JP5976110B2 - Adhesive composition and adhesive tape using the same - Google Patents
Adhesive composition and adhesive tape using the same Download PDFInfo
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- JP5976110B2 JP5976110B2 JP2014522283A JP2014522283A JP5976110B2 JP 5976110 B2 JP5976110 B2 JP 5976110B2 JP 2014522283 A JP2014522283 A JP 2014522283A JP 2014522283 A JP2014522283 A JP 2014522283A JP 5976110 B2 JP5976110 B2 JP 5976110B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
Description
本発明は、防水性、耐荷重性、加工性、耐衝撃性、耐人工皮脂、耐人工汗油等の諸特性に優れた粘着剤組成物及びそれを用いた粘着テープに関する。 The present invention relates to a pressure-sensitive adhesive composition excellent in various properties such as waterproofness, load resistance, workability, impact resistance, artificial sebum resistance, and artificial sweat oil resistance, and a pressure-sensitive adhesive tape using the same.
近年、スマートフォンやタブレットPCの普及に伴い、その使用環境が多岐に渡って来ている。例えば、水没時に製品内部に水が浸入するのを防ぐ為に、カバーパネルと筐体の間には防水性が必要とされる。また、直接人の肌に触れ高温多湿下で使用されるので、耐皮脂性及び耐汗油性が必要とされる。また、製品のスリム化に伴い、カバーパネルと筐体の固定に用いられる粘着テープは細幅化されて来ているので、細幅の加工性と十分な耐荷重性が必要とされる。さらに、パソコンや大型テレビのLCDと筐体側ガイドフレームを固定する際に使用される粘着テープは意匠性を考慮して細幅化が進んでいるので、この用途に使用される材料であるSUS304、ガルバリウム鋼板、EGI鋼板などの金属類や、ポリカーボネート板、アクリル板、ガラス板に対する耐荷重性が必要とされる。 In recent years, with the spread of smartphones and tablet PCs, the usage environment has been diversified. For example, waterproofing is required between the cover panel and the housing in order to prevent water from entering the product when submerged. Moreover, since it touches a human skin directly and is used under high temperature and high humidity, sebum resistance and sweat oil resistance are required. Moreover, since the adhesive tape used for fixing a cover panel and a housing | casing is becoming narrow along with slimming of a product, narrow workability and sufficient load resistance are required. Furthermore, since the adhesive tape used for fixing the LCD of a personal computer or a large TV and the housing side guide frame has been narrowed in consideration of design, SUS304, which is a material used for this application, Load resistance to metals such as galvalume steel plates and EGI steel plates, polycarbonate plates, acrylic plates and glass plates is required.
特許文献1には、発泡体基材の両面に、アクリル系ポリマーを主成分とするアクリル系粘着剤層が設けられた両面粘着テープが記載されている。また、特許文献2には、黒色着色されている発泡体基材の両面に、アクリル系ポリマーを主成分とするアクリル系粘着剤層が設けられた携帯電話のレンズ固定用両面粘着テープが記載されている。
特許文献3には、発泡体基材の両面に、炭素数4〜12の(メタ)アクリレート及びカルボキシル基を有するビニルモノマーをモノマー成分として有するアクリル系共重合体と、重合ロジンエステル系粘着付与樹脂とを含有するアクリル系粘着剤組成物からなる粘着剤層を有する両面粘着テープが記載されている。
特許文献4には、携帯電子機器の部品固定用に用いられる防水用両面粘着テープであって、発泡体基材の両面にアクリル系共重合体と粘着付与樹脂とを含有する粘着剤層が設けられた両面粘着テープが記載されている。
特許文献5には、ポリエチレン発泡体からなる基材の両面にアクリル共重合体と粘着付与樹脂とを含有する粘着剤層が設けられた両面粘着テープが記載されている。 Patent Document 5 describes a double-sided pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer containing an acrylic copolymer and a tackifying resin is provided on both surfaces of a base material made of polyethylene foam.
本発明は、近年の製品の小型化、薄型化、大画面化に伴い細幅の粘着テープであっても十分な防水性や耐荷重性等の特性が必要になる点に鑑み、上述した粘着テープに関する従来技術を更に改良するものである。 The present invention is based on the above-mentioned pressure-sensitive adhesive in view of the need for sufficient waterproof properties and load-bearing characteristics even with a narrow-width pressure-sensitive adhesive tape with the recent downsizing, thinning, and enlargement of products. It is a further improvement over the prior art relating to tape.
すなわち、本発明の目的は、防水性、耐荷重性、加工性、耐衝撃性、耐人工皮脂、耐人工汗油等の諸特性に優れた粘着剤組成物及びそれを用いた粘着テープを提供する事にある。 That is, an object of the present invention is to provide an adhesive composition excellent in various properties such as waterproofness, load resistance, processability, impact resistance, artificial sebum, artificial sweat oil resistance, and an adhesive tape using the same. There is to do.
