JPH0238157B2 - BINIRUPIRIJINKEISETSUCHAKUZAISOSEIBUTSU - Google Patents
BINIRUPIRIJINKEISETSUCHAKUZAISOSEIBUTSUInfo
- Publication number
- JPH0238157B2 JPH0238157B2 JP7337385A JP7337385A JPH0238157B2 JP H0238157 B2 JPH0238157 B2 JP H0238157B2 JP 7337385 A JP7337385 A JP 7337385A JP 7337385 A JP7337385 A JP 7337385A JP H0238157 B2 JPH0238157 B2 JP H0238157B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- methacrylate
- vinylpyridine
- rubber
- adhesive composition
- 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
- 239000000853 adhesive Substances 0.000 claims description 30
- 230000001070 adhesive effect Effects 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 14
- -1 acrylate compound Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 6
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims description 5
- 239000005061 synthetic rubber Substances 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- VMWGBWNAHAUQIO-UHFFFAOYSA-N 2-ethenyl-6-methylpyridine Chemical compound CC1=CC=CC(C=C)=N1 VMWGBWNAHAUQIO-UHFFFAOYSA-N 0.000 claims description 2
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- QMQSEPCBZKJYBC-UHFFFAOYSA-N 2-ethenyl-3-ethylpyridine Chemical compound CCC1=CC=CN=C1C=C QMQSEPCBZKJYBC-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 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 8
- 239000000463 material Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- YQUDMNIUBTXLSX-UHFFFAOYSA-N 2-ethenyl-5-ethylpyridine Chemical compound CCC1=CC=C(C=C)N=C1 YQUDMNIUBTXLSX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- GQVCNZBQZKXBMX-UHFFFAOYSA-N butan-2-one;toluene Chemical compound CCC(C)=O.CC1=CC=CC=C1 GQVCNZBQZKXBMX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
産業上の利用分野
本発明は、ビニルピリジン系接着剤組成物に関
する。
従来の技術
一般式(1)
〔式中R1は水素原子又はアルキル基を示す。〕で
表わされるビニルピリジン類の単独重合体は、ガ
ラス転移点Tgが高く、硬くて脆いという欠点を
有しており、従つて該重合体を単独で接着剤の有
効成分として使用することは困難である。そのた
め上記一般式(1)のビニルピリジン類は、今日まで
ブタジエンとの共重合体として又はブタジエン及
びスチレンとの三元共重合体として接着剤の用途
に使用されている（特公昭36−20584号公報、特
公昭35−5195号公報参照）。しかしながら、これ
らの接着剤は、いずれもゴムとゴムとの接着又は
ゴムと金属との接着を主体としたものである。
発明の目的及び構成
本発明者らは、ゴムとゴムとの接着やゴムと金
属との接着のみならず、金属と金属との接着、金
属と複合体との接着及び複合体と複合体との接着
にも有効な接着剤を開発すべく鋭意研究を重ねた
結果、下記に示す(A)成分と(B)成分とを配合した場
合に本発明の所期の目的を達成し得ることを見い
出し、ここに本発明を完成するに至つた。
即ち、本発明は、
(A) 一般式(1)
［式中、R1は水素原子又はアルキル基を示
す。］で表わされるビニルピリジン類10〜90モ
ル％と一般式(2)
［式中、R2は水素原子又はメチル基を、R3は
アルキル基を示す。］で表わされるアクリレー
ト化合物90〜10モル％とからなる共重合体５〜
95重量％、及び
(B) 粘着付与剤及び合成ゴムから選ばれた少なく
とも１種95〜５重量％
を含有することを特徴とするビニルピリジン系接
着剤組成物に係る。
本発明の接着剤組成物は、上記一般式(1)のビニ
ルピリジン類と一般式(2)のアクリレート化合物と
の共重合体並びに粘着付与剤及び合成ゴムから選
ばれた少なくとも１種を含有するものである。
上記一般式(1)において、R1で示されるアルキ
ル基としては、例えば炭素数１〜８のアルキル
基、好ましくは炭素数１〜４のアルキル基を挙げ
ることができる。また、一般式(2)において、R3
で示されるアルキル基としては、例えば炭素数１
