KR20210049194A - Adhesive composition, adhesive agent, and adhesive sheet - Google Patents

Adhesive composition, adhesive agent, and adhesive sheet Download PDF

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KR20210049194A
KR20210049194A KR1020217012436A KR20217012436A KR20210049194A KR 20210049194 A KR20210049194 A KR 20210049194A KR 1020217012436 A KR1020217012436 A KR 1020217012436A KR 20217012436 A KR20217012436 A KR 20217012436A KR 20210049194 A KR20210049194 A KR 20210049194A
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pressure
meth
sensitive adhesive
acrylic acid
acid ester
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KR1020217012436A
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Korean (ko)
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히토시 오하시
요이치 다카하시
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린텍 가부시키가이샤
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Priority to KR1020227034477A priority Critical patent/KR102658943B1/en
Publication of KR20210049194A publication Critical patent/KR20210049194A/en

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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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3495—Six-membered rings condensed with carbocyclic rings
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Abstract

금속 부재와 접촉해 사용되는 점착제를 구성하기 위한 점착성 조성물로서, 중합체를 구성하는 모노머 단위로서 수산기를 갖는 모노머를 15질량％ 초과 30질량％ 이하 함유하고, 카르복실기를 갖는 모노머를 함유하지 않는 (메트)아크릴산에스테르 중합체(A)와, 벤조트리아졸계 방청제(B)를 함유하는 점착성 조성물. 이러한 점착성 조성물에 의하면, 접촉하는 금속 부재의 부식을 억제할 수 있고, 또한 내습열 백화성도 우수하다.A pressure-sensitive adhesive composition for constituting a pressure-sensitive adhesive used in contact with a metal member, containing more than 15% by mass and not more than 30% by mass of a monomer having a hydroxyl group as a monomer unit constituting a polymer, and not containing a monomer having a carboxyl group (meth) An adhesive composition containing an acrylic acid ester polymer (A) and a benzotriazole type rust inhibitor (B). According to such an adhesive composition, corrosion of a metal member in contact can be suppressed, and it is also excellent in moist heat whitening resistance.

Description

점착성 조성물, 점착제 및 점착 시트{ADHESIVE COMPOSITION, ADHESIVE AGENT, AND ADHESIVE SHEET}Adhesive composition, adhesive, and adhesive sheet {ADHESIVE COMPOSITION, ADHESIVE AGENT, AND ADHESIVE SHEET}

본 발명은, 금속 부재, 특히 터치 패널의 금속 메시 등과 접촉해 사용되는 점착제 및 점착 시트, 그리고 당해 점착제를 구성하기 위한 점착성 조성물에 관한 것이다.The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet used in contact with a metal member, particularly a metal mesh of a touch panel, and a pressure-sensitive adhesive composition for constituting the pressure-sensitive adhesive.

최근의 스마트 폰이나 타블렛 단말 등의 각종 모바일 전자 기기에서는, 디스플레이로서 터치 패널이 사용되는 일이 많아지고 있다. 터치 패널의 방식으로서는, 저항막 방식, 정전 용량 방식 등이 있지만, 상기와 같은 모바일 전자 기기에서는 정전 용량 방식이 주로 채용되고 있다.In recent years, in various mobile electronic devices such as smart phones and tablet terminals, a touch panel is increasingly used as a display. The touch panel method includes a resistive film method, a capacitive method, and the like, but a capacitive method is mainly employed in such mobile electronic devices.

스마트 폰 등의 소형 터치 패널에 사용되고 있는 전극의 상당수는, 주석 도프 산화인듐(ITO)으로 이루어지는 투명 도전막으로 구성된다. 그러나, ITO는 저항값을 10Ω/□ 이하로 낮추는 것이 곤란하기 때문에, 대형 전극 패턴에 ITO를 사용하면 신호의 열화가 발생하고, 따라서 터치 패널을 대형화하는 것은 곤란했다. Many of the electrodes used in small touch panels such as smart phones are made of a transparent conductive film made of tin-doped indium oxide (ITO). However, since it is difficult to lower the resistance value of ITO to 10 Ω/□ or less, signal deterioration occurs when ITO is used for a large electrode pattern, and therefore, it is difficult to increase the size of the touch panel.

그래서, 저항값을 10Ω/□ 이하로 낮출 수 있는 구리가 터치 패널의 전극 재료로서 주목을 모아 구리 전극이 여러 가지 검토되고 있다. 그러나, 구리는 ITO와 비교해 부식되기 쉽기 때문에, ITO 전극에 사용되고 있는 점착제를 그대로 구리 전극에 사용하면, 구리 전극이 부식되어 버린다. 따라서, 구리 전극이 부식되지 않는 점착제가 요구된다.Therefore, copper, which can lower the resistance value to 10 Ω/□ or less, has attracted attention as an electrode material for a touch panel, and various copper electrodes are being studied. However, since copper is more susceptible to corrosion than ITO, if the pressure-sensitive adhesive used for the ITO electrode is used as it is for the copper electrode, the copper electrode will be corroded. Therefore, a pressure-sensitive adhesive that does not corrode the copper electrode is required.

그런데, 터치 패널은, 고온 고습 조건에 놓이는 경우가 있고, 그러한 조건을 거쳐도 문제없이 사용할 수 있는 내구성을 가질 필요가 있다. 그러나, 종래의 터치 패널에 있어서는, 고온 고습 조건 후에 상온 상습으로 되돌렸을 때에, 점착제층이 백화(습열 백화)한다는 문제가 발생하기 쉽다.However, the touch panel may be subjected to high temperature and high humidity conditions, and it is necessary to have durability that can be used without any problems even through such conditions. However, in a conventional touch panel, a problem that the pressure-sensitive adhesive layer is whitened (moist heat whitening) is liable to occur when it is returned to room temperature and humidity after high temperature and high humidity conditions.

특허문헌 1에는, 전자파 차폐 필름에 첩부(貼付)되는 점착제로서, 근적외선 흡수 작용을 부여하기 위해서 근적외선 흡수 색소를 첨가함과 함께, 그 근적외선 흡수 색소의 열화를 방지하기 위해서 벤조트리아졸 화합물을 첨가한 점착제가 개시되어 있다.In Patent Document 1, as a pressure-sensitive adhesive affixed to an electromagnetic wave shielding film, a near-infrared absorbing dye is added to impart a near-infrared absorbing action, and a benzotriazole compound is added to prevent deterioration of the near-infrared absorbing dye. Adhesives are disclosed.

일본 특허 제4818236호Japanese Patent No. 4818236

그러나, 특허문헌 1의 점착제는, 플라즈마 디스플레이 패널의 광학 필터용의 것이고, 이 점착제를 용도가 상이한 터치 패널에 적용할 수는 없다. 예를 들어, 당해 점착제를 터치 패널에 적용하면, 전술한 습열 백화의 문제가 발생한다.However, the pressure-sensitive adhesive of Patent Document 1 is for an optical filter of a plasma display panel, and this pressure-sensitive adhesive cannot be applied to a touch panel having different uses. For example, when the pressure-sensitive adhesive is applied to a touch panel, the above-described wet heat whitening problem occurs.

본 발명은, 상기와 같은 실상을 감안하여 이루어진 것으로, 접촉하는 금속 부재의 부식을 억제할 수 있고, 또한 내습열 백화성도 우수한 점착성 조성물, 점착제 및 점착 시트를 제공하는 것을 목적으로 한다.The present invention has been made in view of the above-described reality, and an object of the present invention is to provide an adhesive composition, an adhesive, and an adhesive sheet, which can suppress corrosion of metal members in contact and are also excellent in moist heat whitening resistance.

상기 목적을 달성하기 위해서, 제1로 본 발명은, 금속 부재와 접촉해 사용되는 점착제를 구성하기 위한 점착성 조성물로서, 중합체를 구성하는 모노머 단위로서 수산기를 갖는 모노머를 15질량％ 초과 30질량％ 이하 함유하고, 카르복실기를 갖는 모노머를 함유하지 않는 (메트)아크릴산에스테르 중합체(A)와, 벤조트리아졸계 방청제(B)를 함유하는 것을 특징으로 하는 점착성 조성물을 제공한다(발명 1).In order to achieve the above object, firstly, the present invention is an adhesive composition for constituting a pressure-sensitive adhesive used in contact with a metal member, comprising more than 15% by mass and not more than 30% by mass of a monomer having a hydroxyl group as a monomer unit constituting the polymer. It contains and contains the (meth)acrylic acid ester polymer (A) which does not contain a monomer which has a carboxyl group, and a benzotriazole type rust inhibitor (B), It provides the adhesive composition characterized by containing (Invention 1).

상기 발명(발명 1)에 관련된 점착성 조성물에 있어서의 (메트)아크릴산에스테르 중합체(A)가, 당해 중합체를 구성하는 모노머 단위로서 수산기 함유 모노머를 상기 양으로 함유함으로써, 얻어지는 점착제는 내습열 백화성이 우수한 것이 된다. 한편, 상기와 같이 수산기 등의 친수성기가 소정량 점착제 중에 존재하면, 점착제는 물을 흡수하기 쉬워지고, 당해 점착제에 접촉하는 금속 부재를 부식시키기 쉬워진다. 그러나, 상기 발명(발명 1)에 관련된 점착성 조성물은, 벤조트리아졸계 방청제(B)를 함유함으로써, 접촉하는 금속 부재가 부식되는 것을 억제할 수 있다. 또, 상기 점착성 조성물(발명 1)에 있어서의 (메트)아크릴산에스테르 중합체(A)는, 카르복실기 함유 모노머를 함유하지 않기 때문에, 카르복실기(산)에 의한 금속 부재의 부식도 방지할 수 있다.When the (meth)acrylic acid ester polymer (A) in the adhesive composition according to the present invention (invention 1) contains a hydroxyl group-containing monomer in the above amount as a monomer unit constituting the polymer, the obtained adhesive has moisture-heat whitening resistance. It becomes excellent. On the other hand, as described above, when a hydrophilic group such as a hydroxyl group is present in the pressure-sensitive adhesive in a predetermined amount, the pressure-sensitive adhesive easily absorbs water, and the metal member in contact with the pressure-sensitive adhesive is easily corroded. However, when the adhesive composition according to the invention (invention 1) contains a benzotriazole-based rust inhibitor (B), corrosion of a metal member in contact can be suppressed. Moreover, since the (meth)acrylic acid ester polymer (A) in the adhesive composition (invention 1) does not contain a carboxyl group-containing monomer, corrosion of a metal member due to a carboxyl group (acid) can also be prevented.

상기 발명(발명 1)에 있어서는, 상기 벤조트리아졸계 방청제(B)로서 1H-벤조트리아졸, 1H-톨릴트리아졸, 1-[N,N-비스(2-에틸헥실)아미노메틸]벤조트리아졸 및 1-[N,N-비스(2-에틸헥실)아미노메틸]메틸벤조트리아졸로 이루어지는 군에서 선택되는 적어도 1종을 함유하는 것이 바람직하다(발명 2).In the above invention (invention 1), as the benzotriazole-based rust inhibitor (B), 1H-benzotriazole, 1H-tolyltriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole And at least one selected from the group consisting of 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole (Invention 2).

상기 발명(발명 1, 2)에 있어서, 상기 (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 호모폴리머로서의 유리 전이 온도가 70℃ 이상인 하드 모노머를 함유하는 것이 바람직하다(발명 3).In the above invention (Inventions 1 and 2), the (meth)acrylic acid ester polymer (A) preferably contains a hard monomer having a glass transition temperature of 70°C or higher as a homopolymer as a monomer unit constituting the polymer ( Invention 3).

상기 발명(발명 1∼3)에 있어서, 상기 (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 (메트)아크릴산 2-에틸헥실을 함유하는 것이 바람직하다(발명 4). In the above invention (Inventions 1 to 3), the (meth)acrylic acid ester polymer (A) preferably contains 2-ethylhexyl (meth)acrylate as a monomer unit constituting the polymer (Invention 4).

상기 발명(발명 1∼4)에 있어서, 상기 점착성 조성물은, 추가로 가교제(C)를 함유하는 것이 바람직하다(발명 5).In the above invention (inventions 1 to 4), it is preferable that the adhesive composition further contains a crosslinking agent (C) (invention 5).

제2로 본 발명은, 상기 점착성 조성물(발명 1∼5)을 가교시켜 이루어지는 점착제를 제공한다(발명 6).Secondly, the present invention provides a pressure-sensitive adhesive formed by crosslinking the pressure-sensitive adhesive composition (invention 1 to 5) (invention 6).

상기 발명(발명 6)에 있어서는, 1.0㎒에 있어서의 유전율이 2.0∼8.0인 것이 바람직하다(발명 7).In the above invention (invention 6), it is preferable that the dielectric constant at 1.0 MHz is 2.0 to 8.0 (invention 7).

제3으로 본 발명은, 2장의 박리 시트와, 상기 2장의 박리 시트의 박리면과 접하도록 상기 박리 시트에 협지된 점착제층을 구비하고, 상기 점착제층이 상기 점착제(발명 6, 7)로 이루어지는 것을 특징으로 하는 점착 시트를 제공한다(발명 8).Thirdly, the present invention comprises two release sheets and an adhesive layer sandwiched between the release sheets so as to contact the release surfaces of the two release sheets, and the adhesive layer is made of the adhesive (inventions 6 and 7). It provides a pressure-sensitive adhesive sheet, characterized in that (invention 8).

