WO2020262697A1 - Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet Download PDF

Info

Publication number
WO2020262697A1
WO2020262697A1 PCT/JP2020/025419 JP2020025419W WO2020262697A1 WO 2020262697 A1 WO2020262697 A1 WO 2020262697A1 JP 2020025419 W JP2020025419 W JP 2020025419W WO 2020262697 A1 WO2020262697 A1 WO 2020262697A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
weight
monomer
adhesive composition
Prior art date
Application number
PCT/JP2020/025419
Other languages
French (fr)
Japanese (ja)
Inventor
純司 柳沢
伸行 島田
Original Assignee
ライオン・スペシャリティ・ケミカルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2019228620A external-priority patent/JP2021008592A/en
Application filed by ライオン・スペシャリティ・ケミカルズ株式会社 filed Critical ライオン・スペシャリティ・ケミカルズ株式会社
Priority to CN202080040062.9A priority Critical patent/CN113891923B/en
Priority to KR1020217029789A priority patent/KR20220023750A/en
Publication of WO2020262697A1 publication Critical patent/WO2020262697A1/en

Links

Classifications

    • 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
    • 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
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive composition and an adhesive sheet.
  • Adhesives and adhesive tapes and adhesive sheets using them are widely used in various fields in industry. Specific applications include, for example, a protective film and a shatterproof film that are attached to the surface of glass or the like.
  • the glass include a cover glass for the front portion of a mobile phone and a smartphone, and a window glass for an automobile, a building, and the like.
  • Adhesives include, for example, acrylic resin adhesives, rubber adhesives, urethane adhesives and the like. Among these, acrylic resin-based adhesives are widely used because they have excellent properties such as heat resistance and durability (Patent Document 1 and the like).
  • Adhesive sheets have been used for various adherends such as various plastics, metals, glass, wood materials, cloths, and ceramics.
  • adherends such as various plastics, metals, glass, wood materials, cloths, and ceramics.
  • glass it is known that it is used as a glass shatterproof adhesive sheet for preventing glass from scattering when the glass is broken by an impact such as dropping.
  • the places where the glass shatterproof sheet is used include the cover glass of the front part of so-called mobile products such as information mobile terminals and electronic dictionaries, windows of vehicles such as automobiles and trains, and windows of buildings.
  • the adhesive used for the glass shatterproof sheet does not foam or peel off in high temperature or high humidity environments (durability), and the adhesive film does not become cloudy (moisture heat whitening resistance). is required.
  • an object of the present invention is to provide an adhesive composition and an adhesive sheet having excellent transparency, high durability and moisture heat whitening resistance.
  • the pressure-sensitive adhesive composition of the present invention is characterized by containing the following components (A), (B), and (C).
  • A A copolymer of a monomer mixture containing the following monomers (a1) to (a4) and having a weight average molecular weight of 200,000 to 1.2 million, the carbon of the copolymer (a1) alkyl group.
  • (Meta) acrylic acid alkyl ester having a number of 3 to 12 (a2)
  • (Meta) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms (a3) Monomer having a hydroxyl group (a4) Monomer having a carboxy group
  • B Metal chelate compound
  • the pressure-sensitive adhesive sheet of the present invention is characterized by having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • an adhesive composition and an adhesive sheet having excellent transparency, high durability and moisture heat whitening resistance.
  • the component (C) may contain at least one of a silane coupling agent having an epoxy group and a silane coupling agent having a mercapto group.
  • the pressure-sensitive adhesive composition of the present invention may further contain, for example, the following component (D).
  • component (D) Isocyanate compound
  • the component (D) may be a polyisocyanate cross-linking agent.
  • the pressure-sensitive adhesive sheet of the present invention may be, for example, a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is formed on at least one surface of a base material.
  • the adhesive sheet of the present invention may be, for example, an adhesive sheet having no base material (base material-less type). More specifically, for example, the pressure-sensitive adhesive sheet of the present invention may be a base material-less type pressure-sensitive adhesive sheet composed of only a pressure-sensitive adhesive layer.
  • the adhesive sheet of the present invention may be, for example, an adhesive tape.
  • the "tape” is a kind of "sheet” and is included in the “sheet”. That is, in the present invention, the “adhesive tape” is a kind of “adhesive sheet” and is included in the “adhesive sheet”. In the present invention, there is no clear distinction between “tape” and “sheet”, but for example, an elongated strip-shaped sheet is referred to as "tape”.
  • the pressure-sensitive adhesive composition of the present invention is characterized by containing the following components (A), (B), and (C). Further, for example, as described above, the component (D) (isocyanate compound) may be further contained.
  • the method for producing the pressure-sensitive adhesive composition of the present invention is not particularly limited, but for example, all the components constituting the pressure-sensitive adhesive composition of the present invention may be simply mixed. Each component constituting the pressure-sensitive adhesive composition of the present invention will be described below with an example.
  • the components (A) (copolymer (A)) are a (meth) acrylic acid alkyl ester in which the alkyl group which is the monomer (a1) has 3 to 12 carbon atoms, and the monomer (meth).
  • It is a copolymer of a monomer mixture containing a monomer having.
  • "monomer” and “monomer” have the same meaning unless otherwise specified.
  • the weight average molecular weight of the component (A) is 200,000 to 1.2 million as described above. If the weight average molecular weight of the component (A) is too low, the cohesive force of the pressure-sensitive adhesive composition may decrease, and the durability may deteriorate. If the weight average molecular weight of the component (A) is too high, the adhesive strength may decrease or the coatability of the pressure-sensitive adhesive composition may decrease.
  • the weight average molecular weight of the component (A) may be, for example, 200,000 or more, or 250,000 or more, and may be, for example, 800,000 or less, 600,000 or less, 350,000 or less, 300,000 or less, or 250,000 or less.
  • the method for measuring the weight average molecular weight is not particularly limited, but for example, it can be measured by the method described in Examples described later.
  • Examples of the (meth) acrylic acid alkyl ester in which the alkyl group which is the monomer (a1) has 3 to 12 carbon atoms includes propyl (meth) acrylic acid, butyl (meth) acrylate, and isobutyl (meth) acrylic acid.
  • (Meta) Acrylic 2-ethylhexylate and the like can be mentioned. These may be used alone or in combination of two or more.
  • the content of the monomer (a1) in the copolymer (A) is not particularly limited, but in 100 parts by weight of the copolymer (A), for example, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more.
  • weight can be read as “mass” unless otherwise specified.
  • parts by weight may be read as “parts by mass”
  • weight ratio may be read as “mass ratio”.
  • the weight of the monomer in the copolymer (A) or the weight ratio of each monomer is converted by replacing the copolymer (A) with a monomer mixture as a raw material thereof. It is a weight or a weight (mass) ratio.
  • the content of the monomer (a1) in 100 parts by weight of the copolymer (A) is 20 parts by weight in 100 parts by weight of the monomer mixture which is the raw material of the copolymer (A). It means that the content of the monomer (a1) is 20 parts by weight.
  • Examples of the (meth) acrylic acid alkyl ester in which the alkyl group which is the monomer (a2) has 1 to 2 carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate. These may be used alone or in combination of two or more.
  • the content of the monomer (a2) in the copolymer (A) is not particularly limited, but in 100 parts by weight of the copolymer (A), for example, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more. , 25 parts by weight or more, for example, 60 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less, for example, 20 to 50 parts by weight. It may be 25 to 45 parts by weight.
  • the weight ratio of the monomer (a1) to the monomer (a2) is not particularly limited, but the weight of the monomer (a2) is, for example, 0, with respect to the weight of the monomer (a1). It may be 1 time or more, 0.15 times or more, and may be, for example, 2.5 times or less, or 2.0 times or less. From the viewpoint of durability and adhesive strength, the weight of the monomer (a2) is preferably 0.1 times or more the weight of the monomer (a1), for example. From the viewpoint of durability and adhesive strength, the weight of the monomer (a2) is preferably 2.5 times or less the weight of the monomer (a1), for example.
  • Examples of the monomer having a hydroxyl group as the monomer (a3) include a hydroxyalkyl ester of acrylic acid or methacrylic acid, a caprolactone adduct of a hydroxy ester of acrylic acid or methacrylic acid, a polyalkylene glycol ester of acrylic acid or methacrylic acid, and the like. can give.
  • the alkyl group may be linear or branched, and the number of carbon atoms may be, for example, 1 to 8.
  • the hydroxyalkyl ester of acrylic acid is not particularly limited, but for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxy acrylate. Examples thereof include butyl, 8-hydroxyoctyl acrylate, and 6-hydroxyhexyl acrylate.
  • the hydroxyalkyl ester of methacrylic acid is not particularly limited, and for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxymethacrylic acid.
  • the content of the monomer (a3) in the copolymer (A) is not particularly limited, but may be 10 to 40 parts by weight, or 15 to 35 parts by weight, based on 100 parts by weight of the copolymer (A). It may be. When the amount is 10 parts by weight or more, the moisture-heat whitening resistance and the adhesive force are further improved, and when the amount is 40 parts by weight or less, a sufficient adhesive force can be obtained.
  • the monomer having a carboxy group examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid. These may be used alone or in combination of two or more.
  • the monomer (a4) is preferably a dicarboxylic acid such as itaconic acid, maleic acid, fumaric acid, and citraconic acid.
  • the content of the monomer (a4) in the copolymer (A) is not particularly limited, but may be 0.05 to 1.0 parts by weight in 100 parts by weight of the copolymer (A), and is 0. It may be 1 to 0.8 parts by weight. If it is 0.05 parts by weight or more, the durability is good. If it is 1.0 part by weight or less, the pressure-sensitive adhesive composition is less likely to float or peel.
  • the metal chelate compound (B) used in the present invention is not particularly limited, but is, for example, di-i-propoxybis (acetylacetone) titanate, di-n-butoxybis (triethanolamine) titanate, dihydroxybistitanate. , Di-i-propoxybis (ethyl acetylacetone) titanate, ethylacetacetate aluminum diisopropilate, aluminum tris (ethylacetate acetate) aluminum di-n-butoxide monomethylacetate, aluminum di-butoxide monoethylacetate, aluminum Examples thereof include tris (acetylacetonate) and zirconium tetraacetylacetonate.
  • the metal chelate compound (B) is not particularly limited, but is, for example, an equivalent amount with respect to the carboxy group-containing monomer (a4).
  • the silane coupling agent (component (C)) used in the present invention is not particularly limited, but is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxy.
  • Silane ⁇ -glycidoxypropyltrimethoxysilane, ⁇ glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, 2- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 Examples thereof include -aminopropylmethyldimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, and ⁇ -mer
  • the silane coupling agent (C) is considered to have, for example, a function of improving the adhesive strength of the pressure-sensitive adhesive composition of the present invention.
  • the content of the silane coupling agent (C) is not particularly limited, but is, for example, 0.05 to 2.0% by weight, preferably 0.1 to 2.0% by weight, based on 100% by weight of the copolymer (A). It is 1.5% by weight. From the viewpoint of adhesive strength, the content of the silane coupling agent (C) is preferably within the above numerical range.
  • the component (D) is an isocyanate compound.
  • the isocyanate compound is used as a cross-linking agent.
  • the isocyanate-based compound is not particularly limited, but a polyisocyanate-based compound is preferable.
  • the amount of the component (D) used is not particularly limited, but is preferably 0.1 to 1.5% by weight, more preferably 0.2 to 1.0% by weight, based on 100% by weight of the copolymer (A). .. If it is 0.1% by weight or more, the durability is good. If it is 1.5% by weight or less, sufficient adhesive strength can be obtained.
  • the pressure-sensitive adhesive composition of the present invention contains the components (A), (B), and (C).
  • the pressure-sensitive adhesive composition of the present invention may or may not contain the component (D).
  • the component (D) crosslinking agent (D)
  • the component (D) may be internally added to the pressure-sensitive adhesive composition of the present invention in advance, or may be added immediately before coating on the substrate. You may.
  • the pressure-sensitive adhesive composition of the present invention may or may not contain components other than the components (A) to (D).
  • the pressure-sensitive adhesive composition of the present invention further comprises, as the other components, a tackifier, a solvent, a plasticizer, an antioxidant, an antioxidant, a filler, a colorant, an ultraviolet absorber, an antifoaming agent, and the like. It may or may not contain a light stabilizer, a leveling agent, an antistatic agent, a cross-linking delaying agent, and the like.
  • the types thereof are not particularly limited, but may be, for example, the same as or similar to a general pressure-sensitive adhesive composition. When the pressure-sensitive adhesive composition of the present invention contains the other components, only one type of each of the other components may be used, or two or more types may be used in combination.
  • the antistatic agent is not particularly limited, and examples thereof include ionic compounds such as inorganic salts and organic salts, and nonionic compounds such as nonionic surfactants.
  • the antistatic agent may be, for example, an ionic compound.
  • the ionic compound is preferably other than an ionic compound capable of exhibiting basicity and an ionic sulfonic acid ester compound.
  • Specific examples of the ionic compound include chloride, perchlorate, acetate, and nitrate, and more specifically, lithium chloride, lithium perchlorate, sodium perchlorate, potassium acetate, and trifluoro. Examples thereof include lithium acetate and lithium nitrate.
  • the plasticizer examples include carboxylic acid esters and the like.
  • the carboxylic acid ester is not particularly limited, and may be, for example, the carboxylic acid ester described in JP-A-2011-190420, JP-A-2015-151429, and JP-A-2016-186029.
  • the carboxylic acid ester may be, for example, the carboxylic acid ester in the examples described later.
  • the content of the plasticizer is not particularly limited, but may be, for example, 1% by weight or more, 5% by weight or more, or 10% by weight or more, for example, 30% by weight, based on the total weight of the copolymer (A). It may be less than or equal to 20% by weight or less.
  • the ultraviolet absorber is not particularly limited, and examples thereof include ultraviolet absorbers such as benzophenone type, benzotriazole type, and triazine type.
  • the defoaming agent is not particularly limited, and examples thereof include silicone-based and mineral oil-based defoaming agents.
  • the light stabilizer is not particularly limited, and examples thereof include a hindered amine-based light stabilizer.
  • the solvent is not particularly limited, and for example, a known solvent can be used.
  • the solvent include ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate and isobutyl acetate, and hydrocarbons such as toluene and xylene.
  • the antioxidant is not particularly limited, and examples thereof include phenol-based and sulfur-based antioxidants.
  • the cross-linking retarder is not particularly limited, and examples thereof include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetylacetone, acetoacetic ester, and malonic acid ester. Further, a blocked isocyanate in which the isocyanate group is blocked with alcohol, phenol, oxime, amine, amide, imide, lactam or the like may be used.
  • the pressure-sensitive adhesive sheet of the present invention may be, for example, a pressure-sensitive adhesive sheet having an pressure-sensitive adhesive layer formed on at least one surface of the base material, or a base material-less type pressure-sensitive adhesive sheet composed of only the pressure-sensitive adhesive layer. There may be. Further, as described above, the pressure-sensitive adhesive sheet of the present invention is characterized in that the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • the method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but may be, for example, the same as or similar to a general method for manufacturing a pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive composition of the present invention is applied (coated) to a substrate or the like, and if necessary, the pressure-sensitive adhesive composition is heated to dry, age, or the like to form an pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention may be produced.
  • the shape of the base material is not particularly limited, and examples thereof include sheets, films, and foams. From the viewpoint of ease of handling, storage, and the like of the pressure-sensitive adhesive sheet after production, the base material is preferably in the form of a long tape that can be wound up, for example. Further, the base material may be, for example, a base material obtained by subjecting the pressure-sensitive adhesive layer forming surface of the base material to an easy-adhesion treatment, if necessary.
  • the easy-adhesion treatment is not particularly limited, and specific examples thereof include a method of treating corona discharge and a method of applying an anchor coating agent.
  • the base film is not particularly limited, but for example, a highly transparent resin film having heat resistance is preferable.
  • the resin constituting the resin film is not particularly limited, and is, for example, a polyester resin such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, a polyethylene terephthalate / isophthalate copolymer, and a cellulose-based resin such as cellulose triacetate and cellophane. Examples thereof include resins, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, and polyamide resins such as aliphatic polyamides and aromatic polyamides.
  • the form of the adhesive sheet of the present invention is not particularly limited, but for example, during storage, a separator is attached onto the adhesive layer to protect the adhesive layer and used (for example, attachment to an image display device, a semiconductor wafer, or the like). It is preferable that the pressure-sensitive pressure-sensitive adhesive sheet is used by peeling off the separator immediately before use.
  • n-butyl acrylate (BA): 11.9 parts by weight, methyl acrylate (MA): 16 parts by weight, acrylic acid (AA): 0.1 parts by weight, -2-hydroxypropyl acrylate ( HPA): 12 parts by weight and 2,2'-azobisisobutyronitrile: 0.04 parts by weight as a polymerization initiator were mixed to prepare a monomer mixture.
  • the monomer mixture was added dropwise to the system under reflux at a temperature of 77 to 88 ° C. over 2 hours, and heating and stirring were continued at the temperature as it was to carry out a polymerization reaction.
  • the acrylic copolymer (A1) produced in Synthesis Example 1 corresponds to the component (A) in the pressure-sensitive adhesive composition of the present invention.
  • Butyl acrylate is a (meth) acrylic acid alkyl ester having an alkyl group having 3 to 12 carbon atoms, and corresponds to the monomer (a1).
  • Methyl acrylate is a (meth) acrylic acid alkyl ester in which the alkyl group has 1 to 2 carbon atoms, and corresponds to the monomer (a2).
  • 2-Hydroxypropyl acrylate is a monomer having a hydroxyl group and corresponds to the monomer (a3).
  • Acrylic acid is a monomer having a carboxy group and corresponds to the monomer (a4).
  • the acrylic copolymer (A2) was prepared by changing the blending amounts and types of the monomers (a1) to (a4) so as to have the monomer compositions shown in Examples 2 to 19 and Comparative Examples 1 and 2 in Tables 1 to 4. ⁇ (A21) was obtained.
  • the pressure-sensitive adhesive composition was produced as follows.
  • Example 1 Polyfunctional hexamethylene diisocyanate as the cross-linking agent (D) with respect to 250 parts by weight of the solution of the acrylic copolymer (A1) prepared in Synthesis Example 1 (corresponding to 100 parts by weight as the solid content of the acrylic copolymer A1).
  • Examples 2 to 19, Comparative Examples 1 to 2 As shown in Tables 1 to 4, the cross-linking agent (D) and the silane cup were added to 100 parts by weight as the solid content of the acrylic copolymers (A2) to (A21) prepared in Synthesis Examples 2 to 21.
  • the ring agent (C) and the metal chelate compound (B) were blended to prepare the pressure-sensitive adhesive compositions of Examples 2 to 19 and Comparative Examples 1 and 2.
  • the thickness of the pressure-sensitive adhesive composition after drying is about 25 ⁇ m on the release-treated surface of a film whose surface has been released-treated (release liner, manufactured by Panac Co., Ltd., trade name “NP-50B”). And dried at 100 ° C. for 2 minutes to form an adhesive layer. After drying, the adhesive layer side was laminated on a polyethylene terephthalate film (Toyobo Co., Ltd. Cosmo Shine A-4300 (thickness: 100 ⁇ m)) and bonded, and aged at 40 ° C. for 2 days to obtain an adhesive sheet. ..
  • ⁇ Durability> A 70 mm ⁇ 140 mm test piece was cut out from the adhesive sheets of Examples and Comparative Examples, respectively. Further, after peeling off the release film (the release liner) from the test piece, the release film (the release liner) is pressure-bonded to a glass plate in an atmosphere of 23 ° C. ⁇ 50% with a 2 kg rubber roller in 3 reciprocations, and under the same atmosphere. It was left for 60 minutes. Then, the attached test piece was left in an oven together with the glass plate for 1000 hours in an atmosphere of 85 ° C. ⁇ 85% RH, then taken out from the oven and further left in an atmosphere of 23 ° C. ⁇ 50% for 60 minutes. ..
  • Tables 1 to 4 below show the types and blending amounts of raw materials in the pressure-sensitive adhesive compositions of Examples and Comparative Examples.
  • the test results of the above-mentioned adhesive strength, durability and moisture-heat bleaching resistance to the pressure-sensitive adhesive sheets produced by using the pressure-sensitive adhesive compositions of Examples and Comparative Examples are also shown in Tables 1 to 4 below.
  • the numerical values in the columns of each raw material represent the blending amount (part by weight) of the raw material.
  • the "molecular weight of the copolymer” represents the weight average molecular weight (10,000) of the copolymer (A).
  • the numerical value of "adhesive strength" represents the 180 degree peel strength (N / 25 mm) measured by the above method.
  • the numerical value of "moisture heat bleaching resistance” represents the haze value (%) measured by the above-mentioned method.
  • the metal chelate compound (B) of each example uses the same aluminum tris (acetyl acetate) as in Example 1 (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name "Narsem Aluminum”), and the amount used is , 1 equivalent with respect to the carboxy group of the monomer (a4). That is, for acrylic acid which is a monocarboxylic acid (monobasic acid), an equal mol amount of the metal chelate compound (B) is used as in Example 1, and for maleic acid which is a dicarboxylic acid (dibasic acid). The metal chelate compound (B) was used in a double mol amount.
  • the pressure-sensitive adhesive composition of Examples and the pressure-sensitive adhesive sheet of Examples using the same had good adhesive strength, durability, and moisture-heat whitening resistance.
  • the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Comparative Example 1 containing no component (B) (metal chelate compound) were inferior in durability, although their adhesive strength and moisture-heat bleaching resistance were comparable to those of Examples. ..
  • the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Comparative Example 2 containing no component (a2) ((meth) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms) are also adhered in the same manner as in Comparative Example 1. Although the force and moisture heat bleaching resistance were comparable to those of the examples, the durability was inferior.
  • Examples 1 to 4 are all the same except for the blending amounts of the components (a1) and (a2), but the adhesive strength of Examples 1, 3 and 4 was higher than that of Example 2. From this, the blending amount of the component (a2) ((meth) acrylic acid alkyl ester in which the alkyl group has 1 to 2 carbon atoms) is the component (a1) (the alkyl group has 3 to 12 carbon atoms). It was confirmed that the adhesive strength was further improved when the amount was higher than that of meta) acrylic acid alkyl ester). Examples 1 and 16 are all the same except for the blending amounts of the components (a1) and (a3), but the adhesive strength of Example 1 was higher.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Provided are a pressure-sensitive adhesive composition having excellent transparency and having high durability and unsusceptibility to blushing by moist heat and a pressure-sensitive adhesive sheet. The pressure-sensitive adhesive composition is characterized by comprising the following ingredients (A), (B), and (C). (A) A copolymer of a monomer mixture comprising the following monomers (a1) to (a4), the copolymer having a weight-average molecular weight of 200,000-1,200,000: (a1) an alkyl (meth)acrylate in which the alkyl group has 3-12 carbon atoms; (a2) an alkyl (meth)acrylate in which the alkyl group has one or two carbon atoms; (a3) a hydroxylated monomer; and (a4) a carboxylated monomer. (B) A chelating metal compound. (C) A silane coupling agent.