〜20のアルキル基、好ましくは炭素数１〜10のア
ルキル基を挙げることができる。
一般式(1)のビニルピリジン類としては、従来公
知のものを広く使用でき、例えば２−ビニルピリ
ジン、４−ビニルピリジン、２−メチル−５−ビ
ニルピリジン、２−メチル−６−ビニルピリジ
ン、５−エチル−２−ビニルピリジン等を挙げる
ことができる。本発明では、これらを単独で又は
２種以上混合して使用できる。
また、一般式(2)のアクリレート化合物として
も、従来公知のものを広く使用でき、例えばメチ
ルアクリレート、メチルメタクリレート、エチル
アクリレート、エチルメタクリレート、ブチルア
クリレート、ブチルメタクリレート、２−エチル
ヘキシルアクリレート、２−エチルヘキシルメタ
クリレート、プロピルアクリレート、プロピルメ
タクリレート、オクチルアクリレート、オクチル
メタクリレート、ラウリルアクリレート、ラウリ
ルメタクリレート、ステアリルアクリレート、ス
テアリルメタクリレート等を挙げることができ
る。本発明では、これらを単独で又は２種以上混
合して使用できる。
本発明において(A)成分として用いられる共重合
体は、上記一般式(1)のビニルピリジン類と一般式
(2)のアクリレート化合物とを共重合させて得られ
るものである。該共重合体は、従来公知の重合方
法、例えばラジカル重合、イオン重合等に伴い容
易に製造され得る。該共重合体を製造するための
好ましい実施態様を示せば、例えば一般式(1)のビ
ニルピリジン類と一般式(2)のアクリレート化合物
を所定量配合し、アゾビスイソブチロニトリル
（AIBN）等のアゾビスシアノ化合物、過酸化ベ
ンゾイル等の過酸化物、アルキルリチウム、エチ
ルアルミニウムジクロリド等の有機金属化合物、
弗化硼素等の無機ハロゲン化合物等の重合開始剤
の存在下、溶液重合、懸濁重合、乳化重合又は塊
状重合させればよい。重合に使用される溶媒とし
てはメタノール、ジメチルホルムアミド、Ｎ−メ
チルピロリドン、ジメチルスルホキシド等が挙げ
られる。これらの重合反応は、通常−80〜120℃
にて行なわれ、一般に反応時間は0.5〜10時間で
ある。このようにして得られる本発明の共重合体
は、その組成がビニルピリジン類10〜90モル％及
びアクリレート化合物90〜10モル％からなるも
の、好ましくはビニルピリジン類30〜70モル％及
びアクリレート化合物70〜30モル％からなるもの
である。共重合体の組成が上記範囲を逸脱する
と、本発明の所期の効果が発揮され得ない。ま
た、該共重合体の平均分子量は、通常約500〜
500000、好ましくは1000〜100000の範囲内であ
る。
本発明において(B)成分として用いられる粘着付
与剤としては、従来公知のものを広く使用でき、
例えばロジン、ロジン誘導体、テルペン系樹脂、
石油樹脂（芳香族系炭化水素樹脂、脂肪族系炭化
水素樹脂）等が挙げられる。この中でも特にテル
ペン系樹脂及び石油樹脂が好ましい。また、合成
ゴムとしても、従来公知のものを広く使用でき、
例えばアクリロニトリル−ブタジエンゴム
（NBR）、スチレン−ブタジエンゴム、ブチルゴ
ム、イソプレン−イソブチレンゴム、クロロプレ
ンゴム等を挙げることができる。本発明では、こ
れらを単独で使用してもよいし、２種以上混合し
て使用してもよい。(A)成分と(B)成分とを併用すれ
ば、(A)成分単独の場合に比し、接着性能をより一
層向上させることができるという利点がある。
本発明の接着剤組成物中に配合されるべき上記
(A)成分と(B)成分との割合としては、通常前者：後
者＝５〜95：95〜５重量％、好ましくは前者：後
者＝30〜80：70〜20重量％とするのがよい。(A)成
分及び(B)成分の配合割合が上記範囲を逸脱する
と、接着性能が低下する傾向となるので好ましく
ない。
本発明の接着剤組成物には、この種接着剤に通
常配合されている添加剤、例えば溶剤（例えばメ
チルエチルケトン等のケトン類、酢酸エチル等の
エステル類、メタノール等のアルコール類、トル
エン等の芳香族炭化水素類等）、酸化防止剤、エ
ラストマー、可塑型、顔料、充填剤等を適宜配合
することができる。
本発明の接着剤組成物を使用するに際しては、
接着すべき基材、例えばゴム、アルミニウム、鉄
等の金属、繊維強化プラスチツク（FRP及び
FRTP）等の複合体等に本発明接着剤組成物を塗
布し、乾燥後加熱加圧するか、又は通常のホツト
メルト接着の手法を用いて上記基材同士を接着さ
せればよい。上記基材に塗布すべき本発明接着剤
組成物の量としては、塗布されるべき基材の種類
等により異なり一概にはいえないが、通常100〜
500ｇ/m2の割合で塗布すればよい。塗布方法とし
ては、従来公知の方法をいずれも採用することが
でき、例えば浸漬法、ハケ塗り法、ロールコート
法、スプレー法等を例示できる。また、乾燥方法
としては、例えば常温乾燥、加熱乾燥等を採用す
ることができる。乾燥後の加熱加圧処理条件とし
ては、例えば100〜250℃、0.1〜10Kg／cm2程度と
するのがよい。
発明の効果
本発明の接着剤組成物は、ゴムとゴムとの接着
やゴムと金属との接着ばかりでなく、金属と金属
との接着、金属と複合体との接着及び複合体と複
合体との接着にも極めて好適なものである。
実施例
実施例 １
４−ビニルピリジン0.25モル、ｎ−ブチルメタ
クリレート0.25モル、２−エチルヘキシルメタク
リレート0.25モル及びAIBN0.01モルを使用し、
メタノール200ｇ中、反応温度68℃にて５時間重
合反応を行なつた。反応終了後ヘキサン溶媒中で
生成する三元共重合体を析出させ、乾燥させた。
上記で得られた三元共重合体のモノマー組成比
は４−ビニルピリジン：ｎ−ブチルメタクリレー
ト：２−エチルヘキシルメタクリレート＝１：
１：１であり、該共重合体の平均分子量は約
40000であつた。
上記で得られた三元共重合体と石油樹脂（粘着
付与剤、アルコンＰ−135、荒川化学(株)製）とを
下記第１表に示す割合で混合し、更にトルエン−
ベンゼン（１：１）の混合溶剤に溶解させて20重
量％溶液の接着剤とした。
基材としてAl／Alを使用し、この基材（25mm