상기 발명(발명 8)에 있어서, 상기 점착제층은, 터치 패널에 있어서 금속 메시와 접촉하도록 배치되는 것이 바람직하다(발명 9).In the above invention (invention 8), it is preferable that the pressure-sensitive adhesive layer is disposed so as to contact a metal mesh in a touch panel (invention 9).

본 발명에 관련된 점착성 조성물, 점착제 및 점착 시트에 의하면, 접촉하는 금속 부재의 부식을 억제할 수 있고, 또한 내습열 백화성도 우수하다.According to the pressure-sensitive adhesive composition, the pressure-sensitive adhesive and the pressure-sensitive adhesive sheet according to the present invention, corrosion of a metal member to be contacted can be suppressed, and also excellent in moist heat whitening resistance.

도 1은 본 발명의 일실시형태에 관련된 점착 시트의 단면도이다.
도 2는 터치 패널의 일구성예를 나타내는 단면도이다. 1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention.
2 is a cross-sectional view showing a configuration example of a touch panel.

이하, 본 발명의 실시형태에 대해 설명한다.Hereinafter, an embodiment of the present invention will be described.

〔점착성 조성물〕[Adhesive composition]

본 실시형태에 관련된 점착성 조성물(이하 「점착성 조성물P」라고 한다)은, 금속 부재와 접촉해 사용되는 점착제를 구성하기 위한 점착성 조성물이다. 금속 부재로서는, 바람직하게는 정전 용량 방식의 터치 패널에 있어서의 전극으로서의 구리 메시가 예시되지만, 이것에 한정되는 것은 아니다.The adhesive composition (hereinafter referred to as "adhesive composition P") according to the present embodiment is an adhesive composition for constituting an adhesive used in contact with a metal member. The metal member is preferably a copper mesh as an electrode in a capacitive touch panel, but is not limited thereto.

점착성 조성물P는, 중합체를 구성하는 모노머 단위로서 수산기를 갖는 모노머(수산기 함유 모노머)를 15질량％ 초과 30질량％ 이하 함유하고, 카르복실기를 갖는 모노머(카르복실기 함유 모노머)를 함유하지 않는 (메트)아크릴산에스테르 중합체(A)와, 벤조트리아졸계 방청제(B)를 함유하고, 바람직하게는 추가로 가교제(C)를 함유한다. 또한, 본 명세서에 있어서, (메트)아크릴산에스테르란, 아크릴산에스테르 및 메타크릴산에스테르 양방을 의미한다. 다른 유사 용어도 동일하다. 또, 「중합체」에는 「공중합체」의 개념도 포함되는 것으로 한다. The adhesive composition P is a (meth)acrylic acid containing more than 15% by mass and not more than 30% by mass of a monomer having a hydroxyl group (a monomer containing a hydroxyl group) as a monomer unit constituting the polymer, and not containing a monomer having a carboxyl group (a monomer containing a carboxyl group). It contains an ester polymer (A) and a benzotriazole-based rust inhibitor (B), and preferably further contains a crosslinking agent (C). In addition, in this specification, (meth)acrylic acid ester means both an acrylic acid ester and a methacrylic acid ester. Other similar terms are the same. In addition, the concept of "copolymer" shall also be included in the "polymer".

상기 점착성 조성물P에 있어서의 (메트)아크릴산에스테르 중합체(A)가, 당해 중합체를 구성하는 모노머 단위로서 수산기 함유 모노머를 상기 양으로 함유함으로써, 얻어지는 점착제는, 고온 고습 조건(예를 들어, 85℃, 85％RH의 조건하에서 240시간)을 실시한 후, 상온 상습으로 되돌렸을 때의 백화가 억제되고, 즉 내습열 백화성이 우수한 것이 된다. (메트)아크릴산에스테르 중합체(A)가 모노머 단위로서 상기 양으로 수산기 함유 모노머를 함유하면, 얻어지는 점착제 중에 소정량의 수산기가 잔존하게 된다. 수산기는 친수성기이고, 그러한 친수성기가 소정량 점착제 중에 존재하면, 점착제가 고온 고습 조건하에 놓인 경우라도, 그 고온 고습 조건하에서 점착제에 침입한 수분과의 상용성이 양호하고, 그 결과 점착제의 백화가 억제되게 된다.The (meth)acrylic acid ester polymer (A) in the adhesive composition P contains a hydroxyl group-containing monomer in the amount described above as a monomer unit constituting the polymer. , Under the condition of 85%RH, for 240 hours), whitening at the time of returning to room temperature and humidity is suppressed, that is, the whitening resistance is excellent. When the (meth)acrylic acid ester polymer (A) contains a hydroxyl group-containing monomer in the above amount as a monomer unit, a predetermined amount of hydroxyl groups will remain in the obtained pressure-sensitive adhesive. The hydroxyl group is a hydrophilic group, and if such a hydrophilic group is present in a predetermined amount of the pressure-sensitive adhesive, even when the pressure-sensitive adhesive is placed under high temperature and high humidity conditions, the compatibility with the moisture that has penetrated the pressure-sensitive adhesive under the high-temperature and high-humidity conditions is good, and as a result, whitening of the pressure-sensitive adhesive is suppressed. It will be.

단, 상기와 같이 친수성기가 소정량 점착제 중에 존재하면, 점착제는 물을 흡수하기 쉬워지고, 당해 점착제에 접촉하는 금속 부재를 부식시키기 쉬워진다. 그러나, 본 실시형태에 관련된 점착성 조성물P는, 벤조트리아졸계 방청제(B)를 함유함으로써, 접촉하는 금속 부재가 부식되는 것을 억제할 수 있다.However, as described above, when a hydrophilic group is present in the pressure-sensitive adhesive in a predetermined amount, the pressure-sensitive adhesive easily absorbs water, and the metal member in contact with the pressure-sensitive adhesive is easily corroded. However, when the adhesive composition P according to the present embodiment contains the benzotriazole-based rust inhibitor (B), it is possible to suppress corrosion of the metal member in contact.

또한, 벤조트리아졸계 방청제(B)의 존재에 의해, 후술하는 가교제(C)와 (메트)아크릴산에스테르 중합체(A)의 반응성이 저하하는 경향이 있지만, (메트)아크릴산에스테르 중합체(A)가 모노머 단위로서 상기 양으로 수산기 함유 모노머를 함유하면, 가교제(C)와 (메트)아크릴산에스테르 중합체(A)의 반응이 양호하게 진행된다.In addition, the reactivity of the crosslinking agent (C) and (meth)acrylic acid ester polymer (A) described later tends to decrease due to the presence of the benzotriazole-based rust inhibitor (B), but the (meth)acrylic acid ester polymer (A) is a monomer. When the hydroxyl-containing monomer is contained in the above amount as a unit, the reaction between the crosslinking agent (C) and the (meth)acrylic acid ester polymer (A) proceeds favorably.

한편, 상기 점착성 조성물P에 있어서의 (메트)아크릴산에스테르 중합체(A)는, 카르복실기 함유 모노머를 함유하지 않기 때문에, 카르복실기(산)에 의한 금속 부재의 부식도 방지할 수 있다.On the other hand, since the (meth)acrylic acid ester polymer (A) in the adhesive composition P does not contain a carboxyl group-containing monomer, corrosion of a metal member due to a carboxyl group (acid) can also be prevented.

(1) (메트)아크릴산에스테르 중합체(A)(1) (meth)acrylic acid ester polymer (A)

(메트)아크릴산에스테르 중합체(A)가, 당해 중합체를 구성하는 모노머 단위로서 함유하는 수산기 함유 모노머로서는, 예를 들어 (메트)아크릴산 2-하이드록시에틸, (메트)아크릴산 2-하이드록시프로필, (메트)아크릴산 3-하이드록시프로필, (메트)아크릴산 2-하이드록시부틸, (메트)아크릴산 3-하이드록시부틸, (메트)아크릴산 4-하이드록시부틸 등의 (메트)아크릴산하이드록시알킬에스테르 등을 들 수 있다. 그 중에서도, 얻어지는 (메트)아크릴산에스테르 중합체(A)에 있어서의 수산기의 가교제(C)와의 반응성 및 다른 단량체와의 공중합성의 점에서 (메트)아크릴산 2-하이드록시에틸이 바람직하다. 이들은 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.Examples of the hydroxyl group-containing monomer contained in the (meth)acrylic acid ester polymer (A) as a monomer unit constituting the polymer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( (Meth)acrylate hydroxyalkyl esters such as 3-hydroxypropyl meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Can be lifted. Among them, 2-hydroxyethyl (meth)acrylate is preferable from the viewpoint of the reactivity of the hydroxyl group in the obtained (meth)acrylic acid ester polymer (A) with the crosslinking agent (C) and copolymerization with other monomers. These may be used alone or in combination of two or more.

전술한 바와 같이, (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 수산기 함유 모노머를 15질량％ 초과 30질량％ 이하 함유한다. (메트)아크릴산에스테르 중합체(A)에 있어서의 모노머 단위로서의 수산기 함유 모노머의 함유량이 15질량％ 이하이면, 점착제층이 내습열 백화성이 열등한 것이 된다. 한편, 수산기 함유 모노머의 함유량이 30질량％를 초과하면, 벤조트리아졸계 방청제(B)를 함유했다고 해도, 점착제에 흡수되는 수분량이 지나치게 많아져, 금속 부재를 부식시키기 쉬워진다. As described above, the (meth)acrylic acid ester polymer (A) contains more than 15% by mass and 30% by mass or less of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. When the content of the hydroxyl group-containing monomer as a monomer unit in the (meth)acrylic acid ester polymer (A) is 15% by mass or less, the pressure-sensitive adhesive layer will have inferior moist heat whitening resistance. On the other hand, when the content of the hydroxyl-containing monomer exceeds 30% by mass, even if the benzotriazole-based rust inhibitor (B) is contained, the amount of water absorbed by the pressure-sensitive adhesive becomes excessively large, and the metal member is easily corroded.

이러한 관점에서, (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 수산기 함유 모노머를 16∼25질량％ 함유하는 것이 바람직하고, 특히 18∼20질량％ 함유하는 것이 바람직하다. From this point of view, the (meth)acrylic acid ester polymer (A) preferably contains 16 to 25% by mass of a hydroxyl group-containing monomer as a monomer unit constituting the polymer, and particularly preferably 18 to 20% by mass.

(메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 카르복실기 함유 모노머를 함유하지 않는다. 여기서, 「카르복실기를 갖는 모노머를 함유하지 않는다」란, 카르복실기를 갖는 모노머를 실질적으로 함유하지 않는 것을 의미하고, 카르복실기 함유 모노머를 전혀 함유하지 않는 것 외에, 카르복실기에 의한 금속 부재의 부식이 생기지 않을 정도로 카르복실기 함유 모노머를 함유하는 것을 허용하는 것이다. 구체적으로는, (메트)아크릴산에스테르 중합체(A) 중에, 모노머 단위로서 카르복실기 함유 모노머를 0.1질량％ 이하, 바람직하게는 0.01질량％ 이하의 양으로 함유하는 것을 허용하는 것이다. The (meth)acrylic acid ester polymer (A) does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Here, "no monomer having a carboxyl group" means substantially not containing a monomer having a carboxyl group, and in addition to not containing a carboxyl group-containing monomer at all, corrosion of a metal member due to a carboxyl group does not occur. It allows to contain a carboxyl group-containing monomer. Specifically, it is allowed to contain a carboxyl group-containing monomer in an amount of 0.1% by mass or less, preferably 0.01% by mass or less as a monomer unit in the (meth)acrylic acid ester polymer (A).

(메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 알킬기의 탄소수가 1∼20인 (메트)아크릴산알킬에스테르를 함유하는 것이 바람직하다. 이것에 의해, 얻어지는 점착제는, 바람직한 점착성을 발현할 수 있다. 또한, 당해 (메트)아크릴산알킬에스테르로부터 후술하는 하드 모노머는 제외된다.It is preferable that the (meth)acrylic acid ester polymer (A) contains an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group as a monomer unit constituting the polymer. Thereby, the obtained adhesive can express preferable adhesiveness. In addition, the hard monomer mentioned later is excluded from the said alkyl (meth)acrylate.

