JPH0359946B2 - - Google Patents
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- Publication number
- JPH0359946B2 JPH0359946B2 JP59127557A JP12755784A JPH0359946B2 JP H0359946 B2 JPH0359946 B2 JP H0359946B2 JP 59127557 A JP59127557 A JP 59127557A JP 12755784 A JP12755784 A JP 12755784A JP H0359946 B2 JPH0359946 B2 JP H0359946B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylate
- parts
- meth
- adhesive
- 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
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- 239000000853 adhesive Substances 0.000 claims description 41
- 230000001070 adhesive effect Effects 0.000 claims description 41
- 239000004925 Acrylic resin Substances 0.000 claims description 22
- 229920000178 Acrylic resin Polymers 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- -1 silane compound Chemical class 0.000 claims description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- KOXQZISAMDUXGH-UHFFFAOYSA-N methyl-tris(oxiran-2-ylmethoxy)silane Chemical compound C1OC1CO[Si](OCC1OC1)(C)OCC1CO1 KOXQZISAMDUXGH-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims 1
- 239000011521 glass Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- MFSBYHNKSXHXII-UHFFFAOYSA-N ethenyl 2-sulfanylacetate Chemical compound SCC(=O)OC=C MFSBYHNKSXHXII-UHFFFAOYSA-N 0.000 description 1
- ZEYMDLYHRCTNEE-UHFFFAOYSA-N ethenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC=C ZEYMDLYHRCTNEE-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polyamides (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
〔発明の目的〕
（産業上の利用分野）
本発明は粘着剤組成物に関する。さらに詳しく
は、プラスチツクフイルムもしくはシートのよう
な基体シートの片面に塗布し、この粘着シートを
窓ガラス面に貼着することにより、事故あるいは
災害の際、破壊された窓ガラスの破片の飛散を防
止するために好適な粘着剤組成物に関する。
（従来の技術）
従来、ガラスの飛散を防止するために、粘着シ
ートをガラス面に粘着することが知られている。
実公昭58−8757号公報には、シート基材の片面に
シランカツプリング剤と粘着剤との混和物の薄層
を塗布してなるガラス用粘着シートが開示されて
いる。窓ガラス等耐侯用の要求される用途では、
天然ゴム系もしくは合成ゴム系の粘着剤よりアク
リル系樹脂からなる粘着剤が好ましいが、一般的
なアクリル系樹脂の粘着剤は、なお、耐湿性が不
十分であり、特に、温水プールや温泉の窓ガラス
のような高温高湿の環境下で使用される場合に
は、長期間の使用に耐えられず、粘着シートが剥
離してしまつたり、ガラス面と粘着剤層間の接着
強度が極めて小さくなり、ガラスの飛散防止の効
果がなくなつてしまうという欠点があつた。
（発明が解決しようとする問題点）
本発明は、従来の粘着剤が高湿環境下に置かれ