Description

粘着剤組成物および粘着シートAdhesive composition and adhesive sheet
　本発明は、粘着剤組成物および粘着シートに関する。 The present invention relates to an adhesive composition and an adhesive sheet.
　粘着剤およびそれを用いた粘着テープ、粘着シートは、産業上の種々の分野において広範に用いられている。具体的な用途としては、例えば、ガラス等の表面に貼付して用いる保護フィルムや飛散防止フィルム等がある。前記ガラスとしては、例えば、携帯電話、スマートフォンのフロント部のカバーガラス、自動車、建物等の窓ガラスが挙げられる。 Adhesives and adhesive tapes and adhesive sheets using them are widely used in various fields in industry. Specific applications include, for example, a protective film and a shatterproof film that are attached to the surface of glass or the like. Examples of the glass include a cover glass for the front portion of a mobile phone and a smartphone, and a window glass for an automobile, a building, and the like.
　粘着剤には、例えば、アクリル樹脂系粘着剤、ゴム系粘着剤、ウレタン粘着剤等がある。これらの中で、アクリル樹脂系粘着剤は、耐熱性、耐久性等の特性に優れるため、広く用いられている（特許文献１等）。 Adhesives include, for example, acrylic resin adhesives, rubber adhesives, urethane adhesives and the like. Among these, acrylic resin-based adhesives are widely used because they have excellent properties such as heat resistance and durability (Patent Document 1 and the like).
特開平８－３４９６２号公報Japanese Unexamined Patent Publication No. 8-34962
　粘着シートは各種プラスチックス、金属、ガラス、木質材料、布、セラミックス等各種の被着体に使用されてきた。特にガラスに対して使用される場合には、ガラスが落下などの衝撃により破損したときに、ガラスの飛散を防止するガラス飛散防止用粘着シートとして使用されることが知られている。 Adhesive sheets have been used for various adherends such as various plastics, metals, glass, wood materials, cloths, and ceramics. In particular, when it is used for glass, it is known that it is used as a glass shatterproof adhesive sheet for preventing glass from scattering when the glass is broken by an impact such as dropping.
　ガラス飛散防止シートが使用される場所としては、情報携帯端末や電子辞書等のいわゆるモバイル製品のフロント部のカバーガラスや、自動車や電車等の乗物の窓、建築物の窓等がある。 The places where the glass shatterproof sheet is used include the cover glass of the front part of so-called mobile products such as information mobile terminals and electronic dictionaries, windows of vehicles such as automobiles and trains, and windows of buildings.
　ガラス飛散防止シートに使用される粘着剤は、透明性に加え、高温や高湿環境下
等で発泡や剥がれを生じない性質（耐久性）や、粘着皮膜が白濁しない性質（耐湿熱白化性）が必要である。 In addition to transparency, the adhesive used for the glass shatterproof sheet does not foam or peel off in high temperature or high humidity environments (durability), and the adhesive film does not become cloudy (moisture heat whitening resistance). is required.
　そこで、本発明は、透明性に優れ、かつ、高い耐久性および耐湿熱白化性を有する粘着剤組成物および粘着シートを提供することを目的とする。 Therefore, an object of the present invention is to provide an adhesive composition and an adhesive sheet having excellent transparency, high durability and moisture heat whitening resistance.
　前記目的を達成するために、本発明の粘着剤組成物は、下記成分（Ａ）、（Ｂ）、および（Ｃ）を含むことを特徴とする。
（Ａ）下記単量体（ａ１）～（ａ４）を含む単量体混合物の共重合体であって、重量平均分子量が２０万～１２０万である、共重合体
　（ａ１）アルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステル
　（ａ２）アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステル
　（ａ３）水酸基を有するモノマー
　（ａ４）カルボキシ基を有するモノマー
（Ｂ）金属キレート化合物
（Ｃ）シランカップリング剤 In order to achieve the above object, the pressure-sensitive adhesive composition of the present invention is characterized by containing the following components (A), (B), and (C).
(A) A copolymer of a monomer mixture containing the following monomers (a1) to (a4) and having a weight average molecular weight of 200,000 to 1.2 million, the carbon of the copolymer (a1) alkyl group. (Meta) acrylic acid alkyl ester having a number of 3 to 12 (a2) (Meta) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms (a3) Monomer having a hydroxyl group (a4) Monomer having a carboxy group (B) Metal chelate compound (C) Silane coupling agent
　本発明の粘着シートは、本発明の粘着剤組成物から形成された粘着層を有することを特徴とする。 The pressure-sensitive adhesive sheet of the present invention is characterized by having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
　本発明によれば、透明性に優れ、かつ、高い耐久性および耐湿熱白化性を有する粘着剤組成物および粘着シートを提供することができる。 According to the present invention, it is possible to provide an adhesive composition and an adhesive sheet having excellent transparency, high durability and moisture heat whitening resistance.
　以下、本発明について、例を挙げて説明する。ただし、本発明は以下の説明により限定されない。 Hereinafter, the present invention will be described with an example. However, the present invention is not limited by the following description.
　本発明の粘着剤組成物において、例えば、前記成分（Ｃ）が、エポキシ基を有するシランカップリング剤、および、メルカプト基を有するシランカップリング剤の少なくとも一方を含んでいてもよい。 In the pressure-sensitive adhesive composition of the present invention, for example, the component (C) may contain at least one of a silane coupling agent having an epoxy group and a silane coupling agent having a mercapto group.
　本発明の粘着剤組成物は、例えば、さらに、下記成分（Ｄ）を含んでいてもよい。
（Ｄ）イソシアネート化合物 The pressure-sensitive adhesive composition of the present invention may further contain, for example, the following component (D).
(D) Isocyanate compound
　本発明の粘着剤組成物は、例えば、成分（Ｄ）が、ポリイソシアネート架橋剤であってもよい。 In the pressure-sensitive adhesive composition of the present invention, for example, the component (D) may be a polyisocyanate cross-linking agent.
　本発明の粘着シートは、例えば、基材の少なくとも一方の面に前記粘着層が形成された粘着シートであってもよい。 The pressure-sensitive adhesive sheet of the present invention may be, for example, a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is formed on at least one surface of a base material.
　また、本発明の粘着シートは、例えば、基材を有しない（基材レスタイプの）粘着シートであってもよい。より具体的には、例えば、本発明の粘着シートは、粘着剤層のみからなる基材レスタイプの粘着シートであってもよい。 Further, the adhesive sheet of the present invention may be, for example, an adhesive sheet having no base material (base material-less type). More specifically, for example, the pressure-sensitive adhesive sheet of the present invention may be a base material-less type pressure-sensitive adhesive sheet composed of only a pressure-sensitive adhesive layer.
　本発明の粘着シートは、例えば、粘着テープであってもよい。 The adhesive sheet of the present invention may be, for example, an adhesive tape.
　なお、本発明において、「テープ」は、「シート」の一種であって、「シート」に含まれるものとする。すなわち、本発明において、「粘着テープ」は、「粘着シート」の一種であって、「粘着シート」に含まれる。本発明において、「テープ」と「シート」とに明確な区別はないが、例えば、細長い帯状のシートを「テープ」という。 In the present invention, the "tape" is a kind of "sheet" and is included in the "sheet". That is, in the present invention, the "adhesive tape" is a kind of "adhesive sheet" and is included in the "adhesive sheet". In the present invention, there is no clear distinction between "tape" and "sheet", but for example, an elongated strip-shaped sheet is referred to as "tape".
　以下、本発明の実施形態について、さらに具体的に説明する。ただし、本発明は、以下の実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following embodiments.
［１．粘着剤組成物］
　前記の通り、本発明の粘着剤組成物は、下記成分（Ａ）、（Ｂ）、および（Ｃ）を含むことを特徴とする。また、例えば、前述のとおり、さらに、前記成分（Ｄ）（イソシアネート化合物）を含んでいてもよい。
（Ａ）下記単量体（ａ１）～（ａ４）を含む単量体混合物の共重合体であって、重量平均分子量が２０万～１２０万である、共重合体
　（ａ１）アルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステル
　（ａ２）アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステル
　（ａ３）水酸基を有するモノマー
　（ａ４）カルボキシ基を有するモノマー
（Ｂ）金属キレート化合物
（Ｃ）シランカップリング剤 [1. Adhesive composition]
As described above, the pressure-sensitive adhesive composition of the present invention is characterized by containing the following components (A), (B), and (C). Further, for example, as described above, the component (D) (isocyanate compound) may be further contained.
(A) A copolymer of a monomer mixture containing the following monomers (a1) to (a4) and having a weight average molecular weight of 200,000 to 1.2 million, the carbon of the copolymer (a1) alkyl group. (Meta) acrylic acid alkyl ester having a number of 3 to 12 (a2) (Meta) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms (a3) Monomer having a hydroxyl group (a4) Monomer having a carboxy group (B) Metal chelate compound (C) Silane coupling agent
　本発明の粘着剤組成物の製造方法は、特に限定されないが、例えば、本発明の粘着剤組成物を構成する全ての成分を単に混合するのみでもよい。本発明の粘着剤組成物を構成する各成分については、以下において例を挙げて説明する。 The method for producing the pressure-sensitive adhesive composition of the present invention is not particularly limited, but for example, all the components constituting the pressure-sensitive adhesive composition of the present invention may be simply mixed. Each component constituting the pressure-sensitive adhesive composition of the present invention will be described below with an example.
［１－１．成分（Ａ）］
　成分（Ａ）（共重合体（Ａ））は、前述の通り、単量体（ａ１）であるアルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステルと、単量体（ａ２）であるアルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステルと、単量体（ａ３）である水酸基を有する単量体と、単量体（ａ４）であるカルボキシ基を有する単量体を含む単量体混合物の共重合体である。なお、本発明において、「単量体」と「モノマー」とは、特に断らない限り、同義とする。 [1-1. Ingredient (A)]
As described above, the components (A) (copolymer (A)) are a (meth) acrylic acid alkyl ester in which the alkyl group which is the monomer (a1) has 3 to 12 carbon atoms, and the monomer (meth). The (meth) acrylic acid alkyl ester having 1 to 2 carbon atoms in the alkyl group a2), the monomer having a hydroxyl group as the monomer (a3), and the carboxy group as the monomer (a4). It is a copolymer of a monomer mixture containing a monomer having. In the present invention, "monomer" and "monomer" have the same meaning unless otherwise specified.
　成分（Ａ）の重量平均分子量は、前述のとおり２０万～１２０万である。成分（Ａ）の重量平均分子量が低すぎると、粘着剤組成物の凝集力が低下し、耐久性が悪化するおそれがある。成分（Ａ）の重量平均分子量が高すぎると、接着力が低下したり、粘着剤組成物の塗工性が低下したりするおそれがある。成分（Ａ）の重量平均分子量は、例えば、２０万以上、または２５万以上でもよく、例えば、８０万以下、６０万以下、以下、３５万以下、３０万以下、または２５万以下でもよく、例えば、２０万～３５万、２０万～３０万、２０万～２５万、２５万～３０万、２５万～１２０万、または３０万～１００万であってもよい。なお、本発明において、重量平均分子量の測定方法は、特に限定されないが、例えば、後述の実施例に記載の方法により測定できる。 The weight average molecular weight of the component (A) is 200,000 to 1.2 million as described above. If the weight average molecular weight of the component (A) is too low, the cohesive force of the pressure-sensitive adhesive composition may decrease, and the durability may deteriorate. If the weight average molecular weight of the component (A) is too high, the adhesive strength may decrease or the coatability of the pressure-sensitive adhesive composition may decrease. The weight average molecular weight of the component (A) may be, for example, 200,000 or more, or 250,000 or more, and may be, for example, 800,000 or less, 600,000 or less, 350,000 or less, 300,000 or less, or 250,000 or less. For example, it may be 200,000 to 350,000, 200,000 to 300,000, 200,000 to 250,000, 250,000 to 300,000, 250,000 to 1.2 million, or 300,000 to 1,000,000. In the present invention, the method for measuring the weight average molecular weight is not particularly limited, but for example, it can be measured by the method described in Examples described later.
