JPH0236631B2 - HORIAMIDOKEISETSUCHAKUZAISOSEIBUTSU - Google Patents
HORIAMIDOKEISETSUCHAKUZAISOSEIBUTSUInfo
- Publication number
- JPH0236631B2 JPH0236631B2 JP7337485A JP7337485A JPH0236631B2 JP H0236631 B2 JPH0236631 B2 JP H0236631B2 JP 7337485 A JP7337485 A JP 7337485A JP 7337485 A JP7337485 A JP 7337485A JP H0236631 B2 JPH0236631 B2 JP H0236631B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- methacrylate
- nylon
- vinylpyridine
- methyl
- 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
- 230000001070 adhesive effect Effects 0.000 claims description 41
- 239000000853 adhesive Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 16
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 14
- 229920006122 polyamide resin Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229920002292 Nylon 6 Polymers 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 7
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- -1 acrylate compound Chemical class 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 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 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 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
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-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
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 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
- 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
- 229920000642 polymer Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 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
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 239000004677 Nylon Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005667 methoxymethylation reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 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
- 239000004831 Hot glue Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 238000005576 amination reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009529 body temperature measurement Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
産業上の利用分野
本発明は、ポリアミド系接着剤組成物に関す
る。
従来の技術
ポリアミド系樹脂は、一般にアミド結合を有す
る樹脂の総称であり、その代表的なものにナイロ
ンがある。ナイロンは、繊維製品、成形品、フイ
ルム等に広く使用され、また一部がホツトメルト
接着剤に用いられている。斯かるポリアミド系接
着剤は、樹脂中のアミド結合により分子量の割に
強靭性を示し、また各種の材質に対する親和性が
よい等の特徴を有しているが、耐熱性の点で充分
ではなく、より一層の改善が望まれている。
発明の目的及び構成
本発明者らは、従来のポリアミド系接着剤の耐
熱性を改善すべく鋭意研究を重ねた結果、ポリア
ミド系樹脂に下記に示す単独重合体又は共重合体
を添加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) ナイロン−６、ナイロン−11、ナイロン−
12、ナイロン−６，６、ナイロン−６，10及び
これらのアルコキシメチル化変性体もしくはジ
メチルアミノ化変性体からなる群から選ばれた
少なくとも１種のポリアミド系樹脂、及び
(B) 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
合体及び／又は該ビニルピリジン類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を
含有し、上記(A)成分と(B)成分との配合割合が前
者：後者＝５〜95：95〜５重量％であるポリア
ミド系接着剤組成物に係る。
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。
本発明においてポリアミド系樹脂に添加配合さ
れる重合体(B)は、上記一般式(1)のビニルピリジン
類の単独重合体又は該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
る共重合体である。これらの重合体は、従来公知
の重合方法、例えばラジカル重合、イオン重合等
に従い容易に製造され得る。該重合体を製造する
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、又はこれと一般式(2)のア
クリレート化合物とを所定量配合し、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。溶液重
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
られる本発明の単独又は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。また、上記で得られる共
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。
本発明の接着剤組成物中に配合されるべき前記
(A)成分のポリアミド系樹脂及び(B)成分の重合体の
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＝30〜70：70〜30
重量％とするのがよい。ポリアミド系樹脂の配合
割合が上記範囲を越えると、両者併用による相乗
効果が発揮され得ず、接着強度が低下する傾向が
生ずる。また、ポリアミド系樹脂の配合割合が上
記範囲より少ないと、接着強度の低下及び耐熱性
の劣化の傾向が生ずる。
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、可塑剤、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の形態としては、特に制
限がなく、溶液の形態であつてもよいし、粉末の
形態であつてもよい。
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
本発明によれば、従来のポリアミド系接着剤の
難点とされている耐熱性が改善され、しかも接着
性もより一層向上された接着剤が提供される。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１モル及びAIBN0.01モル
を仕込み、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４−ビニルピリジン単独重合
