JP3809314B2 - Aqueous pressure-sensitive adhesive composition, production method thereof, and pressure-sensitive adhesive tape or pressure-sensitive adhesive label - Google Patents

Aqueous pressure-sensitive adhesive composition, production method thereof, and pressure-sensitive adhesive tape or pressure-sensitive adhesive label Download PDF

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JP3809314B2
JP3809314B2 JP31845599A JP31845599A JP3809314B2 JP 3809314 B2 JP3809314 B2 JP 3809314B2 JP 31845599 A JP31845599 A JP 31845599A JP 31845599 A JP31845599 A JP 31845599A JP 3809314 B2 JP3809314 B2 JP 3809314B2
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sensitive adhesive
pressure
weight
aqueous
component
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JP2001131514A (en
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敏也 世古
安生 木谷
肇 宮永
泰範 高橋
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Chuo Rika Kogyo Corp
Mitsubishi Chemical Corp
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Chuo Rika Kogyo Corp
Mitsubishi Chemical Corp
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Description

【0001】
【発明の属する技術分野】
本発明は、水性粘着剤組成物およびその製造方法に関する。本発明の水性粘着剤組成物は、特にポリオレフィン等の低極性高分子材料に対しても良好な接着力を有し、また、耐熱性、耐水白化性にも優れる。
【0002】
【従来の技術】
アクリル酸エステル系粘着剤は、ゴム系粘着剤に比べて優れた耐候性および耐熱性を有し、近年、益々多くの用途に使用されている。中でも、水性エマルジョンから成る水性粘着剤は、有機溶剤を使用しないため、作業環境を悪化させず且つ火災の心配もないことから、広く使用されている。ところが、アクリル系粘着剤は、ポリマーの性質上、ポリオレフィンの様な低極性高分子材料のフィルムや成型品に対する接着性が弱いという問題点がある。
【0003】
上記の欠点を補うため、アクリル系樹脂に対し、ロジン樹脂、石油樹脂、テルペン樹脂といった粘着付与剤を添加することが試みられている。ところが、粘着付与剤の添加により、粘着性は向上するが、耐熱保持力が低下するという問題が生じる。
【0004】
そこで、上記の欠点を改良するため、特開平5−311137号公報には、軟化点が150℃を超えて185℃以下である粘着付与剤の水性エマルジョンを添加したアクリル系水性粘着剤組成物が開示されている。ところが、斯かる組成物の場合、接着力や凝集力は問題ないものの、皮膜の耐水性が劣るという問題がある。
【0005】
更に、特開平10−219221号公報には、特定のガラス転移点(Tg)及びゲル分率を有するアクリル樹脂の水性エマルジョンに85℃〜140℃の軟化点を有する粘着付与剤の水性エマルジョンを配合した粘着剤が、特開平6−322352号公報には、自己乳化型ウレタン系樹脂と粘着付与剤の水性エマルジョンから成る水性接着剤組成物が、それぞれ開示されている。
【0006】
しかしながら、各種基材への接着力、高温時の保持力および皮膜の耐水性などの全ての物性を満足する水性粘着剤組成物は、未だ得られていない状況にある。
【0007】
【発明が解決しようとする課題】
本発明の目的は、前記の従来技術の欠点を改良し、ポリオレフィン等の低極性材料だけでなく、ガラス、ステンレス鋼などの各種被着体に対する初期接着力、タック、耐水白化性、耐熱性などに優れ、粘着剤としてのバランスにも優れた性能を有する水性粘着剤組成物、その製造方法および粘着テープ又は粘着ラベルを提供することにある。
【0008】
【課題を解決するための具体的な手段】
すなわち、本発明の第1の要旨は、ガラス転移温度が−20℃以下のアクリル酸アルキルエステル系樹脂(A)、ウレタン系樹脂(B)、140〜180℃の軟化点を有する粘着付与剤(C)の水性エマルジョンから成り、成分(A)100重量部に対する、成分(B)の割合が2〜30重量部、成分(C)の割合が2〜50重量部であることを特徴とする水性粘着剤組成物に存する。
【0009】
本発明の第2の要旨は、上記の水性粘着剤組成物の製造方法であって、ラジカル重合性不飽和基を有する反応性界面活性剤の存在下、ラジカル重合性不飽和単量体とウレタン系樹脂とを乳化重合して得られたアクリル/ウレタン樹脂水性エマルジョンに水分散性粘着付与剤を配合することを特徴とする水性粘着剤組成物の製造方法に存する。
【0010】
そして、本発明の第3の要旨は、支持体上に上記の水性粘着剤組成物を含む粘着剤層を設けたことを特徴とする粘着テープ又は粘着ラベルに存する。
【0011】
【発明の実施の形態】
以下、本発明を詳細に説明する。先ず、本発明の水性粘着剤組成物について説明する。なお、本明細書における「(メタ)アクリル酸」等の表記は「アクリル酸およびメタアクリル酸」を表す。
【0012】
<成分(A)>
本発明で成分(A)として使用するアクリル酸アルキルエステル系樹脂は、ガラス転移温度(Tg)が−20℃以下のものである。Tgが−20℃より高い場合は、常温および低温での接着力が低下する。一方、Tgが余りにも低い場合は、低温時の接着性は優れるが高温時の保持力が低下する。従って、Tgの下限は−90℃であり、好ましいTgは−70℃から−30℃の範囲である。なお、ここで述べるガラス転移温度は、下記の計算式により算出される値を意味する。また、例えばウレタンをシード粒子として複合化したアクリル酸アルキルエステル系樹脂においては、アクリル酸アルキルエステル部分についてのTgが上記の条件を満足すればよい。