ると、粘着剤層と被着体との界面に浸入してくる
水分により経時に亘つて粘着剤が劣化し、本来の
粘着力が維持できないという問題点を解決するも
のである。
〔発明の構成〕
（問題点を解決するための手段）
本発明者等はこのような問題点を解決するため
鋭意検討の結果、本発明に到達したものである。
すなわち本発明は、
(イ) （メタ）アクリル酸アルキルエステル99〜50
重量％
(ロ) 水酸基含有アクリレート１〜20重量％
(ハ) カルボン酸ビニルモノマー０〜30重量％
を成分とするアクリル系樹脂(A)100重量部および
エポキシ基含有シラン化物(B)0.001〜1.0重量部を
含有してなる粘着剤組成物である。
本発明におけるアクリル系樹脂(A)は、（メタ）
アクリル酸アルキルエステル(イ)、水酸基含有アク
リレート(ロ)および必要に応じてカルボン酸ビニル
モノマー(ハ)からなるものである。（メタ）アクリ
ル酸アルキルエステル(イ)としては、（メタ）アク
リル酸エチル、（メタ）アクリル酸ｎ−ブチル、
（メタ）アクリル酸イソブチル、（メタ）アクリル
酸ラウリル、（メタ）アクリル酸２−エチルヘキ
シルなどが挙げられ、水酸基含有アクリレート(ロ)
としては、ヒドロキシメチル（メタ）アクリレー
ト、２−ヒドロキシエチル（メタ）アクリレー
ト、３−ヒドロキシプロピル（メタ）アクリレー
ト、Ｎ−メチロールアクリルアミドなどが挙げら
れ、カルボン酸ビニルモノマー(ハ)としては、ギ酸
ビニル、酢酸ビニル、プロピオン酸ビニル、高級
脂肪酸ビニル、アセト酢酸ビニル、クロル酢酸ビ
ニル、チオグリコール酸ビニル、三フツ素酢酸ビ
ニル、安息香酸ビニルなどが挙げられる。
（メタ）アクリル酸アルキルエステル(イ)はアク
リル系樹脂(A)中の全モノマー成分に対して99〜50
重量％が使用され、水酸基含有アクリレート(ロ)は
１〜20重量％が使用される。(ロ)成分が１重量％よ
り少ないと、特に、高湿時におけるガラス面への
接着性が低下し、また、20重量％より多く使用す
ると、アクリル系樹脂(A)溶液の粘性が上昇するの
で塗工性に支障がある他、粘着力も低下する傾向
があるので好ましくない。
アクリル系樹脂(A)は(イ)(ロ)および(ハ)のモノマー
成
分を酢酸エチル、トルエンなどの有機溶媒中にお
いて、ベンゾイルパーオキサイド、アゾビスイソ
ブチロニトリルなどのラジカル重合開始剤の存在
下で70〜90℃に加熱し、５〜８時間反応させるこ
とにより得ることができる。
本発明におけるエポキシ基含有シラン化合物(B)
としてはメチルトリ（グリシジルオキシ）シラ
ン、３−グリシドキシプロピルトリメトキシシラ
ン、３−グリシドキシトリエトキシシラン、２−
（３，４−エポキシシクロヘキシル）−エチルトリ
メトキシシランなどがある。
上記シラン化合物(B)はアクリル系樹脂(A)の固型
分100重量部に対して、0.001〜1.0重量部、好ま
しくは0.005〜0.5重量部が使用され、上記数値が
0.001より小さくなるとガラス面に対する接着力
が特に高温高湿の環境下において低下し、逆に
1.0重量部より大きいと架橋の密度が大きくなつ
て粘着性が低下する結果、ガラス面への初期接着
力が低下し、特にガラスの飛散防止の効果がなく
なる。
本発明における粘着剤組成物はアクリル系樹脂
(A)の有機溶媒溶液にエポキシ基含有シラン化合物
(B)を配合することにより得ることができる。アク
リル系樹脂(A)中の水酸基とシラン化合物(B)中のエ
ポキシ基は常温ではほとんど反応が進まないの
で、両者を配合して保存することもできるが、基
体シート上に塗布する直前に配合しても良い。ま
た、基体シート上に塗布された粘着剤組成物は、
溶剤を除去するため、80〜100℃で30秒間〜５分
間程度加熱されるので、この際、水酸基とエポキ
シ基は反応し架橋構造が形成されるものと考えら
れる。
本発明に係わる粘着シートは、厚さ20〜100μ
程度の基体シートの片面に粘着剤組成物を乾燥重
量として20〜50ｇ／m2積層したものである。基体
シートとしてはプラスチツクフイルムもしくはシ
ート、紙、金属箔あるいはこれらを材料とする複
合シートであるが、機械的強度、透明性などの点
から、ポリエステル、ポリカーボネート、ポリア
ミド、ポリスチレン、ポリ塩化ビニルなどのプラ
スチツクフイルムが好ましい。また、基体シート
には所望の印刷を施すことにより窓ガラスに貼着
した際に装飾効果を与えることができる。
本発明に係わる粘着シートのガラスへの好まし
い貼着方法としては、ガラス面を水で濡らした
後、粘着シートを重ね、ついで粘着シートの上か
らスキージーなどで水を水泡とともに押し出すこ
とにより粘着シートとガラス面を密着させる。
（作 用）
粘着剤層として使用されるアクリル系樹脂(A)に
含まれる水酸基は、ガラス表面に吸着されている
水分子と水素結合を介してガラスに強固に接着す