×12.5mm）に上記で得られる接着剤を150ｇ/m2の
割合で塗布し、175℃、３Kg／cm2で15分間圧着し
た。接着剤の引張りせん断接着強さ試験方法
（JISK−6850）に従つて引張りせん断接着強度を
求め、その結果を第１表に併せて示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a vinylpyridine adhesive composition. Conventional technology General formula (1) [In the formula, R 1 represents a hydrogen atom or an alkyl group. The vinylpyridine homopolymer represented by ] has a high glass transition point Tg, and has the drawbacks of being hard and brittle, and therefore it is difficult to use this polymer alone as an active ingredient in adhesives. It is. Therefore, vinylpyridines of the above general formula (1) have been used for adhesives to date as a copolymer with butadiene or as a terpolymer with butadiene and styrene (Japanese Patent Publication No. 36-20584 (Refer to the official gazette, Special Publication No. 35-5195). However, all of these adhesives are mainly used for adhesion between rubber and rubber or adhesion between rubber and metal. Purpose and Structure of the Invention The present inventors have discovered not only rubber-to-rubber adhesion and rubber-to-metal adhesion, but also metal-to-metal adhesion, metal-to-composite adhesion, and composite-to-composite adhesion. As a result of extensive research to develop an adhesive that is also effective for adhesion, it was discovered that the intended purpose of the present invention could be achieved when the following components (A) and (B) were combined. This led to the completion of the present invention. That is, the present invention provides (A) general formula (1) [In the formula, R 1 represents a hydrogen atom or an alkyl group. ] 10 to 90 mol% of vinylpyridines represented by general formula (2) [In the formula, R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group. ] Copolymer 5 consisting of 90 to 10 mol% of an acrylate compound represented by
and (B) 95 to 5% by weight of at least one selected from tackifiers and synthetic rubbers. The adhesive composition of the present invention contains at least one member selected from a copolymer of a vinyl pyridine represented by the above general formula (1) and an acrylate compound represented by the general formula (2), a tackifier, and a synthetic rubber. It is something. In the above general formula (1), the alkyl group represented by R 1 includes, for example, an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Furthermore, in general formula (2), R 3
As the alkyl group represented by, for example, a carbon number of 1
