JPS6223797B2 - - Google Patents
Info
- Publication number
- JPS6223797B2 JPS6223797B2 JP7429979A JP7429979A JPS6223797B2 JP S6223797 B2 JPS6223797 B2 JP S6223797B2 JP 7429979 A JP7429979 A JP 7429979A JP 7429979 A JP7429979 A JP 7429979A JP S6223797 B2 JPS6223797 B2 JP S6223797B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- silane
- general formula
- polymerized
- olefin resin
- 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
- 229910000077 silane Inorganic materials 0.000 claims description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 229920005672 polyolefin resin Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000004831 Hot glue Substances 0.000 claims description 16
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 23
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- -1 polyethylene Polymers 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical class CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 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 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 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
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical class CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical class CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical class NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical class CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical class CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical class [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical class CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical class [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Description
【発明の詳細な説明】
本発明はホツトメルト型接着剤組成物に関する
ものである。
従来ホツトメルト接着剤としてポリエチレン、
エチレン−酢酸ビニル共重合体、エチレン−エチ
ルアクリレート共重合体等をベース樹脂とし、こ
れに粘着性付与剤、ワツクス、さらに安定剤、フ
イラー、可塑剤等が必要に応じて配合されたもの
が用いられているが、これらは接着後において高
温にさらされると接着力が著るしく低下する欠
点、すなわち耐熱性が悪いという欠点がある。
上記の如き耐熱性を改善する方法としては、ベ
ース樹脂や配合剤等に軟化点の高いものを用い、
ホツトメルト接着剤の軟化点を高める方法がある
が、この方法では接着時に於ける接着剤の粘度が
高くなり作業性が悪くなるばかりでなく、被着体
へのヌレが悪くなり、接着不良を起す原因にもな
る。又、接着剤の加熱温度を高くすれば接着時の
粘度を低く出来るが、接着剤の熱安定性には限度
があつて加熱温度を高くすれば接着剤構成成分の
熱劣化が起りやすくなり実用上問題がある。
本発明は上記の如き従来のホツトメルト接着剤
の欠点にかんがみ、通常のホツトメルト接着剤と
同程度の温度で使用することが出来て、しかも接
着後に於ける耐熱性がすぐれた接着剤にして、し
かも使用時におけ溶融粘度安定性にすぐれ、同時
に硬化速度も速いホツトメルト接着剤組成物を提
供することを目的としてなされたものであり、そ
の要旨は下記Ａ，Ｂ群より選ばれた１種又は２種
以上の樹脂とシラノール縮合触媒とが含有されて
なり、Ａ，Ｂ群より選ばれた１種又は２種以上の
樹脂におけるビニルトリメトキシシランと下記一
般式で表わされるシランとの比率がモル比で２：
８〜８：２であるホツトメルト接着剤組成物に存
する。
Ａ：ビニルトリメトキシシランと一般式CH2＝
CHSiY3（Ｙは炭素数２以上のアルコキシ基を
表わす）で表わされるシランとがグラフト重合
されたオレフイン系樹脂。
Ｂ：ビニルトリメトキシシランがグラフト重合さ
れたオレフイン系樹脂と、一般式CH2＝
CHSiY3（Ｙは炭素数２以上のアルコキシ基を
表わす）で表わされるシランがグラフト重合さ
れたオレフイン系樹脂との混合物。
本発明におけるオレフイン系樹脂とはオレフイ
ンの単独重合体又は共重合体又はオレフインと他
の単量体との共重合体を表わし、例えばポリエチ
レン、ポリプロピレン、エチレン−酢酸ビニル共
重合体、エチレン−アクリル酸共重合体、エチレ
ン−アクリル酸エステル共重合体、エチレン−プ
ロピレン−アクリル酸共重合体、エチレン−酢酸
ビニル−アクリル酸共重合体、エチレン−酢酸ビ
ニル共重合体のケン化物などが挙げられる。そし
てエチレン−酢酸ビニル共重合体が特に好適であ
る。
そして本発明に用いられるオレフイン系樹脂
は、
Ａ：ビニルトリメトキシシランと一般式CH2＝