体（以下この重合体を「重合体Ａ」という）を析
出させ、乾燥させた。
上記で得られた重合体Ａの平均分子量は約
70000であつた。
上記で得られた重合体Ａとポリアミド系樹脂
（商品名トレジン−F30、ナイロン−６変性品、
メトキメムチル化率33％、帝国化学産業(株)製）と
を下記第１表に示す割合で混合して接着剤とし
た。
基材として鋼材／鋼材、Al／Al又はFRP／Al
を使用し、これらの基材（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 polyamide adhesive composition. BACKGROUND ART Polyamide resin is generally a general term for resins having amide bonds, and a typical example thereof is nylon. Nylon is widely used in textile products, molded products, films, etc., and some are used in hot melt adhesives. Such polyamide adhesives have characteristics such as exhibiting toughness in relation to their molecular weight due to amide bonds in the resin, and good affinity for various materials, but they do not have sufficient heat resistance. , further improvement is desired. Purpose and Structure of the Invention As a result of extensive research in order to improve the heat resistance of conventional polyamide adhesives, the present inventors found that when the following homopolymer or copolymer was added and blended with polyamide resin. The present inventors have discovered that the intended purpose of the present invention can be achieved, and have now completed the present invention. That is, the present invention provides (A) nylon-6, nylon-11, nylon-
12, at least one polyamide resin selected from the group consisting of nylon-6,6, nylon-6,10, and alkoxymethylated or dimethylaminated modified products thereof, and (B) general formula (1 ) [In the formula, R 1 represents a hydrogen atom or an alkyl group. ] A homopolymer of vinylpyridines represented by and/or 10 to 90 mol% of the vinylpyridines and general formula (2) [In the formula, R 2 is a hydrogen atom or a methyl group, R 3
represents an alkyl group. ] Contains a copolymer consisting of 90 to 10 mol% of an acrylate compound represented by The present invention relates to a certain polyamide adhesive composition. 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 vinylpyridines 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 polymer (B) added to the polyamide resin is a homopolymer of vinyl pyridines of the above general formula (1) or a combination of the vinyl pyridines and the general formula
This is a copolymer obtained by copolymerizing (2) with the acrylate compound. These polymers can be easily produced according to conventionally known polymerization methods such as radical polymerization and ionic polymerization. Preferred embodiments for producing the polymer include, for example, the general formula
By blending a predetermined amount of vinylpyridine (1) or an acrylate compound of general formula (2), azobiscyano compounds such as azobisisobutyronitrile (AIBN), peroxides such as benzoyl peroxide, alkyl Solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization may be carried out in the presence of a polymerization initiator such as an organic metal compound such as lithium or ethylaluminum dichloride, or an inorganic halogen compound such as boron fluoride. Examples of the solvent used in solution polymerization include methanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and the like. These polymerization reactions are usually carried out at -80 to 120°C, and the reaction time is generally 0.5 to 10 hours. The average molecular weight of the homopolymer or copolymer of the present invention thus obtained is usually about 500 to 500,000, preferably about 1,000 to 500,000.
Within the range of 100000. The composition of the copolymer obtained above is comprised of 10 to 90 mol% of vinyl pyridines and 90 to 10 mol% of acrylate compounds. If the composition of the copolymer deviates from the above range, the desired effects of the present invention may not be exhibited. The above to be incorporated into the adhesive composition of the present invention
The ratio of the polyamide resin as the component (A) and the polymer as the component (B) is usually the former: the latter = 5 to 95: 95 to 5.