-20 alkyl groups, preferably C1-C10 alkyl groups. As the vinylpyridine of general formula (1), a wide variety of conventionally known ones can be used, such as 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine, Examples include 5-ethyl-2-vinylpyridine. In the present invention, these can be used alone or in combination of two or more. Furthermore, as the acrylate compound of general formula (2), a wide variety of conventionally known compounds can be used, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. , propyl acrylate, propyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, and the like. In the present invention, these can be used alone or in combination of two or more. In the present invention, the copolymer used as component (A) is a vinylpyridine of the above general formula (1) and a copolymer of the general formula
It is obtained by copolymerizing with the acrylate compound (2). The copolymer can be easily produced by conventionally known polymerization methods such as radical polymerization and ionic polymerization. A preferred embodiment for producing the copolymer is, for example, by blending a predetermined amount of vinyl pyridines of general formula (1) and an acrylate compound of general formula (2), and adding azobisisobutyronitrile (AIBN). azobiscyano compounds such as, peroxides such as benzoyl peroxide, organometallic compounds such as alkyl lithium, ethyl aluminum dichloride,
Solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization may be carried out in the presence of a polymerization initiator such as an inorganic halogen compound such as boron fluoride. Examples of the solvent used in the polymerization include methanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and the like. These polymerization reactions are usually carried out at -80 to 120℃.
The reaction time is generally 0.5 to 10 hours. The copolymer of the present invention thus obtained has a composition of 10 to 90 mol% of vinyl pyridines and 90 to 10 mol% of an acrylate compound, preferably 30 to 70 mol% of a vinyl pyridine and an acrylate compound. It consists of 70 to 30 mol%. If the composition of the copolymer deviates from the above range, the desired effects of the present invention may not be exhibited. Further, the average molecular weight of the copolymer is usually about 500 to
500,000, preferably within the range of 1,000 to 100,000. As the tackifier used as component (B) in the present invention, a wide variety of conventionally known tackifiers can be used.
For example, rosin, rosin derivatives, terpene resins,
Examples include petroleum resins (aromatic hydrocarbon resins, aliphatic hydrocarbon resins), and the like. Among these, terpene resins and petroleum resins are particularly preferred. In addition, a wide range of conventionally known synthetic rubbers can be used.