　単量体（ａ１）であるアルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル２－エチルヘキシル酸等が挙げられる。これらは１種のみを用いても２種以上併用してもよい。共重合体（Ａ）中における単量体（ａ１）の含有量は特に限定されないが、共重合体（Ａ）１００重量部中、例えば、１０重量部以上、１５重量部以上、２０重量部以上、または２５重量部以上であってもよく、例えば、９０重量部以下、８０重量部以下、または７０重量部以下であってもよく、２０～７０重量部であってもよく、２５～５０重量部であってもよい。なお、本発明において「重量」という場合は、特に断らない限り「質量」と読み替えることができるものとする。例えば、「重量部」は「質量部」と読み替えてもよく、「重量比」は「質量比」と読み替えてもよいものとする。また、本発明において、共重合体（Ａ）中における単量体の重量または各単量体の重量比は、共重合体（Ａ）を、その原料である単量体混合物に置き換えて換算した重量または重量（質量）比とする。例えば、共重合体（Ａ）１００重量部中の単量体（ａ１）の含有量が２０重量部であることは、共重合体（Ａ）の原料である単量体混合物１００重量部中の単量体（ａ１）の含有量が２０重量部であることを意味する。 Examples of the (meth) acrylic acid alkyl ester in which the alkyl group which is the monomer (a1) has 3 to 12 carbon atoms includes propyl (meth) acrylic acid, butyl (meth) acrylate, and isobutyl (meth) acrylic acid. (Meta) Acrylic 2-ethylhexylate and the like can be mentioned. These may be used alone or in combination of two or more. The content of the monomer (a1) in the copolymer (A) is not particularly limited, but in 100 parts by weight of the copolymer (A), for example, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more. , Or 25 parts by weight or more, for example, 90 parts by weight or less, 80 parts by weight or less, or 70 parts by weight or less, 20 to 70 parts by weight, 25 to 50 parts by weight. It may be a department. In the present invention, the term "weight" can be read as "mass" unless otherwise specified. For example, "parts by weight" may be read as "parts by mass", and "weight ratio" may be read as "mass ratio". Further, in the present invention, the weight of the monomer in the copolymer (A) or the weight ratio of each monomer is converted by replacing the copolymer (A) with a monomer mixture as a raw material thereof. It is a weight or a weight (mass) ratio. For example, the content of the monomer (a1) in 100 parts by weight of the copolymer (A) is 20 parts by weight in 100 parts by weight of the monomer mixture which is the raw material of the copolymer (A). It means that the content of the monomer (a1) is 20 parts by weight.
　単量体（ａ２）であるアルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等が挙げられる。これらは１種のみを用いても２種以上併用してもよい。共重合体（Ａ）中における単量体（ａ２）の含有量は特に限定されないが、共重合体（Ａ）１００重量部中、例えば、１０重量部以上、１５重量部以上、２０重量部以上、または２５重量部以上であってもよく、例えば、６０重量部以下、５０重量部以下、４５重量部以下、または４０重量部以下であってもよく、例えば、２０～５０重量部であってもよく、２５～４５重量部であってもよい。 Examples of the (meth) acrylic acid alkyl ester in which the alkyl group which is the monomer (a2) has 1 to 2 carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate. These may be used alone or in combination of two or more. The content of the monomer (a2) in the copolymer (A) is not particularly limited, but in 100 parts by weight of the copolymer (A), for example, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more. , 25 parts by weight or more, for example, 60 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less, for example, 20 to 50 parts by weight. It may be 25 to 45 parts by weight.
　また、単量体（ａ１）と単量体（ａ２）との重量比は特に限定されないが、単量体（ａ２）の重量が、単量体（ａ１）の重量に対し、例えば、０.１倍以上、または０．１５倍以上であってもよく、例えば、２．５倍以下、または２．０倍以下であってもよい。耐久性と接着力の観点からは、単量体（ａ２）の重量が、単量体（ａ１）の重量に対し、例えば、０．１倍以上であることが好ましい。耐久性と接着力の観点からは、単量体（ａ２）の重量が、単量体（ａ１）の重量に対し、例えば、２．５倍以下であることが好ましい。 The weight ratio of the monomer (a1) to the monomer (a2) is not particularly limited, but the weight of the monomer (a2) is, for example, 0, with respect to the weight of the monomer (a1). It may be 1 time or more, 0.15 times or more, and may be, for example, 2.5 times or less, or 2.0 times or less. From the viewpoint of durability and adhesive strength, the weight of the monomer (a2) is preferably 0.1 times or more the weight of the monomer (a1), for example. From the viewpoint of durability and adhesive strength, the weight of the monomer (a2) is preferably 2.5 times or less the weight of the monomer (a1), for example.
　単量体（ａ３）である水酸基を有するモノマーとしては、アクリル酸またはメタクリル酸のヒドロキシアルキルエステル、アクリル酸またはメタクリル酸のヒドロキシエステルのカプロラクトン付加物、アクリル酸またはメタクリル酸のポリアルキレングリコールエステル等があげられる。前記アクリル酸またはメタクリル酸のヒドロキシアルキルエステルにおいて、前記アルキル基は、直鎖状でも分枝状でもよく、炭素数は、例えば、１～８であってもよい。前記アクリル酸のヒドロキシアルキルエステルとしては、特に限定されないが、例えば、アクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシプロピル、アクリル酸４－ヒドロキシブチル、アクリル酸２－ヒドロキシエチル、アクリル酸３－ヒドロキシブチル、アクリル酸８－ヒドロキシオクチル、アクリル酸６－ヒドロキシヘキシル等があげられる。前記メタクリル酸のヒドロキシアルキルエステルとしては、特に限定されないが、例えば、メタクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシプロピル、メタクリル酸４－ヒドロキシブチル、メタクリル酸２－ヒドロキシエチル、メタクリル酸３－ヒドロキシブチル、メタクリル酸８－ヒドロキシオクチル、メタクリル酸６－ヒドロキシヘキシル等があげられる。これらは１種のみを用いても２種以上併用してもよい。共重合体（Ａ）中における単量体（ａ３）の含有量は特に限定されないが、共重合体（Ａ）１００重量部中、１０～４０重量部であってもよく、１５～３５重量部であってもよい。１０重量部以上の場合、耐湿熱白化性および接着力がさらに良好となり、４０重量部以下であれば十分な接着力が得られる。 Examples of the monomer having a hydroxyl group as the monomer (a3) include a hydroxyalkyl ester of acrylic acid or methacrylic acid, a caprolactone adduct of a hydroxy ester of acrylic acid or methacrylic acid, a polyalkylene glycol ester of acrylic acid or methacrylic acid, and the like. can give. In the hydroxyalkyl ester of acrylic acid or methacrylic acid, the alkyl group may be linear or branched, and the number of carbon atoms may be, for example, 1 to 8. The hydroxyalkyl ester of acrylic acid is not particularly limited, but for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxy acrylate. Examples thereof include butyl, 8-hydroxyoctyl acrylate, and 6-hydroxyhexyl acrylate. The hydroxyalkyl ester of methacrylic acid is not particularly limited, and for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxymethacrylic acid. Examples thereof include butyl, 8-hydroxyoctyl methacrylate, and 6-hydroxyhexyl methacrylate. These may be used alone or in combination of two or more. The content of the monomer (a3) in the copolymer (A) is not particularly limited, but may be 10 to 40 parts by weight, or 15 to 35 parts by weight, based on 100 parts by weight of the copolymer (A). It may be. When the amount is 10 parts by weight or more, the moisture-heat whitening resistance and the adhesive force are further improved, and when the amount is 40 parts by weight or less, a sufficient adhesive force can be obtained.
　単量体（ａ４）であるカルボキシ基を有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、シトラコン酸等が挙げられる。これらは１種のみを用いても２種以上併用してもよい。粘着剤組成物の耐熱性、耐久性の観点から、単量体（ａ４）はイタコン酸、マレイン酸、フマル酸、シトラコン酸等のジカルボン酸が好ましい。共重合体（Ａ）中における単量体（ａ４）の含有量は特に限定されないが、共重合体（Ａ）１００重量部中、０．０５～１．０重量部であってもよく、０．１～０．８重量部であってもよい。０．０５重量部以上であれば、耐久性が良好である。１．０重量部以下であれば、粘着剤組成物の浮き、ハガレが起きにくい。 Examples of the monomer having a carboxy group, which is a monomer (a4), include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid. These may be used alone or in combination of two or more. From the viewpoint of heat resistance and durability of the pressure-sensitive adhesive composition, the monomer (a4) is preferably a dicarboxylic acid such as itaconic acid, maleic acid, fumaric acid, and citraconic acid. The content of the monomer (a4) in the copolymer (A) is not particularly limited, but may be 0.05 to 1.0 parts by weight in 100 parts by weight of the copolymer (A), and is 0. It may be 1 to 0.8 parts by weight. If it is 0.05 parts by weight or more, the durability is good. If it is 1.0 part by weight or less, the pressure-sensitive adhesive composition is less likely to float or peel.
［１－２．成分（Ｂ）］
　本発明で用いる金属キレート化合物（Ｂ）としては、特に限定されないが、例えば、ジ-ｉ-プロポキシ・ビス（アセチルアセトン）チタネート、ジ-ｎ-ブトキシ・ビス（トリエタノールアミン）チタネート、ジヒドロキシ・ビスチタネート、ジ-ｉ-プロポキシ・ビス（アセチル酢酸エチル）チタネート、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリス（エチルアセトアセテート）アルミニウムジ-ｎ-ブトキシドモノメチルアセトアセテート、アルミニウムジ-ブトキシドモノエチルアセトアセテート、アルミニウムトリス（アセチルアセトナート）、ジルコニウムテトラアセチルアセトナートなどが挙げられる。また、金属キレート化合物（Ｂ）は、一種類のみ用いてもよいし、二種類以上併用してもよい。金属キレート化合物（Ｂ）の配合量は、特に限定されないが、例えば、カルボキシ基含有モノマー（ａ４）に対し当量とする。 [1-2. Ingredient (B)]
The metal chelate compound (B) used in the present invention is not particularly limited, but is, for example, di-i-propoxybis (acetylacetone) titanate, di-n-butoxybis (triethanolamine) titanate, dihydroxybistitanate. , Di-i-propoxybis (ethyl acetylacetone) titanate, ethylacetacetate aluminum diisopropilate, aluminum tris (ethylacetate acetate) aluminum di-n-butoxide monomethylacetate, aluminum di-butoxide monoethylacetate, aluminum Examples thereof include tris (acetylacetonate) and zirconium tetraacetylacetonate. Further, only one type of the metal chelate compound (B) may be used, or two or more types may be used in combination. The blending amount of the metal chelate compound (B) is not particularly limited, but is, for example, an equivalent amount with respect to the carboxy group-containing monomer (a4).
［１－３．成分（Ｃ）］
　本発明で用いるシランカップリング剤（成分（Ｃ））としては、特に限定されないが、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルメチルジメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γグリシドキシプロピルメチルジメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリエトキシシラン、メルカプトブチルトリメトキシシラン、およびγ－メルカプトプロピルメチルジメトキシシラン等が挙げられる。上記シランカップリング剤（Ｃ）は、一種類のみ用いてもよいし、二種類以上併用してもよい。なかでも、エポキシ基またはメルカプト基を有するシランカップリング剤が好ましい。シランカップリング剤（Ｃ）は、例えば、本発明の粘着剤組成物の接着力を向上させる機能を有すると考えられる。シランカップリング剤（Ｃ）の含有量は、特に限定されないが、例えば、共重合体（Ａ）１００重量％に対して、０．０５～２．０重量％であり、好ましくは０．１～１．５重量％である。接着力の観点から、シランカップリング剤（Ｃ）の含有量が前記数値範囲内であることが好ましい。 [1-3. Ingredient (C)]