Weight %, preferably former: latter = 30-70: 70-30
It is preferable to express it in weight%. If the blending ratio of the polyamide resin exceeds the above range, a synergistic effect cannot be achieved by using both together, and adhesive strength tends to decrease. Furthermore, if the blending ratio of the polyamide resin is less than the above range, there will be a tendency for the adhesive strength to decrease and the heat resistance to deteriorate. 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, plasticizers, pigments, fillers, etc. can be appropriately blended. The form of the adhesive composition of the present invention is not particularly limited, and may be in the form of a solution or powder. 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 According to the present invention, an adhesive is provided which has improved heat resistance, which is considered to be a drawback of conventional polyamide adhesives, and has further improved adhesive properties. The adhesive composition of the present invention can be used not only for rubber-to-rubber adhesion and rubber-to-metal adhesion, but also for metal-to-metal adhesion, metal-to-composite adhesion, and composite-to-composite adhesion. is also extremely suitable. Examples Example 1 1 mol of 4-vinylpyridine and 0.01 mol of AIBN were charged, and 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, a 4-vinylpyridine homopolymer (hereinafter referred to as "polymer A") produced in a hexane solvent was precipitated and dried. The average molecular weight of Polymer A obtained above is approximately
It was 70,000. Polymer A obtained above and polyamide resin (trade name Torezin-F30, nylon-6 modified product,
(manufactured by Teikoku Kagaku Sangyo Co., Ltd.) with a methoxymethylation rate of 33% was mixed in the proportions shown in Table 1 below to prepare an adhesive. Steel material/steel material, Al/Al or FRP/Al as base material
The adhesive obtained above was applied to these substrates (25 mm x 12.5 mm) at a rate of 150 g/m 2 using
Pressure bonding was carried out at 175° C. and 3 kg/cm 2 for 15 minutes. The tensile shear adhesive strength was determined according to the adhesive tensile shear adhesive strength testing method (JISK-6850), and the results are also shown in Table 1.
【表】
実施例 ２
上記実施例１で得られた重合体Ａとポリアミド
系樹脂（商品名トレジンHF−30、ナイロン−６
変性品、メトキシメチル化率33％、帝国化学産業
(株)製）とを下記第２表に示す割合で混合して接着
剤とした。この接着剤の耐熱性を調べるため、基
材としてAl／Alを使用し、該接着剤を150g／m2
の割合で塗布し、175℃、3Kg／cm2で15分間圧着
したものについて、接着剤の軟化温度測定方法
（JIS Ｋ−6844）に従い軟化温度を測定した。結
果を下記第２表に示す。[Table] Example 2 Polymer A obtained in Example 1 above and polyamide resin (trade name Torezin HF-30, Nylon-6
Modified product, methoxymethylation rate 33%, Teikoku Kagaku Sangyo
Co., Ltd.) in the proportions shown in Table 2 below to prepare an adhesive. In order to investigate the heat resistance of this adhesive, Al/Al was used as the base material, and the adhesive was heated at 150 g/m 2
The softening temperature was measured according to the softening temperature measurement method for adhesives (JIS K-6844). The results are shown in Table 2 below.
【表】
実施例 ３
上記実施例１で得られた重合体Ａとナイロン−
６変性品（商品名可溶性ナイロン、ジメチルアミ
ノ化率33％、東レ(株)製）又はナイロン−６（商品
名東レナイロン６、未変性品、東レ(株)製）とを重
量比で１：１の割合で混合して接着剤とした。
基材として鋼材／鋼材又はAl／Alを使用し、
これらの基材（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℃、３
Kg／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３表に併
せて示す。[Table] Example 3 Polymer A obtained in Example 1 above and nylon
6 modified product (trade name: soluble nylon, dimethyl amination rate 33%, manufactured by Toray Industries, Inc.) or nylon-6 (trade name: Toray Nylon 6, unmodified product, manufactured by Toray Industries, Inc.) at a weight ratio of 1: They were mixed at a ratio of 1:1 to form an adhesive. Using steel/steel or Al/Al as the base material,
The adhesive obtained above was applied to these base materials (25 mm x 12.5 mm) at a rate of 150 g/m 2 and heated at 175°C for 3
Pressure bonding was carried out at Kg/cm 2 for 15 minutes. The tensile shear adhesive strength was determined according to the adhesive tensile shear adhesive strength test method (JISK-6850), and the results are also shown in Table 3.