る。一方、シラン化合物(B)もガラス表面に対して
親和性が良く接着力が向上する。
また、アクリル系樹脂(A)中の水酸基は、シラン
化合物(B)中のエポキシ基と反応し架橋構造を形成
し、粘着剤の凝集力に寄与するので長期に亘つて
安定な接着力が保持される。
（実施例）
実施例 １
モノマー成分としてブチルアクリレート44部
（以下「部」は「重量部」を示す。）イソブチルア
クリレート44部、酢酸ビニル５部、２−ヒドロキ
シエチルメタアクリレート７部、重合開始剤とし
てベンゾイルパーオキサイド0.01部を、酢酸エチ
ルに溶解し酢酸エチルの還流温度で６時間反応さ
せアクリル系樹脂を得た。このアクリル系樹脂
100部を含む37％（以下「％」は「重量％」を示
す。）酢酸エチル溶液にシラン化合物としてメチ
ルトリ（グリシジルオキシ）シランを0.1部添加
し十分に混合した。この混合物を剥離紙上に塗工
し、100℃で２分間乾燥させた。乾燥後の粘着剤
層の厚さは27ｇ／m2であつた。この粘着剤層を厚
さ50μのポリエステルフイルムに転写し粘着シー
トを得た。
比較例 １
実施例１で得られたアクリル系樹脂にシラン化
合物を添加しないで粘着剤として使用した他は実
施例１と同操作にて粘着シートを得た。
実施例 ２
実施例１においてシラン化合物として、３−グ
リシドキシプロピルトリメトキシシランを0.01重
量部使用した他は実施例１と同操作にて粘着シー
トを得た。
比較例 ２
モノマー成分として２−エチルヘキシルアクリ
レート75部、酢酸ビニル23部、アクリル酸２部を
使用して得たアクリル系樹脂の33％酢酸エチル溶
液を使用した他は実施例２と同操作にて粘着シー
トを得た。
実施例 ３
実施例１においてモノマー成分としてブチルア
クリレート44部、イソブチルアクリレート44部、
酢酸ビニル５部、２−ヒドロキシエチルアクリレ
ート５部を使用してアクリル系樹脂を製造した他
は実施例１と同操作にて粘着シートを得た。
比較例 ３
実施例１においてモノマー成分としてブチルア
クリレート47部、イソブチルアクリレート47.5
部、酢酸ビニル５部、２−ヒドロキシエチルメタ
アクリレート0.5部を使用して得たアクリル系樹
脂の45％酢酸エチル溶液を使用した他は実施例１
と同操作にて粘着シートを得た。
比較例 ４
実施例１においてモノマー成分としてブチルア
クリレート36部、イソブチルアクリレート36部、
酢酸ビニル５部、２−ヒドロキシエチルメタアク
リレート23部を使用して得たアクリル系樹脂の15
％酢酸エチル溶液を使用した他は実施例１と同操
作にて粘着シートを得た。
実施例および比較例で得られた粘着シートを水
で濡らしたガラス表面に貼着し、ウエザーメータ
ーで所定時間照射した後、23℃、100％相対湿度
の雰囲気中に24時間放置後、角度180℃、剥離速
度300mm／minで剥離試験を行つた。
結果を表１に示す。表１中数字はｇ／25mmで表
した剥離強度である。
表１から明らかなように本発明による粘着シー
トは、耐候性試験による経時の接着強度の安定性
に優れているのに対して、シラン化合物を使用し
ない比較例１、エポキシ基と反応する官能基がカ
ルボキシル基であるアクリル系樹脂を使用した比
較例２、アクリル系樹脂に水酸基を含むが本発明
の範囲内の使用ではない比較例３および比較例４
では初期接着力も低く、耐候性試験に供した後の
接着強度も著しく低下したものしか得られない。
[Object of the Invention] (Industrial Application Field) The present invention relates to an adhesive composition. More specifically, by applying this adhesive sheet to one side of a base sheet such as a plastic film or sheet, and attaching this adhesive sheet to the window glass surface, it prevents broken window glass fragments from scattering in the event of an accident or disaster. This invention relates to a pressure-sensitive adhesive composition suitable for the present invention. (Prior Art) Conventionally, it has been known to adhere an adhesive sheet to a glass surface in order to prevent glass from scattering.