CHSiY3（Ｙは炭素数２以上のアルコキシ基を
表わす）で表わされるシランとがグラフト重合
されたオレフイン系樹脂若しくは
Ｂ：ビニルトリメトキシシランがグラフト重合さ
れたオレフイン系樹脂と、前記一般式で表わさ
れるシランがグラフト重合されたオレフイン系
樹脂との混合物のいずれかであり、上記Ａ，Ｂ
群の中より適宜選ばれてよい。そして上記一般
式で表わされるシランとしては、ビニルトリエ
トキシシラン、ビニルトリプロポキシシラン、
ビニルトリブトキシシラン、ビニルトリス（β
−メトキシエトキシ）シラン等が挙げられ、と
くにビニルトリエトキシシランが好適である。
又、上記Ａ，Ｂ群において、オレフイン系樹脂
にグラフト重合されたビニルトリメトキシシラン
と前記一般式で表わされるシランとの比率として
は、ビニルトリメトキシシランの比率が低すぎる
と満足出来る硬化速度が得られず、又、該シラン
の比率が高すぎると溶融安定性が低下する傾向に
あるので、該比率はモル比にて５：95〜95：５の
範囲とされる。又、オレフイン系樹脂にグラフト
重合される全シランの量はグラフト前のオレフイ
ン系樹脂100重量部に対し、0.1〜50重量部である
ことが好ましい。オレフイン系樹脂に上記シラン
をグラフト重合させるには、従来行われている方
法が用いられてよく、例えばベンゾイルパーオキ
サイド、ジクミルパーオキサイド等の有機過酸化
物、ターシヤリーブチルパーアセテート等のパー
エステル、アゾビスイソブチロニトリル等のアゾ
化合物などの遊離ラジカル発生剤の存在下でオレ
フイン系樹脂をビニルトリメトキシラン又は前記
一般式で表わされるシラン又はこれらの両方のシ
ランと共に押出機、ミキサー等で100〜200℃の加
熱温度で加熱混練する方法が好適に採用され得
る。
又、本発明に使用されるシラノール縮合触媒と
しては、オレフイン系樹脂にグラフトされた前記
シラン成分が水分の存在下において加水分解し、
相互間に架橋を生じる反応を生ぜしめる作用を有
する物質を指し、従来においてシラノール縮合触
媒として知られている物質がいずれも使用出来
る。上記シラノール縮合触媒としては例えば、ジ
ブチル錫ジラウレート、ジブチル錫ジアセテー
ト、ジブチル錫ジオクトエート、酢酸第１錫、ナ
フテン酸鉛、カプリル酸亜鉛、ナフテン酸コバル
ト、エチルアミン、ジブチルアミン、鉱酸、脂肪
酸などが挙げられるが、本発明においてはとくに
ジブチル錫ジラウレートが好適である。
又、その使用量としては接着剤組成物の0.001
〜１重量％の範囲とするのが通常好適である。本
発明ホツトメルト接着剤組成物を製造するには、
シランがグラフト重合された前記オレフイン系樹
脂に前記シラノール縮合触媒を添加し、好ましく
は加熱下に均一に混合することにより行われる。
この際、必要に応じ粘着性付与剤、ワツクス、安
定剤、フイラー、可塑剤、着色剤が適宜添加され
てよい。
又、上記混合時から接着剤としての使用までの
間は、オレフイン系樹脂中のシラン成分の反応に
もとづく架橋が進行するのを避けるために、大気
中の湿分などの水分となるべく接触しない様に、
乾燥状態に保つのが良い。本発明接着剤組成物は
従来のホツトメルト接着剤と同様な使用法で、
種々の用途、例えば木工、合板、包装、建材、自
動車内装、電気部品組立て等の分野に使用出来
る。
本発明のホツトメルト接着剤組成物は上述の通
りの構成のものであり、特定のシランがグラフト
重合されたオレフイン系樹脂及びシラノール縮合
触媒が含有されているので、被接着体を接着する
際には低い溶融粘度で作業性よく良好な接着を行
うことが出来そして接着後においては接着剤中の
ポリオレフイン系樹脂が大気中の水分との反応に
よりすみやかに架橋するので、接着剤層の耐熱性
が著るしく向上するのである。以上の如く本発明
接着剤組成物は使用後における耐熱性が著るしく
向上するものであるから、耐熱性が要求される用
途に用いられて有効なるものである。
そして特に本発明においては特定の組合せのビ
ニルアルコキシシランがグラフト重合されたオレ
フイン系樹脂が用いられるのであるので、本発明
の接着性組成物は使用時における溶融粘度の安定
性にすぐれ、従つて作業性がすぐれていると共
に、接着後においては硬化速度が早くすみやかに
実用強度にまで到達することが出来るのであり、
ホツトメルト接着剤としてのすぐれた特性を有す
るものである。次に本発明の実施例について説明
する。なお以下において単に部とあるのは重量部
を意味する。
実施例 １
エチレン−酢酸ビニル共重合体（メルトインデ
ツクス400、酢酸ビニル含量28％、以下EVAと略
す）100部に、ジクミルパーオキサイド0.5部、ビ
ニルトリエトキシシラン10部を加えて温度140〜
150℃で混練反応させてシラングラフトEVA
（）を得た。
又、上記EVA100部にビニルトリメトキシシラ
ン10部を加え同様にしてシラングラフトEVA
（）を得た。
次に上記シラングラフトEVA（）、同EVA
（）及び他の成分を下記の通りの割合で加え合
せて140〜150℃で混練しホツトメルト接着剤を得
た。
シラングラフトEVA（） 18.5部
シラングラフトEVA（） 18.5部
脂環族飽和炭化水素樹脂 45部
マイクロクリスタルワツクス 18部
ジブチル錫ジラウレート 0.05部
実施例 ２
実施例１で用いたのと同じEVA100部にジクミ
ルパーオキサイド0.5部、ビニルトリメトキシシ
ラン５部及びビニルトリエトキシシラン５部を加
えて温度140〜150℃で混練反応させてシラングラ
フトEVA（）を得た。次に上記EVA（）及
び他の成分を下記の通りの割合で加え合せて、
140〜150℃で混練し、ホツトメルト接着剤を得
た。
シラングラフトEVA（） 37部
脂環族飽和炭化水素樹脂 45部
マイクロクリスタルワツクス 18部
ジブチル錫ジラウレート 0.05部
比較例 １
実施例１と同じEVA100部にジクミルパーオキ
サイド0.5部、ビニルトリエトキシシラン10部を
加えて140〜150℃で混練反応させてシラングラフ
トEVAを得た。次に上記シラングラフトEVA及
び他の成分を下記割合で加え合せて140〜150℃で
混練しホツトメルト接着剤を得た。
シラングラフトEVA 37部
脂環族飽和炭化水素樹脂 45部
マイクロクリスタルワツクス 18部
ジブチル錫ジラウレート 0.05部
比較例 ２
実施例１と同じEVA100部にジクミルパーオキ
サイド0.5部、ビニルトリメトキシシラン10部を
加えて140〜150℃で混練反応させてシラングラフ
トEVAを得た。以下このシラングラフトEVAを
用いること以外は比較例１と同様にしてホツトメ
ルト接着剤を得た。
得られた各々の接着剤について溶融粘度安定性