The silane coupling agent (component (C)) used in the present invention is not particularly limited, but is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γglycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 Examples thereof include -aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane. Only one type of the silane coupling agent (C) may be used, or two or more types may be used in combination. Of these, a silane coupling agent having an epoxy group or a mercapto group is preferable. The silane coupling agent (C) is considered to have, for example, a function of improving the adhesive strength of the pressure-sensitive adhesive composition of the present invention. The content of the silane coupling agent (C) is not particularly limited, but is, for example, 0.05 to 2.0% by weight, preferably 0.1 to 2.0% by weight, based on 100% by weight of the copolymer (A). It is 1.5% by weight. From the viewpoint of adhesive strength, the content of the silane coupling agent (C) is preferably within the above numerical range.
［１－４．成分（Ｄ）］
　成分（Ｄ）は、イソシアネート系化合物である。本発明でイソシアネート系化合物は架橋剤として用いられる。イソシアネート系化合物としては特に限定されないが、ポリイソシアネート系化合物が好ましい。本発明において、「ポリイソシアネート」は、１分子中に、イソシアネート基（イソシアナト基ともいう）すなわち（－Ｎ＝Ｃ＝Ｏ）を複数（２または３以上）有する有機化合物（多官能イソシアネート）をいう。 [1-4. Ingredient (D)]
The component (D) is an isocyanate compound. In the present invention, the isocyanate compound is used as a cross-linking agent. The isocyanate-based compound is not particularly limited, but a polyisocyanate-based compound is preferable. In the present invention, "polyisocyanate" refers to an organic compound (polyfunctional isocyanate) having a plurality (2 or 3 or more) of isocyanate groups (also referred to as isocyanato groups), that is, (-N = C = O) in one molecule. ..
　成分（Ｄ）の使用量としては特に限定されないが、共重合体（Ａ）１００重量％に対して０.１～１．５重量％が好ましく、０.２～１．０重量％がより好ましい。０．１重量％以上であれば耐久性が良好である。１．５重量％以下であれば十分な接着力が得られる。 The amount of the component (D) used is not particularly limited, but is preferably 0.1 to 1.5% by weight, more preferably 0.2 to 1.0% by weight, based on 100% by weight of the copolymer (A). .. If it is 0.1% by weight or more, the durability is good. If it is 1.5% by weight or less, sufficient adhesive strength can be obtained.
　本発明の粘着剤組成物は、前述のとおり、前記成分（Ａ）、（Ｂ）、および（Ｃ）を含む。本発明の粘着剤組成物は、前記成分（Ｄ）を含んでいてもよいし、含んでいなくてもよい。具体的には、例えば、前記成分（Ｄ）（架橋剤（Ｄ））は、本発明の粘着剤組成物中にあらかじめ内部添加しておいてもよいし、基材に塗工する直前に添加してもよい。 As described above, the pressure-sensitive adhesive composition of the present invention contains the components (A), (B), and (C). The pressure-sensitive adhesive composition of the present invention may or may not contain the component (D). Specifically, for example, the component (D) (crosslinking agent (D)) may be internally added to the pressure-sensitive adhesive composition of the present invention in advance, or may be added immediately before coating on the substrate. You may.
［１－５．他の成分］
　本発明の粘着剤組成物は、前記成分（Ａ）～（Ｄ）以外の他の成分を含んでいてもよいし、含んでいなくてもよい。例えば、本発明の粘着剤組成物は、前記他の成分として、さらに、粘着付与剤、溶媒、可塑剤、酸化防止剤、架橋防止剤、充填剤、着色剤、紫外線吸収剤、消泡剤、光安定剤、レベリング剤、帯電防止剤、架橋遅延剤等を含んでいてもよいし、含んでいなくてもよい。それらの種類等は、特に限定されないが、例えば、一般的な粘着剤組成物と同様またはそれに準じてもよい。また、本発明の粘着剤組成物が前記他の成分を含む場合、前記他の成分は、それぞれ、一種類のみ用いてもよいし、二種類以上併用してもよい。 [1-5. Other ingredients]
The pressure-sensitive adhesive composition of the present invention may or may not contain components other than the components (A) to (D). For example, the pressure-sensitive adhesive composition of the present invention further comprises, as the other components, a tackifier, a solvent, a plasticizer, an antioxidant, an antioxidant, a filler, a colorant, an ultraviolet absorber, an antifoaming agent, and the like. It may or may not contain a light stabilizer, a leveling agent, an antistatic agent, a cross-linking delaying agent, and the like. The types thereof are not particularly limited, but may be, for example, the same as or similar to a general pressure-sensitive adhesive composition. When the pressure-sensitive adhesive composition of the present invention contains the other components, only one type of each of the other components may be used, or two or more types may be used in combination.
　前記帯電防止剤としては、特に限定されないが、例えば、無機塩類、有機塩類等のイオン性化合物、ノニオン性界面活性剤等の非イオン性化合物が挙げられる。前記帯電防止剤は、例えば、イオン性化合物であってもよい。前記イオン性化合物は、塩基性を示しうるイオン性化合物およびイオン性スルホン酸エステル化合物以外であることが好ましい。前記イオン性化合物としては、具体的には、例えば、塩化物、過塩素酸塩、酢酸塩、硝酸塩、より具体的には塩化リチウム、過塩素酸リチウム、過塩素酸ナトリウム、酢酸カリウム、トリフルオロ酢酸リチウム、硝酸リチウム等が挙げられる。 The antistatic agent is not particularly limited, and examples thereof include ionic compounds such as inorganic salts and organic salts, and nonionic compounds such as nonionic surfactants. The antistatic agent may be, for example, an ionic compound. The ionic compound is preferably other than an ionic compound capable of exhibiting basicity and an ionic sulfonic acid ester compound. Specific examples of the ionic compound include chloride, perchlorate, acetate, and nitrate, and more specifically, lithium chloride, lithium perchlorate, sodium perchlorate, potassium acetate, and trifluoro. Examples thereof include lithium acetate and lithium nitrate.
　前記可塑剤としては、例えば、カルボン酸エステル等が挙げられる。前記カルボン酸エステルとしては、特に限定されないが、例えば、特開２０１１－１９０４２０号公報、特開２０１５－１５１４２９号公報、特開２０１６－１８６０２９号公報に記載のカルボン酸エステル等であってもよい。前記カルボン酸エステルは、例えば、後述の実施例におけるカルボン酸エステル等であってもよい。前記可塑剤の含有率は、特に限定されないが、共重合体（Ａ）の全重量に対し、例えば、１重量％以上、５重量％以上、または１０重量％以上でもよく、例えば、３０重量％以下、または２０重量％以下でもよい。 Examples of the plasticizer include carboxylic acid esters and the like. The carboxylic acid ester is not particularly limited, and may be, for example, the carboxylic acid ester described in JP-A-2011-190420, JP-A-2015-151429, and JP-A-2016-186029. The carboxylic acid ester may be, for example, the carboxylic acid ester in the examples described later. The content of the plasticizer is not particularly limited, but may be, for example, 1% by weight or more, 5% by weight or more, or 10% by weight or more, for example, 30% by weight, based on the total weight of the copolymer (A). It may be less than or equal to 20% by weight or less.
　前記紫外線吸収剤としては、特に限定されないが、例えば、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系等の紫外線吸収剤が挙げられる。 The ultraviolet absorber is not particularly limited, and examples thereof include ultraviolet absorbers such as benzophenone type, benzotriazole type, and triazine type.
　前記消泡剤としては、特に限定されないが、例えば、シリコーン系、鉱物油系等の消泡剤が挙げられる。 The defoaming agent is not particularly limited, and examples thereof include silicone-based and mineral oil-based defoaming agents.
　前記光安定剤としては、特に限定されないが、例えば、ヒンダードアミン系等の光安定剤が挙げられる。 The light stabilizer is not particularly limited, and examples thereof include a hindered amine-based light stabilizer.
　前記溶媒は、特に限定されず、例えば、公知の溶媒を使用できる。前記溶媒としては、例えば、メチルエチルケトン、アセトン、メチルイソブチルケトン等のケトン、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル等のエステル、トルエン、キシレン等の炭化水素等が挙げられる。 The solvent is not particularly limited, and for example, a known solvent can be used. Examples of the solvent include ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate and isobutyl acetate, and hydrocarbons such as toluene and xylene.
　前記酸化防止剤としては、特に限定されないが、例えば、フェノール系、イオウ系等の酸化防止剤が挙げられる。 The antioxidant is not particularly limited, and examples thereof include phenol-based and sulfur-based antioxidants.
　前記架橋遅延剤としては、特に限定されないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン等のケトン化合物やアセト酢酸エステル、マロン酸エステル等があげられる。また、アルコール、フェノール、オキシム、アミン、アミド、イミド、ラクタム等でイソシアネート基がブロックされたブロック化イソシアネートを用いてもよい。 The cross-linking retarder is not particularly limited, and examples thereof include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetylacetone, acetoacetic ester, and malonic acid ester. Further, a blocked isocyanate in which the isocyanate group is blocked with alcohol, phenol, oxime, amine, amide, imide, lactam or the like may be used.
［２．粘着シートおよびその用途等］
　つぎに、本発明の粘着シートおよびその用途等について、例を挙げて説明する。 [2. Adhesive sheet and its uses, etc.]
Next, the pressure-sensitive adhesive sheet of the present invention and its uses will be described with reference to examples.
　本発明の粘着シートは、前述のとおり、例えば、基材の少なくとも一方の面に粘着層が形成された粘着シートであってもよく、または、粘着層のみからなる基材レスタイプの粘着シートであってもよい。また、本発明の粘着シートは、前述のとおり、前記粘着層が、本発明の粘着剤組成物から形成された粘着層であることを特徴とする。本発明の粘着シートの製造方法は、特に限定されないが、例えば、一般的な粘着シートの製造方法と同様またはそれに準じてもよい。具体的には、例えば、本発明の粘着剤組成物を基材等に塗布（塗工）し、それを必要に応じて加熱して乾燥、エージング等を行い、粘着層を形成することにより、本発明の粘着シートを製造してもよい。 As described above, the pressure-sensitive adhesive sheet of the present invention may be, for example, a pressure-sensitive adhesive sheet having an pressure-sensitive adhesive layer formed on at least one surface of the base material, or a base material-less type pressure-sensitive adhesive sheet composed of only the pressure-sensitive adhesive layer. There may be. Further, as described above, the pressure-sensitive adhesive sheet of the present invention is characterized in that the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention. The method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but may be, for example, the same as or similar to a general method for manufacturing a pressure-sensitive adhesive sheet. Specifically, for example, the pressure-sensitive adhesive composition of the present invention is applied (coated) to a substrate or the like, and if necessary, the pressure-sensitive adhesive composition is heated to dry, age, or the like to form an pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet of the present invention may be produced.