알킬기의 탄소수가 1∼20인 (메트)아크릴산알킬에스테르로서는, 예를 들어 아크릴산메틸, (메트)아크릴산에틸, (메트)아크릴산프로필, (메트)아크릴산 n-부틸, (메트)아크릴산 n-펜틸, (메트)아크릴산 n-헥실, (메트)아크릴산 2-에틸헥실, (메트)아크릴산이소옥틸, (메트)아크릴산 n-데실, (메트)아크릴산 n-도데실, (메트)아크릴산미리스틸, (메트)아크릴산팔미틸, (메트)아크릴산스테아릴 등을 들 수 있다. 그 중에서도, 점착성을 보다 향상시키는 관점에서, 알킬기의 탄소수가 1∼8인 (메트)아크릴산에스테르가 바람직하고, (메트)아크릴산 n-부틸 및 (메트)아크릴산 2-에틸헥실이 특히 바람직하며, (메트)아크릴산 2-에틸헥실이 더 바람직하다. (메트)아크릴산 2-에틸헥실에 의하면, 얻어지는 점착제의 유전율을 낮게 해, 터치 패널의 오작동을 억제할 수 있다. 또한, 이들은 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.Examples of the alkyl (meth)acrylate ester having 1 to 20 carbon atoms in the alkyl group include methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, N-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, myristyl (meth)acrylate, (meth) ) Palmityl acrylate, stearyl (meth)acrylate, and the like. Among them, from the viewpoint of further improving the adhesiveness, (meth)acrylic acid ester having 1 to 8 carbon atoms in the alkyl group is preferred, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are particularly preferred, and ( 2-ethylhexyl meth)acrylic acid is more preferred. According to 2-ethylhexyl (meth)acrylate, the dielectric constant of the obtained pressure-sensitive adhesive is lowered, and malfunction of the touch panel can be suppressed. In addition, these may be used individually or may be used in combination of 2 or more types.

(메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 알킬기의 탄소수가 1∼20인 (메트)아크릴산알킬에스테르를 30∼85질량％ 함유하는 것이 바람직하고, 특히 40∼75질량％ 함유하는 것이 바람직하며, 나아가서는 50∼65질량％ 함유하는 것이 바람직하다.The (meth)acrylic acid ester polymer (A) preferably contains 30 to 85% by mass of an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group as a monomer unit constituting the polymer, and particularly 40 to 75% by mass It is preferable to contain it in %, and it is preferable to contain it further 50-65 mass %.

또, (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 호모폴리머로서의 유리 전이 온도(Tg)가 70℃ 이상인 하드 모노머를 함유하는 것이 바람직하다. (메트)아크릴산에스테르 중합체(A)를 구성하는 모노머 단위로서 상기 하드 모노머를 함유시킴으로써, 얻어지는 점착제는, 응집력이 향상해, 내구성이 우수한 것이 된다. 특히, (메트)아크릴산에스테르 중합체(A)를 구성하는 모노머 단위로서 (메트)아크릴산 2-에틸헥실을 사용하는 경우에는, 응집력이 낮아지는 경향이 있기 때문에, 상기 하드 모노머를 사용하는 것이 바람직하다. 상기 하드 모노머의 호모폴리머로서의 유리 전이 온도(Tg)는, 75∼200℃인 것이 바람직하고, 특히 80∼180℃인 것이 바람직하다. In addition, it is preferable that the (meth)acrylic acid ester polymer (A) contains a hard monomer having a glass transition temperature (Tg) of 70°C or higher as a homopolymer as a monomer unit constituting the polymer. The adhesive obtained by containing the said hard monomer as a monomer unit which comprises a (meth)acrylic acid ester polymer (A) improves the cohesive force and becomes a thing excellent in durability. In particular, in the case of using 2-ethylhexyl (meth)acrylate as the monomer unit constituting the (meth)acrylic acid ester polymer (A), since the cohesive strength tends to decrease, it is preferable to use the hard monomer. The glass transition temperature (Tg) of the hard monomer as a homopolymer is preferably 75 to 200°C, and particularly preferably 80 to 180°C.

상기 하드 모노머로서는, 예를 들어 메타크릴산메틸(Tg 105℃), 아크릴산이소보르닐(Tg 94℃), 메타크릴산이소보르닐(Tg 180℃), 아크릴로일모르폴린(Tg 145℃), 아크릴산아다만틸(Tg 115℃), 메타크릴산아다만틸(Tg 141℃), 디메틸아크릴아미드(Tg 89℃), 아크릴아미드(Tg 165℃) 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다. Examples of the hard monomer include methyl methacrylate (Tg 105°C), isobornyl acrylate (Tg 94°C), isobornyl methacrylate (Tg 180°C), and acryloylmorpholine (Tg 145°C). , Adamantyl acrylate (Tg 115°C), adamantyl methacrylate (Tg 141°C), dimethylacrylamide (Tg 89°C), and acrylamide (Tg 165°C). These may be used alone or in combination of two or more.

상기 하드 모노머 중에서도, 점착성이나 투명성 등 다른 특성에 대한 악영향을 방지하면서 하드 모노머의 성능을 보다 발휘시키는 관점에서, 메타크릴산메틸, 아크릴산이소보르닐 및 아크릴로일모르폴린이 보다 바람직하고, 메타크릴산메틸이 특히 바람직하다.Among the hard monomers, methyl methacrylate, isobornyl acrylate, and acryloylmorpholine are more preferable from the viewpoint of more exerting the performance of the hard monomer while preventing adverse effects on other properties such as adhesion and transparency. Methyl acid is particularly preferred.

(메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 상기 하드 모노머를 10∼45질량％ 함유하는 것이 바람직하고, 15∼30질량％ 함유하는 것이 특히 바람직하다. 상기 하드 모노머를 10질량％ 이상 함유함으로써, 당해 모노머 단위에 의한 내구성의 개선 효과를 기대할 수 있다. 한편, 상기 하드 모노머를 45질량％ 이하의 함유량으로 함으로써, (메트)아크릴산에스테르 중합체(A) 중에 있어서의 그 이외의 모노머 단위의 상대적인 부족을 방지해, 얻어지는 점착제의 점착성 및 내습열 백화성을 우수한 것으로 할 수 있다.The (meth)acrylic acid ester polymer (A) preferably contains 10 to 45% by mass of the hard monomer as a monomer unit constituting the polymer, and particularly preferably contains 15 to 30% by mass. By containing 10 mass% or more of the said hard monomer, the improvement effect of the durability by the said monomer unit can be expected. On the other hand, by making the content of the hard monomer 45% by mass or less, the relative shortage of other monomer units in the (meth)acrylic acid ester polymer (A) is prevented, and the obtained adhesive has excellent adhesion and moist heat whitening resistance. It can be done.

(메트)아크릴산에스테르 중합체(A)는, 원하는 바에 따라, 당해 중합체를 구성하는 모노머 단위로서 다른 모노머를 함유해도 된다. 다른 모노머로서는, 수산기 함유 모노머의 작용을 방해하지 않기 위해서도, 반응성을 갖는 관능기를 포함하지 않는 모노머가 바람직하다. 이러한 다른 모노머로서는, 예를 들어 (메트)아크릴산메톡시에틸, (메트)아크릴산에톡시에틸 등의 (메트)아크릴산알콕시알킬에스테르, (메트)아크릴산시클로헥실 등의 지방족환을 갖는 (메트)아크릴산에스테르, (메트)아크릴산 N,N-디메틸아미노에틸, (메트)아크릴산 N,N-디메틸아미노프로필 등의 비가교성의 3급 아미노기를 갖는 (메트)아크릴산에스테르, 아세트산비닐, 스티렌 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다. The (meth)acrylic acid ester polymer (A) may contain other monomers as monomer units constituting the polymer as desired. As the other monomer, a monomer that does not contain a reactive functional group is preferable in order not to interfere with the action of the hydroxyl group-containing monomer. Examples of such other monomers include (meth)acrylate alkoxyalkyl esters such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate, and (meth)acrylate esters having an aliphatic ring such as cyclohexyl (meth)acrylate. , (Meth)acrylic acid ester having a non-crosslinkable tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate, vinyl acetate, styrene, and the like. These may be used alone or in combination of two or more.

(메트)아크릴산에스테르 중합체(A)의 중합 양태는, 랜덤 공중합체여도 되고, 블록 공중합체여도 된다.The polymerization aspect of the (meth)acrylic acid ester polymer (A) may be a random copolymer or a block copolymer.

(메트)아크릴산에스테르 중합체(A)의 중량 평균 분자량은 30만∼100만이고, 40만∼90만인 것이 바람직하며, 특히 50만∼70만인 것이 바람직하다. 또한, 본 명세서에 있어서의 중량 평균 분자량은, 겔 퍼미에이션 크로마토그래피(GPC)법에 의해 측정한 폴리스티렌 환산의 값이다.The weight average molecular weight of the (meth)acrylic acid ester polymer (A) is 300,000 to 1 million, preferably 400,000 to 900,000, and particularly preferably 500,000 to 700,000. In addition, the weight average molecular weight in this specification is a value in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

점착성 조성물P의 점착 주제인 (메트)아크릴산에스테르 중합체(A)의 중량 평균 분자량이 30만 이상임으로써, 얻어지는 점착제의 내구성이 향상되고, (메트)아크릴산에스테르 중합체(A)의 중량 평균 분자량이 100만 이하임으로써, 점착성 조성물P의 도공성이 양호해진다. When the weight average molecular weight of the (meth)acrylic acid ester polymer (A), which is the adhesive main substance of the adhesive composition P, is 300,000 or more, the durability of the obtained adhesive is improved, and the weight average molecular weight of the (meth)acrylic acid ester polymer (A) is 1 million. By the following, the coatability of the adhesive composition P becomes good.

또한, 점착성 조성물P에 있어서, (메트)아크릴산에스테르 중합체(A)는, 1종을 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.Moreover, in the adhesive composition P, the (meth)acrylic acid ester polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more types.

(2) 벤조트리아졸계 방청제(B) (2) Benzotriazole-based rust inhibitor (B)

벤조트리아졸계 방청제(B)로서는, 예를 들어 1H-벤조트리아졸, 1H-톨릴트리아졸, 1-[N,N-비스(2-에틸헥실)아미노메틸]벤조트리아졸, 1-[N,N-비스(2-에틸헥실)아미노메틸]메틸벤조트리아졸, 카르복시벤조트리아졸, 2,2'-[[(메틸-1H-벤조트리아졸-1-일)메틸]이미노]비스에탄올 등을 들 수 있다. 그 중에서도, 1H-벤조트리아졸, 1H-톨릴트리아졸, 1-[N,N-비스(2-에틸헥실)아미노메틸]벤조트리아졸 및 1-[N,N-비스(2-에틸헥실)아미노메틸]메틸벤조트리아졸이 바람직하다. 이들에 의하면, 접촉하는 금속 부재의 부식을 특히 효과적으로 억제할 수 있다. 상기 벤조트리아졸계 방청제(B)는, 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다. As the benzotriazole-based rust inhibitor (B), for example, 1H-benzotriazole, 1H-tolyltriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N, N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, carboxybenzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, etc. Can be mentioned. Among them, 1H-benzotriazole, 1H-tolyltriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole and 1-[N,N-bis(2-ethylhexyl) Aminomethyl]methylbenzotriazole is preferred. According to these, corrosion of the metal member in contact can be suppressed particularly effectively. The benzotriazole-based rust inhibitor (B) may be used alone or in combination of two or more.

점착성 조성물P 중에 있어서의 벤조트리아졸계 방청제(B)의 함유량은, (메트)아크릴산에스테르 중합체(A) 100질량부에 대해 0.01∼2.0질량부인 것이 바람직하고, 특히 0.05∼1.0질량부인 것이 바람직하며, 나아가서는 0.1∼0.5질량부인 것이 바람직하다. 벤조트리아졸계 방청제(B)의 함유량이 0.01질량부 이상임으로써, 금속 부재의 부식 억제 효과가 충분히 얻어진다. 또, 벤조트리아졸계 방청제(B)의 함유량이 2.0질량부 이하이면, 점착성에 악영향을 주지 않는다. The content of the benzotriazole-based rust inhibitor (B) in the adhesive composition P is preferably 0.01 to 2.0 parts by mass, particularly preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the (meth)acrylic acid ester polymer (A), Furthermore, it is preferably 0.1 to 0.5 parts by mass. When the content of the benzotriazole-based rust inhibitor (B) is 0.01 parts by mass or more, the effect of inhibiting corrosion of the metal member is sufficiently obtained. Moreover, when the content of the benzotriazole-based rust inhibitor (B) is 2.0 parts by mass or less, the adhesiveness is not adversely affected.

(3) 가교제(C) (3) Crosslinking agent (C)

점착성 조성물P는, 가교제(C)를 함유하는 것이 바람직하다. 점착성 조성물P는, 가교제(C)를 함유함으로써 (메트)아크릴산에스테르 공중합체(A)를 가교시켜 삼차원 망목 구조를 형성해, 얻어지는 점착제의 응집력을 향상시킨다.It is preferable that the adhesive composition P contains a crosslinking agent (C). By containing the crosslinking agent (C), the adhesive composition P crosslinks the (meth)acrylic acid ester copolymer (A) to form a three-dimensional network structure, thereby improving the cohesive strength of the obtained adhesive.

