JP2005089573A - Pressure-sensitive adhesive composition - Google Patents
Pressure-sensitive adhesive composition Download PDFInfo
- Publication number
- JP2005089573A JP2005089573A JP2003323262A JP2003323262A JP2005089573A JP 2005089573 A JP2005089573 A JP 2005089573A JP 2003323262 A JP2003323262 A JP 2003323262A JP 2003323262 A JP2003323262 A JP 2003323262A JP 2005089573 A JP2005089573 A JP 2005089573A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- sensitive adhesive
- pressure
- meth
- acrylic copolymer
- 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.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 40
- 125000000524 functional group Chemical group 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims description 38
- 230000001070 adhesive effect Effects 0.000 claims description 38
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 20
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- -1 isocyanate compound Chemical class 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 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 14
- 238000000034 method Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
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- 239000002685 polymerization catalyst Substances 0.000 description 5
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- 239000012790 adhesive layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 239000012948 isocyanate Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000003960 organic solvent Substances 0.000 description 4
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 239000003292 glue Substances 0.000 description 2
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- 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
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- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent 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
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、非極性被着体への接着性に優れる上、粗面や曲面、角面への接着性に優れ、更に各種被着体に対する再剥離性も優れる粘着剤組成物に関するものである。 The present invention relates to a pressure-sensitive adhesive composition having excellent adhesion to non-polar adherends, excellent adhesion to rough surfaces, curved surfaces, and square surfaces, and excellent removability to various adherends. .
従来より、（メタ）アクリル酸アルキルエステルを主たる構成成分とするアクリル系粘着剤は、タック、粘着力、凝集力等の基本物性に加え、耐熱性、耐候性、耐水性、耐油性に優れていることから、粘着ラベル、粘着シート、粘着テープ等の粘着製品に幅広く用いられている。 Conventionally, acrylic pressure-sensitive adhesives mainly composed of (meth) acrylic acid alkyl ester have excellent heat resistance, weather resistance, water resistance, and oil resistance in addition to basic physical properties such as tack, adhesive strength, and cohesive strength. Therefore, it is widely used for adhesive products such as adhesive labels, adhesive sheets, and adhesive tapes.
一般的に、これらの粘着製品は、被着体に貼付した後は剥離されることがほとんどない永久接着型と被着体に貼付した後に再び剥離されることが想定される再剥離型に分類することができ、近年は、環境対応やリサイクルの必然性から、再剥離型粘着製品の使用量が増大している。 Generally, these adhesive products are classified into a permanent adhesive type that hardly peels after being attached to an adherend and a re-peelable type that is assumed to be peeled again after being attached to an adherend. In recent years, the amount of re-peelable pressure-sensitive adhesive products used has increased due to environmental concerns and the necessity of recycling.
再剥離型粘着製品に用いられる粘着剤は、被着体に貼付されてから長時間経過した後であっても、糊残り等の被着体汚染を起こさず、きれいに剥離できることが要求される。かかる要求に対して、例えば、永久接着型の粘着剤の架橋密度を上げる、あるいは、粘着剤用ポリマーのガラス転移温度を高める、といった方法で、凝集力の向上を図れば、糊残りがなくなって再剥離性が向上すると考えられるが、これらの方法では、再剥離性は向上するものの、粘着力が低下してしまうという問題があった。粘着力の低下は、特に粘着テープ、粘着ラベルを粗面に貼り付けた時に、付きが悪いという粗面接着性の低下や、粘着テープ、粘着ラベルを曲面に貼り付けた時に、粘着テープ・ラベルの端部が浮いてしまうという曲面接着性の低下を招くことになり、特に非極性被着体への接着においてはその低下が顕著に認められる。 The pressure-sensitive adhesive used for the re-peelable pressure-sensitive adhesive product is required to be able to be peeled cleanly without causing adherend contamination such as adhesive residue even after a long time has elapsed since being applied to the adherend. In response to such demands, for example, by increasing the crosslink density of the permanent adhesive type pressure sensitive adhesive or by increasing the glass transition temperature of the pressure sensitive adhesive polymer, if the cohesive force is improved, the adhesive residue is eliminated. Although it is considered that the removability is improved, these methods have the problem that the removability is improved but the adhesive strength is lowered. Decrease in adhesive strength, especially when adhesive tape or adhesive label is applied to a rough surface. Adhesive tape or label decreases when rough surface adhesion is poor, or when adhesive tape or adhesive label is applied to a curved surface. This results in a decrease in curved surface adhesiveness in which the end of the substrate floats, and the decrease is particularly noticeable particularly in adhesion to a nonpolar adherend.
このような諸問題に関して、例えば、（メタ）アクリル酸アルキルエステル、カルボキシル基含有ビニルモノマーからなる（メタ）アクリル系共重合体に、粘着付与剤として特定の水酸基価、軟化点を有する重合ロジンエステル、架橋剤としてイソシアネート化合物及びアジリジン化合物を配合してなるアクリル系粘着剤組成物（例えば、特許文献１参照）や、少なくとも２−エチルヘキシルアクリレート２０〜４０重量部、ブチルアクリレート６０〜８０重量部を主成分として共重合させた粘着剤主剤と、２−エチルヘキシルアクリレート６０〜９０重量部、ブチルアクリレート１０〜４０重量部を主成分として共重合させた粘着剤主剤を混合して得た粘着剤（例えば、特許文献２参照。）が提案されている。 Regarding such problems, for example, a polymerized rosin ester having a specific hydroxyl value and a softening point as a tackifier to a (meth) acrylic copolymer comprising a (meth) acrylic acid alkyl ester and a carboxyl group-containing vinyl monomer An acrylic pressure-sensitive adhesive composition comprising an isocyanate compound and an aziridine compound as a crosslinking agent (for example, see Patent Document 1), and at least 20 to 40 parts by weight of 2-ethylhexyl acrylate and 60 to 80 parts by weight of butyl acrylate A pressure-sensitive adhesive obtained by mixing a pressure-sensitive adhesive main agent copolymerized as a component with a pressure-sensitive adhesive main agent copolymerized mainly with 60 to 90 parts by weight of 2-ethylhexyl acrylate and 10 to 40 parts by weight of butyl acrylate (for example, (See Patent Document 2).
しかしながら、上記特許文献１の開示技術では、各被着体、特にポリオレフィンなどの非極性被着体への接着性や、粗面接着性、曲面接着性についてはまだまだ改善の余地があった。更に、特許文献２の開示技術においても、非極性被着体への接着性には改善の余地があり、また、優れた再剥離性を得るためには、加熱処理が必要であった。 However, the disclosed technique disclosed in Patent Document 1 still has room for improvement with respect to adhesion to each adherend, particularly nonpolar adherends such as polyolefin, rough surface adhesion, and curved surface adhesion. Furthermore, even in the disclosed technique of Patent Document 2, there is room for improvement in adhesion to a nonpolar adherend, and heat treatment is necessary to obtain excellent removability.