【0013】
【数1】
1/Tg=Wa/Tga+Wb/Tgb+・・・・
(式中、Tgは共重合体のガラス転移温度(K)、Tga及びTgbは、それぞれ、単量体a及び単量体bのホモポリマーのガラス転移温度、Wa及びWbは、それぞれ、単量体a及び単量体bの重量分率を示す。)
【0014】
上記のアクリル酸アルキルエステル系樹脂としては、炭素数が4〜12のアルキル基を有するアクリル酸アルキルエステル(a1)60〜99重量部、カルボキシル基含有ラジカル重合性不飽和単量体(a2)0.5〜5重量部、成分(a1)及び(a2)の各不飽和単量体と共重合可能なラジカル重合性不飽和単量体(a3)0.1〜29重量部の共重合体が好適に使用される。
【0015】
成分(a1)の具体例としては、n−ブチルアクリレート、2−エチルヘキシルアクリレート、n−オクチルアクリレート、イソオクチルアクリレート、ラウリルアクリレート等が挙げられ、これらは、2種以上組み合わせて使用してもよい。成分(a1)の共重合比は、好ましくは75〜95重量%である。成分(a1)の共重合比が余りにも低い場合は十分な接着力が得られず、余りにも高い場合は高温での十分な保持力が得られない。すなわち、成分(a1)は、得られる共重合体のTgを下げ且つ粘着性を付与する機能を有する。
【0016】
成分(a2)の具体例としては、アクリル酸、メタクリル酸の様なα、β−不飽和カルボン酸、イタコン酸、マレイン酸、2−メチレングルタル酸の様なα、β−不飽和ジカルボン酸などが挙げられる。これらは、2種以上組み合わせて使用してもよい。成分(a2)の共重合比は、好ましくは1〜4重量%である。成分(a2)の共重合比が余りにも低い場合は接着力およびポリマーの凝集力が得られず、余りにも高い場合は粘着剤組成物の耐水性が低下する傾向がある。
【0017】
成分(a3)の具体例としては、スチレン、α−メチルスチレンの様な芳香族ビニル化合物、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチルメタクリレートの様な(a1)以外のアルキル(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、4−ヒドロキシブチル(メタ)アクリレートの様な末端にヒドロキシ基を含有する(メタ)アクリレート、酢酸ビニルプロピオン、酢酸ビニルの様なビニルエステル、(メタ)アクリルアミド、N−アルキロールアクリルアミド、(メタ)アクリロニトリル、ハロゲン化ビニル等が挙げられる。また、上記の他、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリアクリレートの様な1分子内に2個以上のラジカル重合性二重結合を持つ架橋性単量体を使用することも出来る。
【0018】
成分(a3)としては、得られる共重合体のTgを上げて凝集力を付与するため、メチルメタクリレート、アクリルアミド、アクリロニトリルの様な高Tgモノマー、2−ヒドロキシエチルアクリレートや4−ヒドロキシブチルアクリレートの様に多官能イソシアネートの様な架橋剤と反応し得る官能基を有する単量体が好ましい。上記の各単量体は、2種以上組み合わせて使用してもよい。
【0019】
成分(a3)の共重合比は、好ましくは1〜20重量%、更に好ましくは2〜15重量%である。成分(a3)の共重合比が余りにも低い場合は、ポリマーの凝集力が得られずに高温での保持力が低下し、余りにも高い場合は、接着力およびタックが低下する傾向がある。
【0020】
<成分(B)>
本発明で成分(B)として使用するウレタン系樹脂としては、特に制限されないが、外部界面活性剤を使用せずに乳化(エマルジョン化)し得るアニオン性の自己乳化型ウレタン樹脂(水分散性ウレタン樹脂)が耐水性の点で好ましく、また、ガラス転移点が0℃以上の水分散性ウレタン樹脂が接着性の点で好ましい。斯かる水分散性ウレタン樹脂は数多く市販されており、その具体例としては、ゼネカ社製の商品「NeoRez」シリーズ、旭電化社製の商品「アデカボンタイター」シリーズ、第一工業製薬社製の商品「スーパーフレックス」シリーズ等が挙げられる。
【0021】
<成分(C)>
本発明で成分(C)として使用する粘着付与剤は140〜180℃の軟化点を有する。粘着付与剤の軟化点は、好ましくは140〜170℃である。粘着付与剤の軟化点が余りにも低い場合はタックは得られるものの高温での保持力に欠け、軟化点が余りにも高い場合はタックが低下する。
【0022】
上記の粘着付与剤の具体例としては、ロジン系樹脂、テルペン系樹脂、石油樹脂が挙げられる。これらは、乳化剤により水に分散させることが出来る。中でも、重合ロジン及び/又は重合ロジンと多価アルコール(グリセリン、ペンタエリスリトール等)とを反応して得られるロジン誘導体が好ましい。ここで述べる重合ロジンとは、ガムロジン、ウッドロジン等の樹脂酸モノマーを、硫酸、塩化アルミニウム等の触媒で二量化した樹脂酸ダイマーを言う。
【0023】
本発明で好適に使用し得る粘着付与剤の具体例としては、荒川化学(株)製の「スーパーエステルE−730−55」(軟化点125℃)、「スーパーエステルE−650」(軟化点160℃)、「スーパーエステルE−865」(軟化点160℃)、ハリマ化成(株)製の「SK−130D」(軟化点138℃)等が挙げられる。
【0024】
<任意成分(D)>
本発明においては、前記の共重合体の分子量を調整する目的として、重合時にアルキルメルカプタン等を分子量調整剤として添加することも可能である。更に、本発明の組成物には、その目的とする用途に応じ、架橋剤、浸透剤、造膜助剤、消泡剤、防錆剤、増粘剤、防腐剤、紫外線吸収剤、光安定剤、顔料、シリカ等の無機充填剤などを配合することも可能である。架橋剤は、凝集力向上のために使用され、例えば、従来公知の多官能イソシアネート系架橋剤や多官能エポキシ系架橋剤などを使用することが出来る。
【0025】
本発明の水性粘着剤組成物は、前記各成分の水性エマルジョンから成る。成分(A)100重量部に対する、成分(B)の割合は2〜30重量部、成分(C)の割合は2〜50重量部とされる。
【0026】
成分(B)の割合が上記の範囲より低い場合は皮膜の耐水性が低下し、高い場合は接着力およびタックが低下する。成分(A)100重量部に対する、成分(B)の好ましい割合は5〜20重量部である。
【0027】
成分(C)の割合が上記の範囲より低い場合は十分な接着力が得られず、高い場合は耐熱性および皮膜の耐水性が低下する。成分(A)100重量部に対する、成分(C)の好ましい割合は5〜30重量部である。
【0028】
また、水性エマルジョン中の上記成分(A)〜(C)の合計量は、通常30〜70重量%、好ましくは40〜60重量%とされる。上記成分の合計量が余りにも少ない場合は乾燥に必要な時間およびエネルギーが増大し、余りにも多い場合は粘度が高くなり過ぎて塗工適性に欠ける。
【0029】