가교제(C)로서는, (메트)아크릴산에스테르 공중합체(A)가 갖는 반응성기(모노머 단위인 수산기 함유 모노머의 수산기)와 반응하는 것이면 되고, 예를 들어 이소시아네이트계 가교제, 에폭시계 가교제, 아민계 가교제, 멜라민계 가교제, 아지리딘계 가교제, 하이드라진계 가교제, 알데하이드계 가교제, 옥사졸린계 가교제, 금속 알콕사이드계 가교제, 금속 킬레이트계 가교제, 금속염계 가교제, 암모늄염계 가교제 등을 들 수 있다. 상기 중에서도, (메트)아크릴산에스테르 중합체(A)가 갖는 수산기와의 반응성이 우수한 이소시아네이트계 가교제를 사용하는 것이 바람직하다. 또한, 가교제(C)는, 1종을 단독으로, 또는 2종 이상을 조합하여 사용할 수 있다.As the crosslinking agent (C), any one reacting with the reactive group (hydroxyl group of a hydroxyl group-containing monomer that is a monomer unit) of the (meth)acrylic acid ester copolymer (A) may be used. For example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an amine crosslinking agent , Melamine-based cross-linking agents, aziridine-based cross-linking agents, hydrazine-based cross-linking agents, aldehyde-based cross-linking agents, oxazoline-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, and ammonium salt-based cross-linking agents. Among the above, it is preferable to use an isocyanate-based crosslinking agent excellent in reactivity with a hydroxyl group of the (meth)acrylic acid ester polymer (A). In addition, crosslinking agent (C) can be used individually by 1 type or in combination of 2 or more types.

이소시아네이트계 가교제는, 적어도 폴리이소시아네이트 화합물을 포함하는 것이다. 폴리이소시아네이트 화합물로서는, 예를 들어 톨릴렌디이소시아네이트, 디페닐메탄디이소시아네이트, 자일릴렌디이소시아네이트 등의 방향족 폴리이소시아네이트, 헥사메틸렌디이소시아네이트 등의 지방족 폴리이소시아네이트, 이소포론디이소시아네이트, 수소 첨가 디페닐메탄디이소시아네이트 등의 지환식 폴리이소시아네이트 등, 및 그들의 뷰렛체, 이소시아누레이트체, 나아가서는 에틸렌글리콜, 프로필렌글리콜, 네오펜틸글리콜, 트리메틸올프로판, 피마자유 등의 저분자 활성 수소 함유 화합물과의 반응물인 어덕트체 등을 들 수 있다. 그 중에서도 수산기와의 반응성의 관점에서, 트리메틸올프로판 변성의 방향족 폴리이소시아네이트, 특히 트리메틸올프로판 변성 톨릴렌디이소시아네이트가 바람직하다.The isocyanate crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Adducts which are reactants with low-molecular active hydrogen-containing compounds such as alicyclic polyisocyanates, etc., and their biuret body, isocyanurate body, and further ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Sieves, etc. are mentioned. Among them, from the viewpoint of reactivity with a hydroxyl group, trimethylolpropane-modified aromatic polyisocyanates, particularly trimethylolpropane-modified tolylene diisocyanate are preferred.

점착성 조성물P 중에 있어서의 가교제(C)의 함유량은, (메트)아크릴산에스테르 중합체(A) 100질량부에 대해 0.001∼10질량부인 것이 바람직하고, 특히 0.01∼5질량부인 것이 바람직하며, 나아가서는 0.02∼1질량부인 것이 바람직하다.The content of the crosslinking agent (C) in the adhesive composition P is preferably 0.001 to 10 parts by mass, particularly preferably 0.01 to 5 parts by mass, and further 0.02 to 100 parts by mass of the (meth)acrylic acid ester polymer (A). It is preferable that it is -1 mass part.

가교제(C)의 함유량이 상기 범위에 있음으로써, 얻어지는 점착제의 응집력이 바람직한 것이 되어, 점착제의 내구성이 향상된다. When the content of the crosslinking agent (C) is in the above range, the cohesive strength of the obtained pressure-sensitive adhesive becomes preferable, and the durability of the pressure-sensitive adhesive is improved.

(4) 각종 첨가제 (4) Various additives

점착성 조성물P에는, 원하는 바에 따라 아크릴계 점착제에 통상 사용되고 있는 각종 첨가제, 예를 들어 실란 커플링제, 대전 방지제, 점착 부여제, 산화 방지제, 자외선 흡수제, 광 안정제, 연화제, 충전제, 굴절률 조정제 등을 첨가할 수 있다.To the adhesive composition P, as desired, various additives commonly used in acrylic adhesives, such as a silane coupling agent, an antistatic agent, a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a filler, a refractive index adjuster, etc., may be added. I can.

특히 내구성을 개선하는 관점에서, 점착성 조성물P에는, 첨가제로서 실란 커플링제가 첨가되는 것이 바람직하다. 실란 커플링제로서는, 분자 내에 알콕시실릴기를 적어도 1개 갖는 유기 규소 화합물이고, (메트)아크릴산에스테르 중합체(A)와의 상용성이 양호한 것이 바람직하다. 또, 점착 시트(1)가 광학 용도인 경우에는, 광 투과성을 갖는 실란 커플링제가 바람직하다. In particular, from the viewpoint of improving durability, it is preferable that a silane coupling agent is added to the adhesive composition P as an additive. As a silane coupling agent, it is an organosilicon compound which has at least 1 alkoxysilyl group in a molecule|numerator, and it is preferable that compatibility with the (meth)acrylic acid ester polymer (A) is good. Moreover, when the adhesive sheet 1 is an optical use, a silane coupling agent which has light transmittance is preferable.

이러한 실란 커플링제로서는, 예를 들어 비닐트리메톡시실란, 비닐트리에톡시실란, 메타크릴옥시프로필트리메톡시실란 등의 중합성 불포화기 함유 규소 화합물, 3-글리시독시프로필트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란 등의 에폭시 구조를 갖는 규소 화합물, 3-메르캅토프로필트리메톡시실란, 3-메르캅토프로필트리에톡시실란, 3-메르캅토프로필디메톡시메틸실란 등의 메르캅토기 함유 규소 화합물, 3-아미노프로필트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필메틸디메톡시실란 등의 아미노기 함유 규소 화합물, 3-클로로프로필트리메톡시실란, 3-이소시아네이트프로필트리에톡시실란, 혹은 이들 중 적어도 1개와, 메틸트리에톡시실란, 에틸트리에톡시실란, 메틸트리메톡시실란, 에틸트리메톡시실란 등의 알킬기 함유 규소 화합물의 축합물 등을 들 수 있다. 이들은, 1종을 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.Examples of such silane coupling agents include silicon compounds containing polymerizable unsaturated groups such as vinyl trimethoxysilane, vinyl triethoxysilane, and methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Silicon compounds having an epoxy structure such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl Mercapto group-containing silicon compounds such as dimethoxymethylsilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3 -Amino group-containing silicon compounds such as aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, or at least one of them, methyltriethoxysilane, ethyltriethoxysilane , A condensation product of an alkyl group-containing silicon compound such as methyl trimethoxysilane and ethyl trimethoxysilane. These may be used individually by 1 type, and may be used in combination of 2 or more types.

실란 커플링제의 첨가량은, (메트)아크릴산에스테르 중합체(A) 100질량부에 대해 0.01∼1.0질량부인 것이 바람직하고, 특히 0.05∼0.5질량부인 것이 바람직하다.The amount of the silane coupling agent added is preferably 0.01 to 1.0 parts by mass, and particularly preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the (meth)acrylic acid ester polymer (A).

(5) 점착성 조성물의 제조(5) Preparation of adhesive composition

점착성 조성물P는, (메트)아크릴산에스테르 중합체(A)를 제조하고, 얻어진 (메트)아크릴산에스테르 중합체(A)와, 벤조트리아졸계 방청제(B)를 혼합함과 함께, 원하는 바에 따라 가교제(C) 및 첨가제를 첨가함으로써 제조할 수 있다. The adhesive composition P is prepared by preparing a (meth)acrylic acid ester polymer (A), and mixing the obtained (meth)acrylic acid ester polymer (A) and a benzotriazole-based rust inhibitor (B), and a crosslinking agent (C) as desired. And it can be produced by adding an additive.

(메트)아크릴산에스테르 중합체(A)는, 중합체를 구성하는 모노머 단위의 혼합물을 통상적인 라디칼 중합법으로 중합함으로써 제조할 수 있다. (메트)아크릴산에스테르 중합체(A)의 중합은, 원하는 바에 따라 중합 개시제를 사용하여, 용액 중합법 등에 의해 행할 수 있다. 중합 용매로서는, 예를 들어 아세트산에틸, 아세트산 n-부틸, 아세트산이소부틸, 톨루엔, 아세톤, 헥산, 메틸에틸케톤 등을 들 수 있고, 2종류 이상을 병용해도 된다. The (meth)acrylic acid ester polymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by a conventional radical polymerization method. The polymerization of the (meth)acrylic acid ester polymer (A) can be performed by a solution polymerization method or the like using a polymerization initiator as desired. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more types may be used in combination.

중합 개시제로서는, 아조계 화합물, 유기 과산화물 등을 들 수 있고, 2종류 이상을 병용해도 된다. 아조계 화합물로서는, 예를 들어 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴), 1,1'-아조비스(시클로헥산1-카르보니트릴), 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(2,4-디메틸-4-메톡시발레로니트릴), 디메틸2,2'-아조비스(2-메틸프로피오네이트), 4,4'-아조비스(4-시아노발레르산), 2,2'-아조비스(2-하이드록시메틸프로피오니트릴), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판] 등을 들 수 있다. Examples of the polymerization initiator include an azo compound and an organic peroxide, and two or more types may be used in combination. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane1-carbonitrile) ), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl2,2'-azo Bis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azo Bis[2-(2-imidazolin-2-yl)propane] and the like.

유기 과산화물로서는, 예를 들어 과산화벤조일, t-부틸퍼벤조에이트, 쿠멘하이드로퍼옥사이드, 디이소프로필퍼옥시디카보네이트, 디-n-프로필퍼옥시디카보네이트, 디(2-에톡시에틸)퍼옥시디카보네이트, t-부틸퍼옥시네오데카노에이트, t-부틸퍼옥시피발레이트, (3,5,5-트리메틸헥사노일)퍼옥사이드, 디프로피오닐퍼옥사이드, 디아세틸퍼옥사이드 등을 들 수 있다. Examples of the organic peroxide include benzoyl peroxide, t-butylperbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, diacetyl peroxide, and the like.

또한, 상기 중합 공정에 있어서, 2-메르캅토에탄올 등의 연쇄 이동제를 배합함으로써, 얻어지는 중합체의 중량 평균 분자량을 조절할 수 있다. In addition, in the polymerization step, by blending a chain transfer agent such as 2-mercaptoethanol, the weight average molecular weight of the obtained polymer can be adjusted.

(메트)아크릴산에스테르 중합체(A)가 얻어졌다면, (메트)아크릴산에스테르 중합체(A)의 용액에, 벤조트리아졸계 방청제(B), 그리고 원하는 바에 따라 가교제(C), 첨가제 및 희석 용제를 첨가하고, 충분히 혼합함으로써, 용제로 희석된 점착성 조성물P(도포 용액)를 얻는다. If the (meth)acrylic acid ester polymer (A) was obtained, to the solution of the (meth)acrylic acid ester polymer (A), a benzotriazole-based rust inhibitor (B), and optionally a crosslinking agent (C), an additive, and a diluting solvent were added. , By sufficiently mixing, an adhesive composition P (coating solution) diluted with a solvent is obtained.

상기 희석 용제로서는, 예를 들어 헥산, 헵탄, 시클로헥산 등의 지방족 탄화수소, 톨루엔, 자일렌 등의 방향족 탄화수소, 염화메틸렌, 염화에틸렌 등의 할로겐화탄화수소, 메탄올, 에탄올, 프로판올, 부탄올, 1-메톡시-2-프로판올 등의 알코올, 아세톤, 메틸에틸케톤, 2-펜타논, 이소포론, 시클로헥사논 등의 케톤, 아세트산에틸, 아세트산부틸 등의 에스테르, 에틸셀로솔브 등의 셀로솔브계 용제 등이 사용된다.Examples of the diluting solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, and 1-methoxy Alcohol such as -2-propanol, ketones such as 2-pentanone, isophorone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolve solvents such as ethyl cellosolve, etc. Is used.

이와 같이 하여 조제된 도포 용액의 농도·점도로서는, 코팅 가능한 범위이면 되고, 특별히 제한되지 않고, 상황에 따라 적절히 선정할 수 있다. 예를 들어, 점착성 조성물P의 농도가 10∼40질량％가 되도록 희석한다. 또한, 도포 용액을 얻을 때에 희석 용제 등의 첨가는 필요 조건은 아니고, 점착성 조성물P가 코팅 가능한 점도 등이면 희석 용제를 첨가하지 않아도 된다. 이 경우, 점착성 조성물P는, (메트)아크릴산에스테르 중합체(A)의 중합 용매를 그대로 희석 용제로 하는 도포 용액이 된다. The concentration and viscosity of the coating solution thus prepared may be within a range in which coating is possible, and is not particularly limited, and may be appropriately selected depending on the situation. For example, it is diluted so that the concentration of the adhesive composition P becomes 10-40 mass %. In addition, addition of a diluting solvent or the like is not a necessary condition when obtaining a coating solution, and if the adhesive composition P has a coatable viscosity or the like, it is not necessary to add a diluting solvent. In this case, the adhesive composition P becomes a coating solution using the polymerization solvent of the (meth)acrylic acid ester polymer (A) as a diluting solvent.