Japanese Utility Model Publication No. 58-8757 discloses a pressure-sensitive adhesive sheet for glass comprising a thin layer of a mixture of a silane coupling agent and a pressure-sensitive adhesive coated on one side of a sheet base material. For applications requiring weather resistance such as window glass,
Adhesives made of acrylic resin are preferable to natural rubber-based or synthetic rubber-based adhesives, but common acrylic resin adhesives still have insufficient moisture resistance, especially when used in hot pools or hot springs. When used in high-temperature, high-humidity environments such as window glass, it cannot withstand long-term use, and the adhesive sheet may peel off, or the adhesive strength between the glass surface and the adhesive layer is extremely low. This resulted in a disadvantage that the effect of preventing the glass from scattering was lost. (Problems to be Solved by the Invention) The present invention solves the problem that when a conventional adhesive is placed in a high-humidity environment, it becomes sticky over time due to moisture that enters the interface between the adhesive layer and the adherend. This solves the problem that the adhesive deteriorates and the original adhesive strength cannot be maintained. [Structure of the Invention] (Means for Solving the Problems) The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides (a) (meth)acrylic acid alkyl ester 99-50
Weight% (b) 1-20% by weight of hydroxyl group-containing acrylate (c) 100 parts by weight of acrylic resin (A) containing 0-30% by weight of vinyl carboxylate monomer and 0.001-1.0 parts by weight of epoxy group-containing silanized product (B) This is an adhesive composition containing parts by weight. The acrylic resin (A) in the present invention is (meth)
It consists of an acrylic acid alkyl ester (a), a hydroxyl group-containing acrylate (b), and, if necessary, a carboxylic acid vinyl monomer (c). As the (meth)acrylic acid alkyl ester (a), ethyl (meth)acrylate, n-butyl (meth)acrylate,
Examples include isobutyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and hydroxyl group-containing acrylate (b).
Examples of the carboxylic acid vinyl monomer (c) include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and N-methylol acrylamide. Examples of the carboxylic acid vinyl monomer (c) include vinyl formate, Examples include vinyl acetate, vinyl propionate, vinyl higher fatty acids, vinyl acetoacetate, vinyl chloroacetate, vinyl thioglycolate, vinyl trifluoride acetate, and vinyl benzoate. (Meth)acrylic acid alkyl ester (A) is 99 to 50% of the total monomer components in the acrylic resin (A).
% by weight is used, and the hydroxyl group-containing acrylate (b) is used in an amount of 1 to 20% by weight. If the (b) component is less than 1% by weight, the adhesion to glass surfaces will decrease, especially in high humidity conditions, and if it is used more than 20% by weight, the viscosity of the acrylic resin (A) solution will increase. Therefore, it is not preferable because it not only impairs coating properties but also tends to reduce adhesive strength. Acrylic resin (A) is prepared by adding the monomer components (a), (b) and (c) in an organic solvent such as ethyl acetate or toluene in the presence of a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile. It can be obtained by heating at 70 to 90°C and reacting for 5 to 8 hours. Epoxy group-containing silane compound (B) in the present invention
Examples include methyltri(glycidyloxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxytriethoxysilane, 2-
Examples include (3,4-epoxycyclohexyl)-ethyltrimethoxysilane. The above silane compound (B) is used in an amount of 0.001 to 1.0 parts by weight, preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the solid content of the acrylic resin (A), and the above numerical value is
If it is smaller than 0.001, the adhesive force to the glass surface will decrease, especially in high temperature and high humidity environments, and vice versa.
If it is more than 1.0 part by weight, the density of crosslinking increases and the adhesiveness decreases, resulting in a decrease in the initial adhesion to the glass surface, and in particular, the effect of preventing glass from scattering is lost. The adhesive composition in the present invention is an acrylic resin.