そこで、本発明ではこのような背景下において、非極性被着体への接着性に優れる上、粗面や曲面、角面への接着性にも優れ、更に、各種被着体に対する再剥離性にも優れた粘着剤組成物を提供することを目的とするものである。 Therefore, in the present invention, in such a background, in addition to excellent adhesion to nonpolar adherends, it is also excellent in adhesion to rough surfaces, curved surfaces, and angular surfaces, and further, removability to various adherends. It is another object of the present invention to provide an excellent pressure-sensitive adhesive composition.
しかるに、本発明者はかかる課題を解決すべく鋭意研究を重ねた結果、溶解度パラメーター（ＳＰ値）が８．５未満の（メタ）アクリル酸アルキルエステル（ａ１）６０〜９９．９重量％、官能基含有不飽和単量体（ａ２）０．１〜２０重量％、その他の共重合可能な不飽和単量体（ａ３）０〜３９．９重量％を共重合成分として共重合させたアクリル系共重合体（Ａ）と、溶解度パラメーター（ＳＰ値）が８．５以上の（メタ）アクリル酸アルキルエステル（ｂ１）６０〜９９．９重量％、官能基含有不飽和単量体（ｂ２）０．１〜２０重量％、その他の共重合可能な不飽和単量体（ｂ３）０〜３９．９重量％を共重合成分として共重合させたアクリル系共重合体（Ｂ）、及び架橋剤（Ｃ）を含有してなる粘着剤組成物が上記目的に合致することを見いだし、本発明を完成した。 However, as a result of intensive studies to solve such problems, the present inventor has found that the solubility parameter (SP value) is less than 8.5 (meth) acrylic acid alkyl ester (a1) 60 to 99.9% by weight, Acrylic copolymer obtained by copolymerizing 0.1 to 20% by weight of a group-containing unsaturated monomer (a2) and 0 to 39.9% by weight of another copolymerizable unsaturated monomer (a3) as a copolymerization component Copolymer (A), (meth) acrylic acid alkyl ester (b1) having a solubility parameter (SP value) of 8.5 or more, 60 to 99.9% by weight, functional group-containing unsaturated monomer (b2) 0 0.1 to 20% by weight, an acrylic copolymer (B) obtained by copolymerizing 0 to 39.9% by weight of another copolymerizable unsaturated monomer (b3) as a copolymerization component, and a crosslinking agent ( The pressure-sensitive adhesive composition containing C) meets the above purpose. It found that, and have completed the present invention.
本発明の粘着剤組成物は、非極性被着体への接着性に優れる上、粗面や曲面、角面への接着性に優れ、更に各種被着体に対する再剥離性も優れた効果を示し、各種粘着製品、とりわけ再剥離型粘着製品に非常に有用である。 The pressure-sensitive adhesive composition of the present invention has excellent adhesion to non-polar adherends, excellent adhesion to rough surfaces, curved surfaces, and angular surfaces, and also has excellent removability to various adherends. It is very useful for various adhesive products, especially re-peelable adhesive products.
以下、本発明について具体的に説明する。
本発明に用いるアクリル系共重合体（Ａ）としては、溶解度パラメーター（ＳＰ値）が８．５未満、好ましくは８．０以下の（メタ）アクリル酸アルキルエステル（ａ１）と官能基含有不飽和単量体（ａ２）、更に必要に応じてその他の共重合可能な不飽和単量体（ａ３）を共重合成分として共重合させたさせたものである。かかる（メタ）アクリル酸アルキルエステル（ａ１）の溶解度パラメーター（ＳＰ値）が８．５以上では充分な接着性やタックが得られず、特に非極性被着体に対して充分な接着性が得られない。
Hereinafter, the present invention will be specifically described.
The acrylic copolymer (A) used in the present invention has a solubility parameter (SP value) of less than 8.5, preferably 8.0 or less (meth) acrylic acid alkyl ester (a1) and functional group-containing unsaturated. The monomer (a2) and, if necessary, other copolymerizable unsaturated monomer (a3) are copolymerized as a copolymerization component. When the solubility parameter (SP value) of the (meth) acrylic acid alkyl ester (a1) is 8.5 or more, sufficient adhesion and tack cannot be obtained, and particularly sufficient adhesion to a nonpolar adherend is obtained. I can't.
かかる溶解度パラメーター（ＳＰ値）が８．５未満の（メタ）アクリル酸アルキルエステル（ａ１）としては、例えば、２−エチルヘキシルアクリレート（ＳＰ値＝７．８）、イソデシルアクリレート（ＳＰ値＝８．２）、ドデシルアクリレート（ＳＰ値＝７．９）、ステアリルアクリレート（ＳＰ値＝７．９）、イソボルニルアクリレート（ＳＰ値＝８．４）、シクロヘキシルメタアクリレート（ＳＰ値＝８．３）等が挙げられ、中でも２−エチルヘキシルアクリレートが好ましく用いられる。
尚、溶解度パラメーター（ＳＰ値）は、化合物の極性を表す尺度として一般に用いられており、本発明ではＳｍａｌｌの計算式にＨｏｙの凝集エネルギー定数を代入して導いた値を適用するものとし、単位は（ｃａｌ／ｃｍ3）1/2で表される。
Examples of the (meth) acrylic acid alkyl ester (a1) having a solubility parameter (SP value) of less than 8.5 include 2-ethylhexyl acrylate (SP value = 7.8) and isodecyl acrylate (SP value = 8. 2), dodecyl acrylate (SP value = 7.9), stearyl acrylate (SP value = 7.9), isobornyl acrylate (SP value = 8.4), cyclohexyl methacrylate (SP value = 8.3), etc. Among them, 2-ethylhexyl acrylate is preferably used.
The solubility parameter (SP value) is generally used as a scale representing the polarity of a compound. In the present invention, a value derived by substituting Hoy's cohesive energy constant into Small's formula is applied, and the unit Is represented by (cal / cm 3 ) 1/2 .