【表】
実施例 ４
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（以下この重合体を
「重合体Ｂ」という）を析出させ、乾燥させた。
得られた重合体Ｂ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、該重合体Ｂの平均分子量は約5000
であつた。
上記で得られた重合体Ｂにポリアミド系樹脂
（商品名トレジンHF−30、ナイロン−６変性品、
メトキシメチル化率33％、帝国化学産業(株)製）を
下記第４表に示す割合で混合して接着剤とした。
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４表に併せて示す。[Table] Example 4 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, a copolymer produced in a hexane solvent (hereinafter referred to as "polymer B") was precipitated and dried.
The monomer composition ratio of the obtained polymer B was 4-vinylpyridine:2-ethylhexyl methacrylate=
1:1, and the average molecular weight of the polymer B is about 5000.
It was hot. Polyamide resin (trade name Torezin HF-30, nylon-6 modified product,
A methoxymethylation rate of 33% (manufactured by Teikoku Kagaku Sangyo Co., Ltd.) was mixed in the proportions shown in Table 4 below to prepare an 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 4.
【表】
また、上記で得られる接着剤の耐熱性を調べる
ため、基材としてAl／Alを使用し、該接着剤を
150g／m2の割合で塗布し、175℃、３Kg／cm2で15
分間圧着したものについて、接着剤の軟化温度測
定方法（JISK−6844）に従い軟化温度を測定し
た。結果を下記第５表に示す。[Table] In addition, in order to investigate the heat resistance of the adhesive obtained above, Al/Al was used as the base material, and the adhesive was
Apply at a rate of 150g/ m2 , 15 at 175℃, 3Kg/ cm2
The softening temperature of the adhesive bonded by pressure was measured according to the method for measuring softening temperature of adhesives (JISK-6844). The results are shown in Table 5 below.
Claims (1)
−12、ナイロン−６，６、ナイロン−６，10及
びこれらのアルコキシメチル化変性体もしくは
ジメチルアミノ化変性体からなる群から選ばれ
た少なくとも１種のポリアミド系樹脂、及び (B) 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
合体及び／又は該ビニルピリジン類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を
含有し、上記(A)成分と(B)成分との配合割合が前
者：後者＝５〜95：95〜５重量％であるポリア
ミド系接着剤組成物。 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 上記単独重合体及び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。[Scope of Claims] 1 (A) A group consisting of nylon-6, nylon-11, nylon-12, nylon-6,6, nylon-6,10, and alkoxymethylated or dimethylaminated modified products thereof At least one polyamide resin selected from (B) General formula (1) [In the formula, R 1 represents a hydrogen atom or an alkyl group. ] A homopolymer of vinylpyridines represented by and/or 10 to 90 mol% of the vinylpyridines and general formula (2) [In the formula, R 2 is a hydrogen atom or a methyl group, R 3
represents an alkyl group. ] Contains a copolymer consisting of 90 to 10 mol% of an acrylate compound represented by A certain polyamide adhesive composition. 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 average molecular weight of the above homopolymer and copolymer is
500 to 500,000, the adhesive composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337485A JPH0236631B2 (en) | 1985-04-05 | 1985-04-05 | HORIAMIDOKEISETSUCHAKUZAISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337485A JPH0236631B2 (en) | 1985-04-05 | 1985-04-05 | HORIAMIDOKEISETSUCHAKUZAISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61231073A JPS61231073A (en) | 1986-10-15 |
| JPH0236631B2 true JPH0236631B2 (en) | 1990-08-20 |
Family
ID=13516338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7337485A Expired - Lifetime JPH0236631B2 (en) | 1985-04-05 | 1985-04-05 | HORIAMIDOKEISETSUCHAKUZAISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0236631B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4696965A (en) * | 1985-07-23 | 1987-09-29 | Minnesota Mining And Manufacturing Company | Polyamide-acrylic blends |
-
1985
- 1985-04-05 JP JP7337485A patent/JPH0236631B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61231073A (en) | 1986-10-15 |
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