次に、本発明の水性粘着剤組成物の製造方法について説明する。本発明において、水性エマルジョン化は公知の方法に従って行うことが出来る。しかしながら、成分(A)として、前記の成分(a1)〜(a3)から成る共重合体を使用する場合は、以下に述べる方法に従い、上記の共重合体を含有する水性エマルジョンを調製した後、当該水性エマルジョンに残余の成分を配合する方法が好適に採用される。
【0030】
上記の共重合体を含有する水性エマルジョンの調製方法としては、例えば、乳化重合や懸濁重合の他、有機溶媒中での溶液重合後に減圧下で有機溶媒を除去し転相により水性化する方法を採用し得る。中でも水性媒体中で界面活性剤および/または保護コロイドの存在下に乳化重合する方法が好ましい。乳化重合は、常法に従って行われるが、その際、通常、重合開始剤と界面活性剤が使用される。
【0031】
重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、ベンゾイルパーオキサイド、t−ブチルハイドロパーオキサイド等の過酸化物、アゾビスイソブチロニトリル等のアゾ系開始剤が使用される。また、上記の開始剤にアスコルビン酸やロンガリット等の還元剤を組み合わせたレドックス型開始剤も使用することが出来る。更に、これらの開始剤は、必要に応じ、複数の組み合わせで使用してもよい。開始剤の使用量は、重合性単量体100重量部に対し、通常0.01〜5重量部、好ましくは0.1〜2重量部である。
【0032】
界面活性剤としては、アルキルベンゼンスルホン酸塩、高級アルコール硫酸エステル塩、ポリオキシエチレンアルキルスルホン酸塩などの陰イオン性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェノールエーテル等の非イオン性界面活性剤、カチオン性界面活性剤が挙げられる。中でも、粘着剤皮膜の耐水性を向上させるため、分子内にラジカル重合性不飽和結合を有するいわゆる反応性界面活性剤を使用するのが好ましい。
【0033】
主な反応性界面活性剤としては、アルキルアリルスルホコハク酸ナトリウム(三洋化成社製「エレミノールJS−2」、花王社製「ラテムルS−180」)、メタクリロイルオキシポリオキシアルキレン硫酸ナトリウム(三洋化成社製「エレミノールRS−30」)、ポリオキシエチレンアルキルアリルフェノールエーテル(第一工業製薬社製「アクアロンRN−20」)、ポリオキシエチレンアルキルアリルフェノールエーテル硫酸エステル塩(第一工業製薬社製「アクアロンHS−10」、旭電化工業社製「アデカリアソープSE−10N」)等が挙げられる。これらの界面活性剤は、必要に応じ、複数の組み合わせで使用してもよい。
【0034】
本発明においては、界面活性剤だけでなく、保護コロイドとして、ポリビニルアルコール、ヒドロキシエチルセルロース等の水溶性高分子化合物を添加して重合することも可能である。界面活性剤または保護コロイドの使用量は、使用するラジカル重合性不飽和化合物100重量部に対し、通常0.1〜10重量部、好ましくは1〜5重量部である。
【0035】
乳化重合の反応条件は特に制限はないが、反応温度は、通常40〜95℃、好ましくは50〜70℃、反応時間は、通常1〜12時間、好ましくは2〜8時間である。
【0036】
特に、本発明においては、水性粘着剤組成物の製造方法として、上記のラジカル重合性不飽和基を有する反応性界面活性剤の存在下、ラジカル重合性不飽和単量体(前記の成分(a1)〜(a3))とウレタン系樹脂とを乳化重合して得られた水性エマルジョンに水分散性粘着付与剤を配合する方法が推奨される。斯かる方法によれば、アクリル/ウレタン樹脂の水性エマルジョンを含有する水性粘着剤組成物が得られる。
【0037】
次に、支持体上に前記の水性粘着剤組成物を含む粘着剤層を設けたことを特徴とする本発明の粘着テープ又は粘着ラベルについて説明する。
上記の支持体としては紙またはプラスチックフィルムが使用され、その厚さは、通常10〜1000μm、好ましくは30〜100μmである。支持体の厚さが余りに薄い場合は強度に欠けるとと共に塗工時の作業性などが悪化し、余りに厚い場合は柔軟性に欠ける。上記のプラスチックフィルムの構成材料としては、ポリプロピレン、ポリエチレン等のポリオレフィン樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、塩化ビニル樹脂などが挙げられる。
【0038】
上記の粘着剤層の厚さは、通常5〜200μm、好ましくは10〜50μmである。粘着剤層の厚さが余りに薄い場合は十分な接着力が得られず、余りに厚い場合は塗工・乾燥工程上好ましくない。塗工手段としては、バーコーター、ナイフコーター等の既存の塗工手段が採用される。そして、直接的に水性粘着剤組成物を塗工して乾燥する直接法、離型紙上に水性粘着剤組成物を塗工・乾燥した後に支持体上に転写する転写法の何れを採用してもよい。
【0039】
【実施例】
以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。また、実施例中に記載されている「部」及び「%」は特に記載のない限り「重量部」及び「重量%」である。
【0040】
<アクリル系樹脂の水性エマルジョン(1)〜(9)の調製>
攪拌機、還流冷却器、温度計、滴下漏斗を備えた反応容器に、水分散性ウレタン樹脂(ゼネカ社製「R9617」)34部、反応性界面活性剤(第一工業製薬社製のアニオン性乳化剤「アクアロンHS−10」)0.5部、水30部を入れ、窒素雰囲気下で60℃に加熱した。反応容器内にアゾイソビスブチロニトリル0.3部を添加した後、別途、以下の様に調製しておいた乳化液(プレエマルジョン)を4時間かけて滴下した。
【0041】
上記のプレエマルジョンは、2−エチルヘキシルアクリレート91部、メチルメタクリレート7部、メタクリル酸2部、「アクアロンHS−10」1部、水40部の混合物をホモミキサーにて予め機械乳化することにより、調製した。
【0042】
プレエマルジョン滴下後、tブチルハイドロパーオキサイド0.3部を添加し、更に80℃で2時間反応させ後に冷却し、乳白色のアクリル系樹脂(アクリル/ウレタン樹脂)の水性エマルジョン(1)を得た。
【0043】
表1及び表2に記載の単量体を使用し、上記と同様に乳化重合してアクリル系樹脂の水性エマルジョン(2)〜(9)を調製した。
【0044】
【表1】

Figure 0003809314
【0045】
【表2】
Figure 0003809314
【0046】
上記の表1及び表2中の「シード粒子」及び「モノマー組成」の符号の意義は、次の表3に示す通りである。
【0047】
【表3】
Figure 0003809314
【0048】
実施例1
上記で得られたアクリル/ウレタン樹脂の水性エマルジョン(1)にロジンエマルジョン(荒川化学社製「スーパーエステルE−650」)を添加、攪拌し、水性粘着剤組成物を得た。ロジンエマルジョン/水性エマルジョン(1)の使用割合は、固形分の比率として10/100とした。得られた水性粘着剤組成物について下記に記載の評価を行い、結果を後記の表6に示す。