官能基含有不飽和単量体（ａ２）としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、無水マレイン酸、フマール酸、シトラコン酸、グルタコン酸、イタコン酸、アクリルアミドＮ−グリコール酸、ケイ皮酸、（メタ）アクリル酸のミカエル付加物（例えば、アクリル酸ダイマー、メタクリル酸ダイマー、アクリル酸トリマー、メタクリル酸トリマー、アクリル酸テトラマー、メタクリル酸テトラマー等）などのカルボキシル基含有不飽和単量体や、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド、エチルカルビトールアクリレート、トリプロピレングリコールモノ（メタ）アクリレート、１，４−ブチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、２−ヒドロキシエチルアクリロイルフォスフェート、４−ブチルヒドロキシアクリレート、カプロラクトン変性２−ヒドロキシエチルアクリレート、２−アクリロイルオキシエチルコハク酸、アリルアルコール等のヒドロキシル基含有不飽和単量体、グリシジル（メタ）アクリレート、アリルグリシジル（メタ）アクリレート等のグリシジル基含有不飽和単量体、２−（メタ）アクリロイルオキシエチルイソシアネート等のイソシアネート基含有不飽和単量体、（メタ）アクリルアミド、Ｎ−（ｎ−ブトキシアルキル）（メタ）アクリルアミド等のアミド基含有不飽和単量体、アクリルアミド−３−メチルブチルメチルアミン、ジメチルアミノアルキル（メタ）アクリルアミド等のアミノ基含有不飽和単量体、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、スチレンスルホン酸あるいはその塩等のスルホン酸基含有不飽和単量体などが挙げられるが、中でも、カルボキシル基含有不飽和単量体、ヒドロキシル基含有不飽和単量体が好ましく、特にカルボキシル基含有不飽和単量体では、（メタ）アクリル酸が、ヒドロキシル基含有不飽和単量体では、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等が好ましく用いられる。 Examples of the functional group-containing unsaturated monomer (a2) include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, Carboxylic acid-containing (Meth) acrylic acid Michael adducts (for example, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.) Body, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylate, di Tylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, N-methylol (meth) acrylamide, ethyl carbitol acrylate, tripropylene glycol mono (meth) acrylate, 1,4- Hydroxyl such as butylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 4-butylhydroxyacrylate, caprolactone modified 2-hydroxyethyl acrylate, 2-acryloyloxyethyl succinic acid, allyl alcohol, etc. Group-containing unsaturated monomers, glycidyl group-containing glycidyl (meth) acrylate, allyl glycidyl (meth) acrylate, etc. Monomer, unsaturated monomer containing isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate, amide group-containing unsaturated monomer such as (meth) acrylamide, N- (n-butoxyalkyl) (meth) acrylamide, etc. Isomers, amino group-containing unsaturated monomers such as acrylamide-3-methylbutylmethylamine, dimethylaminoalkyl (meth) acrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2- Examples thereof include sulfonic acid group-containing unsaturated monomers such as acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid or salts thereof. Among them, carboxyl group-containing unsaturated monomers, hydroxyl group-containing unsaturated monomers Are preferred, particularly for unsaturated monomers containing carboxyl groups, 2) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. are preferably used when the acrylic acid is a hydroxyl group-containing unsaturated monomer.
その他の共重合可能な不飽和単量体（ａ３）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート等の溶解度パラメーター（ＳＰ値）が８．５以上の（メタ）アクリル酸アルキルエステルや、スチレン、酢酸ビニル、（メタ）アクリルニトリル等のエチレン性不飽和単量体が挙げられる。 Other copolymerizable unsaturated monomers (a3) have a solubility parameter (SP value) of 8 such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. .5 or more (meth) acrylic acid alkyl esters, ethylenically unsaturated monomers such as styrene, vinyl acetate and (meth) acrylonitrile.
上記（メタ）アクリル酸アルキルエステル（ａ１）、官能基含有不飽和単量体（ａ２）及びその他の共重合可能な不飽和単量体（ａ３）の配合割合（共重合比）は、（メタ）アクリル酸アルキルエステル（ａ１）６０〜９９．９重量％（好ましくは８０〜９９．５重量％、特に好ましくは８５〜９９．５重量％）、官能基含有不飽和単量体（ａ２）０．１〜２０重量％（好ましくは０．５〜２０重量％、特に好ましくは０．５〜１５重量％）、その他の共重合可能な不飽和単量体（ａ３）０〜３９．９重量％（好ましくは０〜１９．５重量％、特に好ましくは０〜１４．５重量％）であることが必要である。かかる配合割合において、（メタ）アクリル酸アルキルエステル（ａ１）が６０重量％未満では充分な接着性やタックが得られず、特に非極性被着体に対して充分な接着性が得られず、９９．９重量％を越えると官能基含有不飽和単量体（ａ２）やその他の共重合可能な不飽和単量体（ａ３）が少量となり充分な再剥離性が得られなくなる。官能基含有不飽和単量体（ａ２）が０．１重量％未満では再剥離性が不充分となり、２０重量％を越えるとガラス転移温度が高くなりすぎ、接着性やタックも低下することとなり、又その他の共重合可能な不飽和単量体（ａ３）が３９．９重量％を越える場合もガラス転移温度が高くなりすぎ、接着性やタックが得られなくなる。 The blending ratio (copolymerization ratio) of the (meth) acrylic acid alkyl ester (a1), the functional group-containing unsaturated monomer (a2) and the other copolymerizable unsaturated monomer (a3) is (meta ) Acrylic acid alkyl ester (a1) 60-99.9% by weight (preferably 80-99.5% by weight, particularly preferably 85-99.5% by weight), functional group-containing unsaturated monomer (a2) 0 0.1 to 20% by weight (preferably 0.5 to 20% by weight, particularly preferably 0.5 to 15% by weight), other copolymerizable unsaturated monomers (a3) 0 to 39.9% by weight (Preferably 0 to 19.5% by weight, particularly preferably 0 to 14.5% by weight). In such a blending ratio, when the (meth) acrylic acid alkyl ester (a1) is less than 60% by weight, sufficient adhesion and tack cannot be obtained, and particularly sufficient adhesion to a nonpolar adherend cannot be obtained. If it exceeds 99.9% by weight, the functional group-containing unsaturated monomer (a2) and other copolymerizable unsaturated monomers (a3) become small, and sufficient removability cannot be obtained. If the functional group-containing unsaturated monomer (a2) is less than 0.1% by weight, the removability is insufficient, and if it exceeds 20% by weight, the glass transition temperature becomes too high, and the adhesiveness and tack are also lowered. In addition, when the other copolymerizable unsaturated monomer (a3) exceeds 39.9% by weight, the glass transition temperature becomes too high, and adhesion and tack cannot be obtained.
本発明で用いるアクリル系共重合体（Ａ）は、前記（ａ１）〜（ａ３）を有機溶媒中でラジカル共重合させる如き、当業者周知の方法によって製造される。
かかる共重合に用いられる有機溶媒としては、トルエン、キシレン等の芳香族炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、ｎ−プロピルアルコール、ｉｓｏ−プロピルアルコール等の脂肪族アルコール類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類等が挙げられる。
また、かかるラジカル共重合に用いられる重合触媒としては、通常のラジカル重合触媒であるアゾビスイソブチロニトリル、ベンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、クメンハイドロパーオキサイド等が挙げられる。
The acrylic copolymer (A) used in the present invention is produced by a method well known to those skilled in the art such as radical copolymerization of the above (a1) to (a3) in an organic solvent.