〔점착제〕〔adhesive〕

본 실시형태에 관련된 점착제는, 점착성 조성물P를 가교시켜 이루어지는 것이다. 점착성 조성물P의 가교는, 가열 처리에 의해 행할 수 있다. 또한, 이 가열 처리는, 점착성 조성물P의 희석 용제 등을 휘발시킬 때의 건조 처리로 겸할 수도 있다. The pressure-sensitive adhesive according to the present embodiment is obtained by crosslinking the pressure-sensitive adhesive composition P. Crosslinking of the adhesive composition P can be performed by heat treatment. In addition, this heat treatment can also serve as a drying treatment when volatilizing the diluted solvent of the adhesive composition P or the like.

가열 처리를 행하는 경우, 가열 온도는 50∼150℃인 것이 바람직하고, 특히 70∼120℃인 것이 바람직하다. 또, 가열 시간은 30초∼10분인 것이 바람직하고, 특히 50초∼2분인 것이 바람직하다. 가열 처리 후, 필요에 따라 상온(예를 들어, 23℃, 50％RH)에서 1∼2주간 정도의 양생 기간을 설정해도 된다. 이 양생 기간이 필요한 경우에는 양생 기간 경과 후, 양생 기간이 불필요한 경우에는 가열 처리 종료 후, 점착제층이 형성된다. When performing heat treatment, the heating temperature is preferably 50 to 150°C, and particularly preferably 70 to 120°C. Moreover, it is preferable that it is 30 seconds-10 minutes, and, as for a heating time, it is especially preferable that it is 50 seconds-2 minutes. After the heat treatment, if necessary, a curing period of about 1 to 2 weeks may be set at room temperature (eg, 23° C., 50% RH). When this curing period is necessary, after the curing period has elapsed, and when the curing period is unnecessary, after the heat treatment is completed, an adhesive layer is formed.

점착성 조성물P를 가교시켜 얻어지는 점착제는, 벤조트리아졸계 방청제(B)에 의해, 접촉하는 금속 부재의 부식을 억제할 수 있고, 또한 상기 서술한 (메트)아크릴산에스테르 중합체(A)가 갖는 수산기에 의해 우수한 내습열 백화성을 발휘한다.The pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition P can be suppressed from corrosion of the metal member in contact with the benzotriazole-based rust preventive agent (B), and further, by the hydroxyl group of the (meth)acrylic acid ester polymer (A) described above. It exhibits excellent moist heat whitening resistance.

본 실시형태에 관련된 점착제는, 1.0㎒에 있어서의 유전율이 2.0∼8.0인 것이 바람직하고, 특히 2.0∼7.0인 것이 바람직하며, 나아가서는 2.0∼6.0인 것이 바람직하다. 점착제의 유전율이 2.0∼8.0임으로써, 점착제에서 기인하는 터치 패널의 오작동을 효과적으로 억제할 수 있다. 또한, 점착제의 유전율 측정 방법은, 후술하는 시험예에 나타내는 바와 같다. The pressure-sensitive adhesive according to the present embodiment preferably has a dielectric constant of 2.0 to 8.0 at 1.0 MHz, particularly preferably 2.0 to 7.0, and further preferably 2.0 to 6.0. When the dielectric constant of the pressure-sensitive adhesive is 2.0 to 8.0, malfunction of the touch panel caused by the pressure-sensitive adhesive can be effectively suppressed. In addition, the dielectric constant measurement method of an adhesive is as shown in the test example mentioned later.

〔점착 시트〕〔Adhesive Sheet〕

도 1에 나타내는 바와 같이, 본 실시형태에 관련된 점착 시트(1)는, 2장의 박리 시트(12a, 12b)와, 그들 2장의 박리 시트(12a, 12b)의 박리면과 접하도록 당해 2장의 박리 시트(12a, 12b)에 협지된 점착제층(11)으로 구성된다. 단, 점착 시트(1)에 있어서 박리 시트(12a, 12b)는 필수 구성 요소는 아니고, 점착 시트(1)의 사용 시에 박리·제거되는 것이다. 또한, 본 명세서에 있어서의 박리 시트의 박리면이란, 박리 시트에 있어서 박리성을 갖는 면을 말하고, 박리 처리를 실시한 면 및 박리 처리를 실시하지 않아도 박리성을 나타내는 면 모두 포함하는 것이다.As shown in Fig. 1, the pressure-sensitive adhesive sheet 1 according to the present embodiment has two release sheets 12a, 12b, and the two release sheets 12a, 12b so as to be in contact with the release surfaces of the two release sheets 12a, 12b. It is composed of the pressure-sensitive adhesive layer 11 sandwiched between the sheets 12a and 12b. However, in the pressure-sensitive adhesive sheet 1, the release sheets 12a and 12b are not essential components, and are peeled and removed when the pressure-sensitive adhesive sheet 1 is used. In addition, the peeling surface of a release sheet in this specification refers to the surface which has peelability in a peeling sheet, and includes both a peeling-treated surface and a surface exhibiting peelability even if no peeling treatment has been performed.

(1) 점착제층(1) adhesive layer

점착제층(11)은, 전술한 점착성 조성물P를 가교시켜 이루어지는 점착제로 구성된다. 점착제층(11)의 두께(JIS K7130에 준해 측정한 값)는, 10∼300㎛인 것이 바람직하고, 특히 25∼250㎛인 것이 바람직하며, 나아가서는 50∼100㎛인 것이 바람직하다. 점착제층(11)의 두께가 10㎛ 이상임으로써, 우수한 점착력이 충분히 발휘되고, 점착제층(11)의 두께가 300㎛ 이하임으로써, 가공성이 양호해진다. 또, 점착제층(11)의 두께가 25∼100㎛이면, 광학 용도, 특히 터치 패널 용도로서 바람직한 것이 된다. 또한, 점착제층(11)은 단층으로 형성해도 되고, 복수층을 적층해 형성할 수도 있다. The pressure-sensitive adhesive layer 11 is composed of a pressure-sensitive adhesive formed by crosslinking the pressure-sensitive adhesive composition P described above. The thickness (measured according to JIS K7130) of the pressure-sensitive adhesive layer 11 is preferably 10 to 300 µm, particularly preferably 25 to 250 µm, and further preferably 50 to 100 µm. When the thickness of the pressure-sensitive adhesive layer 11 is 10 µm or more, excellent adhesive strength is sufficiently exhibited, and when the thickness of the pressure-sensitive adhesive layer 11 is 300 µm or less, the workability is improved. Further, if the thickness of the pressure-sensitive adhesive layer 11 is 25 to 100 µm, it is preferable for optical applications, particularly for touch panel applications. Further, the pressure-sensitive adhesive layer 11 may be formed as a single layer, or may be formed by laminating a plurality of layers.

(2) 박리 시트 (2) release sheet

박리 시트(12a, 12b)로서는, 특별히 한정되지 않고, 공지된 플라스틱 필름을 사용할 수 있다. 예를 들어, 폴리에틸렌 필름, 폴리프로필렌 필름, 폴리부텐 필름, 폴리부타디엔 필름, 폴리메틸펜텐 필름, 폴리염화비닐 필름, 염화비닐 공중합체 필름, 폴리에틸렌테레프탈레이트 필름, 폴리에틸렌나프탈레이트 필름, 폴리부틸렌테레프탈레이트 필름, 폴리우레탄 필름, 에틸렌아세트산비닐 필름, 아이오노머 수지 필름, 에틸렌·(메트)아크릴산 공중합체 필름, 에틸렌·(메트)아크릴산에스테르 공중합체 필름, 폴리스티렌 필름, 폴리카보네이트 필름, 폴리이미드 필름, 불소 수지 필름 등이 사용된다. 또, 이들의 가교 필름도 사용된다. 또한, 이들의 적층 필름이어도 된다. The release sheets 12a and 12b are not particularly limited, and a known plastic film can be used. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate Film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin A film or the like is used. Moreover, these crosslinked films are also used. Moreover, these laminated films may be sufficient.

상기 박리 시트(12a, 12b)의 박리면(특히 점착제층(11)과 접하는 면)에는, 박리 처리가 실시되어 있는 것이 바람직하다. 박리 처리에 사용되는 박리제로서는, 예를 들어 알키드계, 실리콘계, 불소계, 불포화 폴리에스테르계, 폴리올레핀계, 왁스계의 박리제를 들 수 있다. 또한, 박리 시트(12a, 12b) 중, 일방의 박리 시트를 박리력이 큰 중박리형(重剝離型) 박리 시트로 하고, 타방의 박리 시트를 박리력이 작은 경박리형(輕剝離型) 박리 시트로 하는 것이 바람직하다.It is preferable that the peeling treatment is performed on the peeling surface (particularly, the surface in contact with the pressure-sensitive adhesive layer 11) of the peeling sheets 12a and 12b. Examples of the releasing agent used in the releasing treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based releasing agents. In addition, among the release sheets 12a and 12b, one release sheet is a heavy peeling type release sheet having a high peeling force, and the other release sheet is a light peeling type release sheet having a small peeling force. It is preferable to do it.

박리 시트(12a, 12b)의 두께에 대해서는 특별히 제한은 없지만, 통상 20∼150㎛ 정도이다.The thickness of the release sheets 12a and 12b is not particularly limited, but is usually about 20 to 150 µm.

(3) 점착 시트의 제조 (3) Preparation of adhesive sheet

점착 시트(1)의 일제조예로서는, 일방의 박리 시트(12a)(또는 12b)의 박리면에, 상기 점착성 조성물P의 도포액을 도포하고, 가열 처리를 행해 점착성 조성물P를 가교시키고, 도포층을 형성한 후, 그 도포층에 타방의 박리 시트(12b)(또는 12a)의 박리면을 중첩한다. 양생 기간이 필요한 경우에는 양생 기간을 둠으로써, 양생 기간이 불필요한 경우에는 그대로, 상기 도포층이 점착제층(11)이 된다. 이것에 의해, 상기 점착 시트(1)가 얻어진다. 가열 처리 및 양생의 조건에 대해서는 전술한 바와 같다.As an example of manufacturing the pressure-sensitive adhesive sheet 1, a coating liquid of the pressure-sensitive adhesive composition P is applied to the peeling surface of one release sheet 12a (or 12b), and heat treatment is performed to crosslink the pressure-sensitive adhesive composition P, and the coating layer After forming, the peeling surface of the other peeling sheet 12b (or 12a) is superimposed on the coating layer. When a curing period is required, a curing period is provided, and when a curing period is unnecessary, the coating layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained. The heat treatment and curing conditions are as described above.

점착 시트(1)의 다른 제조예로서는, 일방의 박리 시트(12a)의 박리면에, 상기 점착성 조성물P의 도포액을 도포하고, 가열 처리를 행해 점착성 조성물P를 가교시키고, 도포층을 형성하여, 도포층이 형성된 박리 시트(12a)를 얻는다. 또, 타방의 박리 시트(12b)의 박리면에, 상기 점착성 조성물P의 도포액을 도포하고, 가열 처리를 행해 점착성 조성물P를 가교시키고, 도포층을 형성해, 도포층이 형성된 박리 시트(12b)를 얻는다. 그리고, 도포층이 형성된 박리 시트(12a)와 도포층이 형성된 박리 시트(12b)를, 양 도포층이 서로 접촉하도록 첩합(貼合)한다. 양생 기간이 필요한 경우에는 양생 기간을 둠으로써, 양생 기간이 불필요한 경우에는 그대로, 상기 적층된 도포층이 점착제층(11)이 된다. 이것에 의해, 상기 점착 시트(1)가 얻어진다. 이 제조예에 의하면, 점착제층(11)이 두꺼운 경우라도, 안정적으로 제조할 수 있게 된다.As another example of production of the pressure-sensitive adhesive sheet 1, a coating liquid of the pressure-sensitive adhesive composition P is applied to the peeling surface of one release sheet 12a, and heat treatment is performed to crosslink the pressure-sensitive adhesive composition P to form a coating layer, A release sheet 12a on which a coating layer was formed is obtained. Further, the coating liquid of the adhesive composition P is applied to the release surface of the other release sheet 12b, and heat treatment is performed to crosslink the adhesive composition P, to form a coating layer, and the release sheet 12b on which the coating layer is formed. Get Then, the release sheet 12a on which the coating layer is formed and the release sheet 12b on which the coating layer is formed are bonded together so that both coating layers are in contact with each other. When a curing period is required, a curing period is provided. When a curing period is not required, the laminated coating layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained. According to this manufacturing example, even when the pressure-sensitive adhesive layer 11 is thick, it becomes possible to stably manufacture.

상기 점착성 조성물P의 도포액을 도포하는 방법으로서는, 예를 들어 바 코트법, 나이프 코트법, 롤 코트법, 블레이드 코트법, 다이 코트법, 그라비어 코트법 등을 이용할 수 있다.As a method of applying the coating liquid of the adhesive composition P, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.