と硬化速度について試験を行い、第１表の結果を
得た。
溶融粘度安定性
140℃で加熱溶融し初期粘度及び140℃での経時
による粘度変化をＢ型粘度計で測定し、初期粘度
の25％増の粘度になる迄の時間をポツトライフと
した。
硬化速度
厚み2.4mm、巾25mmの普通合板を巾約３mmのビ
ード塗布で接着した試料を温度40℃、相対湿度75
％の雰囲気中に置き、経過日数による耐熱クリー
プ性の変化を測定し、最終耐熱クリープ性を示す
ようになる迄の日数をもつて硬化速度とした。
なお、耐熱クリープ性は上記試料の下端に100
ｇの荷重をかけ１℃／分の速さで昇温し、接着部
分がはがれて落下したときの温度を求め、この温
度で表示した。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hot melt adhesive composition. Conventional hot melt adhesives include polyethylene,
The base resin is ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc., and tackifiers, waxes, stabilizers, fillers, plasticizers, etc. are blended as necessary. However, these have the disadvantage that their adhesive strength decreases significantly when exposed to high temperatures after bonding, that is, they have poor heat resistance. As a method to improve heat resistance as described above, use a base resin or compounding agent that has a high softening point,
There is a method of increasing the softening point of hot melt adhesives, but this method not only increases the viscosity of the adhesive during bonding, making workability worse, but also makes it difficult to wet the adherend, resulting in poor bonding. It can also be a cause. Also, by increasing the heating temperature of the adhesive, the viscosity during adhesion can be lowered, but there is a limit to the thermal stability of the adhesive, and if the heating temperature is increased, the adhesive components tend to thermally deteriorate, making it difficult to put into practical use. There is a problem above. In view of the above-mentioned drawbacks of conventional hot melt adhesives, the present invention provides an adhesive that can be used at temperatures comparable to ordinary hot melt adhesives and has excellent heat resistance after bonding. This was developed with the aim of providing a hot melt adhesive composition that has excellent melt viscosity stability during use and at the same time has a fast curing speed. The above resin and a silanol condensation catalyst are contained, and the ratio of vinyltrimethoxysilane and silane represented by the following general formula in one or more resins selected from Groups A and B is expressed as a molar ratio. 2:
The hot melt adhesive composition has a ratio of 8 to 8:2. A: Vinyltrimethoxysilane and the general formula CH 2 =
An olefin resin graft-polymerized with a silane represented by CHSiY 3 (Y represents an alkoxy group having 2 or more carbon atoms). B: Olefin resin graft-polymerized with vinyltrimethoxysilane and general formula CH 2 =
