper plate was used instead of the stainless steel plate. The results are shown in Table 2. Example 5, Comparative Example 3 Except for using an iron plate instead of a stainless steel plate,
The same procedure as in Example 3 and Comparative Example 1 was carried out. Second result
Shown in the table.
Claims (1)
および、またはその酸無水物、(B)メタクリロイル
基を有するビニル化合物、(C)遊離基発生剤およ
び、または光増感剤および(D)反応性有機シラン系
化合物を含有する接着剤組成物。1 (A) 4-methacryloxyethyl trimellitic acid and/or its acid anhydride, (B) vinyl compound having a methacryloyl group, (C) free radical generator and/or photosensitizer, and (D) reactivity An adhesive composition containing an organic silane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1673179A JPS55110171A (en) | 1979-02-17 | 1979-02-17 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1673179A JPS55110171A (en) | 1979-02-17 | 1979-02-17 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55110171A JPS55110171A (en) | 1980-08-25 |
| JPS6335679B2 true JPS6335679B2 (en) | 1988-07-15 |
Family
ID=11924401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1673179A Granted JPS55110171A (en) | 1979-02-17 | 1979-02-17 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55110171A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0580979U (en) * | 1992-04-07 | 1993-11-02 | 日本トレールモービル株式会社 | Support device for luggage rack of transport box |
| JPH0627309U (en) * | 1992-09-21 | 1994-04-12 | 株式会社矢野特殊自動車 | Luggage carton structure |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2504603B2 (en) * | 1990-03-14 | 1996-06-05 | 日本合成化学工業株式会社 | Paint composition |
| JP4633236B2 (en) * | 2000-07-19 | 2011-02-16 | 株式会社クラレ | Dental adhesive composition |
| KR100852330B1 (en) * | 2006-01-17 | 2008-08-18 | 주식회사 엘지화학 | New multi-functional monomer and thermosetting resin composition comprising the same |
| JP6739781B2 (en) * | 2016-04-15 | 2020-08-12 | 竹本油脂株式会社 | Dispersion holding agent for hydraulic composition, method for using dispersion holding agent for hydraulic composition, and method for preparing hydraulic composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411149A (en) * | 1977-10-13 | 1979-01-27 | Mitsui Petrochem Ind Ltd | Adhesive composition |
-
1979
- 1979-02-17 JP JP1673179A patent/JPS55110171A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411149A (en) * | 1977-10-13 | 1979-01-27 | Mitsui Petrochem Ind Ltd | Adhesive composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0580979U (en) * | 1992-04-07 | 1993-11-02 | 日本トレールモービル株式会社 | Support device for luggage rack of transport box |
| JPH0627309U (en) * | 1992-09-21 | 1994-04-12 | 株式会社矢野特殊自動車 | Luggage carton structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55110171A (en) | 1980-08-25 |
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