【0049】
<試験片作成>
上記で得られた水性粘着剤組成物を50μmのアプリケーターにてポリエステルフィルム(厚み50μm)に塗工し、120℃にて2分間乾燥した。その後、離型性フィルムをシート上に被せ、23℃、65%RHにて24時間状態調整した。
【0050】
<評価方法>
(1)接着力:
23℃、65%RHの条件下で、25mm巾に裁断された試験片を荷重2kgのローラーを1往復させて被着体(ステンレス鋼/ガラス/ポリプロピレン)に圧着し、引っ張り速度300mm/分の速度で180度剥離試験を実施した。
【0051】
(2)タック:
JIS Z0237に記載されたJ.DOW法により、傾斜角度30度、測定温度23℃におけるボールタックを測定した。数字はボールナンバーを表す。
【0052】
(3)耐水白化性試験:
試験片を常温(23℃)にて蒸留水に1日浸漬し、試験片の状態を目視にて判定した。判定基準は次の表4に示す通りである。
【0053】
【表4】
5:白化の無い透明な塗膜である。
4:若干塗膜の白化が認められるが良好である。
3:塗膜の白化が認められるが使用可能である。
2:塗膜の白化により使用不可能である。
1:塗膜の白化が著しく使用不可能である。
【0054】
(4)耐熱保持力:
25mm巾に切断した粘着テープを接着面積が25×25mmとなる様にステンレス鋼板(ステンレス鋼#304・鏡面加工)に貼り合わせ、荷重2kgのローラーを1往復させて被着体に圧着した。上記試験片の剪断方向に1kgの荷重をかけて、60℃において放置した。そして、試験片が落下するまでの時間を測定した。
【0055】
実施例2〜9及び比較例1〜4
実施例1において、前記のアクリル/ウレタン樹脂の水性エマルジョン(2)〜(7)を調製し且つこれらの水性エマルジョンを使用した以外は、実施例1と同様にして水性粘着剤組成物を得、評価を行った。結果を表6〜表8に示す。
【0056】
表6〜表8中の「粘着付与剤の水性エマルジュンの種類」の符号の意義は、次の表5に示す通りである。
【0057】
【表5】
Figure 0003809314
【0058】
【表6】
Figure 0003809314
【0059】
【表7】
Figure 0003809314
【0060】
【表8】
Figure 0003809314
【0061】
【発明の効果】
以上説明した本発明によれば、ポリオレフィン等の低極性材料だけでなく、ガラス、ステンレス鋼などの各種被着体に対する初期接着力、タック、耐水白化性、耐熱性などに優れ、粘着剤としてのバランスにも優れた性能を有する水性粘着剤組成物、その製造方法および粘着テープ又は粘着ラベルが提供され、本発明の工業的価値は顕著である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous pressure-sensitive adhesive composition and a method for producing the same. The aqueous pressure-sensitive adhesive composition of the present invention has a good adhesive force especially to low-polar polymer materials such as polyolefin, and is excellent in heat resistance and water whitening resistance.
[0002]
[Prior art]
Acrylic ester-based pressure-sensitive adhesives have superior weather resistance and heat resistance compared to rubber-based pressure-sensitive adhesives, and are being increasingly used in recent years. Among them, an aqueous pressure-sensitive adhesive composed of an aqueous emulsion is widely used because it does not use an organic solvent and does not deteriorate the working environment and does not cause a fire. However, the acrylic pressure-sensitive adhesive has a problem that the adhesiveness to a film or molded product of a low-polarity polymer material such as polyolefin is weak due to the properties of the polymer.
[0003]
In order to compensate for the above drawbacks, attempts have been made to add tackifiers such as rosin resins, petroleum resins, and terpene resins to acrylic resins. However, the addition of a tackifier improves the tackiness, but causes a problem that the heat-resistant holding power is reduced.
[0004]
Therefore, in order to improve the above drawbacks, JP-A-5-31137 discloses an acrylic aqueous pressure-sensitive adhesive composition to which an aqueous emulsion of a tackifier having a softening point exceeding 150 ° C. and not higher than 185 ° C. is added. It is disclosed. However, in the case of such a composition, there is a problem that the water resistance of the film is inferior although there is no problem with the adhesive force and the cohesive force.