An epoxy group-containing silane compound is added to the organic solvent solution of (A).
It can be obtained by blending (B). The hydroxyl groups in the acrylic resin (A) and the epoxy groups in the silane compound (B) hardly react at room temperature, so they can be combined and stored, but it is best to combine them immediately before coating on the base sheet. You may do so. In addition, the adhesive composition applied on the base sheet is
In order to remove the solvent, it is heated at 80 to 100°C for about 30 seconds to 5 minutes, so it is thought that at this time, the hydroxyl groups and epoxy groups react to form a crosslinked structure. The adhesive sheet according to the present invention has a thickness of 20 to 100 μm.
A pressure-sensitive adhesive composition is laminated on one side of a base sheet of about 100 mL to 20 to 50 g/m 2 in terms of dry weight. The base sheet can be a plastic film or sheet, paper, metal foil, or a composite sheet made of these materials, but from the viewpoint of mechanical strength and transparency, plastics such as polyester, polycarbonate, polyamide, polystyrene, and polyvinyl chloride are preferable. Film is preferred. Moreover, by applying desired printing to the base sheet, it is possible to give a decorative effect when it is attached to a window glass. A preferred method for attaching the adhesive sheet to glass according to the present invention is to wet the glass surface with water, overlap the adhesive sheets, and then use a squeegee or the like to push out the water along with the water bubbles from the top of the adhesive sheet. Close the glass surface. (Function) The hydroxyl groups contained in the acrylic resin (A) used as the adhesive layer firmly adhere to the glass through hydrogen bonds with water molecules adsorbed on the glass surface. On the other hand, the silane compound (B) also has good affinity for the glass surface and improves adhesive strength. In addition, the hydroxyl groups in the acrylic resin (A) react with the epoxy groups in the silane compound (B) to form a crosslinked structure and contribute to the cohesive force of the adhesive, ensuring stable adhesive strength over a long period of time. be done. (Example) Example 1 Monomer components: 44 parts of butyl acrylate (hereinafter "parts" indicate "parts by weight"), 44 parts of isobutyl acrylate, 5 parts of vinyl acetate, 7 parts of 2-hydroxyethyl methacrylate, polymerization initiator 0.01 part of benzoyl peroxide was dissolved in ethyl acetate and reacted for 6 hours at the reflux temperature of ethyl acetate to obtain an acrylic resin. This acrylic resin
0.1 part of methyltri(glycidyloxy)silane as a silane compound was added to a 37% (hereinafter "%" refers to "wt%") ethyl acetate solution containing 100 parts and thoroughly mixed. This mixture was coated onto release paper and dried at 100°C for 2 minutes. The thickness of the adhesive layer after drying was 27 g/m 2 . This adhesive layer was transferred to a polyester film with a thickness of 50 μm to obtain an adhesive sheet. Comparative Example 1 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that the acrylic resin obtained in Example 1 was used as a pressure-sensitive adhesive without adding a silane compound. Example 2 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that 0.01 part by weight of 3-glycidoxypropyltrimethoxysilane was used as the silane compound. Comparative Example 2 The same procedure as in Example 2 was used except that a 33% ethyl acetate solution of an acrylic resin obtained using 75 parts of 2-ethylhexyl acrylate, 23 parts of vinyl acetate, and 2 parts of acrylic acid as monomer components was used. An adhesive sheet was obtained. Example 3 In Example 1, 44 parts of butyl acrylate, 44 parts of isobutyl acrylate,
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1, except that 5 parts of vinyl acetate and 5 parts of 2-hydroxyethyl acrylate were used to produce an acrylic resin. Comparative Example 3 In Example 1, 47 parts of butyl acrylate and 47.5 parts of isobutyl acrylate were used as monomer components.
Example 1 except that a 45% ethyl acetate solution of an acrylic resin obtained using 1 part, 5 parts of vinyl acetate, and 0.5 parts of 2-hydroxyethyl methacrylate was used.