本発明は、炭素原子数が4〜12のアルキル基を有する(メタ)アクリル酸アルキルエステル(A1)50〜90質量%、
カルボキシル基含有モノマー(A2)3〜20質量%、
水酸基含有モノマー(A3)3〜20質量%、及び、
炭素原子数1〜3のアルキル基を有する(メタ)アクリル酸アルキルエステル(A4)3〜15質量%
を構成成分として含み、重量平均分子量が70万〜200万、理論Tgが−40℃以下である、ヒドロキシル基及びカルボキシル基を有するアクリル系共重合体(A)と、
架橋剤(B)と
を含有する粘着剤組成物であって、
カルボキシル基含有モノマー(A2)と水酸基含有モノマー(A3)の合計含有量が15質量%以上である粘着剤組成物である。
In the present invention, the (meth) acrylic acid alkyl ester (A1) having an alkyl group having 4 to 12 carbon atoms is 50 to 90% by mass,
3-20% by mass of a carboxyl group-containing monomer (A2),
3 to 20% by mass of a hydroxyl group-containing monomer (A3), and
(Meth) acrylic acid alkyl ester (A4) having an alkyl group having 1 to 3
An acrylic copolymer (A) having a hydroxyl group and a carboxyl group, having a weight average molecular weight of 700,000 to 2,000,000 and a theoretical Tg of −40 ° C. or less,
A pressure-sensitive adhesive composition containing a crosslinking agent (B) ,
The pressure-sensitive adhesive composition has a total content of carboxyl group-containing monomer (A2) and hydroxyl group-containing monomer (A3) of 15% by mass or more .
また本発明は、基材の片面又は両面に、本発明の粘着剤組成物から形成された粘着剤層を有する片面又は両面粘着テープである。 Moreover, this invention is a single-sided or double-sided adhesive tape which has the adhesive layer formed from the adhesive composition of this invention in the single side | surface or both surfaces of a base material.
本発明の粘着剤組成物は、吸水性成分を比較的多く含むにもかかわらず防水性に優れており、さらに耐荷重性、加工性、耐衝撃性、耐人工皮脂、耐人工汗油等の諸特性も優れている。そして、本発明の片面又は両面粘着テープは上記各特性に優れるので、そのような特性が必要な分野における様々な用途に利用可能である。 The pressure-sensitive adhesive composition of the present invention is excellent in waterproofness despite containing a relatively large amount of water-absorbing components, and further, such as load resistance, workability, impact resistance, artificial sebum, artificial sweat oil, and the like. Various characteristics are also excellent. And since the single-sided or double-sided adhesive tape of this invention is excellent in said each characteristic, it can be utilized for various uses in the field | area which requires such a characteristic.
本発明の粘着剤組成物は、アクリル系共重合体(A)と架橋剤(B)を含有する組成物である。 The pressure-sensitive adhesive composition of the present invention is a composition containing an acrylic copolymer (A) and a crosslinking agent (B).
アクリル系共重合体(A)は、以下に説明する(メタ)アクリル酸アルキルエステル(A1)、カルボキシル基含有モノマー(A2)、水酸基含有モノマー(A3)及び(メタ)アクリル酸アルキルエステル(A4)を構成成分として含む、ヒドロキシル基及びカルボキシル基を有するアクリル系重合体である。 The acrylic copolymer (A) includes (meth) acrylic acid alkyl ester (A1), carboxyl group-containing monomer (A2), hydroxyl group-containing monomer (A3), and (meth) acrylic acid alkyl ester (A4) described below. Is an acrylic polymer having a hydroxyl group and a carboxyl group.
(メタ)アクリル酸アルキルエステル(A1)は、炭素原子数が4〜12のアルキル基を有する(メタ)アクリル酸アルキルエステルである。具体例としては、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、イソブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、イソノニル(メタ)アクリレート、ラウリル(メタ)アクリレートが挙げられる。 The (meth) acrylic acid alkyl ester (A1) is a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl. (Meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate may be mentioned.
カルボキシル基含有モノマー(A2)の具体例として、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、2−カルボキシ−1−ブテン、2−カルボキシ−1−ペンテン、2−カルボキシ−1−ヘキセン、2−カルボキシ−1−ヘプテンが挙げられる。カルボキシル基含有モノマー(A2)は、防水性及び耐荷重性を向上する為の成分である。カルボキシル基含有モノマー(A2)の含有量が本発明の範囲よりも低いと、十分な防水性及び耐荷重性が得られない。 Specific examples of the carboxyl group-containing monomer (A2) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, and 2-carboxy- Examples include 1-hexene and 2-carboxy-1-heptene. The carboxyl group-containing monomer (A2) is a component for improving waterproofness and load resistance. When the content of the carboxyl group-containing monomer (A2) is lower than the range of the present invention, sufficient waterproofness and load resistance cannot be obtained.
水酸基含有モノマー(A3)の具体例としては、2−ヒドロキシエチル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレートが挙げられる。 Specific examples of the hydroxyl group-containing monomer (A3) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
(メタ)アクリル酸アルキルエステル(A4)は、炭素原子数1〜3のアルキル基を有する(メタ)アクリル酸アルキルエステルである。具体例として、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)アクリレートが挙げられる。中でも、メチル(メタ)アクリレートが好ましい。 The (meth) acrylic acid alkyl ester (A4) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Of these, methyl (meth) acrylate is preferred.
