JPS6124426B2 - - Google Patents
Info
- Publication number
- JPS6124426B2 JPS6124426B2 JP54089710A JP8971079A JPS6124426B2 JP S6124426 B2 JPS6124426 B2 JP S6124426B2 JP 54089710 A JP54089710 A JP 54089710A JP 8971079 A JP8971079 A JP 8971079A JP S6124426 B2 JPS6124426 B2 JP S6124426B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- adhesive
- weight
- film
- group
- 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
- 239000000853 adhesive Substances 0.000 claims description 33
- 230000001070 adhesive effect Effects 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- -1 butyl urea Chemical compound 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- NFTVTXIQFYRSHF-UHFFFAOYSA-N 1-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)C(C)OC(=O)C=C NFTVTXIQFYRSHF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- UJURFSDRMQAYSU-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC2=C(C=CC=C3)C3=C21 Chemical compound N=C=O.N=C=O.C1=CC=CC2=C(C=CC=C3)C3=C21 UJURFSDRMQAYSU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 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
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical compound CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は表面保護フイルム用粘着剤及び該粘着
剤を塗布してなる表面保護用粘着フイルムに関す
るものである。
表面保護用粘着フイルムは、ステンレス板、ア
ルミニユウム板の如き金属板、塗装鋼板、樹脂板
ガラス板などの板状物品の運搬時或いは加工時の
表面保護のために用いられている。
該フイルムの粘着成分として用いられている粘
着剤は、アクリル酸アルキルエステルと共重合性
モノマーとの共重合物を架橋剤で架橋したもので
あつて、このものは耐候性及び透明性に優れてい
るので最適であるが、前記の表面保護を目的とす
るには更にいくつかの性能を具備させる必要があ
る。例えば板状物品に適度な接着力を有し、経日
による接着力の上昇が少なく、しかも物品面に粘
着剤の残留や粘着剤による汚れがないことであ
る。
しかして共重合性モノマーとしてカルボキシル
基を有するアクリル酸などを用いると、経日の接
着力は剥離時にフイルムが破断される程上昇した
り、粘着剤が板状物品面に残留したりするなどし
て、性能の向上は得られ難く、またアミノ基を有
するＮ・Ｎ−ジメチルアミノエチルアクリレート
など或いはアミド基を有するアクリル酸アミドな
どは、共重合物の架橋方法に制約を受けるため
に、各れも汎用されるに至つていないのが現状で
ある。
またこれまでかかる欠点の比較的少ないヒドロ
キシル基を有するアクリル酸−２−ヒドロキシエ
チルエステルなどが、表面保護フイルム用粘着剤
に使用されてきたが、末だ得られる粘着剤のゴム
弾性の大きさに基因する板金加工後のフイルムの
浮きが充分に解決できず、しかも粘着剤溶液の可
使時間が短くて塗設作業性に劣るという問題があ
り、その改善が要望されている。
本発明者達はかかる従来技術の種々の欠点を解
決する新規な表面保護フイルム用粘着剤について
種々研究の結果、特定の官能基を有する二種類の
共重合性モノマーと架橋剤としてメラミン、尿素
樹脂及び分子内に２個以上のNCO基を有する化
合物の群から選ばれた一種以上とを用いることに
よつて上記の種々の欠点を解決できることを見い
出し、本発明に至つたものである。
即ち本発明は、（メタ）アクリル酸アルキルエ
ステルモノマー（アルキル基のＣ数１〜８個）
100重量部に対して下記(i)及び(ii)成分を共重合さ
せると共に(iii)で架橋してなることを特徴とする表
面保護フイルム用粘着剤を提供するものである。
(i) ヒドロキシル基含有共重合性モノマー0.1〜
５重量部。
(ii) カルボキシル基含有共重合性モノマー0.1〜
10重量部。
(iii) メラミン、尿素樹脂及び分子内に２個以上の
NCO基を有する化合物の群から選ばれた一種
以上0.5〜10重量部。
上記（メタ）アクリル酸アルキルエステルモノ
マーは、表面保護フイルム用粘着剤に所望の粘着
性、凝集性及び可撓性などを付与する成分であ
り、例えばアクリル酸ブチル、アクリル酸２−エ
チルヘキシル、メタクリル酸メチル、メタクリル
酸エチルなどが好適に使用されるが、他の（メ
タ）アクリル酸アルキルエステルでアルキル基の
Ｃ数が８個以下のものを使用してもよいし、これ
らを併用することもできる。
なお上記（メタ）アクリル酸アルキルエステル
モノマーと共に該モノマーと共重合可能なビニル
系モノマー例えばスチレン、酢酸ビニル、アクリ
ロニトリル、メタクリロニトリルなどを適量使用
することができる。
(i)成分は、ヒドロキシル基により板状物品面に
対するぬれ特性を良好にし、且つ物品面へ貼り付
け後の接着力の上昇を抑制するのに有効なモノマ
ーであり、２−ヒドロキシエチルアクリレート、
２−ヒドロキシエチルメタクリレート、２−ヒド
ロキシプロピルアクリレート、２−ヒドロキシプ
ロピルメタクリレートなどが含まれる。前記（メ
タ）アクリル酸アルキルエステルモノマー100重
量部に対してヒドロキシル基含有モノマーが0.1
重量部以下ではぬれ特性の向上が得られず、５重
量部以下では粘着剤組成物の可使時間が短く塗布
作業が悪いので好ましくないものである。
(ii)成分は、カルボキシル基により板状物品面へ
の接着性を付与すると共に前記(i)成分のヒドロキ
シル基含有モノマーと次に述べる(iii)成分の架橋剤
の架橋作用の助けをかりて、架橋を行う反応点と
して作用するモノマーであり、アクリル酸、メタ