Examples of the organic solvent used for the copolymerization include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and iso-propyl alcohol, methyl ethyl ketone, Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone.
Examples of the polymerization catalyst used for such radical copolymerization include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like, which are ordinary radical polymerization catalysts.
かくしてアクリル系共重合体（Ａ）が得られるが、かかるアクリル系共重合体（Ａ）の重量平均分子量は、１０万〜１２０万であることが好ましく、更には２０万〜１００万、特には３０万〜９０万が好ましい。かかる重量平均分子量が１０万未満では保持力が弱くなり、１２０万を越えると接着性が低下し好ましくない。
また、アクリル系共重合体（Ａ）のガラス転移温度としては、−１００〜０℃であることが好ましく、更には−８０〜−２０℃が好ましい。かかるガラス転移温度が−１００℃未満では保持力が弱くなり、０℃を越えると接着力が低下し好ましくない。
Thus, an acrylic copolymer (A) is obtained. The weight average molecular weight of the acrylic copolymer (A) is preferably 100,000 to 1,200,000, more preferably 200,000 to 1,000,000. 300,000 to 900,000 are preferable. When the weight average molecular weight is less than 100,000, the holding power becomes weak, and when it exceeds 1.2 million, the adhesiveness is lowered, which is not preferable.
The glass transition temperature of the acrylic copolymer (A) is preferably −100 to 0 ° C., more preferably −80 to −20 ° C. When the glass transition temperature is less than −100 ° C., the holding power becomes weak, and when it exceeds 0 ° C., the adhesive strength is lowered, which is not preferable.
本発明に用いるアクリル系共重合体（Ｂ）としては、溶解度パラメーター（ＳＰ値）が８．５以上の（メタ）アクリル酸アルキルエステル（ｂ１）と官能基含有不飽和単量体（ｂ２）、更に必要に応じてその他の共重合可能な不飽和単量体（ｂ３）を共重合成分として共重合させたさせたものである。かかる（メタ）アクリル酸アルキルエステル（ｂ１）の溶解度パラメーター（ＳＰ値）が８．５未満では再剥離性が不良となる。 As the acrylic copolymer (B) used in the present invention, a (meth) acrylic acid alkyl ester (b1) having a solubility parameter (SP value) of 8.5 or more, a functional group-containing unsaturated monomer (b2), If necessary, other copolymerizable unsaturated monomer (b3) is copolymerized as a copolymerization component. When the solubility parameter (SP value) of the (meth) acrylic acid alkyl ester (b1) is less than 8.5, the removability becomes poor.
溶解度パラメーター（ＳＰ値）が８．５以上の（メタ）アクリル酸アルキルエステル（ｂ１）としては、例えば、メチルアクリレート（ＳＰ値＝８．９）、エチルアクリレート（ＳＰ値＝８．６）、ｎ−ブチルアクリレート（ＳＰ値＝８．９）、ｔ−ブチルアクリレート（ＳＰ値＝８．７）、イソブチルアクリレート（ＳＰ値＝８．５）、メチルメタクリレート（ＳＰ値＝８．８）等が挙げられ、中でもブチルアクリレートが好ましく用いられる。 Examples of the (meth) acrylic acid alkyl ester (b1) having a solubility parameter (SP value) of 8.5 or more include, for example, methyl acrylate (SP value = 8.9), ethyl acrylate (SP value = 8.6), n -Butyl acrylate (SP value = 8.9), t-butyl acrylate (SP value = 8.7), isobutyl acrylate (SP value = 8.5), methyl methacrylate (SP value = 8.8) and the like. Of these, butyl acrylate is preferably used.
官能基含有不飽和単量体（ｂ２）としては、上記の官能基含有不飽和単量体（ａ２）と同様のものが挙げられる Examples of the functional group-containing unsaturated monomer (b2) include the same functional group-containing unsaturated monomers (a2) as those described above.
その他の共重合可能な不飽和単量体（ｂ３）としては、２−エチルヘキシルアクリレート、ドデシルアクリレート、ステアリルアクリレート、イソボルニルアクリレート、シクロヘキシルメタアクリレートなどの溶解度パラメーター（ＳＰ値）が８．５未満の（メタ）アクリル酸アルキルエステルや、スチレン、酢酸ビニル、（メタ）アクリルニトリル等のエチレン性不飽和単量体が挙げられる。 Other copolymerizable unsaturated monomers (b3) have a solubility parameter (SP value) of less than 8.5, such as 2-ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, isobornyl acrylate, and cyclohexyl methacrylate. Examples include (meth) acrylic acid alkyl esters, ethylenically unsaturated monomers such as styrene, vinyl acetate, and (meth) acrylonitrile.
上記（メタ）アクリル酸アルキルエステル（ｂ１）、官能基含有不飽和単量体（ｂ２）及びその他の共重合可能な不飽和単量体（ｂ３）の配合割合（共重合比）は、（メタ）アクリル酸アルキルエステル（ｂ１）６０〜９９．９重量％（好ましくは８０〜９９．５重量％、特に好ましくは８５〜９９．５重量％）、官能基含有不飽和単量体（ｂ２）０．１〜２０重量％（好ましくは０．５〜２０重量％、特に好ましくは０．５〜１５重量％）、その他の共重合可能な不飽和単量体（ｂ３）０〜３９．９重量％（好ましくは０〜１９．５重量％、特に好ましくは０〜１４．５重量％）であることが必要である。かかる配合割合において、（メタ）アクリル酸アルキルエステル（ｂ１）が６０重量％未満では充分な再剥離性が得られず、９９．９重量％を越えると官能基含有不飽和単量体（ｂ２）やその他の共重合可能な不飽和単量体（ｂ３）が少量となり充分な再剥離性が得られない。官能基含有不飽和単量体（ｂ２）が０．１重量％未満では再剥離性が不充分となり、２０重量％を越えるとガラス転移温度が高くなりすぎ、接着性やタックも低下することとなり、その他の共重合可能な不飽和単量体（ｂ３）が３９．９重量％を越えると接着性やタックと再剥離性の両立が困難となる。 The blending ratio (copolymerization ratio) of the (meth) acrylic acid alkyl ester (b1), the functional group-containing unsaturated monomer (b2) and the other copolymerizable unsaturated monomer (b3) is (meta ) Acrylic acid alkyl ester (b1) 60-99.9 wt% (preferably 80-99.5 wt%, particularly preferably 85-99.5 wt%), functional group-containing unsaturated monomer (b2) 0 0.1 to 20% by weight (preferably 0.5 to 20% by weight, particularly preferably 0.5 to 15% by weight), other copolymerizable unsaturated monomer (b3) 0 to 39.9% by weight (Preferably 0 to 19.5% by weight, particularly preferably 0 to 14.5% by weight). In such a blending ratio, if the (meth) acrylic acid alkyl ester (b1) is less than 60% by weight, sufficient removability cannot be obtained, and if it exceeds 99.9% by weight, the functional group-containing unsaturated monomer (b2) And other copolymerizable unsaturated monomers (b3) become small, and sufficient removability cannot be obtained. If the functional group-containing unsaturated monomer (b2) is less than 0.1% by weight, the removability is insufficient, and if it exceeds 20% by weight, the glass transition temperature becomes too high, and the adhesiveness and tack are also lowered. If the other copolymerizable unsaturated monomer (b3) exceeds 39.9% by weight, it becomes difficult to achieve both adhesion and tack and removability.