　前記基材の形状も特に限定されず、例えば、シート、フィルム、発泡体等が挙げられる。前記基材は、製造後の粘着シートの取扱いやすさ、保存のしやすさ等の観点から、例えば、巻き取り可能な長尺のテープ状であることが好ましい。また、前記基材は、例えば、必要に応じて、前記基材の粘着剤層形成面に、易接着処理を施した基材であってもよい。前記易接着処理は、特に限定されないが、具体的には、例えば、コロナ放電を処理する方法、アンカーコート剤を塗布する方法等が挙げられる。 The shape of the base material is not particularly limited, and examples thereof include sheets, films, and foams. From the viewpoint of ease of handling, storage, and the like of the pressure-sensitive adhesive sheet after production, the base material is preferably in the form of a long tape that can be wound up, for example. Further, the base material may be, for example, a base material obtained by subjecting the pressure-sensitive adhesive layer forming surface of the base material to an easy-adhesion treatment, if necessary. The easy-adhesion treatment is not particularly limited, and specific examples thereof include a method of treating corona discharge and a method of applying an anchor coating agent.
　基材フィルムとしては、特に限定されないが、例えば、高透明であって、耐熱性を備えた樹脂フィルムが好ましい。樹脂フィルムを構成する樹脂としては、特に限定されないが、例えば、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート／イソフタレート共重合体等のポリエステル系樹脂、三酢酸セルロース、セロファン等のセルロース系樹脂、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン系樹脂、脂肪族ポリアミド、芳香族ポリアミド等のポリアミド系樹脂等が挙げられる。 The base film is not particularly limited, but for example, a highly transparent resin film having heat resistance is preferable. The resin constituting the resin film is not particularly limited, and is, for example, a polyester resin such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, a polyethylene terephthalate / isophthalate copolymer, and a cellulose-based resin such as cellulose triacetate and cellophane. Examples thereof include resins, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, and polyamide resins such as aliphatic polyamides and aromatic polyamides.
　本発明の粘着シートの形態も特に限定されないが、例えば、保管時には、前記粘着層上にセパレータを貼付して前記粘着層を保護し、使用（例えば、画像表示装置や半導体ウェハ等への貼付）直前に前記セパレータを剥離して使用する感圧式粘着シートであることが好ましい。 The form of the adhesive sheet of the present invention is not particularly limited, but for example, during storage, a separator is attached onto the adhesive layer to protect the adhesive layer and used (for example, attachment to an image display device, a semiconductor wafer, or the like). It is preferable that the pressure-sensitive pressure-sensitive adhesive sheet is used by peeling off the separator immediately before use.
　以下、本発明の実施例について説明する。なお、本発明はこれらの実施例に限定されるものではない。 Hereinafter, examples of the present invention will be described. The present invention is not limited to these examples.
＜アクリル共重合体の合成例＞
［合成例１]
　攪拌機、還流冷却器、温度計及び窒素導入管を備えた反応装置に、酢酸エチル２９３.０重量部を仕込み、系内（前記反応装置の、反応を行なう容器内）を窒素ガス置換し、酢酸エチルの沸点まで昇温した。モノマー成分として、アクリル酸ｎ-ブチル（ＢＡ）：１１．９重量部、アクリル酸メチル（ＭＡ）:１６重量部、アクリル酸（ＡＡ）：０．１重量部、アクリル酸-２-ヒドロキシプロピル（ＨＰＡ）：１２重量部、重合開始剤として２，２´-アゾビスイソブチロニトリル：０．０４重量部、を混合し、モノマー混合物を調製した。そのモノマー混合物を、温度７７～８８℃の還流下で２時間かけて前記系内に滴下し、そのまま前記温度で加熱および攪拌を継続して重合反応を行った。前記モノマー混合物を前記系内に全量添加してから１．５時間後および３．０時間後に、それぞれ、酢酸エチル１０重量部にｔ－ヘキシルパーオキシピバレート　０．０２重量部を添加した混合溶液を、追加重合開始剤として系内に添加した。そして、前記モノマー混合物の全量添加から２時間後まで還流下で重合反応を継続した。重合反応終了後、酢酸エチル　９３．９重量部を添加して固形分４０重量％のアクリル共重合体溶液（Ａ１）を得た。 <Synthesis example of acrylic copolymer>
[Synthesis Example 1]
293.0 parts by weight of ethyl acetate was charged into a reaction device equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and the inside of the system (inside the container in which the reaction was carried out in the reaction device) was replaced with nitrogen gas to obtain acetate. The temperature was raised to the boiling point of ethyl. As monomer components, n-butyl acrylate (BA): 11.9 parts by weight, methyl acrylate (MA): 16 parts by weight, acrylic acid (AA): 0.1 parts by weight, -2-hydroxypropyl acrylate ( HPA): 12 parts by weight and 2,2'-azobisisobutyronitrile: 0.04 parts by weight as a polymerization initiator were mixed to prepare a monomer mixture. The monomer mixture was added dropwise to the system under reflux at a temperature of 77 to 88 ° C. over 2 hours, and heating and stirring were continued at the temperature as it was to carry out a polymerization reaction. A mixed solution in which 0.02 part by weight of t-hexyl peroxypivalate was added to 10 parts by weight of ethyl acetate 1.5 hours and 3.0 hours after the total amount of the monomer mixture was added to the system. Was added into the system as an additional polymerization initiator. Then, the polymerization reaction was continued under reflux until 2 hours after the addition of the entire amount of the monomer mixture. After completion of the polymerization reaction, 93.9 parts by weight of ethyl acetate was added to obtain an acrylic copolymer solution (A1) having a solid content of 40% by weight.
　なお、合成例１で製造したアクリル共重合体（Ａ１）は、本発明の粘着剤組成物における成分（Ａ）に該当する。アクリル酸ブチルは、アルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステルであり、単量体（ａ１）に該当する。アクリル酸メチルは、アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステルであり、単量体（ａ２）に該当する。アクリル酸２－ヒドロキシプロピルは、水酸基を有するモノマーであり、単量体（ａ３）に該当する。アクリル酸は、カルボキシ基を有するモノマーであり、単量体（ａ４）に該当する。また、合成例１で製造したアクリル共重合体（Ａ１）の原料モノマー組成は、アクリル酸ブチル／アクリル酸メチル／アクリル酸２－ヒドロキシプロピル／アクリル酸＝２９．８重量％／４０．０重量％／３０．０重量％／０．２重量％であり、下記の測定方法により測定した重量平均分子量は２８万であった。 The acrylic copolymer (A1) produced in Synthesis Example 1 corresponds to the component (A) in the pressure-sensitive adhesive composition of the present invention. Butyl acrylate is a (meth) acrylic acid alkyl ester having an alkyl group having 3 to 12 carbon atoms, and corresponds to the monomer (a1). Methyl acrylate is a (meth) acrylic acid alkyl ester in which the alkyl group has 1 to 2 carbon atoms, and corresponds to the monomer (a2). 2-Hydroxypropyl acrylate is a monomer having a hydroxyl group and corresponds to the monomer (a3). Acrylic acid is a monomer having a carboxy group and corresponds to the monomer (a4). The raw material monomer composition of the acrylic copolymer (A1) produced in Synthesis Example 1 is butyl acrylate / methyl acrylate / 2-hydroxypropyl acrylate / acrylic acid = 29.8% by weight / 40.0% by weight. It was / 30.0% by weight / 0.2% by weight, and the weight average molecular weight measured by the following measuring method was 280,000.
［合成例２～２１]
　表１～４の実施例２～１９、比較例１～２に示すモノマー組成となるよう単量体（ａ１）～（ａ４）の配合量、種類を変更して、アクリル共重合体（Ａ２）～（Ａ２１）を得た。 [Synthesis Examples 2 to 21]
The acrylic copolymer (A2) was prepared by changing the blending amounts and types of the monomers (a1) to (a4) so as to have the monomer compositions shown in Examples 2 to 19 and Comparative Examples 1 and 2 in Tables 1 to 4. ~ (A21) was obtained.
（重量平均分子量の測定方法）
　下記の条件のゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）で測定した。
装置：Ｗａｔｅｒｓ製Ａｌｌｉａｎｃｅ　ｅ２６９５
カラム構成：Ｗａｔｅｒｓ製ＨＳＰｇｅｌ　ＲＴ　ＭＢ－Ｈ(適用分子量 ５，０００－１０，０００，０００)×２本、ＲＴ２．０(適用分子量 ５００－１０，０００)×1本
カラム温度：４０℃
移動相：テトラヒドロフラン
試料濃度：０．３ｗｔ％
標準物質：標準ポリスチレン
なお、測定する試料に応じて、カラムへの試料の吸着を防ぐために、必要に応じて移動相に適量のトリエチルアミンを加えた。 (Measuring method of weight average molecular weight)
It was measured by a gel permeation chromatography method (GPC method) under the following conditions.
Equipment: Waters Alliance e2695
Column configuration: Waters HSPgel RT MB-H (applicable molecular weight 5,000-10,000,000) x 2, RT2.0 (applicable molecular weight 500-10,000) x 1 Column temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Sample concentration: 0.3 wt%
Standard substance: Standard polystyrene Depending on the sample to be measured, an appropriate amount of triethylamine was added to the mobile phase as needed to prevent adsorption of the sample on the column.
＜粘着剤組成物の製造例＞
　以下のようにして、粘着剤組成物を製造した。 <Production example of adhesive composition>
The pressure-sensitive adhesive composition was produced as follows.
［実施例１］
　合成例１で調製したアクリル共重合体（Ａ１）の溶液２５０重量部（アクリル共重合体Ａ１の固形分として１００重量部に相当）に対して、架橋剤（Ｄ）として多官能ヘキサメチレンジイソシアネート系化合物（東ソー株式会社製、商品名「コロネートＨＬ」）０．２５重量部、シランカップリング剤（Ｃ）として３-メルカプトプロピルトリメトキシシラン（信越化学工業株式会社製、商品名「ＫＢＭ－８０３」）０．２５重量部、金属キレート化合物（Ｂ）としてアクリル酸と等ｍｏｌ量のアルミニウムトリス（アセチルアセテート）（日本化学産業株式会社製、商品名「ナーセムアルミニウム」）を配合し、粘着剤組成物を調製した。 [Example 1]
Polyfunctional hexamethylene diisocyanate as the cross-linking agent (D) with respect to 250 parts by weight of the solution of the acrylic copolymer (A1) prepared in Synthesis Example 1 (corresponding to 100 parts by weight as the solid content of the acrylic copolymer A1). Compound (manufactured by Toso Co., Ltd., trade name "Coronate HL") 0.25 parts by weight, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-803") as a silane coupling agent (C) ) 0.25 parts by weight, as a metal chelate compound (B), an equal mol amount of aluminum tris (acetylacetate) (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name "Narsem Aluminum") is blended with acrylic acid to form an adhesive composition. The thing was prepared.
［実施例２～１９、比較例１～２］
　合成例２～２１で調製したアクリル共重合体（Ａ２）～（Ａ２１）のアクリル共重合体の固形分として１００重量部に対して、表１～４のように架橋剤（Ｄ）、シランカップリング剤（Ｃ）、金属キレート化合物（Ｂ）を配合し、実施例２～１９、比較例１～２の粘着剤組成物を調製した。 [Examples 2 to 19, Comparative Examples 1 to 2]
As shown in Tables 1 to 4, the cross-linking agent (D) and the silane cup were added to 100 parts by weight as the solid content of the acrylic copolymers (A2) to (A21) prepared in Synthesis Examples 2 to 21. The ring agent (C) and the metal chelate compound (B) were blended to prepare the pressure-sensitive adhesive compositions of Examples 2 to 19 and Comparative Examples 1 and 2.
＜粘着シートの製造方法＞
　前記粘着剤組成物を、表面が離型処理されたフィルム（剥離ライナー、パナック株式会社製、商品名「ＮＰ－５０Ｂ」）の離型処理面上に、乾燥後の厚さが約２５μｍとなるように塗工し、１００℃で２分間乾燥させて粘着層を形成した。乾燥後、前記粘着層側をポリエチレンテレフタレートフィルム（東洋紡株式会社コスモシャインＡ－４３００（厚さ：１００μｍ））にラミネートして貼り合わせ、４０℃で２日エージングを行うことで、粘着シートを得た。 <Manufacturing method of adhesive sheet>
The thickness of the pressure-sensitive adhesive composition after drying is about 25 μm on the release-treated surface of a film whose surface has been released-treated (release liner, manufactured by Panac Co., Ltd., trade name “NP-50B”). And dried at 100 ° C. for 2 minutes to form an adhesive layer. After drying, the adhesive layer side was laminated on a polyethylene terephthalate film (Toyobo Co., Ltd. Cosmo Shine A-4300 (thickness: 100 μm)) and bonded, and aged at 40 ° C. for 2 days to obtain an adhesive sheet. ..