クリル酸、無水マレイン酸、イタコン酸などが含
まれる。カルボキシル基含有モノマーが0.1重量
部以下では接着性が得られず、10重量部以上では
架橋に長時間要すると共に貼り付け後の接着力の
上昇が大きいので好ましくないものである。
(iii)成分は、前記ヒドロキシル基含有モノマーと
カルボキシル基含有モノマーとを架橋する成分で
あり、ｎ−ブチルエーテル化メラミン、iso−ブ
チルエーテル化メラミン、メチルエーテル化メラ
ミンの如きメラミン、ｎ−ブタノールエーテル尿
素、ブチル尿素の如き尿素樹脂、及びトリレンジ
イソシアネート、ジフエニルメタンジイソシアネ
ート、ｍ−フエニレンジイソシアネート、ビフエ
ニレンジイソシアネート、テトラメチレンジイソ
シアネート、ヘキサメチレンジイソシアネート、
キシリレンジイソシアネートの如き分子内に２個
以上のNCO基（イソシアネート基）を有する化
合物が含くまれる。0.5重量部以下では架橋効果
が少なく、15重量部以上では架橋が過度に起り、
接着力が低下するので好ましくないものである。
本発明の表面保護フイルム用粘着剤は、上記の
４成分を必須成分とするものであるが、紫外線吸
収剤、防錆剤、架橋促進剤、着色剤などの配合剤
を添加してもよいことは勿論である。
このように構成された粘着剤は、厚さ約0.01〜
0.2mmのプラスチツクフイルム又は紙などの表面
に、0.05〜0.08mmの厚さを有するように塗布さ
れ、使用に供される。
次の本発明の実施例を示す。文中部とあるのは
重量部を示す。
実施例 １
アクリル酸エチル：アクリル酸２−エチルヘキ
シル：２−ヒドロキシエチルアクリレート：アク
リル酸＝60：40：１：１（重量比）の割合いで共
重合してなる共重合体溶液（固形分30％）を得
る。
該共重合体溶液の固形分100部に対してトリレ
ンジイソシアネート３部及び架橋促進剤としての
オクチルチンジラウレート0.5部を添加混合して
本発明の表面保護フイルム用粘着剤を得る。
次に該粘着剤の特性を評価するために、該粘着
剤を片面にコロナ放電処理を施してなるポリエチ
レンフイルム（厚さ0.03mm）の処理面に、乾燥後
の厚みが0.05mmとなるように塗布し、90℃で２分
間乾燥して表面保護用粘着フイルムを得る。該フ
イルムの試験結果は第１表に示す。
実施例 ２〜４
実施例１において、トリレンジイソシアネート
３部に代えて下記(A)、(B)及び(C)の架橋剤を加えた
ほかは実施例１と同様に表面保護用粘着フイルム
を得る。該フイルムの試験結果は第１表に示す。
(A) iso−ブチルエーテル化メラミン５部（実施
例２）
(B) iso−ブチルエーテル化メラミン５部とトリ
レンジイソシアネート３部（実施例３）
(C) ｎ−ブタノールエーテル尿素５部（実施例
４）
実施例 ５
アクリル酸ブチル：アクリロニトリル：２−ヒ
ドロキシエチルアクリレート：アクリル酸＝80：
20：１：１（重量比）の割合いで共重合してなる
共重合体溶液（固形分25％）を得る。
以下実施例１と同様の操作にて表面保護用粘着
フイルムを得る。該フイルムの試験結果は第１表
に示す。
比較例
下記(a)、(b)、(c)及び(d)に示す割合いからなる共
重合体溶液（固形分30％）を作り、以下実施例１
と同様にトリレンジイソシアネート３部及びオク
チルチンジラウレート0.5部を添加混合して、実
施例１のポリエチレンフイルムに塗布乾燥して表
面保護用粘着フイルムを得る。該フイルムの試験
結果は第１表に示す。
(a) アクリル酸エチル 60部
アクリル酸２−エチルヘキシル 40部
アクリル酸 １部
(b) アクリル酸エチル 60部
アクリル酸２−エチルヘキシル 40部
２−ヒドロキシエチルアクリレート １部
(c) アクリル酸ブチル 80部
アクリロニトリル 20部
アクリル酸 １部
(d) アクリル酸ブチル 80部
アクリロニトリル 20部
２−ヒドロキシエチルアクリレート １部
The present invention relates to a pressure-sensitive adhesive for surface protection films and a pressure-sensitive adhesive film for surface protection coated with the pressure-sensitive adhesive. Surface protection adhesive films are used to protect the surfaces of plate-shaped articles such as stainless steel plates, metal plates such as aluminum plates, painted steel plates, resin plates and glass plates during transportation or processing. The adhesive used as the adhesive component of the film is a copolymer of an acrylic acid alkyl ester and a copolymerizable monomer crosslinked with a crosslinking agent, and this adhesive has excellent weather resistance and transparency. However, in order to achieve the above-mentioned surface protection, it is necessary to provide some additional performance. For example, it has a suitable adhesive strength to a plate-shaped article, has little increase in adhesive strength over time, and has no adhesive residue or stains on the surface of the article. However, if acrylic acid or the like having a carboxyl group is used as a copolymerizable monomer, the adhesive strength over time increases to the extent that the film breaks when peeled off, or the adhesive remains on the surface of the plate-shaped article. However, it is difficult to obtain improved performance, and N/N-dimethylaminoethyl acrylate, which