本発明で用いるアクリル系共重合体（Ｂ）は、上記アクリル系共重合体（Ａ）の場合と同様にして、前記（ｂ１）〜（ｂ３）を有機溶媒中でラジカル重合させる如き、当業者周知の方法によって製造される。かかる共重合に用いられる有機溶媒及び重合触媒は、上記と同様である。 The acrylic copolymer (B) used in the present invention is a person skilled in the art such as radical polymerization of the above (b1) to (b3) in an organic solvent in the same manner as in the case of the acrylic copolymer (A). It is manufactured by a known method. The organic solvent and polymerization catalyst used for such copolymerization are the same as described above.
かくしてアクリル系共重合体（Ｂ）が得られるが、かかるアクリル系共重合体（Ｂ）の重量平均分子量は、１０万〜１２０万であることが好ましく、更には２０万〜１００万、特には３０万〜９０万が好ましい。かかる重量平均分子量が１０万未満では保持力が弱くなり、１２０万を越えると接着性が低下し好ましくない。
また、アクリル共重合体（Ｂ）のガラス転移温度としては、−１００〜０℃であることが好ましく、更には−８０〜−２０℃が好ましい。かかるガラス転移温度が−１００℃未満では保持力が弱くなり、０℃を越えると接着力が低下し好ましくない。
Thus, an acrylic copolymer (B) is obtained. The weight average molecular weight of the acrylic copolymer (B) is preferably 100,000 to 1,200,000, more preferably 200,000 to 1,000,000. 300,000 to 900,000 are preferable. When the weight average molecular weight is less than 100,000, the holding power becomes weak, and when it exceeds 1.2 million, the adhesiveness is lowered, which is not preferable.
The glass transition temperature of the acrylic copolymer (B) is preferably -100 to 0 ° C, and more preferably -80 to -20 ° C. When the glass transition temperature is less than −100 ° C., the holding power becomes weak, and when it exceeds 0 ° C., the adhesive strength is lowered, which is not preferable.
更に本発明では、上記アクリル系共重合体（Ａ）とアクリル系共重合体（Ｂ）の含有割合が、アクリル系共重合体（Ａ）／アクリル系共重合体（Ｂ）＝９９．９／０．１〜６０／４０（重量比）であることが好ましく、更には９９／１〜７０／３０（重量比）であることが好ましい。かかる含有割合が９９．９／０．１（重量比）を越えると再剥離性が低下する傾向にあり、６０／４０（重量比）未満では接着性と再剥離性の両立が困難となり好ましくない。 Furthermore, in the present invention, the content ratio of the acrylic copolymer (A) and the acrylic copolymer (B) is such that the acrylic copolymer (A) / acrylic copolymer (B) = 99.9 / It is preferably 0.1 to 60/40 (weight ratio), and more preferably 99/1 to 70/30 (weight ratio). When the content ratio exceeds 99.9 / 0.1 (weight ratio), the removability tends to decrease. When the content ratio is less than 60/40 (weight ratio), it is difficult to achieve both adhesion and removability. .
又、本発明で用いる架橋剤（Ｃ）としては、エポキシ系、金属塩、金属アルコシド、アルデヒド系化合物、非アミノ樹脂系アミノ化合物、尿素系、イソシアネート系、金属キレート系、メラミン系、アジリジン系等、通常の粘着剤に使用される架橋剤を挙げることができ、これらのうち特に好ましくは多官能イソシアネート、例えばトリレンジイソシアネートのトリメチロールプロパン付加物、エチレンジイソシアネート、１，４−ブタンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、シクロヘキサンジイソシアネート、２，６−トリレンジイソシアネート、４，４‘−ジフェニルメタンジイソシアネート、イソホロンジイソシアネート等が挙げられる。 Moreover, as a crosslinking agent (C) used by this invention, an epoxy type, a metal salt, a metal alcoside, an aldehyde type compound, a non-amino resin type amino compound, a urea type, an isocyanate type, a metal chelate type, a melamine type, an aziridine type etc. Among them, a polyfunctional isocyanate such as a trimethylolpropane adduct of tolylene diisocyanate, ethylene diisocyanate, 1,4-butane diisocyanate, dicyclohexylmethane is particularly preferable. Examples include diisocyanate, cyclohexane diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and isophorone diisocyanate.
かかる架橋剤（Ｃ）の含有量については特に限定されないが、粘着剤組成物全体に対して０．１〜５重量％であることが好ましく、特に好ましくは０．５〜３重量％であり、かかる含有量が０．１重量％未満では架橋反応に乏しく、逆に５重量％を越えると架橋反応が過剰となってしまい好ましくない。 The content of the crosslinking agent (C) is not particularly limited, but is preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the entire pressure-sensitive adhesive composition. If the content is less than 0.1% by weight, the crosslinking reaction is poor. Conversely, if the content exceeds 5% by weight, the crosslinking reaction becomes excessive.
尚、架橋を促進するために酸触媒、例えばパラトルエンスルホン酸、リン酸、塩酸等の架橋促進剤を併用することも可能で、かかる架橋促進剤の添加量は架橋剤（Ｃ）に対して１０〜５０重量％であることが好ましい。 In order to promote crosslinking, an acid catalyst, for example, a crosslinking accelerator such as p-toluenesulfonic acid, phosphoric acid, hydrochloric acid or the like can be used in combination. The addition amount of the crosslinking accelerator is relative to the crosslinking agent (C). It is preferably 10 to 50% by weight.