　以上のようにして作製した実施例および比較例の粘着シートについて、以下の方法により、接着力、耐久性、および耐湿熱白化性を評価した。 The adhesive strength, durability, and moisture-heat bleaching resistance of the adhesive sheets of Examples and Comparative Examples produced as described above were evaluated by the following methods.
＜接着力＞
　２３℃、５０％ＲＨの雰囲気下でおよび実施例、比較例の粘着シートから、それぞれ、２５ｍｍ×１００ｍｍの試験片を切り出した。さらに、その試験片から前記離型フィルム（前記剥離ライナー）を剥がしたうえで、ガラス板に２３℃、相対湿度５０％の雰囲気下にて２ｋｇゴムローラーで３往復で加圧貼付した。それを同雰囲気下で２４時間放置した後、剥離速度３００ｍｍ／ｍｉｎで前記ガラス板からの１８０度剥離強度（Ｎ／２５ｍｍ）を測定した。 <Adhesive strength>
25 mm × 100 mm test pieces were cut out from the adhesive sheets of Examples and Comparative Examples at 23 ° C. and 50% RH, respectively. Further, the release film (the release liner) was peeled off from the test piece, and then pressure-bonded to a glass plate with a 2 kg rubber roller in an atmosphere of 23 ° C. and a relative humidity of 50% in 3 reciprocations. After allowing it to stand in the same atmosphere for 24 hours, the 180-degree peel strength (N / 25 mm) from the glass plate was measured at a peeling speed of 300 mm / min.
＜耐久性＞
　実施例および比較例の粘着シートから、それぞれ、７０ｍｍ×１４０ｍｍの試験片を切り出した。さらに、その試験片から前記離型フィルム（前記剥離ライナー）を剥がしたうえで、ガラス板に２３℃×５０％の雰囲気下にて２ｋｇゴムローラーで３往復で加圧貼付し、同雰囲気下で６０分放置した。その後、貼付した前記試験片を、前記ガラス板とともにオーブン中に８５℃×８５％ＲＨの雰囲気下で１０００ｈｒ放置した後、前記オーブンから取り出し、さらに２３℃×５０％の雰囲気下で６０分放置した。この耐久性試験後のサンプル片（試験片）を目視で観察し、「気泡」や「浮き」が全く見られなかった場合には耐久性良好（○）、「気泡」や「浮き」が僅かでも見られた場合には耐久性不良（×）と判断した。 <Durability>
A 70 mm × 140 mm test piece was cut out from the adhesive sheets of Examples and Comparative Examples, respectively. Further, after peeling off the release film (the release liner) from the test piece, the release film (the release liner) is pressure-bonded to a glass plate in an atmosphere of 23 ° C. × 50% with a 2 kg rubber roller in 3 reciprocations, and under the same atmosphere. It was left for 60 minutes. Then, the attached test piece was left in an oven together with the glass plate for 1000 hours in an atmosphere of 85 ° C. × 85% RH, then taken out from the oven and further left in an atmosphere of 23 ° C. × 50% for 60 minutes. .. Visually observe the sample piece (test piece) after this durability test, and if no "bubbles" or "floats" are seen, the durability is good (○), and "bubbles" or "floats" are slight. However, if it was seen, it was judged to have poor durability (x).
　＜耐湿熱白化性＞
　実施例および比較例で得られた各粘着シートを、スライドガラス（全光線透過率９１．８％、ヘイズ値０．４％）に貼り合わせ、その後ＰＥＴフィルムを剥離して、粘着剤層／スライドガラスの層構成を有する試験片を作製した。その試験片を６０℃×９０％ＲＨ条件下で７２時間放置した後、室温に戻した前記試験片のヘイズ値（％）を、ヘイズメータ（日本電色工業株式会社製、商品名「ＣＯＨ３００」）を用いて測定した。ヘイズ値が低いほど透明性が高く、ヘイズ値が高いほど透明性が低下している（すなわち白化している）ことを示す。 <Moisture heat whitening resistance>
Each of the adhesive sheets obtained in Examples and Comparative Examples was attached to a slide glass (total light transmittance 91.8%, haze value 0.4%), and then the PET film was peeled off to obtain an adhesive layer / slide. A test piece having a glass layer structure was prepared. The haze value (%) of the test piece returned to room temperature after being left to stand for 72 hours under 60 ° C. × 90% RH conditions was measured by a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “COH300”). Was measured using. The lower the haze value, the higher the transparency, and the higher the haze value, the lower the transparency (that is, whitening).
　下記表１～４に、実施例および比較例の粘着剤組成物における原料の種類および配合量を示す。また、実施例および比較例の粘着剤組成物を用いて製造した前記粘着シートに対する前述の接着力、耐久性および耐湿熱白化性の試験結果も、併せて下記表１～４に示す。下記表１～４において、各原料の欄の数値は、その原料の配合量（重量部）を表す。「共重合体の分子量」は、共重合体（Ａ）の重量平均分子量（万）を表す。「接着力」の数値は、前述の方法で測定した１８０度剥離強度（Ｎ／２５ｍｍ）を表す。「耐湿熱白化性」の数値は、前述の方法で測定したヘイズ値（％）を表す。また、各実施例の金属キレート化合物（Ｂ）は、全て、実施例１と同じアルミニウムトリス（アセチルアセテート）（日本化学産業株式会社製、商品名「ナーセムアルミニウム」）を用い、その使用量は、単量体（ａ４）のカルボキシ基に対し１当量とした。すなわち、モノカルボン酸（一塩基酸）であるアクリル酸に対しては、実施例１と同様に金属キレート化合物（Ｂ）を等ｍｏｌ量用い、ジカルボン酸（二塩基酸）であるマレイン酸に対しては、金属キレート化合物（Ｂ）を２倍ｍｏｌ量用いた。 Tables 1 to 4 below show the types and blending amounts of raw materials in the pressure-sensitive adhesive compositions of Examples and Comparative Examples. In addition, the test results of the above-mentioned adhesive strength, durability and moisture-heat bleaching resistance to the pressure-sensitive adhesive sheets produced by using the pressure-sensitive adhesive compositions of Examples and Comparative Examples are also shown in Tables 1 to 4 below. In Tables 1 to 4 below, the numerical values in the columns of each raw material represent the blending amount (part by weight) of the raw material. The "molecular weight of the copolymer" represents the weight average molecular weight (10,000) of the copolymer (A). The numerical value of "adhesive strength" represents the 180 degree peel strength (N / 25 mm) measured by the above method. The numerical value of "moisture heat bleaching resistance" represents the haze value (%) measured by the above-mentioned method. The metal chelate compound (B) of each example uses the same aluminum tris (acetyl acetate) as in Example 1 (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name "Narsem Aluminum"), and the amount used is , 1 equivalent with respect to the carboxy group of the monomer (a4). That is, for acrylic acid which is a monocarboxylic acid (monobasic acid), an equal mol amount of the metal chelate compound (B) is used as in Example 1, and for maleic acid which is a dicarboxylic acid (dibasic acid). The metal chelate compound (B) was used in a double mol amount.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１～４に示したとおり、実施例の粘着剤組成物およびそれを用いた実施例の粘着シートは、接着力、耐久性および耐湿熱白化性が全て良好であった。これに対し、成分（Ｂ）（金属キレート化合物）を含まない比較例１の粘着剤組成物および粘着シートは、接着力および耐湿熱白化性は実施例と遜色ないものの、耐久性が劣っていた。また、成分（ａ２）（アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステル）を含まない比較例２の粘着剤組成物および粘着シートも、比較例１と同様に、接着力および耐湿熱白化性は実施例と遜色ないものの、耐久性が劣っていた。 As shown in Tables 1 to 4, the pressure-sensitive adhesive composition of Examples and the pressure-sensitive adhesive sheet of Examples using the same had good adhesive strength, durability, and moisture-heat whitening resistance. On the other hand, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Comparative Example 1 containing no component (B) (metal chelate compound) were inferior in durability, although their adhesive strength and moisture-heat bleaching resistance were comparable to those of Examples. .. Further, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Comparative Example 2 containing no component (a2) ((meth) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms) are also adhered in the same manner as in Comparative Example 1. Although the force and moisture heat bleaching resistance were comparable to those of the examples, the durability was inferior.
　実施例１～４は、成分（ａ１）および（ａ２）の配合量以外は全て同じであるが、実施例２よりも、実施例１、３および４の方が接着力が高かった。このことから、成分（ａ２）（アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステル）の配合量が、成分（ａ１）（アルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステル）に対してある程度多い方が、接着力がさらに向上することが確認された。実施例１と実施例１６とは、成分（ａ１）および（ａ３）の配合量以外は全て同じであるが、実施例１の方が接着力が高かった。このことから、成分（ａ３）（水酸基を有するモノマー）の配合量がある程度多い方が、接着力がさらに向上することが確認された。実施例１と実施例１７とは、共重合体（Ａ）の分子量以外は全て同じであるが、実施例１の方が接着力が高かった。このことから、共重合体（Ａ）の分子量がある程度小さい方が、接着力がさらに向上することが確認された。実施例１と実施例１８とは、成分（ａ１）および（ａ２）の配合量以外は全て同じであるが、実施例１の方が接着力が高かった。このことから、成分（ａ２）（アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステル）の配合量が多すぎない方が、接着力がさらに向上することが確認された。実施例１と実施例１９とは、成分（Ｃ）の配合量以外は全て同じであるが、実施例１の方が接着力が高かった。このことから、成分（Ｃ）（シランカップリング剤）の配合量が多すぎない方が、接着力がさらに向上することが確認された。 Examples 1 to 4 are all the same except for the blending amounts of the components (a1) and (a2), but the adhesive strength of Examples 1, 3 and 4 was higher than that of Example 2. From this, the blending amount of the component (a2) ((meth) acrylic acid alkyl ester in which the alkyl group has 1 to 2 carbon atoms) is the component (a1) (the alkyl group has 3 to 12 carbon atoms). It was confirmed that the adhesive strength was further improved when the amount was higher than that of meta) acrylic acid alkyl ester). Examples 1 and 16 are all the same except for the blending amounts of the components (a1) and (a3), but the adhesive strength of Example 1 was higher. From this, it was confirmed that the adhesive strength was further improved when the blending amount of the component (a3) (monomer having a hydroxyl group) was large to some extent. Examples 1 and 17 are all the same except for the molecular weight of the copolymer (A), but Example 1 has a higher adhesive force. From this, it was confirmed that the adhesive strength was further improved when the molecular weight of the copolymer (A) was small to some extent. Examples 1 and 18 are all the same except for the blending amounts of the components (a1) and (a2), but the adhesive strength of Example 1 was higher. From this, it was confirmed that the adhesive strength was further improved when the amount of the component (a2) ((meth) acrylic acid alkyl ester having 1 to 2 carbon atoms in the alkyl group) was not too large. Examples 1 and 19 are all the same except for the blending amount of the component (C), but the adhesive strength of Example 1 was higher. From this, it was confirmed that the adhesive strength was further improved when the blending amount of the component (C) (silane coupling agent) was not too large.
　この出願は、２０１９年６月２８日に出願された日本出願特願２０１９－１２０６３４、および、２０１９年１２月１８日に出願された日本出願特願２０１９－２２８６２０を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese application Japanese Patent Application No. 2019-120634 filed on June 28, 2019 and Japanese application Japanese Patent Application No. 2019-228620 filed on December 18, 2019. , All of its disclosures are taken here.