(4) 헤이즈값(4) Haze value

본 실시형태에 있어서의 점착제층(11)은, 헤이즈값(JIS K7136 : 2000에 준해 측정한 값)이, 1.0％ 이하인 것이 바람직하고, 특히 0.8％ 이하인 것이 바람직하며, 나아가서는 0.6％ 이하인 것이 바람직하다. 헤이즈값이 1.0％ 이하이면, 투명성이 매우 높아, 광학 용도로서 바람직한 것이 된다. 또한, 점착제층(11)의 헤이즈값은, 후술하는 내습열 백화성의 평가 시험 후에 있어서도 상기 범위 내에 있는 것이 특히 바람직하다. The pressure-sensitive adhesive layer 11 in this embodiment has a haze value (a value measured according to JIS K7136:2000) of 1.0% or less, particularly preferably 0.8% or less, and further preferably 0.6% or less. Do. When the haze value is 1.0% or less, transparency is very high, and it becomes a preferable thing as an optical use. In addition, it is particularly preferable that the haze value of the pressure-sensitive adhesive layer 11 is within the above range even after an evaluation test for moist heat whitening resistance described later.

(5) 점착 시트의 사용 (5) Use of adhesive sheet

상기 점착 시트(1)를 사용함으로써, 예를 들어 도 2에 나타내는 정전 용량 방식의 터치 패널(2)을 제조할 수 있다. 터치 패널(2)은, 표시체 모듈(3)과, 그 위에 점착제층(4)을 개재하여 적층된 제 1 필름 센서(5a)와, 그 위에 점착제층(11)을 개재하여 적층된 제 2 필름 센서(5b)와, 그 위에 점착제층(11)을 개재하여 적층된 커버재(6)를 구비하여 구성된다.By using the pressure-sensitive adhesive sheet 1, for example, a capacitive touch panel 2 shown in FIG. 2 can be manufactured. The touch panel 2 includes a display module 3, a first film sensor 5a laminated thereon with an adhesive layer 4 interposed thereon, and a second film sensor 5a laminated thereon with an adhesive layer 11 interposed therebetween. It comprises a film sensor 5b and a cover member 6 laminated thereon through an adhesive layer 11 therebetween.

상기 터치 패널(2)에 있어서의 점착제층(11)은, 상기 점착 시트(1)의 점착제층(11)이다.The pressure-sensitive adhesive layer 11 in the touch panel 2 is the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1.

상기 표시체 모듈(3)로서는, 예를 들어 액정(LCD) 모듈, 발광 다이오드(LED) 모듈, 유기 일렉트로 루미네선스(유기 EL) 모듈, 전자 페이퍼 등을 들 수 있다.Examples of the display module 3 include a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper.

점착제층(4)은, 상기 점착 시트(1)의 점착제층(11)에 의해 형성해도 되고, 다른 점착제 또는 점착 시트에 의해 형성해도 된다. 후자의 경우, 점착제층(4)을 구성하는 점착제로서는, 아크릴계 점착제, 고무계 점착제, 실리콘계 점착제, 우레탄계 점착제, 폴리에스테르계 점착제, 폴리비닐에테르계 점착제 등을 들 수 있지만, 그 중에서도 아크릴계 점착제가 바람직하다. The pressure-sensitive adhesive layer 4 may be formed of the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1, or may be formed of another pressure-sensitive adhesive or pressure-sensitive adhesive sheet. In the latter case, examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 4 include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polyvinyl ether-based pressure-sensitive adhesives, but among them, acrylic pressure-sensitive adhesives are preferred. .

본 실시형태에 있어서의 제 1 필름 센서(5a) 및 제 2 필름 센서(5b)는, 각각 기재 필름(51)과, 기재 필름(51)에 형성된 금속 메시로 이루어지는 전극(52)을 구비한다. 기재 필름(51)으로서는 특별히 한정되지 않지만, 예를 들어 폴리에틸렌테레프탈레이트 필름, 아크릴 필름, 폴리카보네이트 필름 등이 사용된다. The first film sensor 5a and the second film sensor 5b in this embodiment each include a base film 51 and an electrode 52 made of a metal mesh formed on the base film 51. Although it does not specifically limit as the base film 51, For example, a polyethylene terephthalate film, an acrylic film, a polycarbonate film, etc. are used.

전극(52)을 구성하는 금속 메시의 금속으로서는, 구리, 은 등을 들 수 있지만, 특히 구리가 바람직하다. 구리에 의하면, 저항값을 10Ω/□ 이하로 낮출 수 있어 터치 패널을 대형화할 수 있다. 단, 구리는, 백금, 금, 은 등의 귀금속과 비교해, 또 주석 도프 산화인듐(ITO) 등의 투명 도전 재료와 비교해, 부식되기 쉽다. 그러나, 전술한 점착성 조성물P로부터 형성된 점착제층(11)에 의하면, 구리 메시로 이루어지는 전극(52)의 부식을 억제할 수 있다. Examples of the metal of the metal mesh constituting the electrode 52 include copper, silver, and the like, but copper is particularly preferable. According to copper, the resistance value can be lowered to 10 Ω/□ or less, and the touch panel can be enlarged. However, copper is easily corroded compared to noble metals such as platinum, gold, and silver, and compared with transparent conductive materials such as tin-doped indium oxide (ITO). However, according to the pressure-sensitive adhesive layer 11 formed from the pressure-sensitive adhesive composition P described above, corrosion of the electrode 52 made of a copper mesh can be suppressed.

제 1 필름 센서(5a)의 전극(52) 및 제 2 필름 센서(5b)의 전극(52)은, 통상 일방이 X축 방향의 회로 패턴을 구성하고, 타방이 Y축 방향의 회로 패턴을 구성한다.As for the electrode 52 of the first film sensor 5a and the electrode 52 of the second film sensor 5b, one of them constitutes a circuit pattern in the X-axis direction and the other constitutes a circuit pattern in the Y-axis direction. do.

본 실시형태에 있어서의 제 2 필름 센서(5b)의 전극(52)은, 도 2 중 제 2 필름 센서(5b)의 상측에 위치하고 있다. 한편, 제 1 필름 센서(5a)의 전극(52)은, 도 2 중 제 1 필름 센서(5a)의 상측에 위치하고 있지만, 이것에 한정되는 것은 아니고, 제 1 필름 센서(5a)의 하측에 위치해도 된다.The electrode 52 of the 2nd film sensor 5b in this embodiment is located above the 2nd film sensor 5b in FIG. On the other hand, the electrode 52 of the first film sensor 5a is located above the first film sensor 5a in FIG. 2, but is not limited thereto, and is located below the first film sensor 5a. Can also be done.

커버재(6)는, 통상 유리판 또는 플라스틱판을 주체로 한다. 유리판으로서는, 특별히 한정되지 않고, 예를 들어 화학 강화 유리, 무알칼리 유리, 석영 유리, 소다라임 유리, 바륨·스트론튬 함유 유리, 알루미노규산 유리, 납 유리, 붕규산 유리, 바륨붕규산 유리 등을 들 수 있다. 플라스틱판으로서는, 특별히 한정되지 않고, 예를 들어 폴리메틸메타크릴레이트 등으로 이루어지는 아크릴판, 폴리카보네이트판 등을 들 수 있다.The cover material 6 is usually mainly made of a glass plate or a plastic plate. The glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda-lime glass, barium-strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass, and the like. have. The plastic plate is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate or the like, a polycarbonate plate, and the like.

또한, 상기 유리판이나 플라스틱판의 편면 또는 양면에는, 하드 코트층, 반사 방지층, 방현층 등의 기능층이 형성되어 있어도 되고, 하드 코트 필름, 반사 방지 필름, 방현 필름 등의 광학 부재가 적층되어 있어도 된다.Further, functional layers such as a hard coat layer, an anti-reflection layer, and an anti-glare layer may be formed on one or both sides of the glass plate or plastic plate, and an optical member such as a hard coat film, an anti-reflection film, and an anti-glare film may be laminated. do.

본 실시형태에 있어서, 상기 커버재(6)는, 점착제층(11)측의 면에 단차를 가지고 있고, 구체적으로는 인쇄층(7)의 유무에 의한 단차를 가지고 있다. 인쇄층(7)은, 커버재(6)에 있어서의 점착제층(11)측에 프레임상으로 형성되는 것이 일반적이다. In the present embodiment, the cover member 6 has a level difference on the surface on the side of the pressure-sensitive adhesive layer 11, and specifically has a level difference due to the presence or absence of the printing layer 7. The printing layer 7 is generally formed in a frame shape on the side of the pressure-sensitive adhesive layer 11 in the cover material 6.

인쇄층(7)을 구성하는 재료는 특별히 한정되지 않고, 인쇄용의 공지된 재료가 사용된다. 인쇄층(7)의 두께, 즉 단차의 높이는 3∼45㎛인 것이 바람직하고, 5∼35㎛인 것이 보다 바람직하며, 7∼25㎛인 것이 특히 바람직하고, 7∼15㎛인 것이 더 바람직하다. The material constituting the printing layer 7 is not particularly limited, and a known material for printing is used. The thickness of the printing layer 7, that is, the height of the step, is preferably 3 to 45 µm, more preferably 5 to 35 µm, particularly preferably 7 to 25 µm, and still more preferably 7 to 15 µm. .

또, 인쇄층(7)의 두께(단차의 높이)는, 점착제층(11)의 두께의 3∼30％인 것이 바람직하고, 특히 3.2∼20％인 것이 바람직하며, 나아가서는 3.5∼15％인 것이 바람직하다. 이것에 의해, 점착제층(11)은, 인쇄층(7)에 의한 단차에 추종하기 쉽고, 단차 근방에 들뜸이나 기포 등이 발생하는 것이 억제된다.In addition, the thickness (height of the step) of the printing layer 7 is preferably 3 to 30% of the thickness of the pressure-sensitive adhesive layer 11, particularly preferably 3.2 to 20%, and further 3.5 to 15%. It is desirable. Thereby, the pressure-sensitive adhesive layer 11 easily follows the level difference caused by the printing layer 7, and it is suppressed that lift, air bubbles, or the like occur in the vicinity of the level difference.

상기 터치 패널(2)의 제조 방법의 일례를, 이하에 설명한다.An example of a method of manufacturing the touch panel 2 will be described below.

점착 시트(1)로서, 제 1 점착 시트(1) 및 제 2 점착 시트(1)를 준비한다. 제 1 점착 시트(1)로부터 일방의 박리 시트(12a)를 박리하고, 노출된 점착제층(11)(제 1 점착제층(11))을 제 2 필름 센서(5b)의 전극(52)과 접하도록 당해 제 2 필름 센서(5b)와 첩합한다. 또, 제 2 점착 시트(1)로부터 일방의 박리 시트(12a)를 박리하고, 노출된 점착제층(11)(제 2 점착제층)을 제 1 필름 센서(5a)의 전극(52)과 접하도록 당해 제 1 필름 센서(5a)와 첩합한다.As the pressure-sensitive adhesive sheet 1, the first pressure-sensitive adhesive sheet 1 and the second pressure-sensitive adhesive sheet 1 are prepared. One release sheet 12a is peeled from the first adhesive sheet 1, and the exposed adhesive layer 11 (the first adhesive layer 11) is brought into contact with the electrode 52 of the second film sensor 5b. It bonds with the said 2nd film sensor 5b so that it might be. In addition, one release sheet 12a is peeled from the second adhesive sheet 1, and the exposed adhesive layer 11 (second adhesive layer) is brought into contact with the electrode 52 of the first film sensor 5a. It bonds with the said 1st film sensor 5a.

그리고, 제 2 점착 시트에 있어서의 타방의 박리 시트(12b)를 박리하고, 노출된 제 2 점착제층(11)이, 상기 제 2 필름 센서(5b)에 있어서의 제 1 점착제층(11)이 적층된 측과는 반대측의 면(제 2 필름 센서(5b)의 기재 필름(51)의 노출면)에 접하도록 양자를 첩합한다. 이것에 의해, 박리 시트(12b), 제 1 점착제층(11), 제 2 필름 센서(5b), 제 2 점착제층(11) 및 제 1 필름 센서(5a)가 순차 적층되어 이루어지는 적층체가 얻어진다.And the other peeling sheet 12b in the 2nd adhesive sheet is peeled, and the exposed 2nd adhesive layer 11 is the 1st adhesive layer 11 in the said 2nd film sensor 5b Both are bonded so as to be in contact with the side opposite to the laminated side (exposed surface of the base film 51 of the second film sensor 5b). Thereby, a laminate obtained by sequentially laminating the release sheet 12b, the first adhesive layer 11, the second film sensor 5b, the second adhesive layer 11, and the first film sensor 5a is obtained. .