かくして本発明の粘着剤組成物が得られるが、かかる粘着剤組成物には、必要に応じて、粘着付与剤が配合されていてもよい。粘着付与剤としては、（重合）ロジン系、（重合）ロジンエステル系、テルペン系、テルペンフェノール系、クマロン系、クマロンインデン系、スチレン樹脂系、キシレン樹脂系、フェノール樹脂系、石油樹脂系等が挙げられる。 Thus, although the pressure-sensitive adhesive composition of the present invention is obtained, a tackifier may be blended in the pressure-sensitive adhesive composition as necessary. Tackifiers include (polymerized) rosin, (polymerized) rosin ester, terpene, terpene phenol, coumarone, coumarone indene, styrene resin, xylene resin, phenol resin, petroleum resin, etc. Is mentioned.
粘着付与剤の添加量は、特に限定されないが、アクリル系共重合体（Ａ）とアクリル系共重合体（Ｂ）の合計１００重量部に対して、通常、５〜１００重量部、更には１０〜５０重量部とするのが好ましい。粘着付与剤の添加量が５重量部より少ないと粘着付与剤による粘着力向上効果が発揮されないことがあり、一方、１００重量部より多いと逆にタックが減少して粘着力が低下する恐れがある。 The addition amount of the tackifier is not particularly limited, but is usually 5 to 100 parts by weight, more preferably 10 parts per 100 parts by weight in total of the acrylic copolymer (A) and the acrylic copolymer (B). It is preferable to be -50 parts by weight. If the addition amount of the tackifier is less than 5 parts by weight, the effect of improving the adhesive force by the tackifier may not be exhibited. On the other hand, if it exceeds 100 parts by weight, the tack may be reduced and the adhesive force may be reduced. is there.
又、本発明の粘着剤組成物には、更に、必要に応じて、通常配合される充填剤、顔料、希釈剤、老化防止剤、紫外線吸収剤、紫外線安定剤等の従来公知の添加剤を添加してもよい。これらの添加剤は、１種類又は２種以上使用可能である。これらの添加剤の添加量は、所望する物性が得られるように適時設定すればよい。 Further, the pressure-sensitive adhesive composition of the present invention may further contain conventionally known additives such as fillers, pigments, diluents, anti-aging agents, ultraviolet absorbers, and ultraviolet stabilizers that are usually blended as necessary. It may be added. These additives can be used alone or in combination of two or more. What is necessary is just to set the addition amount of these additives timely so that the desired physical property may be acquired.
本発明において、アクリル系共重合体（Ａ）とアクリル系共重合体（Ｂ）及び架橋剤（Ｃ）、必要に応じて、上記各種添加剤や溶剤を混合して調製された粘着剤組成物は、例えば、粘着シート、粘着ラベル、粘着テープ、両面テープ等の各種粘着製品の製造に好適に用いることができる。このような粘着製品は、基材レスで、又は基材に粘着剤組成物の層を形成し、架橋反応させることにより製造される。 In the present invention, the pressure-sensitive adhesive composition prepared by mixing the acrylic copolymer (A), the acrylic copolymer (B), the crosslinking agent (C), and, if necessary, the above various additives and solvents. Can be suitably used for the production of various pressure-sensitive adhesive products such as pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels, pressure-sensitive adhesive tapes, and double-sided tapes. Such a pressure-sensitive adhesive product is produced without a base material or by forming a layer of a pressure-sensitive adhesive composition on a base material and causing a crosslinking reaction.
基材としては、上質紙、クラフト紙、クレープ紙、グラシン紙等の従来公知の紙類、ポリエチレン、ポリプロピレン、ポリエステル、ポリスチレン、ポリエチレンテレフタレート、ポリ塩化ビニル、セロファン等のプラスチック、織布、不織布等の繊維製品等を利用することができる。基材の形状は、例えば、フィルム状、シート状、テープ状、板状等が挙げられ、これらの性状としては発泡体でもよく、特に限定されるものではない。基材の片面に粘着剤組成物を公知の方法によって塗布することによって、粘着シート、粘着テープ、粘着ラベル等を得ることができる。 Examples of the base material include conventionally known papers such as high-quality paper, kraft paper, crepe paper, and glassine paper, plastics such as polyethylene, polypropylene, polyester, polystyrene, polyethylene terephthalate, polyvinyl chloride, and cellophane, woven fabric, and non-woven fabric. Textile products can be used. Examples of the shape of the substrate include a film shape, a sheet shape, a tape shape, and a plate shape, and these properties may be a foam and are not particularly limited. An adhesive sheet, an adhesive tape, an adhesive label, etc. can be obtained by apply | coating an adhesive composition to the single side | surface of a base material by a well-known method.
粘着剤組成物を基材に塗布する方法は、特に限定されるものではなく、ロールコーティング法、スプレーコーティング法、ディッピング法等の公知の方法を採用することができる。この場合、粘着剤組成物を基材に直接塗布する方法、離型紙等に粘着剤組成物を塗布した後、この塗布物を基材上に転写する方法等いずれも採用可能である。 The method for applying the pressure-sensitive adhesive composition to the substrate is not particularly limited, and a known method such as a roll coating method, a spray coating method, or a dipping method can be employed. In this case, any of a method for directly applying the pressure-sensitive adhesive composition to the substrate, a method for applying the pressure-sensitive adhesive composition to a release paper, and then transferring the coated material onto the substrate can be employed.
粘着剤組成物を塗布した後、乾燥させることにより、基材上に粘着剤層が形成される。乾燥温度は、特に限定されるものではないが、加熱乾燥時に架橋反応が進行するので、架橋剤の種類に応じて架橋反応が速やかに進行する温度で乾燥することが好ましい。又、粘着剤層の厚みは特に限定されないが、５〜１００μｍ、更には１０〜６０μｍであることが接着力と再剥離性の点で好ましい。 After apply | coating an adhesive composition, an adhesive layer is formed on a base material by making it dry. The drying temperature is not particularly limited. However, since the crosslinking reaction proceeds at the time of heat drying, it is preferable to dry at a temperature at which the crosslinking reaction proceeds rapidly according to the type of the crosslinking agent. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 5 to 100 μm, and more preferably 10 to 60 μm from the viewpoint of adhesive strength and removability.
基材上に形成された粘着剤層の表面には、例えば、粘着剤表面を好適に保護、保存するために離型紙を貼着してもよい。離型紙は、粘着製品を使用する際に、粘着剤層表面から引き剥がされる。尚、シート状やテープ状等の基材の背面に粘着剤層が形成されている場合は、この基材の背面に公知の離型剤を塗布して離型剤層を形成しておけば、粘着剤層を内側にして、粘着シート（テープ）をロール状に巻くことにより、粘着剤層は、基材背面の離型剤層と当接することになるので、粘着剤層表面が保護、保存される。 For example, a release paper may be attached to the surface of the pressure-sensitive adhesive layer formed on the substrate in order to suitably protect and preserve the pressure-sensitive adhesive surface. The release paper is peeled off from the pressure-sensitive adhesive layer surface when the pressure-sensitive adhesive product is used. If a pressure-sensitive adhesive layer is formed on the back side of a base material such as a sheet or tape, a known release agent may be applied to the back side of the base material to form a release agent layer. By rolling the adhesive sheet (tape) in a roll shape with the adhesive layer inside, the adhesive layer comes into contact with the release agent layer on the back of the substrate, so the adhesive layer surface is protected. Saved.