アクリル系共重合体(A)の構成成分(単量体単位)100質量%中、成分(A1)の含有量は50〜90質量%(好ましくは50〜80質量%)、成分(A2)の含有量は3〜20質量%(好ましくは3〜12質量%)、成分(A3)の含有量は3〜20質量%(好ましくは3〜18質量%)。成分(A4)の含有量は3〜15質量%(好ましくは3〜12質量%)である。また成分(A2)と成分(A3)の合計含有量は、好ましくは13質量%以上である。 In 100% by mass of the constituent component (monomer unit) of the acrylic copolymer (A), the content of the component (A1) is 50 to 90% by mass (preferably 50 to 80% by mass) and the component (A2). Content is 3-20 mass% (preferably 3-12 mass%), and content of a component (A3) is 3-20 mass% (preferably 3-18 mass%). Content of a component (A4) is 3-15 mass% (preferably 3-12 mass%). The total content of the component (A2) and the component (A3) is preferably 13% by mass or more.
アクリル系共重合体(A)は、少なくとも以上説明した成分(A1)〜(A4)を共重合させることにより得られる。重合方法は特に限定されないが、ポリマー設計が容易な点からラジカル溶液重合が好ましい。またアクリル系共重合体(A)とそのモノマーとからなるアクリルシロップをまず調製し、このアクリルシロップに架橋剤(B)と追加の光重合開始剤を配合して重合させても良い。 The acrylic copolymer (A) can be obtained by copolymerizing at least the components (A1) to (A4) described above. The polymerization method is not particularly limited, but radical solution polymerization is preferable from the viewpoint of easy polymer design. Alternatively, an acrylic syrup composed of the acrylic copolymer (A) and its monomer may be prepared first, and the acrylic syrup may be blended with a crosslinking agent (B) and an additional photopolymerization initiator for polymerization.
アクリル系共重合体(A)の製造には、本発明の効果を損なわない範囲内で、成分(A1)〜(A4)以外のモノマーを共重合させても良い。 In the production of the acrylic copolymer (A), monomers other than the components (A1) to (A4) may be copolymerized within a range not impairing the effects of the present invention.
アクリル系共重合体(A)の重量平均分子量は70万〜200万、好ましくは70〜150万である。これら範囲の下限値は、耐荷重性及び加工性の点で意義が有る。また上限値は粘着剤組成物の塗工性の点で意義が有る。この重量平均分子量はGPC法により測定される値である。 The weight average molecular weight of the acrylic copolymer (A) is 700,000 to 2,000,000, preferably 700 to 1,500,000. The lower limit of these ranges is significant in terms of load resistance and workability. The upper limit is significant in terms of the coating properties of the pressure-sensitive adhesive composition. This weight average molecular weight is a value measured by the GPC method.
アクリル系共重合体(A)の理論Tgは−40℃以下、好ましくは−50℃〜−75℃である。この理論TgはFOXの式により算出される値である。 The theoretical Tg of the acrylic copolymer (A) is −40 ° C. or lower, preferably −50 ° C. to −75 ° C. This theoretical Tg is a value calculated by the formula of FOX.
本発明においては、以上説明したアクリル系共重合体(A)を樹脂成分として用いるが、本発明の効果を損なわない範囲内において他の種類の樹脂成分を併用することもできる。ただし、ロジン系樹脂は含まないことが好ましい。ロジン系樹脂を併用すると、粘着剤中の低分子量分が増えて耐荷重性や耐人工皮脂性が低下してしまうからである。 In the present invention, the acrylic copolymer (A) described above is used as a resin component, but other types of resin components can be used in combination as long as the effects of the present invention are not impaired. However, it is preferable not to contain a rosin resin. This is because when the rosin resin is used in combination, the low molecular weight component in the pressure-sensitive adhesive increases and the load resistance and artificial sebum resistance decrease.
本発明に用いる架橋剤(B)は、アクリル系共重合体(A)と反応して架橋構造を形成する為に配合される化合物である。特に、アクリル系共重合体(A)のカルボキシル基及び/又は水酸基と反応し得る化合物が好ましい。架橋剤(B)の配合量は、アクリル系共重合体(A)100質量部に対して、好ましくは0.001〜1質量部である。 The crosslinking agent (B) used in the present invention is a compound blended to react with the acrylic copolymer (A) to form a crosslinked structure. In particular, a compound capable of reacting with a carboxyl group and / or a hydroxyl group of the acrylic copolymer (A) is preferred. The amount of the crosslinking agent (B) is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the acrylic copolymer (A).
架橋剤(B)は、イソシアネート系架橋剤(B1)又はエポキシ系架橋剤(B2)、若しくはその両方を含むことが好ましい。これにより、防水性、耐荷重性、加工性、耐衝撃性、耐人工皮脂、耐人工汗油等の諸特性に優れた粘着テープが得られる。 The crosslinking agent (B) preferably contains an isocyanate crosslinking agent (B1) or an epoxy crosslinking agent (B2), or both. Thereby, an adhesive tape excellent in various properties such as waterproofness, load resistance, processability, impact resistance, artificial sebum resistance and artificial sweat oil resistance can be obtained.