has an amino group, or acrylamide, which has an amide group, is subject to restrictions on the crosslinking method of the copolymer. The current situation is that it has not yet reached the point where it is widely used. In addition, acrylic acid-2-hydroxyethyl ester having a hydroxyl group with relatively few such drawbacks has been used as an adhesive for surface protection films, but the rubber elasticity of the resulting adhesive has There is a problem that the lifting of the film after sheet metal processing, which is the underlying cause, cannot be solved satisfactorily, and the pot life of the adhesive solution is short, resulting in poor coating workability, and improvements are desired. As a result of various studies on a new adhesive for surface protection films that solves the various drawbacks of the conventional techniques, the present inventors discovered two types of copolymerizable monomers having specific functional groups, melamine and urea resin as crosslinking agents. The present inventors have discovered that the various drawbacks mentioned above can be overcome by using one or more selected from the group of compounds having two or more NCO groups in the molecule, and have thus arrived at the present invention. That is, the present invention provides a (meth)acrylic acid alkyl ester monomer (alkyl group having 1 to 8 carbon atoms)
The present invention provides an adhesive for a surface protection film, which is characterized by copolymerizing 100 parts by weight of the following components (i) and (ii) and crosslinking with (iii). (i) Hydroxyl group-containing copolymerizable monomer 0.1~
5 parts by weight. (ii) Carboxyl group-containing copolymerizable monomer 0.1~
10 parts by weight. (iii) Melamine, urea resin and 2 or more molecules in the molecule
0.5 to 10 parts by weight of one or more selected from the group of compounds having an NCO group. The above-mentioned (meth)acrylic acid alkyl ester monomer is a component that imparts desired tackiness, cohesiveness, flexibility, etc. to the adhesive for surface protection film, and examples include butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, etc. Methyl, ethyl methacrylate, etc. are preferably used, but other (meth)acrylic acid alkyl esters with an alkyl group of 8 or less carbon atoms may be used, or these may be used in combination. . In addition, an appropriate amount of a vinyl monomer copolymerizable with the above-mentioned (meth)acrylic acid alkyl ester monomer, such as styrene, vinyl acetate, acrylonitrile, methacrylonitrile, etc., can be used. Component (i) is a monomer that is effective in improving the wetting properties on the surface of a plate-shaped article with a hydroxyl group and suppressing an increase in adhesive strength after pasting on the surface of the article, and includes 2-hydroxyethyl acrylate,
These include 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and the like. The amount of hydroxyl group-containing monomer is 0.1 per 100 parts by weight of the (meth)acrylic acid alkyl ester monomer.