かくして本発明の粘着剤組成物を用いた粘着製品（粘着テープ、粘着シート等）が得られるが、被着体としては特に限定されることなく、ステンレス、アルミニウム、鋼、銅、鉄、ニッケル等をはじめとする金属類、ポリアミド、ポリエステル、ポリカーボネート、ポリプロピレン、ポリエチレン、フェノール樹脂、エポキシ樹脂、ポリウレタン、ＡＢＳ、塩化ビニル等の樹脂類、木材類、ガラス類等が挙げられる。特に本発明では、非極性被着体であっても優れた接着性を発揮するのである。
又、本発明の粘着剤組成物は、再剥離性にも優れた効果を有するものであり、マスキング用などの再剥離型の粘着製品として非常に有用である。
Thus, pressure-sensitive adhesive products (pressure-sensitive adhesive tape, pressure-sensitive adhesive sheet, etc.) using the pressure-sensitive adhesive composition of the present invention are obtained, but the adherend is not particularly limited, and stainless steel, aluminum, steel, copper, iron, nickel, etc. And other metals such as polyamide, polyester, polycarbonate, polypropylene, polyethylene, phenol resin, epoxy resin, polyurethane, ABS, vinyl chloride and the like, wood, and glass. In particular, in the present invention, even a nonpolar adherend exhibits excellent adhesion.
Moreover, the pressure-sensitive adhesive composition of the present invention has an effect excellent in removability, and is very useful as a re-peelable pressure-sensitive adhesive product for masking and the like.
以下、実施例を挙げて本発明を具体的に説明する。尚、実施例中、「部」「％」とあるのは、特にことわりのない限り重量基準とする。 Hereinafter, the present invention will be specifically described with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.
〔アクリル系共重合体（Ａ）の調製〕
温度計、撹拌機、滴下ロート及び還流冷却器を備えた反応器内に、表１に示す如きモノマー、及びアゾビスイソブチロニトリル（ＡＩＢＮ）０．１部及び酢酸エチル１００部を仕込み、９０℃に加温して重合させ、重合途中にトルエン１０部にＡＩＢＮ０．１部を溶解させた重合触媒液を逐次追加しながら７時間重合させた後、トルエンで希釈して、アクリル系共重合体（Ａ）の４０％溶液を得た。
又、同様にして、比較例となるアクリル系共重合体（Ａ′）も調製した。
[Preparation of acrylic copolymer (A)]
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, a monomer as shown in Table 1, 0.1 part of azobisisobutyronitrile (AIBN) and 100 parts of ethyl acetate were charged. Polymerized by heating to ℃, polymerized for 7 hours while sequentially adding a polymerization catalyst solution in which 0.1 part of AIBN was dissolved in 10 parts of toluene during the polymerization, then diluted with toluene, acrylic copolymer A 40% solution of (A) was obtained.
Similarly, an acrylic copolymer (A ′) as a comparative example was also prepared.
〔アクリル系共重合体（Ｂ）の調製〕
温度計、撹拌機、滴下ロート及び還流冷却器を備えた反応器内に、表２に示す如きモノマー、及びアゾビスイソブチロニトリル（ＡＩＢＮ）０．１部及び酢酸エチル１００部を仕込み、９０℃に加温して重合させ、重合途中にトルエン１０部にＡＩＢＮ０．１部を溶解させた重合触媒液を逐次追加しながら７時間重合させた後、トルエンで希釈して、アクリル系共重合体（Ｂ）の４０％溶液を得た。
又、同様にして、比較例となるアクリル系共重合体（Ｂ′）も調製した。
[Preparation of acrylic copolymer (B)]
In a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, a monomer as shown in Table 2, 0.1 part of azobisisobutyronitrile (AIBN) and 100 parts of ethyl acetate were charged. Polymerized by heating to ℃, polymerized for 7 hours while sequentially adding a polymerization catalyst solution in which 0.1 part of AIBN was dissolved in 10 parts of toluene during the polymerization, then diluted with toluene, acrylic copolymer A 40% solution of (B) was obtained.
Similarly, an acrylic copolymer (B ′) as a comparative example was also prepared.
ＡＡｃ：アクリル酸
ＶＡｃ：酢酸ビニル
ｎＢＡ：ｎ−ブチルアクリレート（ＳＰ値＝８．９）
AAc: acrylic acid VAc: vinyl acetate nBA: n-butyl acrylate (SP value = 8.9)
ＡＡｃ：アクリル酸
ＶＡｃ：酢酸ビニル
２ＥＨＡ：２−エチルへキシルアクリレート（ＳＰ値＝７．８）
AAc: Acrylic acid VAc: Vinyl acetate 2EHA: 2-ethylhexyl acrylate (SP value = 7.8)
［実施例及び比較例］
表１に示す如くアクリル系共重合体（Ａ）、アクリル系共重合体（Ｂ）、架橋剤（Ｃ）を配合し、粘着剤組成物を得た（固形分４０％）。
尚、架橋剤（Ｃ）としては、多官能性芳香族イソシアネート（商品名「コロネートＬ５５Ｅ」、日本ポリウレタン工業株式会社製）を用いた。
[Examples and Comparative Examples]
As shown in Table 1, an acrylic copolymer (A), an acrylic copolymer (B), and a crosslinking agent (C) were blended to obtain an adhesive composition (solid content 40%).
In addition, as the crosslinking agent (C), polyfunctional aromatic isocyanate (trade name “Coronate L55E”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used.
得られた粘着剤組成物を用いて、以下の通り粘着シートを作製した。
（粘着シートの作製）
基材としてポリエチレンテレフタレート（ＰＥＴ）フィルム（厚さ２５μｍ）を用い、得られた粘着剤組成物を乾燥後の厚さが２５μｍになるように塗布した後、１００℃で３分間乾燥させた。その後、粘着剤層表面に離型紙（サンエー化研株式会社製、商品名「Ｋ−８０ＨＳ」）を貼着して保護した後、温度２３℃、相対湿度５０％の雰囲気下で７日間養生し、粘着シートを得た。
得られた粘着シートについて、以下の評価を行った。尚、離型紙は各種測定試験を実施する際に引き剥がした。
Using the obtained adhesive composition, an adhesive sheet was prepared as follows.