イソシアネート系架橋剤(B1)の具体例としては、トリレンジイソシアネート、キシ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、イソホロンジイソシアネート及びこれらの変性プレポリマーが挙げられる。これらは二種以上を併用しても良い。イソシアネート系架橋剤(B1)の配合量は、アクリル系共重合体(A)100質量部に対して好ましくは0.02〜1質量部、より好ましくは0.05〜0.2質量部である。 Specific examples of the isocyanate-based crosslinking agent (B1) include tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and modified prepolymers thereof. Two or more of these may be used in combination. The amount of the isocyanate-based crosslinking agent (B1) is preferably 0.02 to 1 part by mass, more preferably 0.05 to 0.2 part by mass with respect to 100 parts by mass of the acrylic copolymer (A). .
エポキシ系架橋剤(B2)の具体例としては、N,N,N’,N’−テトラグリシジル−m−キシリレンジアミン、1,3−ビス(N,N’−ジグリシジルアミノメチル)シクロヘキサン等のエポキシ基を2個以上有する化合物が挙げられる。これらは二種以上を併用しても良い。エポキシ系架橋剤(B2)の配合量は、アクリル系共重合体(A)100質量部に対して好ましくは0.001〜0.5質量部、より好ましくは0.001〜0.1質量部である。 Specific examples of the epoxy crosslinking agent (B2) include N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, and the like. And compounds having two or more epoxy groups. Two or more of these may be used in combination. The amount of the epoxy-based crosslinking agent (B2) is preferably 0.001 to 0.5 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). It is.
本発明の粘着剤組成物は、更に遮光性フィラー又は顔料を含んでいても良い。遮光性フィラーの具体例としては、カーボンブラック、カーボンナノチューブ、黒色無機フィラー等が挙げられる。顔料の具体例としては、カーボンブラック、アニリンブラック、アセチレンブラック、ケッチェンブラック等が挙げられる。 The pressure-sensitive adhesive composition of the present invention may further contain a light-shielding filler or a pigment. Specific examples of the light-shielding filler include carbon black, carbon nanotube, and black inorganic filler. Specific examples of the pigment include carbon black, aniline black, acetylene black, ketjen black and the like.
本発明の粘着テープは、基材の片面又は両面に本発明の粘着剤組成物から形成された粘着剤層を有する。粘着剤層の厚さは、好ましくは5〜100μm、より好ましくは10〜100μmである。 The adhesive tape of this invention has the adhesive layer formed from the adhesive composition of this invention on the single side | surface or both surfaces of a base material. The thickness of the pressure-sensitive adhesive layer is preferably 5 to 100 μm, more preferably 10 to 100 μm.
粘着剤層は、本発明の粘着剤組成物を架橋反応させることにより形成できる。例えば、粘着剤組成物を基材上に塗布し、加熱又は紫外線照射により架橋反応させて基材上に粘着剤層を形成できる。また例えば、粘着剤組成物を離型紙又はその他のフィルム上に塗布し、加熱又は紫外線照射により架橋反応させて粘着剤層を形成し、この粘着剤層を基材の片面又は両面に貼り合せることもできる。 The pressure-sensitive adhesive layer can be formed by crosslinking reaction of the pressure-sensitive adhesive composition of the present invention. For example, the pressure-sensitive adhesive composition can be applied on a substrate and subjected to a crosslinking reaction by heating or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the substrate. Further, for example, the pressure-sensitive adhesive composition is applied onto a release paper or other film, and is subjected to a crosslinking reaction by heating or ultraviolet irradiation to form a pressure-sensitive adhesive layer, and this pressure-sensitive adhesive layer is bonded to one or both sides of the substrate. You can also.
粘着剤組成物の塗布には、例えば、ロールコーター、ダイコーター、リップコーター等の塗布装置を使用できる。塗布後に加熱する場合は、加熱による架橋反応と共に粘着剤組成物中の溶剤も除去できる。 For application of the pressure-sensitive adhesive composition, for example, a coating device such as a roll coater, a die coater, or a lip coater can be used. When heating after application, the solvent in the pressure-sensitive adhesive composition can be removed together with the crosslinking reaction by heating.
粘着テープの基材の具体例としては、発泡体(例えば、ポリエチレンフォーム、ポリプロピレンフォーム、ポリウレタンフォーム)、プラスチックフィルム、光学用フィルム(例えば、フィルム導光板、反射防止フィルム、導電性フィルム、視野角拡大フィルム、位相差フィルム、偏光板)が挙げられる。 Specific examples of the base material of the adhesive tape include foam (for example, polyethylene foam, polypropylene foam, polyurethane foam), plastic film, optical film (for example, film light guide plate, antireflection film, conductive film, wide viewing angle). Film, retardation film, polarizing plate).
