JP7145230B2 - 自動車用ウレタン系接着剤 - Google Patents
自動車用ウレタン系接着剤 Download PDFInfo
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- JP7145230B2 JP7145230B2 JP2020559105A JP2020559105A JP7145230B2 JP 7145230 B2 JP7145230 B2 JP 7145230B2 JP 2020559105 A JP2020559105 A JP 2020559105A JP 2020559105 A JP2020559105 A JP 2020559105A JP 7145230 B2 JP7145230 B2 JP 7145230B2
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Description
(A)末端にイソシアネート基を有するウレタンプレポリマー;
(B)1分子内に2個以上のアルコキシシリル基を有するシラン化合物と、末端にイソシアネート基を有するポリイソシアネートとの反応により得られる、アルコキシシリル基含有多官能性イソシアネート化合物;および
(C)硬化触媒
を含む。
(A)末端にイソシアネート基を有するウレタンプレポリマー;
(B)1分子内に2個以上のアルコキシシリル基を有するシラン化合物と、末端にイソシアネート基を有するポリイソシアネートとの反応により得られる、アルコキシシリル基含有多官能性イソシアネート化合物;および
(C1)第1の硬化触媒
を含有する主剤と、
(D)ポリオール;および
(C2)第2の硬化触媒
を含有する硬化剤と
を含む、二液型の接着剤組成物とすることもできる。
下式:
下式:
式:
下式:
また、本発明に用いる密着剤中、NCO基/NH基が1.5以上、好ましくは2.0以上、さらに好ましくは2.7以上である。上限は、4.0以下、好ましくは3.7以下、最も好ましくは3.5以下である。NCO基/NH基が1.5を下回ると、密着剤の系中にNCO基が少なくなり、プレポリマーとの反応が少なくなり、密着性を向上できない。NCO基/NH基が4.0を超えると、密着剤中のシリル基の含有量が少なくなり、密着剤の添加量を増やす必要が出てくるが、経済性やその他物性への悪影響がある。
また、重量平均分子量が100~10000程度であるポリオールが好ましく、1000~5000であるポリオールがより好ましい。重量平均分子量がこの範囲であると、後述するポリイソシアネート化合物との反応によって生成するウレタンプレポリマーの物性(例えば、硬度、破断強度、破断伸び)および粘度が良好となる。
上記充填剤としては、例えば、炭酸カルシウム、シリカ、カーボンブラック、クレー、ガラスバルーン、シリカバルーン、セラミックバルーン、プラスチックバルーン、タルク、酸化チタン、生石灰、カオリン、ゼオライト、珪藻土などが挙げられる。充填剤の配合量は、通常、組成物全量中5~50%の範囲で選定され得る。
上記可塑剤としては、例えば、ジイソノニルフタレート、ジイソノニルシクロヘキサン1,2-ジカルボキシレート(DINCH)、ジオクチルフタレート(DOP)、ジブチルフタレート、ジラウリルフタレート、ブチルベンジルフタレート、ジオクチルアジペート、ジイソデシルアジペート、トリオクチルホスフェート、トリス(クロロエチル)ホスフェート、トリス(ジクロロプロピル)ホスフェート、アジピン酸プロピレングリコールポリエステル、アジピン酸ブチレングリコールポリエステル、エポキシステアリン酸アルキル、アルキルベンゼン、エポキシ化大豆油などが挙げられる。可塑剤の配合量は、通常、組成物全量中5~50%の範囲で選定され得る。
その他、老化防止剤、酸化防止剤、発泡剤、紫外線吸収剤、難燃剤、顔料等を、適量加えてもよい。
水酸基価25.0のポリオキシプロピレントリオール3000gに4,4’-ジフェニルメタンジイソシアネート(MDI)350gを加え、窒素雰囲気下に80℃で3時間反応させて得られた、NCO%含有量1.90%および粘度50000mPa・S(20℃)のNCO末端プレポリマーを用いた。ここで、NCO%含有量は、電位差滴定法により、JISK0113に準拠して測定した。
(1)比較用の密着剤
比較のため、従来のシラン化合物として、下式:
本発明の密着剤として、下式:
NCO末端プレポリマーは、接着剤の主成分として用いるプレポリマーと同一であっても異なっていてもよいが、ここでは、水酸基価25.0のポリオキシプロピレントリオール3000gに4,4’-ジフェニルメタンジイソシアネート(MDI)350gを加え、窒素雰囲気下に80℃で3時間反応させて得られた、NCO%含有量1.90%および粘度50000mPa・S(20℃)のNCO末端プレポリマーを用いた。
表1に示す配合で、二液型接着剤組成物の主剤を調製した。
サンスター技研株式会社保有の3 mmtのガラスファイバー強化ポリプロピレン(「PP-GF40」、以下、「PPGF」という)にプラズマ処理を行って、2種類の表面処理レベルのPPGFプレートを得た。