[0005]
Furthermore, in JP-A-10-219221, an aqueous emulsion of a tackifier having a softening point of 85 ° C. to 140 ° C. is added to an aqueous emulsion of an acrylic resin having a specific glass transition point (Tg) and a gel fraction. JP-A-6-322352 discloses an aqueous adhesive composition comprising a self-emulsifying urethane resin and an aqueous emulsion of a tackifier.
[0006]
However, an aqueous pressure-sensitive adhesive composition that satisfies all physical properties such as adhesive strength to various substrates, holding power at high temperatures, and water resistance of the film has not yet been obtained.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to improve the above-mentioned drawbacks of the prior art, not only low polarity materials such as polyolefin, but also initial adhesion to various adherends such as glass and stainless steel, tack, water whitening resistance, heat resistance, etc. It is providing the water-based adhesive composition which has the performance excellent also in the balance as an adhesive, and its outstanding method, its manufacturing method, and an adhesive tape or an adhesive label.
[0008]
[Specific means for solving the problem]
That is, the first gist of the present invention is that an acrylic acid alkyl ester resin (A) having a glass transition temperature of −20 ° C. or lower, a urethane resin (B), a tackifier having a softening point of 140 to 180 ° C. ( C) aqueous emulsion, wherein the ratio of component (B) to 2 to 30 parts by weight and the ratio of component (C) to 2 to 50 parts by weight with respect to 100 parts by weight of component (A) It exists in an adhesive composition.
[0009]
The second gist of the present invention is a method for producing the above aqueous pressure-sensitive adhesive composition, in the presence of a reactive surfactant having a radically polymerizable unsaturated group, a radically polymerizable unsaturated monomer and urethane. The present invention resides in a method for producing an aqueous pressure-sensitive adhesive composition, which comprises blending a water-dispersible tackifier with an acrylic / urethane resin aqueous emulsion obtained by emulsion polymerization with a base resin.
[0010]
And the 3rd summary of this invention exists in the adhesive tape or adhesive label characterized by providing the adhesive layer containing said aqueous adhesive composition on a support body.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. First, the aqueous pressure-sensitive adhesive composition of the present invention will be described. In addition, notations such as “(meth) acrylic acid” in the present specification represent “acrylic acid and methacrylic acid”.
[0012]
<Component (A)>
The acrylic acid alkyl ester resin used as the component (A) in the present invention has a glass transition temperature (Tg) of −20 ° C. or lower. When Tg is higher than −20 ° C., the adhesive strength at normal temperature and low temperature decreases. On the other hand, when Tg is too low, the adhesiveness at low temperatures is excellent, but the holding power at high temperatures decreases. Therefore, the lower limit of Tg is -90 ° C, and the preferable Tg is in the range of -70 ° C to -30 ° C. In addition, the glass transition temperature described here means a value calculated by the following calculation formula. In addition, for example, in an acrylic acid alkyl ester resin compounded with urethane as seed particles, the Tg of the acrylic acid alkyl ester portion may satisfy the above condition.
[0013]
[Expression 1]
1 / Tg = Wa / Tga + Wb / Tgb +
(Wherein Tg is the glass transition temperature (K) of the copolymer, Tga and Tgb are the glass transition temperatures of the homopolymers of monomer a and monomer b, respectively, and Wa and Wb are each a single amount) (The weight fraction of the body a and the monomer b is shown.)
[0014]
As said acrylic-acid alkylester type-resin, 60-99 weight part of acrylic acid alkylester (a1) which has a C4-C12 alkyl group, carboxyl group-containing radically polymerizable unsaturated monomer (a2) 0 0.5 to 5 parts by weight of a copolymer of 0.1 to 29 parts by weight of a radically polymerizable unsaturated monomer (a3) copolymerizable with each unsaturated monomer of components (a1) and (a2) Preferably used.
[0015]
Specific examples of the component (a1) include n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate and the like, and these may be used in combination of two or more. The copolymerization ratio of component (a1) is preferably 75 to 95% by weight. When the copolymerization ratio of the component (a1) is too low, sufficient adhesive strength cannot be obtained, and when it is too high, sufficient holding strength at high temperature cannot be obtained. That is, the component (a1) has a function of lowering the Tg of the obtained copolymer and imparting tackiness.
[0016]
Specific examples of the component (a2) include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated dicarboxylic acids such as itaconic acid, maleic acid, and 2-methyleneglutaric acid. Is mentioned. You may use these in combination of 2 or more types. The copolymerization ratio of component (a2) is preferably 1 to 4% by weight. When the copolymerization ratio of the component (a2) is too low, adhesive strength and polymer cohesive strength cannot be obtained, and when it is too high, the water resistance of the pressure-sensitive adhesive composition tends to decrease.
[0017]
Specific examples of the component (a3) include styrene, aromatic vinyl compounds such as α-methylstyrene, alkyl (meth) other than (a1) such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl methacrylate. Acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate-containing (meth) acrylate containing a hydroxyl group, vinyl acetate, vinyl acetate such as vinyl acetate, (meth) acrylamide N-alkylolacrylamide, (meth) acrylonitrile, vinyl halide and the like. In addition to the above, a crosslinkable monomer having two or more radical polymerizable double bonds in one molecule such as allyl (meth) acrylate, ethylene glycol di (meth) acrylate, and trimethylolpropane triacrylate. Can also be used.
[0018]
As the component (a3), in order to increase the Tg of the resulting copolymer and impart cohesion, high Tg monomers such as methyl methacrylate, acrylamide and acrylonitrile, such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate A monomer having a functional group capable of reacting with a crosslinking agent such as a polyfunctional isocyanate is preferred. Each of the above monomers may be used in combination of two or more.
[0019]
The copolymerization ratio of component (a3) is preferably 1 to 20% by weight, more preferably 2 to 15% by weight. When the copolymerization ratio of the component (a3) is too low, the cohesive force of the polymer cannot be obtained and the holding power at high temperature is lowered, and when it is too high, the adhesive force and tack tend to be lowered.