다음으로, 상기 적층체의 제 1 필름 센서(5a)측의 면(제 1 필름 센서(5a)의 기재 필름(51)의 노출면)에, 박리 시트 상에 형성된 점착제층(4)을 첩합한다. 계속해서, 상기 적층체로부터 박리 시트(12b)를 박리하고, 노출된 제 1 점착제층(11)에 대해, 커버재(6)의 인쇄층(7)측이 당해 점착제층(11)에 접하도록, 당해 커버재(6)를 첩합한다. 이것에 의해, 커버재(6), 제 1 점착제층(11), 제 2 필름 센서(5b), 제 2 점착제층(11), 제 1 필름 센서(5a), 점착제층(4) 및 박리 시트가 순차 적층되어 이루어지는 구성체가 얻어진다. Next, the pressure-sensitive adhesive layer 4 formed on the release sheet is bonded to the surface on the side of the first film sensor 5a of the laminate (the exposed surface of the base film 51 of the first film sensor 5a). . Subsequently, the release sheet 12b is peeled from the laminate, and the printed layer 7 side of the cover material 6 is in contact with the pressure-sensitive adhesive layer 11 with respect to the exposed first pressure-sensitive adhesive layer 11. , The cover member 6 is bonded together. Thereby, the cover material 6, the 1st adhesive layer 11, the 2nd film sensor 5b, the 2nd adhesive layer 11, the 1st film sensor 5a, the adhesive layer 4, and the peeling sheet A structure formed by sequentially stacking is obtained.

마지막으로, 상기 구성체로부터 박리 시트를 박리하고, 노출된 점착제층(4)이 표시 모듈(3)에 접하도록, 당해 구성체를 표시 모듈(3)에 첩합한다. 이것에 의해, 도 2에 나타내는 터치 패널(2)이 제조된다. Finally, the release sheet is peeled from the constitution, and the constitution is bonded to the display module 3 so that the exposed pressure-sensitive adhesive layer 4 contacts the display module 3. Thereby, the touch panel 2 shown in FIG. 2 is manufactured.

상기 터치 패널(2)이 고온 고습 조건(예를 들어, 85℃, 85％RH의 조건하에서 240시간)에 놓인 후, 상온 상습으로 되돌려졌을 때에도, 점착제층(11)(제 1 점착제층(11), 제 2 점착제층(11))은 내습열 백화성이 우수하기 때문에, 백화하는 것이 억제된다. 구체적으로는, 점착제층(11)의 헤이즈값은 1.0％ 이하를 유지할 수 있다.Even when the touch panel 2 is placed in a high temperature and high humidity condition (for example, 240 hours under a condition of 85°C and 85% RH) and then returned to room temperature and humidity, the adhesive layer 11 (the first adhesive layer 11 ), the second pressure-sensitive adhesive layer 11) is excellent in moist heat whitening resistance, and therefore whitening is suppressed. Specifically, the haze value of the pressure-sensitive adhesive layer 11 can be maintained at 1.0% or less.

이상 설명한 실시형태는, 본 발명의 이해를 용이하게 하기 위해서 기재된 것이고, 본 발명을 한정하기 위해서 기재된 것은 아니다. 따라서, 상기 실시형태에 개시된 각 요소는, 본 발명의 기술적 범위에 속하는 모든 설계 변경이나 균등물도 포함하는 취지이다. The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents falling within the technical scope of the present invention.

예를 들어, 점착 시트(1)에 있어서의 박리 시트(12a, 12b) 중 어느 일방은 생략되어도 된다.For example, any one of the release sheets 12a and 12b in the pressure-sensitive adhesive sheet 1 may be omitted.

실시예Example

이하, 실시예 등에 의해 본 발명을 더욱 구체적으로 설명하지만, 본 발명의 범위는 이들 실시예 등에 한정되는 것은 아니다. Hereinafter, the present invention will be described more specifically by examples and the like, but the scope of the present invention is not limited to these examples and the like.

〔실시예 1〕[Example 1]

1. (메트)아크릴산에스테르 공중합체의 조제1. Preparation of (meth)acrylic acid ester copolymer

아크릴산 2-에틸헥실 60질량부, 메타크릴산메틸 20질량부 및 아크릴산 2-하이드록시에틸 20질량부를 공중합시켜, (메트)아크릴산에스테르 중합체(A)를 조제했다. 이 (메트)아크릴산에스테르 중합체(A)의 분자량을 후술하는 방법으로 측정한 바, 중량 평균 분자량(Mw) 60만이었다. 60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate, and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized to prepare a (meth)acrylic acid ester polymer (A). When the molecular weight of this (meth)acrylic acid ester polymer (A) was measured by the method described later, it was 600,000 in weight average molecular weight (Mw).

2. 점착성 조성물의 조제2. Preparation of adhesive composition

상기 공정(1)에서 얻어진 (메트)아크릴산에스테르 중합체(A) 100질량부(고형분 환산값 ; 이하 동일)와, 벤조트리아졸계 방청제(B)로서의 1H-벤조트리아졸(조호쿠카가쿠코교사 제조, 제품명 「BT-120」) 0.3질량부와, 가교제(C)로서의 트리메틸올프로판 변성 톨릴렌디이소시아네이트(닛폰폴리우레탄사 제조, 제품명 「코로네이트L」) 0.15질량부와, 실란 커플링제로서의 3-글리시독시프로필트리메톡시실란(신에츠카가쿠코교사 제조, 제품명 「KBM-403」) 0.2질량부를 혼합해, 충분히 교반하고, 메틸에틸케톤으로 희석함으로써, 고형분 농도 25질량％의 점착성 조성물의 도포 용액을 얻었다. 100 parts by mass of the (meth)acrylic acid ester polymer (A) obtained in the above step (1) (in terms of solid content; the same below) and 1H-benzotriazole (manufactured by Johoku Chemical Co., Ltd., as a benzotriazole-based rust inhibitor (B), Product name ``BT-120'') 0.3 parts by mass, trimethylolpropane-modified tolylene diisocyanate (manufactured by Nippon Polyurethane, product name ``Coronate L'') 0.15 parts by mass as a crosslinking agent (C), and 3-gly as a silane coupling agent A coating solution of an adhesive composition having a solid content concentration of 25% by mass by mixing 0.2 parts by mass of sidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403"), sufficiently stirring, and diluting with methyl ethyl ketone Got it.

여기서, 당해 점착성 조성물의 배합을 표 1에 나타낸다. 또한, 표 1에 기재된 약호 등의 자세한 것은 이하와 같다. Here, the formulation of the adhesive composition is shown in Table 1. In addition, details, such as the abbreviation shown in Table 1, are as follows.

[(메트)아크릴산에스테르 중합체(A)] [(Meth)acrylic acid ester polymer (A)]

2EHA : 아크릴산 2-에틸헥실 2EHA: 2-ethylhexyl acrylic acid

MMA : 메타크릴산메틸 MMA: methyl methacrylate

HEA : 아크릴산 2-하이드록시에틸 HEA: 2-hydroxyethyl acrylic acid

BA : 아크릴산 n-부틸 BA: n-butyl acrylate

[벤조트리아졸계 방청제(B)] [Benzotriazole-based rust inhibitor (B)]

방청제B1 : 1H-벤조트리아졸(조호쿠카가쿠코교사 제조, 제품명 「BT-120」)Antirust agent B1: 1H-benzotriazole (manufactured by Johoku Chemical Co., Ltd., product name "BT-120")

방청제B2 : 1H-톨릴트리아졸(시프로카세이사 제조, 제품명 「SEETEC TT-R」)Antirust agent B2: 1H-tolyltriazole (manufactured by Ciprocasey, product name "SEETEC TT-R")

방청제B3 : 1-[N,N-비스(2-에틸헥실)아미노메틸]벤조트리아졸(조호쿠카가쿠코교사 제조, 제품명 「BT-LX」) Antirust agent B3: 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (manufactured by Johoku Chemical Co., Ltd., product name "BT-LX")

방청제B4 : 1-[N,N-비스(2-에틸헥실)아미노메틸]메틸벤조트리아졸(조호쿠카가쿠코교사 제조, 제품명 「TT-LX」)Antirust agent B4: 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole (manufactured by Johoku Chemical Co., Ltd., product name "TT-LX")

3. 점착 시트의 제조3. Preparation of adhesive sheet

얻어진 점착성 조성물의 도포 용액을, 폴리에틸렌테레프탈레이트 필름의 편면을 실리콘계 박리제로 박리 처리한 중박리형 박리 시트(린텍사 제조, 제품명 「SP-PET382150」, 두께 : 38㎛)의 박리 처리면에, 건조 후의 두께가 50㎛가 되도록 나이프 코터로 도포한 후, 90℃에서 1분간 가열 처리해 도포층을 형성했다. The obtained adhesive composition coating solution was applied to the peeling-treated surface of a heavy-release type release sheet (manufactured by Lintec, product name "SP-PET382150", thickness: 38 µm) in which one side of a polyethylene terephthalate film was peeled off with a silicone-based release agent After coating with a knife coater so that the thickness became 50 µm, the coating layer was formed by heating at 90° C. for 1 minute.

폴리에틸렌테레프탈레이트 필름의 편면을 실리콘계 박리제로 박리 처리한 경박리형 박리 시트(린텍사 제조, 제품명 「SP-PET382120」, 두께 : 38㎛)의 박리 처리면이 상기 도포층에 접하도록, 당해 경박리형 박리 시트를 상기 도포층에 첩합했다. 그 후, 23℃, 50％RH의 조건하에서 7일간 양생함으로써, 중박리형 박리 시트/점착제층(두께 : 50㎛)/경박리형 박리 시트의 구성으로 이루어지는 점착 시트를 제조했다.The light release type release sheet (manufactured by Lintec, product name “SP-PET382120”, thickness: 38 μm) of a light release type release sheet obtained by removing one side of a polyethylene terephthalate film with a silicone release agent is in contact with the coating layer. The sheet was attached to the coating layer. Thereafter, by curing for 7 days under conditions of 23°C and 50%RH, a pressure-sensitive adhesive sheet consisting of a heavy-release type release sheet/adhesive layer (thickness: 50 μm)/a light-release type release sheet was produced.

〔실시예 2∼5, 비교예 1∼2〕[Examples 2 to 5, Comparative Examples 1 to 2]

(메트)아크릴산에스테르 중합체(A)를 구성하는 각 모노머의 종류 및 비율, (메트)아크릴산에스테르 중합체(A)의 중량 평균 분자량(Mw), 그리고 벤조트리아졸계 방청제(B)의 종류를 표 1에 나타내는 바와 같이 변경하는 것 이외, 실시예 1과 마찬가지로 해 점착 시트를 제조했다. Table 1 shows the type and ratio of each monomer constituting the (meth)acrylic acid ester polymer (A), the weight average molecular weight (Mw) of the (meth)acrylic acid ester polymer (A), and the type of benzotriazole-based rust inhibitor (B). Except having changed as shown, it carried out similarly to Example 1, and produced the adhesive sheet.

여기서, 전술한 중량 평균 분자량(Mw)은, 겔 퍼미에이션 크로마토그래피(GPC)를 사용하여 이하의 조건으로 측정(GPC 측정)한 폴리스티렌 환산의 중량 평균 분자량이다.Here, the above-described weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).

＜측정 조건＞<Measurement conditions>

·GPC 측정 장치 : 토소사 제조, HLC-8020 GPC measuring device: manufactured by Tosoh Corporation, HLC-8020

·GPC 칼럼(이하의 순서로 통과) : 토소사 제조 GPC column (passed in the following order): manufactured by Tosoh Corporation

TSK guard column HXL-H TSK guard column HXL-H

TSK gel GMHXL(×2) TSK gel GMHXL(×2)

TSK gel G2000HXL TSK gel G2000HXL

·측정 용매 : 테트라하이드로푸란 ·Measurement solvent: Tetrahydrofuran

·측정 온도 : 40℃·Measurement temperature: 40℃

〔시험예 1〕(내습열 백화성 평가) [Test Example 1] (Moisture heat whitening resistance evaluation)

실시예 및 비교예에서 얻어진 점착 시트의 점착제층을, 70㎜×70㎜ 사이즈의 무알칼리 유리(두께 : 1㎜) 2장으로 사이에 두고, 그 적층체를 50℃, 0.5㎫의 조건으로 30분간 오토클레이브 처리해, 이것을 샘플로 했다.The pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were sandwiched between two sheets of 70 mm×70 mm sized alkali-free glass (thickness: 1 mm), and the laminate was placed at 50° C. under the conditions of 0.5 MPa. Autoclave treatment was performed for a minute, and this was used as a sample.

얻어진 샘플을, 85℃, 85％RH의 습열 조건하에서 240시간 보관했다. 그 후, 23℃, 50％RH(상온 상습)의 분위기로 되돌려, 점착제층의 헤이즈값을 측정했다. 헤이즈값은, 샘플을 상기 상온 상습의 분위기로 되돌리고 나서 30분 이내에, JIS K7136 : 2000에 준해, 헤이즈미터(닛폰덴쇼쿠코교사 제조, 제품명 「NDH-5000」)를 사용하여 측정했다. 측정한 헤이즈값에 근거해, 이하의 기준에 의해 내습열 백화성을 평가했다. 결과를 표 1에 나타낸다.The obtained sample was stored for 240 hours under a humid heat condition of 85°C and 85% RH. Then, it returned to the atmosphere of 23 degreeC and 50% RH (normal temperature and humidity), and the haze value of the adhesive layer was measured. The haze value was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH-5000") within 30 minutes after returning the sample to the ambient temperature and humidity atmosphere, according to JIS K7136:2000. Based on the measured haze value, moist heat whitening resistance was evaluated according to the following criteria. Table 1 shows the results.