If it is less than 5 parts by weight, no improvement in wetting properties can be obtained, and if it is less than 5 parts by weight, the pot life of the adhesive composition will be short and the coating operation will be poor, which is not preferable. Component (ii) imparts adhesion to the surface of the plate-like article through its carboxyl group, and also uses the crosslinking action of the hydroxyl group-containing monomer of component (i) and the crosslinking agent of component (iii) described below. , is a monomer that acts as a reaction site for crosslinking, and includes acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, etc. If the amount of the carboxyl group-containing monomer is less than 0.1 parts by weight, adhesiveness cannot be obtained, and if it is more than 10 parts by weight, crosslinking takes a long time and the adhesive strength after pasting increases significantly, which is not preferable. Component (iii) is a component that crosslinks the hydroxyl group-containing monomer and the carboxyl group-containing monomer, and includes melamine such as n-butyl etherified melamine, iso-butyl etherified melamine, methyl etherified melamine, n-butanol ether urea, Urea resins such as butyl urea, and tolylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, biphenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,
It includes compounds having two or more NCO groups (isocyanate groups) in the molecule, such as xylylene diisocyanate. If it is less than 0.5 parts by weight, the crosslinking effect will be small, and if it is more than 15 parts by weight, crosslinking will occur excessively.
This is undesirable because it reduces adhesive strength. The adhesive for surface protection film of the present invention has the above four components as essential components, but compounding agents such as an ultraviolet absorber, a rust preventive agent, a crosslinking accelerator, and a coloring agent may also be added. Of course. The adhesive configured in this way has a thickness of approximately 0.01~
It is applied to the surface of a 0.2 mm plastic film or paper to a thickness of 0.05 to 0.08 mm, and then used. The following examples of the present invention are shown. The words "part of the text" indicate parts by weight. Example 1 A copolymer solution (solid content 30%) obtained by copolymerizing ethyl acrylate: 2-ethylhexyl acrylate: 2-hydroxyethyl acrylate: acrylic acid at a ratio of 60:40:1:1 (weight ratio) ). To 100 parts of the solid content of the copolymer solution, 3 parts of tolylene diisocyanate and 0.5 parts of octyltin dilaurate as a crosslinking accelerator are added and mixed to obtain the adhesive for a surface protection film of the present invention. Next, in order to evaluate the properties of the adhesive, the adhesive was applied to the treated side of a polyethylene film (thickness 0.03 mm), which had been subjected to corona discharge treatment on one side, so that the thickness after drying was 0.05 mm. It is coated and dried at 90°C for 2 minutes to obtain an adhesive film for surface protection. The test results for the film are shown in Table 1. Examples 2 to 4 A surface protective adhesive film was prepared in the same manner as in Example 1, except that the following crosslinking agents (A), (B), and (C) were added in place of 3 parts of tolylene diisocyanate. obtain. The test results for the film are shown in Table 1. (A) 5 parts of iso-butyl etherified melamine (Example 2) (B) 5 parts of iso-butyl etherified melamine and 3 parts of tolylene diisocyanate (Example 3) (C) 5 parts of n-butanol ether urea (Example 4) ) Example 5 Butyl acrylate: Acrylonitrile: 2-hydroxyethyl acrylate: Acrylic acid = 80:
A copolymer solution (solid content 25%) is obtained by copolymerizing at a ratio of 20:1:1 (weight ratio). Thereafter, a surface protective adhesive film was obtained in the same manner as in Example 1. The test results for the film are shown in Table 1. Comparative Example A copolymer solution (solid content 30%) having the proportions shown in (a), (b), (c) and (d) below was prepared, and the following Example 1 was prepared.