An adhesive sheet was obtained in the same manner as above. Comparative Example 4 In Example 1, 36 parts of butyl acrylate, 36 parts of isobutyl acrylate,
15 of acrylic resin obtained using 5 parts of vinyl acetate and 23 parts of 2-hydroxyethyl methacrylate.
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that a % ethyl acetate solution was used. The adhesive sheets obtained in Examples and Comparative Examples were attached to a glass surface wetted with water, irradiated with a weather meter for a predetermined period of time, and then left in an atmosphere of 23°C and 100% relative humidity for 24 hours. A peel test was conducted at a temperature of 300 mm/min at a peel rate of 300 mm/min. The results are shown in Table 1. The numbers in Table 1 are peel strengths expressed in g/25mm. As is clear from Table 1, the pressure-sensitive adhesive sheet according to the present invention has excellent adhesive strength stability over time in weather resistance tests, whereas Comparative Example 1, which does not use a silane compound, has functional groups that react with epoxy groups. Comparative Example 2 using an acrylic resin in which is a carboxyl group, Comparative Example 3 and Comparative Example 4 in which the acrylic resin contains a hydroxyl group but is not used within the scope of the present invention
In this case, the initial adhesive strength is low, and the adhesive strength after being subjected to a weather resistance test is also significantly reduced.
【表】
実施例および比較例で得られた粘着シートを
JIS A575−1982の5.6.1に規定するＡ法で試験し、
粘着シートのガラス飛散防止性能を調べた。
結果を表２に示した。表２において試験片の飛
散したガラスの大きな破片を10個選び出し、その
総重量が80ｇ以下であり、かつ落下した１片の重
量が55ｇ以下であるものを「〇」で示し、それ以
外のものを「×」で示した。[Table] Adhesive sheets obtained in Examples and Comparative Examples
Tested according to method A specified in 5.6.1 of JIS A575-1982,
The glass shatter prevention performance of the adhesive sheet was investigated. The results are shown in Table 2. In Table 2, select 10 large pieces of glass that were scattered from the test piece, and mark those whose total weight is 80 g or less and the weight of each piece that fell is 55 g or less, and indicate with "O", and other pieces are indicated with an "x".
【表】
表２から明らかなように、本発明の粘着シー
ト、比較例１および比較例２の粘着シートは飛散
防止試験に合格したが比較例４の粘着シートでは
ガラス飛散防止の効果が認められず、ガラス飛散
防止のためには接着強度は少なくとも300ｇ／25
mmが必要であることが判つた。
次に、実施例１、比較例１および比較例２で得
られた粘着シートをそれぞれガラス板に貼着して
試料とし、90℃のオーブン中に所定時間保存して
促進試験をした後、23℃、相対湿度100％の環境
下で24時間放置し上記と同操作にて剥離強度
（ｇ／25mm）を測定した。
結果を表３に示した。[Table] As is clear from Table 2, the adhesive sheet of the present invention, the adhesive sheets of Comparative Examples 1 and 2 passed the shatter prevention test, but the adhesive sheet of Comparative Example 4 was not effective in preventing glass from scattering. The adhesive strength must be at least 300g/25 to prevent glass from shattering.
It turned out that mm was necessary. Next, the pressure-sensitive adhesive sheets obtained in Example 1, Comparative Example 1, and Comparative Example 2 were each attached to a glass plate as a sample, and after being stored in an oven at 90°C for a predetermined period of time for an accelerated test, 23 ℃ and 100% relative humidity for 24 hours, and the peel strength (g/25 mm) was measured in the same manner as above. The results are shown in Table 3.
本発明により得られる粘着剤組成物は、高温高
湿の環境下に置かれても、ほとんど接着力の低下
がなく、ガラスの飛散防止用の粘着シートとして
通常使用される範囲における最も苛酷な条件にお
いても長期間飛散防止の効果を保持することがで
きる。
The adhesive composition obtained by the present invention shows almost no decrease in adhesive strength even when placed in a high temperature and high humidity environment, and can be used under the harshest conditions in the range normally used as an adhesive sheet for preventing glass from scattering. The effect of preventing scattering can be maintained for a long period of time.