Examples include acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber, butyl rubber, isoprene-isobutylene rubber, and chloroprene rubber. In the present invention, these may be used alone or in combination of two or more. If component (A) and component (B) are used together, there is an advantage that the adhesive performance can be further improved compared to when component (A) is used alone. The above to be incorporated into the adhesive composition of the present invention
The ratio of component (A) and component (B) is usually the former: the latter = 5-95: 95-5% by weight, preferably the former: the latter = 30-80: 70-20% by weight. . If the blending ratio of component (A) and component (B) deviates from the above range, adhesive performance tends to decrease, which is not preferable. The adhesive composition of the present invention may contain additives that are usually added to adhesives of this type, such as solvents (e.g., ketones such as methyl ethyl ketone, esters such as ethyl acetate, alcohols such as methanol, aromatic substances such as toluene, etc.). group hydrocarbons, etc.), antioxidants, elastomers, plastic molds, pigments, fillers, etc. can be appropriately blended. When using the adhesive composition of the present invention,
Substrates to be bonded, such as rubber, aluminum, metals such as iron, fiber reinforced plastics (FRP and
The adhesive composition of the present invention may be applied to a composite such as FRTP, dried, and then heated and pressed, or the base materials may be bonded together using a conventional hot melt bonding method. The amount of the adhesive composition of the present invention to be applied to the above substrate varies depending on the type of substrate to be applied, etc., but cannot be determined unconditionally, but is usually 100 to
It can be applied at a rate of 500g/ m2 . As the coating method, any conventionally known method can be employed, such as a dipping method, a brush coating method, a roll coating method, a spraying method, and the like. Further, as a drying method, for example, normal temperature drying, heating drying, etc. can be adopted. The heat and pressure treatment conditions after drying are preferably, for example, 100 to 250°C and about 0.1 to 10 kg/cm 2 . Effects of the Invention The adhesive composition of the present invention is applicable not only to rubber-to-rubber adhesion and rubber-to-metal adhesion, but also to metal-to-metal adhesion, metal-to-composite adhesion, and composite-to-composite adhesion. It is also extremely suitable for bonding. Examples Example 1 Using 0.25 mol of 4-vinylpyridine, 0.25 mol of n-butyl methacrylate, 0.25 mol of 2-ethylhexyl methacrylate and 0.01 mol of AIBN,
A polymerization reaction was carried out in 200 g of methanol at a reaction temperature of 68° C. for 5 hours. After the reaction was completed, the resulting terpolymer was precipitated in a hexane solvent and dried. The monomer composition ratio of the terpolymer obtained above was 4-vinylpyridine:n-butyl methacrylate:2-ethylhexyl methacrylate=1:
1:1, and the average molecular weight of the copolymer is approximately
It was 40,000. The terpolymer obtained above and a petroleum resin (tackifier, Alcon P-135, manufactured by Arakawa Chemical Co., Ltd.) were mixed in the proportions shown in Table 1 below, and then toluene-
It was dissolved in a mixed solvent of benzene (1:1) to obtain a 20% by weight solution of adhesive. Al/Al was used as the base material, and this base material (25 mm
x 12.5 mm) at a rate of 150 g/m 2 and pressure bonded at 175° C. and 3 Kg/cm 2 for 15 minutes. The tensile shear adhesive strength was determined according to the tensile shear adhesive strength testing method for adhesives (JISK-6850), and the results are also shown in Table 1.
【表】
実施例 ２
上記実施例１で得られた三元共重合体にNBR
（商品名ニポール、アクリロニトリル含有量41重
量％、日本ゼオン(株)製）を下記第２表に示す割合
で混合し、更にメチルエチルケトン−トルエン
（１：１）の混合溶剤に溶解させて20重量％溶液
の接着剤とした。
基材としてAl／FRPを使用し、この基材（25
mm×125mm）に上記で得られた接着剤を150ｇ/m2
の割合で塗布し、175℃、３Kg／cm2で15分間圧着
した。接着剤の剥離接着強さ試験方法（JIS Ｋ−
6854）に従つて剥離接着強度を求め、その結果を
第２表に併せて示す。[Table] Example 2 NBR was added to the terpolymer obtained in Example 1 above.