In the same manner as above, 3 parts of tolylene diisocyanate and 0.5 part of octyltin dilaurate were added and mixed, and the mixture was coated on the polyethylene film of Example 1 and dried to obtain an adhesive film for surface protection. The test results for the film are shown in Table 1. (a) Ethyl acrylate 60 parts 2-ethylhexyl acrylate 40 parts Acrylic acid 1 part (b) Ethyl acrylate 60 parts 2-ethylhexyl acrylate 40 parts 2-hydroxyethyl acrylate 1 part (c) Butyl acrylate 80 parts Acrylonitrile 20 parts Acrylic acid 1 part (d) Butyl acrylate 80 parts Acrylonitrile 20 parts 2-Hydroxyethyl acrylate 1 part
【表】
第１表中の測定及び判別法
初期接着力：製作直後の試料フイルムを、
SUS430 ブライトアニーリング仕上げステン
レス板に室温で貼り付けて試料体を作成し、こ
れを30分間放置し、その後引き剥し速度300mm/
ｍｉｎで180度ピーリングして測定する。
経日接着力：上記試料体を70℃で３日間（室内保
存約１年に相当）放置し、その後常温に戻して
引き剥し速度300mm/minで180度ピーリングし
て測定する。
加工性：厚さ0.4mm、直径100mmφのステンレス円
板に試料フイルムを貼り付け、直径50mmφのポ
ンチで10mm絞り、絞り後のフイルムの浮き及び
糊残りを目視で判別する。浮きについては、浮
きが殆んどないか或いは若干あつても傷防止効
果がある場合を〇とし、浮きが大きく傷防止効
果に効果がない場合を×とした。また糊残りに
ついて、全く或いは殆んどないものを〇とし、
部分的に目視で判別きるものを×とした。
本発明の表面保護フイルム用粘着剤は上記実施
例からも明らかなように、ヒドロキシル基含有共
重合性モノマーとカルボキシル基含有共重合性モ
ノマーとを併用して特定の架橋剤で架橋してなる
粘着剤は、貼り付け後の接着力の上昇が小さく、
貼り付け後に剥離される表面保護用材料に要求さ
れる特性を充分に満足しうるものである。また加
工性の点においても、フイルムの浮きを防止し、
粘着剤自体は板状物品面に残留しないという、表
面保護用粘着フイルムとして特異な性能を有する
事実が顕著である。[Table] Measurement and discrimination method in Table 1 Initial adhesion strength: The sample film immediately after production was
A specimen was created by attaching it to a SUS430 bright annealed stainless steel plate at room temperature, left for 30 minutes, and then peeled off at a speed of 300mm/
Measure by peeling 180 degrees at min. Adhesive strength over time: The sample is left at 70°C for 3 days (equivalent to about 1 year of indoor storage), then returned to room temperature, peeled 180 degrees at a peeling speed of 300 mm/min, and measured. Workability: Paste a sample film on a stainless steel disc with a thickness of 0.4 mm and a diameter of 100 mmφ, squeeze it by 10 mm using a punch with a diameter of 50 mmφ, and visually determine the lifting of the film and the adhesive residue after squeezing. Regarding lifting, cases where there is almost no lifting or even a slight amount of lifting is still effective in preventing scratches are marked as 0, and cases where lifting is large and there is no effect on preventing scratches are marked as ×. Regarding the adhesive residue, if there is no or almost no adhesive residue, mark it as 0.