粘着テープの基材としては、発泡体が好ましく、両面にスキン層を有する発泡体がより好ましい。この発泡体は、好ましくは0.05〜2.0mm厚のテープ状物である。スキン層の厚さは、発泡体の全体厚に対して好ましくは0.5%〜15%である。両面にスキン層を有する発泡体を用いると、粘着剤層の表面状態が均一になり、粘着テープを強く巻き取ることが可能となり、また粘着剤層の表面の平滑性に優れるので被着体への密着性が向上し、その結果、より優れた防水性と耐荷重性が発現する。両面にスキン層を有する発泡体の厚さ方向の割裂力は、15N/cm2以上であることが好ましい。これにより、更に優れた耐荷重性が発現する。As a base material of an adhesive tape, a foam is preferable and a foam having a skin layer on both sides is more preferable. This foam is preferably a tape-like material having a thickness of 0.05 to 2.0 mm. The thickness of the skin layer is preferably 0.5% to 15% with respect to the total thickness of the foam. When a foam having a skin layer on both sides is used, the surface state of the pressure-sensitive adhesive layer becomes uniform, the pressure-sensitive adhesive tape can be strongly wound, and the surface of the pressure-sensitive adhesive layer is excellent in smoothness. As a result, better waterproofness and load resistance are exhibited. The splitting force in the thickness direction of the foam having skin layers on both sides is preferably 15 N / cm 2 or more. Thereby, the further excellent load resistance is expressed.
以下、実施例及び比較例を挙げて、本発明を更に詳細に説明する。以下の記載において「部」は質量部、「%」は質量%を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following description, “parts” means parts by mass, and “%” means mass%.
<製造例1〜17(アクリル系共重合体(A)の調製)>
攪拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応装置に、表1に示す量(%)の成分(A1)〜(A4)と、酢酸エチル、連鎖移動剤としてn−ドデカンチオール及びラジカル重合開始剤としてラウリルパーオキサイド0.1部を仕込んだ。反応装置内に窒素ガスを封入し、攪拌しながら窒素ガス気流下で68℃、3時間、その後78℃、3時間で重合反応させた。その後、室温まで冷却し、酢酸エチルを添加した。これにより、固形分濃度30%のアクリル系共重合体(A)を得た。<Production Examples 1 to 17 (Preparation of acrylic copolymer (A))>
In a reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, the components (A1) to (A4) in the amounts (%) shown in Table 1, ethyl acetate, and n-dodecanethiol as a chain transfer agent And 0.1 part of lauryl peroxide was charged as a radical polymerization initiator. Nitrogen gas was sealed in the reactor, and the polymerization reaction was carried out at 68 ° C. for 3 hours and then at 78 ° C. for 3 hours under a nitrogen gas stream while stirring. Then, it cooled to room temperature and added ethyl acetate. As a result, an acrylic copolymer (A) having a solid content concentration of 30% was obtained.
<実施例1〜13及び比較例1〜11(粘着テープの作製)>
表2に示す通り、製造例1〜17で得たアクリル系共重合体(A)の固形分100部に対して、架橋剤(B)としてイソシアネート系架橋剤(B1)又はエポキシ系架橋剤(B2)を加えて混合し、粘着剤組成物を調製した。<Examples 1 to 13 and Comparative Examples 1 to 11 (production of adhesive tape)>
As shown in Table 2, with respect to 100 parts of the solid content of the acrylic copolymers (A) obtained in Production Examples 1 to 17, as the crosslinking agent (B), an isocyanate crosslinking agent (B1) or an epoxy crosslinking agent ( B2) was added and mixed to prepare an adhesive composition.
この粘着剤組成物を、シリコーン処理された離型紙上に乾燥後の厚みが0.05mmになるように塗布した。次いで、120℃で溶媒を除去・乾燥すると共に架橋反応させて、粘着剤層を形成した。この粘着剤層を、両面に約0.005mm厚のスキン層を有するPE発泡体(0.2mm厚)の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。 This pressure-sensitive adhesive composition was applied on a silicone-treated release paper so that the thickness after drying was 0.05 mm. Next, the solvent was removed and dried at 120 ° C. and a crosslinking reaction was performed to form an adhesive layer. This pressure-sensitive adhesive layer was bonded to both sides of a PE foam (0.2 mm thickness) having a skin layer of about 0.005 mm thickness on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
<製造例18:(アクリルシロップの調製)>
攪拌機、温度計、還流冷却器、UVランプ及び窒素ガス導入口を備えた反応容器に、表1に示す量(%)の成分(A1)〜(A4)と、連鎖移動剤としてn−ドデシルメルカプタン0.01部及び光重合開始剤(BASFジャパン社製、商品名ダロキュア1173)0.01部を添加し、窒素雰囲気下でUV光を照射してアクリルシロップを調製した。アクリルシロップ中のアクリルポリマー濃度は約13%、重量平均分子量は約150万であった。<Production Example 18: (Preparation of acrylic syrup)>
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, UV lamp and nitrogen gas inlet, the components (A1) to (A4) in the amounts (%) shown in Table 1 and n-dodecyl mercaptan as a chain transfer agent An acrylic syrup was prepared by adding 0.01 part and 0.01 part of a photopolymerization initiator (trade name DAROCURE 1173, manufactured by BASF Japan Ltd.) and irradiating with UV light in a nitrogen atmosphere. The acrylic polymer concentration in the acrylic syrup was about 13%, and the weight average molecular weight was about 1.5 million.