[0020]
<Component (B)>
The urethane resin used as the component (B) in the present invention is not particularly limited, but an anionic self-emulsifying urethane resin (water-dispersible urethane) that can be emulsified (emulsified) without using an external surfactant. Resin) is preferable in terms of water resistance, and a water dispersible urethane resin having a glass transition point of 0 ° C. or higher is preferable in terms of adhesiveness. A large number of such water-dispersible urethane resins are commercially available. Specific examples thereof include the product “NeoRez” series manufactured by Zeneca, the product “Adekabon titer” series manufactured by Asahi Denka, and the products manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Products such as the “Superflex” series.
[0021]
<Ingredient (C)>
The tackifier used as the component (C) in the present invention has a softening point of 140 to 180 ° C. The softening point of the tackifier is preferably 140 to 170 ° C. If the softening point of the tackifier is too low, tack can be obtained, but lacks the holding power at high temperatures, and if the softening point is too high, the tack is lowered.
[0022]
Specific examples of the tackifier include rosin resins, terpene resins, and petroleum resins. These can be dispersed in water with an emulsifier. Among these, a polymerized rosin and / or a polymerized rosin and a rosin derivative obtained by reacting a polyhydric alcohol (such as glycerin or pentaerythritol) are preferable. The polymerized rosin described herein refers to a resin acid dimer obtained by dimerizing a resin acid monomer such as gum rosin or wood rosin with a catalyst such as sulfuric acid or aluminum chloride.
[0023]
Specific examples of tackifiers that can be suitably used in the present invention include “Superester E-730-55” (softening point 125 ° C.) and “Superester E-650” (softening point) manufactured by Arakawa Chemical Co., Ltd. 160 ° C.), “Super Ester E-865” (softening point 160 ° C.), “SK-130D” (softening point 138 ° C.) manufactured by Harima Kasei Co., Ltd., and the like.
[0024]
<Arbitrary component (D)>
In the present invention, for the purpose of adjusting the molecular weight of the copolymer, an alkyl mercaptan or the like can be added as a molecular weight adjusting agent during the polymerization. Furthermore, the composition of the present invention includes a crosslinking agent, a penetrating agent, a film forming aid, an antifoaming agent, a rust inhibitor, a thickener, an antiseptic, an ultraviolet absorber, and a light stabilizer depending on the intended use. It is also possible to blend an agent, pigment, inorganic filler such as silica. The cross-linking agent is used for improving cohesion, and for example, a conventionally known polyfunctional isocyanate-based cross-linking agent or polyfunctional epoxy-based cross-linking agent can be used.
[0025]
The aqueous pressure-sensitive adhesive composition of the present invention comprises an aqueous emulsion of the above components. The ratio of the component (B) to 2 to 30 parts by weight and the ratio of the component (C) to 2 to 50 parts by weight with respect to 100 parts by weight of the component (A).
[0026]
When the proportion of the component (B) is lower than the above range, the water resistance of the film is lowered, and when it is high, the adhesive strength and tack are lowered. A preferred ratio of component (B) to 100 parts by weight of component (A) is 5 to 20 parts by weight.
[0027]
When the ratio of the component (C) is lower than the above range, sufficient adhesive strength cannot be obtained, and when it is high, the heat resistance and the water resistance of the film are lowered. A preferred ratio of the component (C) to 100 parts by weight of the component (A) is 5 to 30 parts by weight.
[0028]
The total amount of the components (A) to (C) in the aqueous emulsion is usually 30 to 70% by weight, preferably 40 to 60% by weight. When the total amount of the above components is too small, the time and energy required for drying increase, and when too large, the viscosity becomes too high and the coating suitability is poor.
[0029]
Next, the manufacturing method of the aqueous adhesive composition of this invention is demonstrated. In the present invention, the aqueous emulsion can be carried out according to a known method. However, when using a copolymer comprising the components (a1) to (a3) as the component (A), according to the method described below, after preparing an aqueous emulsion containing the copolymer, A method of blending the remaining components in the aqueous emulsion is preferably employed.
[0030]
Examples of the preparation method of the aqueous emulsion containing the above-mentioned copolymer include emulsion polymerization and suspension polymerization, and a method of removing the organic solvent under reduced pressure after solution polymerization in an organic solvent and making it aqueous by phase inversion Can be adopted. Among them, a method of emulsion polymerization in the presence of a surfactant and / or a protective colloid in an aqueous medium is preferable. Emulsion polymerization is carried out according to a conventional method. In this case, a polymerization initiator and a surfactant are usually used.
[0031]
Examples of the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide, benzoyl peroxide and t-butyl hydroperoxide, and azo series such as azobisisobutyronitrile. An initiator is used. Moreover, the redox type | mold initiator which combined reducing agents, such as ascorbic acid and Rongalite, with said initiator can also be used. Furthermore, these initiators may be used in a plurality of combinations as required. The usage-amount of an initiator is 0.01-5 weight part normally with respect to 100 weight part of polymerizable monomers, Preferably it is 0.1-2 weight part.
[0032]
Surfactants include anionic surfactants such as alkylbenzene sulfonates, higher alcohol sulfates and polyoxyethylene alkyl sulfonates, and nonionic interfaces such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenol ethers. An activator and a cationic surfactant are mentioned. Among these, in order to improve the water resistance of the pressure-sensitive adhesive film, it is preferable to use a so-called reactive surfactant having a radical polymerizable unsaturated bond in the molecule.
[0033]
The main reactive surfactants include sodium alkylallylsulfosuccinate (“Eleminol JS-2” manufactured by Sanyo Chemical Co., Ltd., “Latemul S-180” manufactured by Kao Corporation), sodium methacryloyloxypolyoxyalkylene sulfate (manufactured by Sanyo Chemical Co., Ltd.) “ELEMINOL RS-30”), polyoxyethylene alkylallylphenol ether (“AQUALON RN-20” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene alkylallylphenol ether sulfate ester salt (“AQUALON HS manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) -10 "," Adekaria soap SE-10N "manufactured by Asahi Denka Kogyo Co., Ltd.) and the like. These surfactants may be used in a plurality of combinations as required.