(trade name Nipole, acrylonitrile content 41% by weight, manufactured by Nippon Zeon Co., Ltd.) in the proportions shown in Table 2 below, and then dissolved in a mixed solvent of methyl ethyl ketone and toluene (1:1) to 20% by weight. It was used as a solution adhesive. Al/FRP was used as the base material, and this base material (25
mm x 125 mm) with 150 g/m 2 of the adhesive obtained above.
The coating was applied at a rate of 100° C. and pressed at 3 kg/cm 2 for 15 minutes at 175°C. Peel adhesion strength test method for adhesives (JIS K-
6854), and the results are also shown in Table 2.
【表】
実施例 ３
４−ビニルピリジン0.4モル、２−エチルヘキ
シルメタクリレート0.4モル及びAIBN0.05モルを
使用し、メタノール400ｇ中、反応温度68℃にて
５時間重合反応を行なつた。反応終了後ヘキサン
溶媒中で生成する共重合体を析出させ、乾燥させ
た。得られた共重合体のモノマー組成比は４−ビ
ニルピリジン：２−エチルヘキシルメタクリレー
ト＝１：１であり、該共重合体の平均分子量は約
5000であつた。
上記で得られた共重合体にNBR（商品名ニポー
ル）、アクリロニトリル含有量41重量％、日本ゼ
オン(株)製）を下記第３表に示す割合で混合し、更
にメチルエチルケトン−トルエン（１：１）の混
合溶剤に溶解させて20重量％溶液の接着剤とし
た。
基材としてAl／FRPを使用し、この基材（25
mm×125mm）に上記で得られた接着剤を150ｇ/m2
の割合で塗布し、175℃、３Kg／cm2で15分間圧着
した。接着剤の剥離接着強さ試験方法（JIS Ｋ−
6854）に従つて剥離接着強度を求め、その結果を
第３表に併せて示す。[Table] Example 3 Using 0.4 mol of 4-vinylpyridine, 0.4 mol of 2-ethylhexyl methacrylate, and 0.05 mol of AIBN, a polymerization reaction was carried out in 400 g of methanol at a reaction temperature of 68° C. for 5 hours. After the reaction was completed, the copolymer produced was precipitated in a hexane solvent and dried. The monomer composition ratio of the obtained copolymer was 4-vinylpyridine:2-ethylhexyl methacrylate=1:1, and the average molecular weight of the copolymer was approximately
It was 5000. The copolymer obtained above was mixed with NBR (trade name Nipole), acrylonitrile content 41% by weight, manufactured by Nippon Zeon Co., Ltd., in the ratio shown in Table 3 below, and further methyl ethyl ketone-toluene (1:1 ) was dissolved in a mixed solvent to obtain a 20% by weight solution of adhesive. Al/FRP was used as the base material, and this base material (25
mm x 125 mm) with 150 g/m 2 of the adhesive obtained above.
The coating was applied at a rate of 100° C. and pressed at 3 kg/cm 2 for 15 minutes at 175°C. Peel adhesion strength test method for adhesives (JIS K-
6854), and the results are also shown in Table 3.