(Preparation of adhesive sheet)
A polyethylene terephthalate (PET) film (thickness: 25 μm) was used as a substrate, and the obtained pressure-sensitive adhesive composition was applied so that the thickness after drying was 25 μm, and then dried at 100 ° C. for 3 minutes. Thereafter, a release paper (trade name “K-80HS”, manufactured by Sanei Kaken Co., Ltd.) is attached to the surface of the pressure-sensitive adhesive layer for protection, and then cured for 7 days in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. A pressure-sensitive adhesive sheet was obtained.
The following evaluation was performed about the obtained adhesive sheet. The release paper was peeled off during various measurement tests.
（初期接着力）
被着体［（１）ＳＵＳ板、（２）ポリエチレン板、（３）ベニヤ板］に、２５ｍｍ×１００ｍｍの上記粘着シートを２３℃、相対湿度５０％の雰囲気下で２ｋｇゴムローラー２往復で加圧貼付し、同雰囲気下で３０分放置した後、常温で剥離速度３００ｍｍ／ｍｉｎで１８０度剥離強度（Ｎ／２５ｍｍ）を測定した。
尚、ベニヤ板での評価は粗面接着力の評価にもなるのである。
(Initial adhesive strength)
The above adhesive sheet of 25 mm × 100 mm is pressed on the adherend [(1) SUS plate, (2) polyethylene plate, (3) veneer plate] in an atmosphere of 23 ° C. and 50% relative humidity with two reciprocations of a 2 kg rubber roller. Affixed and allowed to stand in the same atmosphere for 30 minutes, and then measured 180 ° peel strength (N / 25 mm) at a peel rate of 300 mm / min at room temperature.
In addition, evaluation with a plywood board also becomes evaluation of rough surface adhesive force.
（再剥離性）
被着体［（１）ＳＵＳ板、（２）ポリエチレン板、（３）ベニヤ板、（４）塩化ビニル板］に、２５ｍｍ×１００ｍｍの上記粘着シートを２３℃、相対湿度５０％の雰囲気下で２ｋｇゴムローラー２往復で加圧貼付し、６５℃、相対湿度８０％の雰囲気下で７日間放置した後、常温で手で１３５度方向に粘着シートをゆっくりと剥離したときの粘着剤組成物の被着体への糊残りを観察し、下記の通り評価した。
○・・・糊残りは見られなかった。
△・・・若干の糊残りが見られた。
×・・・糊残りが多く見られた。
(Removability)
Adhering [[1) SUS plate, (2) polyethylene plate, (3) veneer plate, (4) vinyl chloride plate] and 2 kg of the above adhesive sheet of 25 mm × 100 mm in an atmosphere of 23 ° C. and 50% relative humidity. The pressure-sensitive adhesive sheet was applied by reciprocating two rubber rollers and left for 7 days in an atmosphere of 65 ° C. and 80% relative humidity. The adhesive residue on the kimono was observed and evaluated as follows.
○ ... No glue residue was seen.
Δ: Some glue residue was observed.
×: Many adhesive residues were observed.
（曲面接着性）
２５ｍｍφのポリエチレン製の円柱に、粘着シート（幅２５ｍｍ、長さ４０ｍｍ）を貼り付けて、４０℃で５日放置後の粘着シートの浮き具合を観察して、以下の基準で評価した。
○・・・剥がれは全く認められない。
△・・・剥がれは認められるが、端部から平均１０ｍｍ未満である。
×・・・端部から平均１０ｍｍ以上の剥がれが認められる。
(Curved surface adhesion)
A pressure-sensitive adhesive sheet (width 25 mm, length 40 mm) was attached to a 25 mmφ polyethylene cylinder, and the degree of floating of the pressure-sensitive adhesive sheet after standing at 40 ° C. for 5 days was observed and evaluated according to the following criteria.
○: No peeling at all.
Δ: Peeling is observed, but the average is less than 10 mm from the end.
X: Peeling of an average of 10 mm or more is recognized from the end.
（ボールタック）
ＪＩＳ−Ｚ−０２３７に準拠し、２３℃、相対湿度５０％の雰囲気におけるボールタック試験を行った。
(Ball tack)
Based on JIS-Z-0237, a ball tack test was performed in an atmosphere of 23 ° C. and 50% relative humidity.
実施例、比較例の評価結果を表３に示す。 Table 3 shows the evaluation results of Examples and Comparative Examples.
本発明の粘着剤組成物は、溶解度パラメーター（ＳＰ値）が８．５未満の（メタ）アクリル酸アルキルエステル（ａ１）６０〜９９．９重量％、官能基含有不飽和単量体（ａ２）０．１〜２０重量％、その他の共重合可能な不飽和単量体（ａ３）０〜３９．９重量％を共重合成分として共重合させたアクリル系共重合体（Ａ）と、溶解度パラメーター（ＳＰ値）が８．５以上の（メタ）アクリル酸アルキルエステル（ｂ１）６０〜９９．９重量％、官能基含有不飽和単量体（ｂ２）０．１〜２０重量％、その他の共重合可能な不飽和単量体（ｂ３）０〜３９．９重量％を共重合成分として共重合させたアクリル系共重合体（Ｂ）、及び架橋剤（Ｃ）を含有してなる粘着剤組成物であり、非極性被着体への接着力に優れるうえ、粗面や曲面、角面への接着力にも優れ、更に、各種被着体での再剥離性にも優れた効果を有するものであり、粘着テープ、粘着シート等の粘着製品、とりわけ再剥離型の粘着製品に非常に有用である。 The pressure-sensitive adhesive composition of the present invention has a solubility parameter (SP value) of less than 8.5 (meth) acrylic acid alkyl ester (a1) 60 to 99.9% by weight, functional group-containing unsaturated monomer (a2) Acrylic copolymer (A) obtained by copolymerizing 0.1 to 20 wt%, other copolymerizable unsaturated monomer (a3) 0 to 39.9 wt% as a copolymerization component, and solubility parameter (Meth) acrylic acid alkyl ester (b1) 60 to 99.9% by weight (SP value) 8.5 or more, functional group-containing unsaturated monomer (b2) 0.1 to 20% by weight, A pressure-sensitive adhesive composition comprising an acrylic copolymer (B) obtained by copolymerizing 0 to 39.9% by weight of a polymerizable unsaturated monomer (b3) as a copolymerization component, and a crosslinking agent (C). In addition to excellent adhesion to non-polar substrates, rough surfaces, curved surfaces, and corners It has excellent adhesive strength and also has an excellent effect on removability on various adherends. It is very suitable for pressure sensitive adhesive products such as pressure sensitive adhesive tapes and pressure sensitive adhesive sheets, especially removable pressure sensitive adhesive products. Useful.
Claims (4)
The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is used for a re-peelable pressure-sensitive adhesive product.
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