[0034]
In the present invention, not only the surfactant but also a water-soluble polymer compound such as polyvinyl alcohol or hydroxyethyl cellulose can be added as a protective colloid for polymerization. The amount of the surfactant or protective colloid used is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the radical polymerizable unsaturated compound used.
[0035]
The reaction conditions for emulsion polymerization are not particularly limited, but the reaction temperature is usually 40 to 95 ° C., preferably 50 to 70 ° C., and the reaction time is usually 1 to 12 hours, preferably 2 to 8 hours.
[0036]
In particular, in the present invention, as a method for producing an aqueous pressure-sensitive adhesive composition, in the presence of the above-mentioned reactive surfactant having a radical polymerizable unsaturated group, a radical polymerizable unsaturated monomer (the aforementioned component (a1 ) To (a3)) and a urethane resin are emulsion-polymerized, and a method of blending a water-dispersible tackifier into an aqueous emulsion is recommended. According to such a method, an aqueous pressure-sensitive adhesive composition containing an acrylic / urethane resin aqueous emulsion is obtained.
[0037]
Next, the pressure-sensitive adhesive tape or pressure-sensitive adhesive label of the present invention, in which a pressure-sensitive adhesive layer containing the aqueous pressure-sensitive adhesive composition is provided on a support, will be described.
As the support, paper or plastic film is used, and the thickness is usually 10 to 1000 μm, preferably 30 to 100 μm. When the thickness of the support is too thin, the strength is insufficient and workability at the time of coating deteriorates, and when it is too thick, the flexibility is insufficient. Examples of the constituent material of the plastic film include polyolefin resins such as polypropylene and polyethylene, polyester resins such as polyethylene terephthalate, and vinyl chloride resins.
[0038]
The thickness of said adhesive layer is 5-200 micrometers normally, Preferably it is 10-50 micrometers. When the thickness of the pressure-sensitive adhesive layer is too thin, sufficient adhesive force cannot be obtained, and when it is too thick, it is not preferable in terms of the coating / drying process. As the coating means, existing coating means such as a bar coater and a knife coater are employed. Either a direct method in which the aqueous pressure-sensitive adhesive composition is directly applied and dried, or a transfer method in which the aqueous pressure-sensitive adhesive composition is applied and dried on the release paper and then transferred onto the support is employed. Also good.
[0039]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. Further, “parts” and “%” described in the examples are “parts by weight” and “% by weight” unless otherwise specified.
[0040]
<Preparation of aqueous emulsion (1) to (9) of acrylic resin>
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 34 parts of a water dispersible urethane resin (“R9617” manufactured by Zeneca), a reactive surfactant (anionic emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) "Aqualon HS-10") 0.5 part and 30 parts of water were added and heated to 60 ° C under a nitrogen atmosphere. After adding 0.3 part of azoisobisbutyronitrile into the reaction vessel, an emulsion (pre-emulsion) prepared separately as follows was added dropwise over 4 hours.
[0041]
The above pre-emulsion was prepared by mechanically emulsifying a mixture of 91 parts of 2-ethylhexyl acrylate, 7 parts of methyl methacrylate, 2 parts of methacrylic acid, 1 part of “Aqualon HS-10” and 40 parts of water in advance with a homomixer. did.
[0042]
After dropwise addition of the pre-emulsion, 0.3 part of t-butyl hydroperoxide was added, and further reacted at 80 ° C. for 2 hours and then cooled to obtain an aqueous emulsion (1) of milky white acrylic resin (acrylic / urethane resin). .
[0043]
Aqueous emulsions (2) to (9) of acrylic resins were prepared by emulsion polymerization in the same manner as described above using the monomers listed in Tables 1 and 2.
[0044]
[Table 1]
Figure 0003809314
[0045]
[Table 2]
Figure 0003809314
[0046]
The meanings of the symbols “seed particles” and “monomer composition” in Tables 1 and 2 are as shown in Table 3 below.
[0047]
[Table 3]
Figure 0003809314
[0048]
Example 1
A rosin emulsion ("Superester E-650" manufactured by Arakawa Chemical Co., Ltd.) was added to the acrylic / urethane resin aqueous emulsion (1) obtained above and stirred to obtain an aqueous pressure-sensitive adhesive composition. The ratio of rosin emulsion / aqueous emulsion (1) used was 10/100 as the solid content ratio. The obtained aqueous pressure-sensitive adhesive composition was evaluated as described below, and the results are shown in Table 6 below.
[0049]
<Specimen creation>
The aqueous pressure-sensitive adhesive composition obtained above was applied to a polyester film (thickness 50 μm) with a 50 μm applicator and dried at 120 ° C. for 2 minutes. Thereafter, a releasable film was placed on the sheet and conditioned at 23 ° C. and 65% RH for 24 hours.
[0050]
<Evaluation method>
(1) Adhesive strength:
Under the conditions of 23 ° C. and 65% RH, the test piece cut to a width of 25 mm was reciprocated once by a roller with a load of 2 kg and pressed onto the adherend (stainless steel / glass / polypropylene), and the pulling speed was 300 mm / min. A 180 degree peel test was performed at speed.
[0051]
(2) Tack:
As described in JIS Z0237. Ball tack at an inclination angle of 30 degrees and a measurement temperature of 23 ° C. was measured by the DOW method. The number represents the ball number.
[0052]
(3) Water whitening resistance test:
The test piece was immersed in distilled water for 1 day at room temperature (23 ° C.), and the state of the test piece was judged visually. The judgment criteria are as shown in Table 4 below.
[0053]
[Table 4]
5: A transparent coating without whitening.
4: Slight whitening of the coating film is observed but good.
3: Although whitening of a coating film is recognized, it can be used.
2: Unusable due to whitening of the coating film.
1: Whitening of the coating film is remarkably unusable.