<実施例14(粘着テープの作製)>
製造例18で得たアクリルシロップ100部に対して、架橋剤(B)としてヘキサンジオールジアクリレート(新中村化学工業社製、商品名NKエステルA−HD−N)0.08部、追加の光重合開始剤(BASFジャパン社製、商品名ダロキュア1173)0.5部を添加して均一に撹拌した。撹拌混合時に混入した空気泡を脱泡操作により除去して、UV硬化型粘着剤組成物を調製した。<Example 14 (Production of adhesive tape)>
To 100 parts of the acrylic syrup obtained in Production Example 18, hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester A-HD-N) as a crosslinking agent (B), 0.08 part, additional light 0.5 part of a polymerization initiator (BASF Japan, trade name Darocur 1173) was added and stirred uniformly. Air bubbles mixed during stirring and mixing were removed by a defoaming operation to prepare a UV curable pressure-sensitive adhesive composition.
このUV硬化型粘着剤組成物を、表面を離型剤処理した厚さ0.05mのポリエチレンテレフタレート(PET)フィルム上に硬化後の厚さが0.05mmになるように塗布した。その上を厚さ50μmのPETフィルムで被覆し、紫外線を照射して粘着剤層を形成した。この粘着剤層を、両面に約0.005mm厚のスキン層を有するPE発泡体(0.2mm厚)の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。 This UV curable pressure-sensitive adhesive composition was applied on a 0.05 m thick polyethylene terephthalate (PET) film whose surface was treated with a release agent so that the thickness after curing was 0.05 mm. The top was covered with a 50 μm thick PET film and irradiated with ultraviolet rays to form an adhesive layer. This pressure-sensitive adhesive layer was bonded to both sides of a PE foam (0.2 mm thickness) having a skin layer of about 0.005 mm thickness on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
<実施例15(粘着テープの作製)>
実施例1に記載の粘着剤組成物を、両面に約0.20mm厚のスキン層を有するPP発泡体(2.0mm厚)の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。<Example 15 (Production of adhesive tape)>
The pressure-sensitive adhesive composition described in Example 1 was bonded to both sides of a PP foam (2.0 mm thickness) having a skin layer of about 0.20 mm thickness on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
<参考例1(粘着テープの作製)>
実施例1に記載の粘着剤組成物を、両面にスキン層を有しないPE発泡体の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。<Reference Example 1 (Preparation of adhesive tape)>
The pressure-sensitive adhesive composition described in Example 1 was bonded to both sides of a PE foam having no skin layer on both sides. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
<参考例2(粘着テープの作製)>
実施例1に記載の粘着剤組成物を、両面にスキン層を有しないウレタンフォーム発泡体の両面に貼り合せた。そして23℃、50%Rhで7日間養生して、粘着テープを得た。<Reference Example 2 (Preparation of adhesive tape)>
The pressure-sensitive adhesive composition described in Example 1 was bonded to both surfaces of a urethane foam foam having no skin layer on both surfaces. And it cured at 23 degreeC and 50% Rh for 7 days, and obtained the adhesive tape.
「2−EHA」:2−エチルヘキシルアクリレート、
「BA」:n−ブチルアクリレート、
「MA」:メチルアクリレート、
「AA」:アクリル酸、
「2−HEA」:2−ヒドロキシエチルアクリレート。
“2-EHA”: 2-ethylhexyl acrylate,
“BA”: n-butyl acrylate,
“MA”: methyl acrylate,
“AA”: acrylic acid,
“2-HEA”: 2-hydroxyethyl acrylate.
「コロネートL」:日本ポリウレタン社製イソシアネート系架橋剤、
「TETRAD−C」:三菱瓦斯化学社製エポキシ系架橋剤。
“Coronate L”: an isocyanate-based crosslinking agent manufactured by Nippon Polyurethane Co., Ltd.
“TETRAD-C”: an epoxy-based crosslinking agent manufactured by Mitsubishi Gas Chemical Company.
<評価試験>
各実施例及び比較例で得た粘着テープを、以下の方法で評価した。結果を表3〜5に示す。<Evaluation test>
The adhesive tapes obtained in each example and comparative example were evaluated by the following methods. The results are shown in Tables 3-5.
(防水性)
粘着テープを幅5mmで40mm×50mmの枠状に裁断し、一方の離型紙を剥離して2.0mm厚のガラス板に貼り合せ、更にもう一方の離型紙を剥離して2.0mm厚のガラス板を貼り合せた。このサンプルに対して、オートクレーブを用いて23℃で1時間の加圧処理(0.5Mpa)を行い、その後JIS IPX7(防水規格)に基づき一時的に水没させて、以下の基準で防水性を評価した。また、このサンプルに対して、オートクレーブを用いて23℃で1時間の加圧処理(0.1Mpa、0.25Mpa、0.5Mpa)を行い、その後JIS IPX8(防水規格)に基づき水深10cmの水中に沈め、以下の基準で防水性を評価した。
「○」:枠内に水が浸入しなかった。
「×」:枠内に水が浸入した。(Waterproof)
The adhesive tape is cut into a frame of 40 mm × 50 mm with a width of 5 mm, one release paper is peeled off and bonded to a 2.0 mm thick glass plate, and the other release paper is peeled off to a 2.0 mm thickness. A glass plate was bonded. This sample was subjected to pressure treatment (0.5 Mpa) for 1 hour at 23 ° C. using an autoclave, and then submerged temporarily based on JIS IPX7 (waterproof standard). evaluated. In addition, this sample was subjected to pressure treatment (0.1 Mpa, 0.25 Mpa, 0.5 Mpa) for 1 hour at 23 ° C. using an autoclave, and then underwater at a depth of 10 cm based on JIS IPX8 (waterproof standard). The water resistance was evaluated according to the following criteria.