Claims (1)
す。］で表わされるビニルピリジン類10〜90モ
ル％と一般式(2) ［式中、R2は水素原子又はメチル基を、R3は
アルキル基を示す。］で表わされるアクリレー
ト化合物90〜10モル％とからなる共重合体５〜
95重量％、及び (B) 粘着付与剤及び合成ゴムから選ばれた少なく
とも１種95〜５重量％ を含有することを特徴とするビニルピリジン系接
着剤組成物。 ２ ビニルピリジン類が２−ビニルピリジン、４
−ビニルピリジン、２−メチル−５−ビニルピリ
ジン、２−メチル−６−ビニルピリジン及び５−
エチル−２−ビニルピリジンからなる群から選ば
れた少なくとも１種である特許請求の範囲第１項
記載の接着剤組成物。 ３ アクリレート化合物がメチルアクリレート、
メチルメタクリレート、エチルアクリレート、エ
チルメタクリレート、ブチルアクリレート、ブチ
ルメタクリレート、２−エチルヘキシルアクリレ
ート、２−エチルヘキシルメタクリレート、プロ
ピルアクリレート、プロピルメタクリレート、オ
クチルアクリレート、オクチルメタクリレート、
ラウリルアクリレート、ラウリルメタクリレー
ト、ステアリルアクリレート及びステアリルメタ
クリレートからなる群から選ばれた少なくとも１
種である特許請求の範囲第１項記載の接着剤組成
物。 ４ 共重合体の平均分子量が500〜500000である
特許請求の範囲第１項記載の接着剤組成物。 ５ 粘着付与剤がロジン、ロジン誘導体、テルペ
ン系樹脂又は石油樹脂である特許請求の範囲第１
項記載の接着剤組成物。 ６ 合成ゴムがアクリロニトリル−ブタジエンゴ
ム、スチレン−ブタジエンゴム、ブチルゴム、イ
ソプレン−イソブチレンゴム又はクロロプレンゴ
ムである特許請求の範囲第１項記載の接着剤組成
物。[Claims] 1 (A) General formula (1) [In the formula, R 1 represents a hydrogen atom or an alkyl group. ] 10 to 90 mol% of vinylpyridines represented by general formula (2) [In the formula, R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group. ] Copolymer 5 consisting of 90 to 10 mol% of an acrylate compound represented by
95% by weight, and (B) 95 to 5% by weight of at least one selected from tackifiers and synthetic rubbers. 2 Vinylpyridines are 2-vinylpyridine, 4
-vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine and 5-
The adhesive composition according to claim 1, which is at least one member selected from the group consisting of ethyl-2-vinylpyridine. 3 The acrylate compound is methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, propyl acrylate, propyl methacrylate, octyl acrylate, octyl methacrylate,
At least one selected from the group consisting of lauryl acrylate, lauryl methacrylate, stearyl acrylate, and stearyl methacrylate
The adhesive composition according to claim 1, which is a seed. 4. The adhesive composition according to claim 1, wherein the copolymer has an average molecular weight of 500 to 500,000. 5 Claim 1 in which the tackifier is rosin, rosin derivative, terpene resin, or petroleum resin
The adhesive composition described in . 6. The adhesive composition according to claim 1, wherein the synthetic rubber is acrylonitrile-butadiene rubber, styrene-butadiene rubber, butyl rubber, isoprene-isobutylene rubber, or chloroprene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337385A JPH0238157B2 (en) | 1985-04-05 | 1985-04-05 | BINIRUPIRIJINKEISETSUCHAKUZAISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337385A JPH0238157B2 (en) | 1985-04-05 | 1985-04-05 | BINIRUPIRIJINKEISETSUCHAKUZAISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61231072A JPS61231072A (en) | 1986-10-15 |
| JPH0238157B2 true JPH0238157B2 (en) | 1990-08-29 |
Family
ID=13516308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7337385A Expired - Lifetime JPH0238157B2 (en) | 1985-04-05 | 1985-04-05 | BINIRUPIRIJINKEISETSUCHAKUZAISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0238157B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63314218A (en) * | 1986-12-09 | 1988-12-22 | Terumo Corp | Ultraviolet absorbing high-molecular material |
| CA2549549C (en) * | 2003-12-15 | 2010-05-04 | Council Of Scientific & Industrial Research | Ph sensitive polymer and process for preparation thereof |
-
1985
- 1985-04-05 JP JP7337385A patent/JPH0238157B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61231072A (en) | 1986-10-15 |
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