[0054]
(4) Heat resistance retention:
The pressure-sensitive adhesive tape cut to a width of 25 mm was bonded to a stainless steel plate (stainless steel # 304, mirror finish) so that the adhesion area was 25 × 25 mm, and the roller with a load of 2 kg was reciprocated once to pressure-bond to the adherend. A load of 1 kg was applied in the shear direction of the test piece and the test piece was left at 60 ° C. And time until a test piece fell was measured.
[0055]
Examples 2-9 and Comparative Examples 1-4
In Example 1, an aqueous pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the aqueous emulsions (2) to (7) of the acrylic / urethane resin were prepared and these aqueous emulsions were used. Evaluation was performed. The results are shown in Tables 6-8.
[0056]
The significance of the sign of “type of tackifier aqueous emulsion” in Tables 6 to 8 is as shown in Table 5 below.
[0057]
[Table 5]
Figure 0003809314
[0058]
[Table 6]
Figure 0003809314
[0059]
[Table 7]
Figure 0003809314
[0060]
[Table 8]
Figure 0003809314
[0061]
【The invention's effect】
According to the present invention described above, not only low-polarity materials such as polyolefins, but also excellent initial adhesive strength, tack, water whitening resistance, heat resistance, etc. for various adherends such as glass and stainless steel, as an adhesive An aqueous pressure-sensitive adhesive composition having excellent performance in balance, a production method thereof, and a pressure-sensitive adhesive tape or pressure-sensitive adhesive label are provided, and the industrial value of the present invention is remarkable.

Claims (8)

ガラス転移温度が−20℃以下のアクリル酸アルキルエステル系樹脂(A)、ウレタン系樹脂(B)、140〜180℃の軟化点を有する粘着付与剤(C)の水性エマルジョンから成り、成分(A)100重量部に対する、成分(B)の割合が2〜30重量部、成分(C)の割合が2〜50重量部であることを特徴とする水性粘着剤組成物。It consists of an aqueous emulsion of an alkyl acrylate resin (A) having a glass transition temperature of -20 ° C. or lower, a urethane resin (B), and a tackifier (C) having a softening point of 140 to 180 ° C. ) An aqueous pressure-sensitive adhesive composition, wherein the proportion of component (B) is 2 to 30 parts by weight and the proportion of component (C) is 2 to 50 parts by weight with respect to 100 parts by weight. 成分(A)が、炭素数が4〜12のアルキル基を有するアクリル酸アルキルエステル(a1)60〜99重量部、カルボキシル基含有ラジカル重合性不飽和単量体(a2)0.5〜5重量部、成分(a1)及び(a2)の各不飽和単量体と共重合可能なラジカル重合性不飽和単量体(a3)0.1〜29重量部の共重合体である請求項1に記載の組成物。  Component (A) is an acrylic acid alkyl ester (a1) having an alkyl group having 4 to 12 carbon atoms (a1) 60 to 99 parts by weight, a carboxyl group-containing radical polymerizable unsaturated monomer (a2) 0.5 to 5 parts by weight 2. The copolymer of 0.1 to 29 parts by weight of a radically polymerizable unsaturated monomer (a3) copolymerizable with each unsaturated monomer of components (a1) and (a2). The composition as described. ラジカル重合性不飽和単量体(a3)が、アクリルアミド、アクリロニトリル、2−ヒドロキシエチルアクリレート、4−ヒドロキシブチルアクリレートの群から選択される何れかの1種または2種以上の単量体である請求項2に記載の組成物。The radically polymerizable unsaturated monomer (a3) is one or more monomers selected from the group consisting of acrylamide, acrylonitrile, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. Item 3. The composition according to Item 2. 成分(B)が、アニオン性の自己乳化型ウレタン系樹脂であり且つ0℃以上のガラス転移点を有する請求項1〜3の何れかに記載の組成物。The composition according to any one of claims 1 to 3 , wherein the component (B) is an anionic self-emulsifying urethane resin and has a glass transition point of 0 ° C or higher. 成分(C)が、重合ロジン及び/又は重合ロジンと多価アルコールとを反応して得られるロジン誘導体である請求項1〜の何れかに記載の組成物。The composition according to any one of claims 1 to 4 , wherein the component (C) is a polymerized rosin and / or a rosin derivative obtained by reacting a polymerized rosin and a polyhydric alcohol. 成分(A)及び(B)が、ラジカル重合性不飽和基を有する反応性界面活性剤の存在下、ラジカル重合性不飽和単量体とウレタン系樹脂とを乳化重合して得られたアクリル/ウレタン樹脂水性エマルジョンである請求項1〜の何れかに記載の組成物。Components (A) and (B) are acrylic / polymers obtained by emulsion polymerization of a radically polymerizable unsaturated monomer and a urethane resin in the presence of a reactive surfactant having a radically polymerizable unsaturated group. It is a urethane resin aqueous emulsion, The composition in any one of Claims 1-5 . 請求項1に記載の水性粘着剤組成物の製造方法であって、ラジカル重合性不飽和基を有する反応性界面活性剤の存在下、ラジカル重合性不飽和単量体とウレタン系樹脂とを乳化重合して得られたアクリル/ウレタン樹脂水性エマルジョンに水分散性粘着付与剤を配合することを特徴とする水性粘着剤組成物の製造方法。 It is a manufacturing method of the water-based adhesive composition of Claim 1, Comprising: A radically polymerizable unsaturated monomer and urethane resin are emulsified in presence of the reactive surfactant which has a radically polymerizable unsaturated group. A method for producing an aqueous pressure-sensitive adhesive composition comprising blending a water-dispersible tackifier with an acrylic / urethane resin aqueous emulsion obtained by polymerization. 支持体上に請求項1〜の何れかに記載の水性粘着剤組成物を含む粘着剤層を設けたことを特徴とする粘着テープ又は粘着ラベル。A pressure-sensitive adhesive tape or pressure-sensitive adhesive label, comprising a pressure-sensitive adhesive layer comprising the aqueous pressure-sensitive adhesive composition according to any one of claims 1 to 6 on a support.
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