Claims (9)

  1. 　下記成分（Ａ）、（Ｂ）、および（Ｃ）を含むことを特徴とする粘着剤組成物。
    （Ａ）下記単量体（ａ１）～（ａ４）を含む単量体混合物の共重合体であって、重量平均分子量が２０万～１２０万である、共重合体
    　（ａ１）アルキル基の炭素数が３～１２である（メタ）アクリル酸アルキルエステル
    　（ａ２）アルキル基の炭素数が１～２である（メタ）アクリル酸アルキルエステル
    　（ａ３）水酸基を有するモノマー
    　（ａ４）カルボキシ基を有するモノマー
    （Ｂ）金属キレート化合物
    （Ｃ）シランカップリング剤     A pressure-sensitive adhesive composition containing the following components (A), (B), and (C).
    (A) A copolymer of a monomer mixture containing the following monomers (a1) to (a4) and having a weight average molecular weight of 200,000 to 1.2 million, the carbon of the copolymer (a1) alkyl group. (Meta) acrylic acid alkyl ester having a number of 3 to 12 (a2) (Meta) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms (a3) Monomer having a hydroxyl group (a4) Monomer having a carboxy group (B) Metal chelate compound (C) Silane coupling agent
  2. 　前記成分（Ｃ）が、エポキシ基を有するシランカップリング剤、および、メルカプト基を有するシランカップリング剤の少なくとも一方を含む請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the component (C) contains at least one of a silane coupling agent having an epoxy group and a silane coupling agent having a mercapto group.
  3. 　さらに、下記成分（Ｄ）を含む請求項１または２記載の粘着剤組成物。
    （Ｄ）イソシアネート化合物     The pressure-sensitive adhesive composition according to claim 1 or 2, further comprising the following component (D).
    (D) Isocyanate compound
  4. 　成分（Ｄ）が、ポリイソシアネート架橋剤である、請求項３記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 3, wherein the component (D) is a polyisocyanate cross-linking agent.
  5. 　請求項１から４のいずれかに記載の粘着剤組成物から形成された粘着層を有することを特徴とする粘着シート。 An adhesive sheet having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 4.
  6. 　基材の少なくとも一方の面に前記粘着層が形成された請求項５記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive layer is formed on at least one surface of the base material.
  7. 　基材を有しない、請求項５記載の粘着シート。 The adhesive sheet according to claim 5, which does not have a base material.
  8. 　前記粘着層のみからなる請求項５記載の粘着シート。 The adhesive sheet according to claim 5, which comprises only the adhesive layer.
  9. 　粘着テープである請求項５から８のいずれか一項に記載の粘着シート。 The adhesive sheet according to any one of claims 5 to 8, which is an adhesive tape.
PCT/JP2020/025419 2019-06-28 2020-06-26 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet WO2020262697A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202080040062.9A CN113891923B (en) 2019-06-28 2020-06-26 Adhesive composition and adhesive sheet
KR1020217029789A KR20220023750A (en) 2019-06-28 2020-06-26 Adhesive composition and adhesive sheet