A mixture with an olefin resin in which a silane represented by CHSiY 3 (Y represents an alkoxy group having 2 or more carbon atoms) is graft-polymerized. In the present invention, the olefin resin refers to a homopolymer or copolymer of olefin, or a copolymer of olefin and other monomers, such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid. Copolymers, ethylene-acrylic acid ester copolymers, ethylene-propylene-acrylic acid copolymers, ethylene-vinyl acetate-acrylic acid copolymers, saponified products of ethylene-vinyl acetate copolymers, and the like. Ethylene-vinyl acetate copolymer is particularly preferred. The olefin resin used in the present invention has the following formula: A: vinyltrimethoxysilane and the general formula CH 2 =
An olefin resin graft-polymerized with a silane represented by CHSiY 3 (Y represents an alkoxy group having 2 or more carbon atoms) or B: an olefin resin graft-polymerized with vinyltrimethoxysilane and an olefin resin represented by the above general formula. It is either a mixture of olefin resin in which the silane is graft-polymerized, and the above-mentioned A, B
It may be selected as appropriate from the group. The silanes represented by the above general formula include vinyltriethoxysilane, vinyltripropoxysilane,
Vinyltributoxysilane, vinyltris (β
-methoxyethoxy)silane, etc., and vinyltriethoxysilane is particularly suitable. In addition, in the above groups A and B, as for the ratio of the vinyltrimethoxysilane graft-polymerized to the olefin resin and the silane represented by the above general formula, if the ratio of vinyltrimethoxysilane is too low, the curing speed will not be satisfactory. Furthermore, if the ratio of the silane is too high, the melt stability tends to decrease, so the molar ratio is set in the range of 5:95 to 95:5. Further, the total amount of silane to be graft-polymerized to the olefin resin is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the olefin resin before grafting. To graft-polymerize the above-mentioned silane to an olefin resin, conventional methods may be used, such as organic peroxides such as benzoyl peroxide and dicumyl peroxide, and peresters such as tert-butyl peracetate. In the presence of a free radical generator such as an azo compound such as azobisisobutyronitrile, an olefinic resin is mixed with vinyltrimethoxylan, a silane represented by the above general formula, or both of these silanes in an extruder, mixer, etc. A method of heating and kneading at a heating temperature of 100 to 200°C can be suitably employed. Further, as the silanol condensation catalyst used in the present invention, the silane component grafted to the olefinic resin is hydrolyzed in the presence of moisture,
It refers to a substance that has the effect of causing a reaction that causes mutual crosslinking, and any substance conventionally known as a silanol condensation catalyst can be used. Examples of the silanol condensation catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, lead naphthenate, zinc caprylate, cobalt naphthenate, ethylamine, dibutylamine, mineral acids, fatty acids, and the like. However, dibutyltin dilaurate is particularly suitable in the present invention. In addition, the amount used is 0.001 of the adhesive composition.