Claims (1)
〜50重量％ (ロ) 水酸基含有アクリレート１〜20重量％ (ハ) カルボン酸ビニルモノマー０〜30重量％ を成分とするアクリル系樹脂(A)100重量部および
エポキシ基含有シラン化合物(B)0.001〜1.0重量部
を含有してなる粘着剤組成物。 ２ 水酸基含有アクリレート(ロ)がヒドロキシメチ
ル（メタ）アクリレート、２−ヒドロキシルエチ
ル（メタ）アクリレート、３−ヒドロキシプロピ
ル（メタ）アクリレートから選ばれる１種もしく
は２種以上である特許請求の範囲第１項記載の粘
着剤組成物。 ３ エポキシ基含有シラン化合物がメチルトリ
（グリシジルオキシ）シランである特許請求の範
囲第１項もしくは２項記載の粘着剤組成物。 ４ エポキシ基含有シラン化合物が３−グリシド
キシプロピルトリメトキシシラン、３−グリシド
キシプロピルトリエトキシシラン、２−（３，４
−エポキシシクロヘキシル）−エチルトリメトキ
シシランから選ばれる１種もしくは２種以上であ
る特許請求の範囲第１項記載もしくは２項記載の
粘着剤組成物。[Claims] 1 (a) (meth)acrylic acid alkyl ester 99
~50% by weight (b) 1 to 20% by weight of hydroxyl group-containing acrylate (c) 100 parts by weight of acrylic resin (A) containing 0 to 30% by weight of vinyl carboxylate monomer and 0.001 parts by weight of epoxy group-containing silane compound (B) A pressure-sensitive adhesive composition containing ~1.0 part by weight. 2. Claim 1, wherein the hydroxyl group-containing acrylate (b) is one or more selected from hydroxymethyl (meth)acrylate, 2-hydroxylethyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. The adhesive composition described. 3. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the epoxy group-containing silane compound is methyltri(glycidyloxy)silane. 4 The epoxy group-containing silane compound is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4
The pressure-sensitive adhesive composition according to claim 1 or 2, which is one or more selected from the group consisting of -epoxycyclohexyl)-ethyltrimethoxysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12755784A JPS617369A (en) | 1984-06-22 | 1984-06-22 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12755784A JPS617369A (en) | 1984-06-22 | 1984-06-22 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS617369A JPS617369A (en) | 1986-01-14 |
| JPH0359946B2 true JPH0359946B2 (en) | 1991-09-12 |
Family
ID=14962963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12755784A Granted JPS617369A (en) | 1984-06-22 | 1984-06-22 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS617369A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3911945A1 (en) * | 1989-04-12 | 1990-10-25 | Basf Ag | AQUEOUS RESIN DISPERSION |
| JP3123378B2 (en) * | 1994-12-15 | 2001-01-09 | ジェイエスアール株式会社 | Water-based pressure-sensitive adhesive |
| JP2014040498A (en) * | 2012-08-21 | 2014-03-06 | Panac Co Ltd | Self-adhesive film and method for manufacturing shatterproof glass using the same |
| JP7078465B2 (en) * | 2018-06-18 | 2022-05-31 | リンテック株式会社 | Anti-scattering film |
| WO2021053430A1 (en) * | 2019-09-20 | 2021-03-25 | 3M Innovative Properties Company | High temperature sterilizable adhesive articles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52121644A (en) * | 1976-04-06 | 1977-10-13 | Nagoya Yukagaku Kogyo Kk | Adhesive composition and adhesive tape |
| JPS5778443A (en) * | 1980-10-31 | 1982-05-17 | Nitto Electric Ind Co Ltd | Primer composition |
-
1984
- 1984-06-22 JP JP12755784A patent/JPS617369A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52121644A (en) * | 1976-04-06 | 1977-10-13 | Nagoya Yukagaku Kogyo Kk | Adhesive composition and adhesive tape |
| JPS5778443A (en) * | 1980-10-31 | 1982-05-17 | Nitto Electric Ind Co Ltd | Primer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS617369A (en) | 1986-01-14 |
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