プラズマ処理における表面処理レベルは、JIS K 6768に準拠して濡れ指数(dyne)を測定する。濡れ指数の測定は、23℃にて、相対湿度50%の標準試験室雰囲気下で行う。試験片の上に、段階的に増加する濡れ張力を示す試験用混合液(エチレングリコールモノエチルエーテル、ホルムアミド、メタノールおよび水を段階的に所定の割合で混合した液体)を試験片表面にめん棒を用いて塗り広げる。2秒後に明るいところで液膜を目視観察し、破れが生じているか否かを確認する。破れが生じていれば、表面張力の低い混合液で同様の手順を行い、破れが生じていなければ、表面張力の高い混合液で同様の手順を行う。この操作を繰り返して、濡れ指数を測定する。このようにして測定された濡れ指数が大きいほど親水性が高く、すなわち、表面処理レベルが向上していることを示す。通常、自動車製造において求められる表面処理レベルの仕様は、42 dyne~55 dyneである。したがって、42 dyne未満の濡れ指数のものは表面処理が不十分であり、その条件でも高い接着強度を示す接着剤は優れていると判断される。
各表面処理PPGFプレートを、100 mm×25 mmの大きさに切断して、PPGF試験片1を作製した。100 mm×25 mmの大きさに切断した電着塗装鋼板2との間に、各接着剤を、厚みが3 mmtとなるように塗布し、硬化して、せん断接着強度試験サンプル(図1)を作製した。前記厚みは、硬化前の値で示すが、硬化前後で接着剤の厚みは変化しない。ここで、被着体に電着塗装鋼板を使用したのは、試験片の片側は確実に接着剤と接着させるためである。
このように作製したせん断接着強度試験サンプルを引張強度テスターに搭載し、PPGF試験片1と電着塗装鋼板2とを逆方向に200 mm/分の速度で引っ張り、破壊状態を確認した。破壊状態の評価基準は以下の通りである。
A:接着層の凝集破壊
B:PPGFと接着層との間の部分的界面破壊
C:PPGFと接着層との間の完全界面破壊
せん断接着強度試験サンプルを20℃65%RHにて3日間養生した後に測定したせん断接着強度の値を初期特性とし、上記養生後、さらに100℃400時間の加熱履歴後に測定したせん断接着強度の値(MPa)を耐熱特性として評価した結果を表3に示す。
(1)密着剤を構成するシラン化合物の接着性に対する影響
比較例1は、密着剤を含まない接着剤の結果である。
初期段階で42 dyneの表面処理レベルのPPGFプレートAに対しても、100%の面積で接着層がPPGFから界面破断を起こした。
比較例2~4は、それぞれ、従来の密着剤(密着剤A~C)で調製した接着剤の結果である。初期特性は向上したものの、特に、35 dyneの不十分な表面処理レベルのPPGFプレートBに対して、耐熱特性が悪かった。
実施例1は、密着剤を構成するシラン化合物としてビス[3-(トリメトキシ)シリルプロピル]アミンを用いた、本発明の密着剤Dで調製した接着剤の結果である。
初期特性が向上し、35 dyneの不十分な表面処理レベルのPPGFプレートBに対しても接着層の凝集破壊が観察され、すなわち、PPGFに対する接着強度が優れていた。さらに、耐熱特性も向上し、35 dyneの不十分な表面処理レベルのPPGFプレートBに対しても、接着層はPPGFから完全には界面破断を起こさなかった。
実施例2~4は、それぞれ、密着剤を構成するシラン化合物としてビス[3-(トリメトキシ)シリルプロピル]アミンと、各種多官能性イソシアネートとの反応により得られた、本発明の密着剤E~Gで調製した接着剤の結果である。
実施例1と同様に、初期特性が向上し、35 dyneの不十分な表面処理レベルのPPGFプレートBに対しても接着層の凝集破壊が観察され、すなわち、PPGFに対する接着強度が優れていた。さらに、耐熱特性も向上し、35 dyneの不十分な表面処理レベルのPPGFプレートBに対しても、接着層はPPGFから完全には界面破断を起こさなかった。
実施例5~7は、密着剤として、実施例1と同様に、密着剤を構成するシラン化合物としてビス[3-(トリメトキシ)シリルプロピル]アミンを用いた、本発明の密着剤Dおよび、ポリオールとして、それぞれ、PPGジオールの一部を水添ポリイソプレンジオール、ロジン変性ジオール、ポリブタジエンジオールで置き換えて調製した接着剤の結果である。
ポリオールの少なくとも一部に水添ポリイソプレンジオール、ロジン変性ジオール、ポリブタジエンジオールなどの疎水性ポリオールを用いると、35 dyneの不十分な表面処理レベルのPPGFプレートBに対して、耐熱特性がさらに向上し、接着層の凝集破壊が観察され、すなわち、PPGFに対する接着強度が優れていた。
2 電着塗装鋼板
3 接着層
Claims (5)
- 二液型の接着剤組成物であるウレタン系接着剤であって、
(A)末端にイソシアネート基を有するウレタンプレポリマー;
(B)1分子内に2個以上のアルコキシシリル基を有するシラン化合物と、末端にイソシアネート基を有するポリイソシアネートとの反応により得られる、アルコキシシリル基含有多官能性イソシアネート化合物;および
(C1)第1の硬化触媒
を含有する主剤と、
(D)ポリオール;および
(C2)第2の硬化触媒
を含有する硬化剤と
を含み、
前記1分子内に2個以上のアルコキシシリル基を有するシラン化合物が、下式:
前記末端にイソシアネート基を有するポリイソシアネートが、下式:
前記(D)ポリオールが、水添ポリイソプレンポリオール、ロジン変性ポリオールおよびポリブタジエンポリオールからなる群から選択される疎水性ポリオールである、
ウレタン系接着剤。 - 前記末端にイソシアネート基を有するウレタンプレポリマーが、ポリオールとイソシアネートとの反応によって形成されたプレポリマーである、請求項1に記載のウレタン系接着剤。
- 少なくも一部の前記ポリオールがポリブタジエンポリオールである、請求項2に記載のウレタン系接着剤。
- 充填剤または可塑剤をさらに含む、請求項1~4いずれかに記載のウレタン系接着剤。
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