A range of 1% by weight is usually suitable. To produce the hot melt adhesive composition of the present invention,
This is carried out by adding the silanol condensation catalyst to the olefin resin graft-polymerized with silane and uniformly mixing, preferably under heating.
At this time, tackifiers, waxes, stabilizers, fillers, plasticizers, and colorants may be added as appropriate. In addition, from the time of mixing to the time of use as an adhesive, in order to prevent crosslinking from proceeding due to the reaction of the silane component in the olefin resin, avoid contact with moisture such as atmospheric moisture as much as possible. To,
It is best to keep it dry. The adhesive composition of the present invention can be used in the same manner as conventional hot melt adhesives.
It can be used in various fields, such as woodworking, plywood, packaging, building materials, automobile interiors, and electrical parts assembly. The hot melt adhesive composition of the present invention has the above-mentioned structure, and contains an olefin resin graft-polymerized with a specific silane and a silanol condensation catalyst. The low melt viscosity allows for good adhesion with good workability, and after adhesion, the polyolefin resin in the adhesive quickly crosslinks by reaction with moisture in the atmosphere, so the heat resistance of the adhesive layer is extremely high. This will improve your performance. As described above, the adhesive composition of the present invention has significantly improved heat resistance after use, and therefore is effective when used in applications requiring heat resistance. In particular, in the present invention, since an olefin resin graft-polymerized with a specific combination of vinyl alkoxysilane is used, the adhesive composition of the present invention has excellent melt viscosity stability during use, and is therefore easy to work with. It not only has excellent properties, but also has a fast curing speed and can quickly reach practical strength after bonding.
It has excellent properties as a hot melt adhesive. Next, examples of the present invention will be described. Note that in the following, parts simply mean parts by weight. Example 1 0.5 parts of dicumyl peroxide and 10 parts of vinyltriethoxysilane were added to 100 parts of ethylene-vinyl acetate copolymer (melt index 400, vinyl acetate content 28%, hereinafter abbreviated as EVA), and the mixture was heated at a temperature of 140 to 100 parts.
Silane grafted EVA by kneading reaction at 150℃
I got (). Also, 10 parts of vinyltrimethoxysilane was added to 100 parts of the above EVA and silane grafted EVA was prepared in the same manner.
I got (). Next, the above silane grafted EVA (), the same EVA
() and other ingredients were added in the following proportions and kneaded at 140-150°C to obtain a hot melt adhesive. Silange grafted EVA () 18.5 parts Silange grafted EVA () 18.5 parts Alicyclic saturated hydrocarbon resin 45 parts Microcrystal wax 18 parts Dibutyltin dilaurate 0.05 parts Example 2 Add 100 parts of the same EVA used in Example 1 to 0.5 parts of mill peroxide, 5 parts of vinyltrimethoxysilane, and 5 parts of vinyltriethoxysilane were added and kneaded and reacted at a temperature of 140 to 150°C to obtain silane grafted EVA (). Next, add the above EVA () and other ingredients in the following proportions,
The mixture was kneaded at 140 to 150°C to obtain a hot melt adhesive. Silang grafted EVA () 37 parts Alicyclic saturated hydrocarbon resin 45 parts Microcrystal wax 18 parts Dibutyltin dilaurate 0.05 parts Comparative example 1 100 parts of EVA same as in Example 1, 0.5 parts of dicumyl peroxide, 10 parts of vinyltriethoxysilane The mixture was kneaded and reacted at 140 to 150°C to obtain silane-grafted EVA. Next, the above silane grafted EVA and other components were added in the following proportions and kneaded at 140 to 150°C to obtain a hot melt adhesive. Silane grafted EVA 37 parts Alicyclic saturated hydrocarbon resin 45 parts Microcrystal wax 18 parts Dibutyltin dilaurate 0.05 parts Comparative Example 2 To 100 parts of the same EVA as in Example 1, 0.5 parts of dicumyl peroxide and 10 parts of vinyltrimethoxysilane were added. In addition, silane grafted EVA was obtained by kneading and reacting at 140 to 150°C. A hot melt adhesive was obtained in the same manner as in Comparative Example 1 except that this silane grafted EVA was used. Each of the obtained adhesives was tested for melt viscosity stability and curing speed, and the results shown in Table 1 were obtained. Melt viscosity stability The initial viscosity after melting at 140°C and the change in viscosity over time at 140°C were measured using a B-type viscometer, and the time until the viscosity reached a 25% increase from the initial viscosity was defined as the pot life. Curing speed A sample of ordinary plywood with a thickness of 2.4 mm and a width of 25 mm is glued with a bead coating of about 3 mm in width at a temperature of 40℃ and a relative humidity of 75.