○ : 헤이즈값이 1.0％ 이하였다○: Haze value was 1.0% or less

× : 헤이즈값이 1.0％ 초과였다X: Haze value was more than 1.0%

〔시험예 2〕(부식 억제 평가)[Test Example 2] (Evaluation of corrosion inhibition)

(1) 구리 메시 적층 필름의 제작 (1) Preparation of a copper mesh laminated film

폴리에틸렌테레프탈레이트(PET) 필름(토요보세키사 제조, 제품명 「PET100A4100」, 두께 : 100㎛)과, 편면을 흑화 처리한 구리박(후루카와서킷포일사 제조, 제품명 「BW-S」, 두께 : 10㎛)과, 폴리우레탄계 접착제(타케다야쿠힝코교사 제조, 타케락A310/타케네이트A10/아세트산에틸=12/1/21(질량비))를 준비했다.Polyethylene terephthalate (PET) film (manufactured by Toyoboseki, product name “PET100A4100”, thickness: 100 μm) and copper foil with blackening treatment on one side (manufactured by Furukawa Circuit Foil, product name “BW-S”, thickness: 10 μm ) And a polyurethane-based adhesive (manufactured by Takedayakuhinko Co., Ltd., Takerak A310/Takenate A10/ethyl acetate = 12/1/21 (mass ratio)) were prepared.

상기 폴리우레탄계 접착제를 사용하여, 상기 구리박의 흑화 처리면과는 반대측의 표면과 상기 PET 필름을 첩합해, PET 필름/접착제층/구리박으로 이루어지는 적층체를 얻었다. Using the polyurethane-based adhesive, the surface opposite to the blackened surface of the copper foil and the PET film were bonded to each other to obtain a laminate made of a PET film/adhesive layer/copper foil.

얻어진 적층체의 구리박측(흑화 처리면)에 카세인을 도포하고, 건조시켜, 감광성 수지층으로 했다. 그리고, 패턴이 형성된 마스크를 개재하여 상기 감광성 수지층에 대해 자외선의 밀착 노광을 행하고, 물로 현상했다. 마스크로서는, 선폭 10㎛, 피치 300㎛의 패턴을 갖는 것을 사용했다. 이어서, 경화 처리를 실시한 후, 100℃에서 베이킹을 행해, 레지스트 패턴을 형성했다.Casein was applied to the copper foil side (blackened surface) of the obtained laminate and dried to obtain a photosensitive resin layer. Then, the photosensitive resin layer was subjected to close contact exposure of ultraviolet rays through a patterned mask, and developed with water. As the mask, a pattern having a line width of 10 µm and a pitch of 300 µm was used. Subsequently, after curing treatment, baking was performed at 100°C to form a resist pattern.

레지스트 패턴이 형성된 적층체에, 레지스트 패턴측으로부터 염화 제2철 용액(보메도 : 42, 온도 : 30℃)을 분사해 에칭을 실시하고, 수세했다. 이어서, 알칼리 용액을 사용하여 레지스트 패턴을 박리한 후, 세정 및 건조 처리를 행했다. 이와 같이 하여, PET 필름/접착제층/구리 메시로 이루어지는 구리 메시 적층 필름을 얻었다. The layered product on which the resist pattern was formed was sprayed with a ferric chloride solution (bomedo: 42, temperature: 30°C) from the resist pattern side to perform etching, followed by washing with water. Subsequently, after peeling the resist pattern using an alkali solution, washing and drying treatment were performed. In this way, a copper mesh laminated film composed of a PET film/adhesive layer/copper mesh was obtained.

(2) 부식 억제 평가 (2) corrosion inhibition evaluation

실시예 및 비교예에서 얻어진 점착 시트로부터 경박리형 박리 시트를 박리하고, 노출된 점착제층을, 상기 구리 메시 적층 필름의 구리 메시측에 첩부했다. 그 후, 점착제층으로부터 중박리형 박리 시트를 박리하고, 노출된 점착제층에 대해 PET 필름(토요보세키사 제조, 제품명 「PET A4100」, 두께 : 100㎛)을 첩부해, PET 필름/접착제층/구리 메시/점착제층/PET 필름으로 이루어지는 적층체를 얻고, 이것을 샘플로 했다. The light-release type release sheet was peeled from the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and the exposed pressure-sensitive adhesive layer was affixed to the copper mesh side of the copper mesh laminated film. Thereafter, the heavy-release type release sheet was peeled from the pressure-sensitive adhesive layer, and a PET film (manufactured by Toyobo Seki, product name “PET A4100”, thickness: 100 μm) was affixed to the exposed pressure-sensitive adhesive layer, and PET film/adhesive layer/copper A laminate composed of a mesh/adhesive layer/PET film was obtained, and this was taken as a sample.

상기 샘플을, 85℃, 85％RH의 습열 조건하에서 250시간 보관했다. 그 후, 구리 메시의 부식 유무를 육안에 의해 확인하고, 이하의 기준에 의해 부식 억제 성능을 평가했다. 결과를 표 1에 나타낸다.The sample was stored for 250 hours under a humid heat condition of 85°C and 85% RH. After that, the presence or absence of corrosion of the copper mesh was visually checked, and the corrosion inhibiting performance was evaluated according to the following criteria. Table 1 shows the results.

○ : 구리 메시에 부식이 없었다○: There was no corrosion in the copper mesh

× : 구리 메시에 부식이 있었다X: There was corrosion in the copper mesh

〔시험예 3〕(유전율의 산출) [Test Example 3] (Calculation of dielectric constant)

두께 50㎛의 폴리에틸렌테레프탈레이트 필름의 편면에, 실시예 및 비교예와 마찬가지로 해 두께 100㎛의 점착제층을 형성하고, 그 점착제층에, 두께 50㎛의 폴리에틸렌테레프탈레이트 필름을 첩합한 후, 50㎜×50㎜로 재단했다. 얻어진 적층체에 대해, 임피던스 애널라이저(니혼휴렛팩커드사 제조, 「HP-4194A」)를 사용해 정전 용량(C1)을 측정했다. 또, 상기 두께 50㎛의 폴리에틸렌테레프탈레이트 필름을 2장 겹쳐 50㎜×50㎜로 재단하고, 마찬가지로 하여 정전 용량(C2)를 측정했다. 그리고, C1로부터 C2를 빼서 점착제의 정전 용량(C3)을 산출했다. 이 정전 용량C3에 근거해, 하기 식으로부터 점착제의 유전율εs를 산출했다. 결과를 표 1에 나타낸다.On one side of a 50 µm-thick polyethylene terephthalate film, a 100 µm-thick adhesive layer was formed in the same manner as in Examples and Comparative Examples, and a 50 µm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer. It was cut into x 50 mm. About the obtained laminated body, the electrostatic capacity (C1) was measured using an impedance analyzer (made by Nippon Hewlett-Packard, "HP-4194A"). In addition, two polyethylene terephthalate films having a thickness of 50 μm were stacked and cut into 50 mm×50 mm, and the electrostatic capacity (C2) was measured in the same manner. And C2 was subtracted from C1, and the electrostatic capacity (C3) of an adhesive was calculated. Based on this capacitance C3, the dielectric constant ε s of the pressure-sensitive adhesive was calculated from the following equation. Table 1 shows the results.

εs=(C3×d)/(ε0×S)ε s =(C3×d)/(ε 0 ×S)

εs : 점착제의 유전율ε s : permittivity of the adhesive

ε0 : 진공의 유전율(8.854×10-12) ε 0 : Dielectric constant of vacuum (8.854×10 -12 )

C3 : 점착제의 정전 용량 C3: Electrostatic capacity of the adhesive

S : 점착제층의 면적 S: area of the pressure-sensitive adhesive layer

d : 점착제층의 두께d: thickness of the pressure-sensitive adhesive layer

상기 결과로부터, 점착제층의 유전율εs가 2.0∼8.0인 것을 양호(○), 8.0 초과인 것을 불량(×)으로 평가했다. 이 평가 결과도 아울러 표 1에 나타낸다.From the above results, the dielectric constant ε s of the pressure-sensitive adhesive layer was evaluated as good (○), and the one exceeding 8.0 was evaluated as poor (x). Table 1 also shows this evaluation result.

Figure pat00001
Figure pat00001

표 1로부터 알 수 있는 바와 같이, 실시예에서 얻어진 점착 시트는, 내습열 백화성 및 부식 억제 효과가 우수하고, 또 유전율도 충분히 낮아 양호했다.As can be seen from Table 1, the pressure-sensitive adhesive sheet obtained in Examples was excellent in moist heat whitening resistance and corrosion inhibiting effect, and also had a sufficiently low dielectric constant and was good.

<산업상 이용 가능성><Industrial availability>

본 발명에 관련된 점착성 조성물, 점착제 및 점착 시트는, 예를 들어 전극으로서 구리 메시를 사용한 정전 용량 방식의 터치 패널에 바람직하게 사용할 수 있다.The pressure-sensitive adhesive composition, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet according to the present invention can be preferably used for a capacitive touch panel using a copper mesh as an electrode, for example.

1 : 점착 시트
11 : 점착제층
12a, 12b : 박리 시트
2 : 터치 패널
3 : 표시체 모듈
4 : 점착제층
5a : 제 1 필름 센서
5b : 제 2 필름 센서
51 : 기재 필름
52 : 전극
6 : 커버재
7 : 인쇄층1: adhesive sheet
11: pressure-sensitive adhesive layer
12a, 12b: release sheet
2: touch panel
3: display module
4: adhesive layer
5a: first film sensor
5b: second film sensor
51: base film
52: electrode
6: cover material
7: printing layer

Claims (7)

은 또는 구리를 함유하는 금속 메시의 전극이 형성된 필름 센서와,
상기 필름 센서의 상기 금속 메시와 접촉하도록 배치된 점착제층을 갖고,
상기 점착제층이,
중합체를 구성하는 모노머 단위로서 수산기를 갖는 모노머를 15질량％ 초과 30질량％ 이하 함유하고, 카르복실기를 갖는 모노머를 함유하지 않는 (메트)아크릴산에스테르 중합체(A)와,
벤조트리아졸계 방청제(B)
를 함유하는 점착성 조성물을 가교하여 이루어지는 점착제로 이루어지고,
상기 점착제층의 두께가, 25㎛ 이상, 300㎛ 이하인 것을 특징으로 하는 구성체. A film sensor on which an electrode of a metal mesh containing silver or copper is formed,
Having a pressure-sensitive adhesive layer disposed to contact the metal mesh of the film sensor,
The pressure-sensitive adhesive layer,
A (meth)acrylic acid ester polymer (A) containing more than 15% by mass and not more than 30% by mass of a monomer having a hydroxyl group as a monomer unit constituting the polymer and not containing a monomer having a carboxyl group;
Benzotriazole-based rust inhibitor (B)
Consisting of an adhesive formed by crosslinking an adhesive composition containing,
The constitution, wherein the thickness of the pressure-sensitive adhesive layer is 25 μm or more and 300 μm or less. 제 1 항에 있어서, 상기 벤조트리아졸계 방청제(B)로서 1H-벤조트리아졸, 1H-톨릴트리아졸, 1-[N,N-비스(2-에틸헥실)아미노메틸]벤조트리아졸 및 1-[N,N-비스(2-에틸헥실)아미노메틸]메틸벤조트리아졸로 이루어지는 군에서 선택되는 적어도 1종을 함유하는 것을 특징으로 하는 구성체.According to claim 1, 1H-benzotriazole, 1H-tolyltriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole and 1- Constituent comprising at least one selected from the group consisting of [N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole. 제 1 항에 있어서, 상기 (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 호모폴리머로서의 유리 전이 온도가 70℃ 이상인 하드 모노머를 함유하는 것을 특징으로 하는 구성체.The constituent according to claim 1, wherein the (meth)acrylic acid ester polymer (A) contains a hard monomer having a glass transition temperature of 70°C or higher as a homopolymer as a monomer unit constituting the polymer. 제 1 항에 있어서, 상기 (메트)아크릴산에스테르 중합체(A)는, 당해 중합체를 구성하는 모노머 단위로서 (메트)아크릴산 2-에틸헥실을 함유하는 것을 특징으로 하는 구성체.The constituent according to claim 1, wherein the (meth)acrylic acid ester polymer (A) contains 2-ethylhexyl (meth)acrylate as a monomer unit constituting the polymer. 제 1 항에 있어서, 상기 점착성 조성물은, 추가로 가교제(C)를 함유하는 것을 특징으로 하는 구성체.The constitution according to claim 1, wherein the adhesive composition further contains a crosslinking agent (C). 제 1 항에 있어서, 상기 점착제의 1.0㎒에 있어서의 유전율이 2.0∼8.0인 것을 특징으로 하는 구성체.The structural body according to claim 1, wherein the pressure-sensitive adhesive has a dielectric constant of 2.0 to 8.0 at 1.0 MHz. 제 1 항 내지 제 6 항 중 어느 한 항에 기재된 구성체를 갖는 터치 패널.A touch panel having the constitution according to any one of claims 1 to 6.
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