“◯”: Water did not enter the frame.
“×”: Water entered the frame.
(耐人工皮脂・人工肝油性)
粘着テープを幅5mmで40mm×50mmの枠状に裁断し、一方の離型紙を剥離して2.0mm厚のガラス板に貼り合せ、更にもう一方の離型紙を剥離して2.0mm厚のガラス板を貼り合せた。そして、オートクレーブを用いて23℃、0.5Mpa、1時間の加圧処理を行った。このサンプルを、人工皮脂(トリオレイン33.3%、オレイン酸20.0%、スクワレン13.3%、ミリスチルオクタドデシレート33.4%)又は人工汗油に1時間浸漬した。その後サンプルを取り出し、85℃、85%Rhの雰囲気下で72時間静置し、その後通常の雰囲気下に240時間放置した。そのサンプルを目視観察し、以下の基準で耐人工皮脂・人工肝油性を評価した。
「○」:テープの剥れ無し。
「×」:テープの剥れ有り。(Artificial sebum / artificial liver oil resistance)
The adhesive tape is cut into a frame of 40 mm × 50 mm with a width of 5 mm, one release paper is peeled off and bonded to a 2.0 mm thick glass plate, and the other release paper is peeled off to a 2.0 mm thickness. A glass plate was bonded. And the pressurization process of 23 degreeC, 0.5 Mpa, and 1 hour was performed using the autoclave. This sample was immersed in artificial sebum (33.3% triolein, 20.0% oleic acid, 13.3% squalene, 33.4% myristyl octadodecylate) or artificial sweat oil for 1 hour. Thereafter, the sample was taken out, allowed to stand for 72 hours in an atmosphere of 85 ° C. and 85% Rh, and then left in a normal atmosphere for 240 hours. The sample was visually observed, and artificial sebum resistance and artificial liver oil resistance were evaluated according to the following criteria.
“O”: No tape peeling.
“×”: The tape is peeled off.
(耐荷重性)
粘着テープを25mm×25mmのサイズに裁断し、一方の離型紙を剥離した。そして図1示すように、フック2に粘着テープ1(基材1a、粘着層1b)を貼り合せ、次いでもう一方の離型紙を剥離し、被着体3に貼り合せた。この被着体3としては、SUS304、ポリカーボネート板、アクリル板、EGI鋼板、ガルバリウム鋼板、ガラス板を用いた。そしてフック2に1kgfの荷重(錘4)をかけ、85℃で60分間保持し、以下の基準で耐荷重性を評価した。
「○」:60分間フック2は落下しなかった。
「×」:60分以内にフック2が落下した。(Load resistance)
The adhesive tape was cut into a size of 25 mm × 25 mm, and one release paper was peeled off. Then, as shown in FIG. 1, the adhesive tape 1 (
“◯”: The
"X": The
(加工性)
粘着テープを5mm×125mmのサイズで10本に細断した状態のまま、65℃、80%Rh雰囲気下に1日放置した。そして1本毎に180°方向に離型紙ごと剥離し、隣接した部分との癒着を目視にて確認し、以下の基準で加工性を評価した。
「○」:隣接した部分との癒着がほとんど無く、隣接部分を剥すことなく剥離できた。
「×」:隣接した部分に著しい癒着があり、隣接部分が同時に剥れてしまった。(Processability)
The adhesive tape was left for 1 day in an atmosphere of 65 ° C. and 80% Rh with the adhesive tape being chopped into 10 pieces having a size of 5 mm × 125 mm. And it peeled with the release paper in the 180 degree direction for every one, the adhesion with the adjacent part was confirmed visually, and the workability was evaluated on the following references | standards.
“◯”: There was almost no adhesion with the adjacent part, and it was able to peel without peeling off the adjacent part.
"X": There was remarkable adhesion in the adjacent part, and the adjacent part was peeled off at the same time.
(耐衝撃性)
粘着テープを幅5mmで40mm×50mmの枠状に裁断し、一方の離型紙を剥離して、4mm厚のポリカーボネート板に貼り合せ、更にもう一方の剥離紙を剥離し、4mm厚のアクリル板に貼り合せ、20分間養生した。このサンプルを23℃、50%Rh下で、デュポン式衝撃試験機にて300gの錘を高さ600mmから落下させ、テープが剥離した時の落下させた回数を測定し、以下の基準で耐衝撃性を評価した。
「○」:テープが剥離した時に錘を落下させた回数が5回以上。
「×」:テープが剥離した時に錘を落下させた回数が5回未満。(Impact resistance)
Cut the adhesive tape into a 40mm x 50mm frame with a width of 5mm, peel off one release paper and paste it onto a 4mm thick polycarbonate plate, and then peel off the other release paper to form a 4mm thick acrylic plate Bonding and curing for 20 minutes. This sample was dropped at a temperature of 23 ° C. and 50% Rh using a DuPont impact tester and a 300 g weight was dropped from a height of 600 mm, and the number of drops when the tape was peeled was measured. Sex was evaluated.