% atmosphere, and the change in heat-resistant creep property was measured over the number of days that had elapsed, and the number of days until the final heat-resistant creep property was exhibited was defined as the curing rate. In addition, the heat resistance creep property is 100% at the lower end of the above sample.
The temperature was increased at a rate of 1° C./min under a load of 1.5 g, and the temperature at which the adhesive part peeled off and fell was determined and expressed as this temperature. 【table】
Claims (1)
の樹脂とシラノール縮合触媒とが含有されてな
り、Ａ，Ｂ群より選ばれた１種又は２種以上の樹
脂におけるビニルトリメキシシランと下記一般式
で表わされるシランとの比率がモル比で２：８〜
８：２であるホツトメルト接着剤組成物。 Ａ：ビニルトリメトキシシランと一般式CH2＝
CHSiY3（Ｙは炭素数２以上のアルコキシ基を
表わす）で表わされるシランとがグラフト重合
されたオレフイン系樹脂。 Ｂ：ビニルトリメトキシシランがグラフト重合さ
れたオレフイン系樹脂と、一般式CH2＝
CHSiY3（Ｙは炭素数２以上のアルコキシ基を
表わす）で表わされるシランがグラフト重合さ
れたオレフイン系樹脂との混合物。 ２ 一般式で表わされるシランがビニルトリエト
キシシランである第１項記載の組成物。 ３ シラノール縮合触媒の使用量が組成物の0.1
〜１重量％に相当する量である第１項記載の組成
物。[Scope of Claims] 1 Contains one or more resins selected from Groups A and B below and a silanol condensation catalyst, and contains one or more resins selected from Groups A and B below. The molar ratio of vinyl trimexysilane and silane represented by the following general formula in the resin is from 2:8 to
8:2 hot melt adhesive composition. A: Vinyltrimethoxysilane and the general formula CH 2 =
An olefin resin graft-polymerized with a silane represented by CHSiY 3 (Y represents an alkoxy group having 2 or more carbon atoms). B: Olefin resin graft-polymerized with vinyltrimethoxysilane and general formula CH 2 =
A mixture with an olefinic resin graft-polymerized with a silane represented by CHSiY 3 (Y represents an alkoxy group having 2 or more carbon atoms). 2. The composition according to item 1, wherein the silane represented by the general formula is vinyltriethoxysilane. 3 The amount of silanol condensation catalyst used is 0.1 of the composition.
2. The composition of claim 1 in an amount corresponding to ~1% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7429979A JPS55165973A (en) | 1979-06-12 | 1979-06-12 | Hot-melt adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7429979A JPS55165973A (en) | 1979-06-12 | 1979-06-12 | Hot-melt adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55165973A JPS55165973A (en) | 1980-12-24 |
| JPS6223797B2 true JPS6223797B2 (en) | 1987-05-25 |
Family
ID=13543106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7429979A Granted JPS55165973A (en) | 1979-06-12 | 1979-06-12 | Hot-melt adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55165973A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4840693A (en) * | 1987-07-23 | 1989-06-20 | Toray Silicone Co., Ltd. | Organopolysiloxane hot-melt adhesive |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4783504A (en) * | 1986-02-28 | 1988-11-08 | Shell Oil Company | Hot melt adhesive containing a silane grafted hydrogenated block polymer |
| CA1312408C (en) * | 1987-10-09 | 1993-01-05 | Peter W. Merz | Reactive, thixotropic hot-melt adhesive on silane basis |
| EP0821018A3 (en) * | 1996-07-22 | 1998-09-30 | PCD-Polymere Gesellschaft m.b.H. | Crosslinkable olefinic polymers and method for their preparation |
-
1979
- 1979-06-12 JP JP7429979A patent/JPS55165973A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4840693A (en) * | 1987-07-23 | 1989-06-20 | Toray Silicone Co., Ltd. | Organopolysiloxane hot-melt adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55165973A (en) | 1980-12-24 |
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