Items that could be partially determined visually were marked with an x. As is clear from the above examples, the adhesive for surface protection film of the present invention is an adhesive formed by using a combination of a hydroxyl group-containing copolymerizable monomer and a carboxyl group-containing copolymerizable monomer and crosslinking with a specific crosslinking agent. The adhesive has a small increase in adhesive strength after pasting,
This sufficiently satisfies the characteristics required of a surface protection material that is peeled off after being pasted. Also, in terms of processability, it prevents the film from lifting,
The fact that the adhesive itself does not remain on the surface of a plate-shaped article is remarkable, and it has unique performance as a surface protection adhesive film.
Claims (1)
ー（アルキル基のＣ数１〜８個）100重量部に対
して下記(i)及び(ii)成分を共重合させる共に下記(iii)
で架橋してなることを特徴とする表面保護フイル
ム用粘着剤。 (i) ヒドロキシル基含有共重合性モノマー0.1〜
５重量部。 (ii) カルボキシル基含有共重合性モノマー0.1〜
10重量部。 (iii) メラミン、尿素樹脂及び分子内に２個以上の
NCO基を有する化合物の群から選ばれた一種
以上0.5〜15重量部。[Scope of Claims] 1 100 parts by weight of a (meth)acrylic acid alkyl ester monomer (alkyl group with 1 to 8 carbon atoms) is copolymerized with the following components (i) and (ii), and the following (iii)
An adhesive for surface protection films characterized by being crosslinked with. (i) Hydroxyl group-containing copolymerizable monomer 0.1~
5 parts by weight. (ii) Carboxyl group-containing copolymerizable monomer 0.1~
10 parts by weight. (iii) Melamine, urea resin, and 2 or more molecules in the molecule
0.5 to 15 parts by weight of one or more selected from the group of compounds having an NCO group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8971079A JPS5614565A (en) | 1979-07-13 | 1979-07-13 | Self-adhesive for surface protecting film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8971079A JPS5614565A (en) | 1979-07-13 | 1979-07-13 | Self-adhesive for surface protecting film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5614565A JPS5614565A (en) | 1981-02-12 |
| JPS6124426B2 true JPS6124426B2 (en) | 1986-06-11 |
Family
ID=13978318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8971079A Granted JPS5614565A (en) | 1979-07-13 | 1979-07-13 | Self-adhesive for surface protecting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5614565A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61501856A (en) * | 1984-04-12 | 1986-08-28 | エイベリ インタナシヨナル コ−ポレイシヨン | peelable label |
| JPS6232166A (en) * | 1985-08-06 | 1987-02-12 | Mitsui Toatsu Chem Inc | Adhesive for fabrication of foams |
| JP2573181B2 (en) * | 1986-05-09 | 1997-01-22 | ニチバン 株式会社 | Adhesive |
| JPS63225677A (en) * | 1987-03-13 | 1988-09-20 | Nitto Electric Ind Co Ltd | Pressure-sensitive adhesive |
| DE3721097A1 (en) * | 1987-06-26 | 1989-01-05 | Dow Chemical Rheinwerk Gmbh | IMPROVED ACRYLATE-BASED ADHESIVE POLYMER |
| JP2619830B2 (en) * | 1987-11-28 | 1997-06-11 | 日本合成化学工業株式会社 | Adhesive |
| CN1045971C (en) * | 1993-01-19 | 1999-10-27 | 江苏石油化工学院 | Method for preparation of polyurethane acrylic ester copolymerized emulsion |
| US9079381B2 (en) * | 2008-10-01 | 2015-07-14 | Toray Industries, Inc. | Gas barrier film |
| JP5683370B2 (en) * | 2011-04-22 | 2015-03-11 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP5683369B2 (en) * | 2011-04-22 | 2015-03-11 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6174847B2 (en) * | 2012-07-27 | 2017-08-02 | 藤森工業株式会社 | Surface protection film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4889234A (en) * | 1972-02-29 | 1973-11-21 | ||
| JPS5349032A (en) * | 1976-09-20 | 1978-05-04 | Hitachi Chem Co Ltd | Tackifier for surface-protecting film |
-
1979
- 1979-07-13 JP JP8971079A patent/JPS5614565A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4889234A (en) * | 1972-02-29 | 1973-11-21 | ||
| JPS5349032A (en) * | 1976-09-20 | 1978-05-04 | Hitachi Chem Co Ltd | Tackifier for surface-protecting film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5614565A (en) | 1981-02-12 |
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