“◯”: The number of times the weight was dropped when the tape peeled was 5 times or more.
“X”: The number of times the weight was dropped when the tape peeled was less than 5 times.
(発泡体のスキン層厚さ)
175倍のマイクロスコープにて、基材である発泡体のスキン層の厚さを測定した。(Thickness of foam skin layer)
The thickness of the skin layer of the foam as a base material was measured with a 175-fold microscope.
(発泡体の厚さ方向の割裂力)
粘着テープを25mm×25mmにサイズに裁断し、一方の離型紙を剥離した。そして図2示すように、フック2に粘着テープ1(基材1a、粘着層1b)を貼り合せ、次いでもう一方の離型紙を剥離し、被着体3に貼り合せた。そしてフック2を上方向に50mm/minの速度で引張り、発泡体が切れた時の強度[N/cm2]を測定した。(Split force in the thickness direction of the foam)
The adhesive tape was cut into a size of 25 mm × 25 mm, and one release paper was peeled off. Then, as shown in FIG. 2, the adhesive tape 1 (
1 粘着テープ
1a 基材
1b 粘着層
2 フック
3 被着体
4 錘DESCRIPTION OF
Claims (7)
カルボキシル基含有モノマー(A2)3〜20質量%、
水酸基含有モノマー(A3)3〜20質量%、及び、
炭素原子数1〜3のアルキル基を有する(メタ)アクリル酸アルキルエステル(A4)3〜15質量%
を構成成分として含み、重量平均分子量が70万〜200万、理論Tgが−40℃以下である、ヒドロキシル基及びカルボキシル基を有するアクリル系共重合体(A)と、
架橋剤(B)と
を含有する粘着剤組成物であって、
カルボキシル基含有モノマー(A2)と水酸基含有モノマー(A3)の合計含有量が15質量%以上である粘着剤組成物。 (Meth) acrylic acid alkyl ester (A1) having an alkyl group having 4 to 12 carbon atoms, 50 to 90% by mass,
3-20% by mass of a carboxyl group-containing monomer (A2),
3 to 20% by mass of a hydroxyl group-containing monomer (A3), and
(Meth) acrylic acid alkyl ester (A4) having an alkyl group having 1 to 3 carbon atoms 3 to 15% by mass
An acrylic copolymer (A) having a hydroxyl group and a carboxyl group, having a weight average molecular weight of 700,000 to 2,000,000 and a theoretical Tg of −40 ° C. or less,
A pressure-sensitive adhesive composition containing a crosslinking agent (B) ,
The adhesive composition whose sum total content of a carboxyl group-containing monomer (A2) and a hydroxyl-containing monomer (A3) is 15 mass% or more.
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JP6140491B2 (en) * | 2012-08-07 | 2017-05-31 | 日東電工株式会社 | Double-sided adhesive sheet and portable electronic device |
US9976065B2 (en) | 2014-06-06 | 2018-05-22 | 3M Innovative Properties Company | Polyurethane laminating adhesive composition |
WO2016063685A1 (en) | 2014-10-20 | 2016-04-28 | Dic株式会社 | Adhesive composition and adhesive sheet |
KR102316411B1 (en) * | 2014-11-25 | 2021-10-21 | 가부시키가이샤 데라오카 세이사쿠쇼 | Adhesive agent composition and adhesive tape |
JP2016125026A (en) * | 2015-01-07 | 2016-07-11 | 日東電工株式会社 | Pressure-sensitive adhesive tape |
JP6528199B2 (en) * | 2015-05-01 | 2019-06-12 | サイデン化学株式会社 | Pressure-sensitive adhesive composition for marking film, method for producing the same, and marking film |
CN107636106B (en) * | 2015-06-15 | 2019-09-10 | 株式会社寺冈制作所 | Adhesion agent composition and adhesive tape |
KR102422205B1 (en) * | 2016-02-25 | 2022-07-18 | 가부시키가이샤 데라오카 세이사쿠쇼 | Adhesive composition and adhesive tape |
CN113528053B (en) * | 2016-03-02 | 2022-11-08 | 积水化学工业株式会社 | Adhesive tape, adhesive tape for fixing electronic device component, and transparent adhesive tape for optical use |
JP6014781B1 (en) * | 2016-03-02 | 2016-10-25 | 積水化学工業株式会社 | Adhesive tape and adhesive tape for fixing electronic device parts |
US20190292397A1 (en) * | 2016-03-30 | 2019-09-26 | Zeon Corporation | Spray coating sol, vinyl chloride resin molded product having spray coating layer and method for manufacturing the same, and laminate |
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