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019-120634 2019-06-28
JP2019120634 2019-06-28
JP2019228620A JP2021008592A (en) 2019-06-28 2019-12-18 Adhesive composition and adhesive sheet
JP2019-228620 2019-12-18

Publications (1)

Publication Number Publication Date
WO2020262697A1 true WO2020262697A1 (en) 2020-12-30

Family

ID=74060408

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/025419 WO2020262697A1 (en) 2019-06-28 2020-06-26 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet

Country Status (3)

Country Link
KR (1) KR20220023750A (en)
CN (1) CN113891923B (en)
WO (1) WO2020262697A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138014A (en) * 2005-11-18 2007-06-07 Toyo Ink Mfg Co Ltd Adhesive sheet and decoration method using the same
JP2012136660A (en) * 2010-12-27 2012-07-19 Ipposha Oil Industries Co Ltd Adhesive composition, and adhesive sheet and optical member by using the same
JP2014136753A (en) * 2013-01-17 2014-07-28 Fujimori Kogyo Co Ltd Adhesive agent layer and adhesive film
WO2016072198A1 (en) * 2014-11-04 2016-05-12 綜研化学株式会社 Adhesive composition for polarizing plates and polarizing plate having adhesive layer
JP2017171777A (en) * 2016-03-23 2017-09-28 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and display body
JP2017179076A (en) * 2016-03-29 2017-10-05 日本カーバイド工業株式会社 Adhesive composition and polarizer with adhesive layer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6206969B2 (en) * 2014-09-10 2017-10-04 藤森工業株式会社 Adhesive composition and surface protective film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138014A (en) * 2005-11-18 2007-06-07 Toyo Ink Mfg Co Ltd Adhesive sheet and decoration method using the same
JP2012136660A (en) * 2010-12-27 2012-07-19 Ipposha Oil Industries Co Ltd Adhesive composition, and adhesive sheet and optical member by using the same
JP2014136753A (en) * 2013-01-17 2014-07-28 Fujimori Kogyo Co Ltd Adhesive agent layer and adhesive film
WO2016072198A1 (en) * 2014-11-04 2016-05-12 綜研化学株式会社 Adhesive composition for polarizing plates and polarizing plate having adhesive layer
JP2017171777A (en) * 2016-03-23 2017-09-28 リンテック株式会社 Adhesive composition, adhesive, adhesive sheet and display body
JP2017179076A (en) * 2016-03-29 2017-10-05 日本カーバイド工業株式会社 Adhesive composition and polarizer with adhesive layer

Also Published As

Publication number Publication date
KR20220023750A (en) 2022-03-02
CN113891923B (en) 2023-05-26
CN113891923A (en) 2022-01-04

Similar Documents

Publication Publication Date Title
TWI516563B (en) Adhesive composition
US20160185083A1 (en) Pressure-sensitive-adhesive-layer-attached polarizing film, and image display device
TWI461499B (en) Acrylic pressure sensitive adhesive compositions
EP2484738A1 (en) Adhesive agent and adhesive sheet
TWI545167B (en) Adhesive composition, adhesive film and surface protective film
TW201339270A (en) Adhesive composition, adhesive film and surface protection film
CN111133070B (en) Adhesive sheet
KR20080041265A (en) Adhesive sheet for glass protection and protective film for automobile glass
JP6139808B2 (en) Surface protection film
US9443751B2 (en) Back grinding sheet
US20160209566A1 (en) Double-sided pressure-sensitive-adhesive-layer-attached polarizing film, method for producing thereof, and image display device
KR101716545B1 (en) Adhesive composition for optical member, optical member comprising the same and optical display comprising the same
KR20140120262A (en) Adhesive composition
JP2021008592A (en) Adhesive composition and adhesive sheet
JPH11116927A (en) Acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive tape, and formation of pressure-sensitive adhesive layer
WO2020262697A1 (en) Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP4592291B2 (en) Adhesive composition and surface protective film using the same
EP3026090A1 (en) Adhesive composition
JP2020139005A (en) Adhesive and adhesive tape
KR101881186B1 (en) Adhesive composition
JP2009029947A (en) Pressure-sensitive adhesive composition and optical member
KR20150025843A (en) Adhesive composition
KR20140120490A (en) Acrylic copolmer, adhesive composition containing threrof and polarizing plate
KR101836366B1 (en) Acrylic copolymer and adhesive composition comprising the same
CN117120568A (en) Optical laminate, image display device, and adhesive composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20832189

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20832189

Country of ref document: EP

Kind code of ref document: A1