WO2020122229A1 - Composition de résine d'agent adhésif, article durci de résine d'agent adhésif, feuille adhésive et empilement de dispositif d'affichage d'image - Google Patents

Composition de résine d'agent adhésif, article durci de résine d'agent adhésif, feuille adhésive et empilement de dispositif d'affichage d'image Download PDF

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Publication number
WO2020122229A1
WO2020122229A1 PCT/JP2019/048943 JP2019048943W WO2020122229A1 WO 2020122229 A1 WO2020122229 A1 WO 2020122229A1 JP 2019048943 W JP2019048943 W JP 2019048943W WO 2020122229 A1 WO2020122229 A1 WO 2020122229A1
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Prior art keywords
sensitive adhesive
pressure
meth
resin composition
acrylate
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PCT/JP2019/048943
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English (en)
Japanese (ja)
Inventor
かほる 石井
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三菱ケミカル株式会社
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Priority to CN201980081863.7A priority Critical patent/CN113242790A/zh
Priority to KR1020217010242A priority patent/KR20210104019A/ko
Publication of WO2020122229A1 publication Critical patent/WO2020122229A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers 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
    • 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
    • C09J133/04—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
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Definitions

  • the present invention relates to a pressure-sensitive adhesive resin composition, and a pressure-sensitive adhesive resin cured product, a pressure-sensitive adhesive sheet, an image display device laminate and the like obtained by using the pressure-sensitive adhesive resin composition.
  • an image display panel such as an LCD (Liquid Crystal Display), a PDP (Plasma Display Panel) or an EL (Electro-Luminescence) and a front side (viewing side) thereof are arranged.
  • LCD Liquid Crystal Display
  • PDP Plasma Display Panel
  • EL Electro-Luminescence
  • gas (called outgas) may be generated from the protective panel. Therefore, the adhesive or the sheet may be adhesive enough to withstand this gas pressure. If it has no cohesive force and cohesive force, gas remains in the pressure-sensitive adhesive or the sheet, and when the temperature rises, the residual gas foams and reduces the visibility of the screen.
  • Patent Document 1 proposes an adhesive sheet that can be attached so as not to foam under a high temperature environment of about 80°C.
  • Patent Documents 2 and 3 as a pressure-sensitive adhesive sheet having both foaming resistance under the high temperature environment as described above and conformability to an adherend, the pressure-sensitive adhesive sheet after being adhered to the adherend There is proposed a so-called post-curable pressure-sensitive adhesive sheet that can be photo-cured to improve cohesive force.
  • organic electroluminescence (organic EL) display is mainly used.
  • the double-sided pressure-sensitive adhesive sheet used for bonding these image display device constituent members has the optical properties required for conventional flat display panels. In addition to the characteristics and durability, it is required that bending, peeling, and floating do not occur even after a bending test.
  • Patent Document 4 as a pressure-sensitive adhesive for an optical film, which does not cause peeling or floating even when a bonded film is deformed for a long time holding or bending test, (a1) alkyl (meth)acrylic 10 to 95% by mass of structural unit derived from acid ester monomer, 5 to 90% by mass of structural unit derived from (meth)acrylic acid ester monomer having (a2) alkoxyalkyl group or alkylene oxide group, and (a3) radical polymerization Having a glass transition temperature of -70 to -55°C, which is obtained by polymerizing 0 to 20% by mass of a structural unit derived from a functional group-containing monomer that is a (meth)acrylic acid ester monomer having no plural functional groups.
  • a pressure-sensitive adhesive for an optical film which contains a (meth)acrylic acid ester copolymer (A) having a mass average molecular weight of more than 1,000,000 to 2,500,000, has been proposed.
  • a pressure-sensitive adhesive sheet used for a flexible optical display device has a hydroxyl group (meth) formed from a monomer mixture containing a hydroxyl group-containing (meth)acrylate and an alkyl group-containing (meth)acrylate.
  • a pressure-sensitive adhesive sheet containing an acrylic copolymer and having a glass transition temperature of ⁇ 35° C. or lower has been proposed.
  • A-1 a structural unit (1) derived from the (meth)acrylic acid ester monomer (a-1-a), and the hydroxyl group-containing (meth)acrylic monomer (a-1).
  • the cross-linking agent (B) is an acrylic polymer having urethane acrylate in a side chain.
  • a pressure-sensitive adhesive composition having a glass transition temperature after curing of ⁇ 57.5° C. or lower.
  • Patent Documents 4 to 6 in order to impart sufficient flexibility to the cured product of the pressure-sensitive adhesive composition at low temperature and to obtain folding resistance at low temperature, a base polymer having a low glass transition temperature is used. By using it, the pressure-sensitive adhesive sheet is provided with bending resistance at high and low temperatures.
  • the base polymer with a low glass transition temperature lacks adhesive strength and cohesive strength, and is inferior in wet heat whitening resistance.
  • the present invention has excellent flex resistance after curing, and a pressure-sensitive adhesive resin composition obtained by using the pressure-sensitive adhesive resin composition having improved adhesive strength, and the pressure-sensitive adhesive resin composition, a pressure-sensitive adhesive sheet, and An object is to provide an image display device laminate.
  • the present invention is a pressure-sensitive adhesive resin composition containing a base polymer (A) composed of a (meth)acrylic acid ester copolymer, a photocurable compound (B), and a photoinitiator (C),
  • the photocurable compound (B) has a glass transition temperature (TgB) after photocuring lower than the glass transition temperature (TgA) of the base polymer (A), and proposes an adhesive resin composition. To do.
  • the present invention also provides a pressure-sensitive adhesive resin composition containing a base polymer (A) composed of a (meth)acrylic acid ester copolymer, a photocurable compound (B), and a photoinitiator (C), A pressure-sensitive adhesive resin composition is proposed, wherein the photocurable compound (B) is a (meth)acrylate (b-1) having a glycol skeleton.
  • the present invention also proposes a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive resin cured product obtained by curing the above-mentioned pressure-sensitive adhesive resin composition and a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive resin composition.
  • the present invention also provides that two component members for an image display device are laminated via a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive resin cured product obtained by curing the pressure-sensitive adhesive resin composition or a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive resin cured product obtained by curing the pressure-sensitive adhesive resin composition or a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer.
  • At least one of the two constituent members for an image display device is selected from the group consisting of a polarizing plate, a polarizing film, a retardation film, an image display panel, an organic EL display panel, a plasma display panel, a touch panel, a protection panel and a touch sensor.
  • the present invention proposes a laminated body for constituting an image display device, which is characterized by being any one of the above-mentioned members.
  • the pressure-sensitive adhesive resin composition proposed by the present invention contains a base polymer (A) and a photocurable compound (B), and has a glass transition temperature (TgB) after photocuring of the photocurable compound (B), It is lower than the base polymer (A). That is, it is a design in which a photocurable compound (B) having a low glass transition temperature is added to a base polymer (A) having a high cohesive force, and the flex resistance and the adhesiveness (cohesive force that resists peeling or foaming (cohesive force) ) And can be combined.
  • the photocurable compound (B) is a (meth)acrylate (b-1) having a glycol skeleton, it has both flex resistance and adhesiveness (cohesive force) withstanding peeling and foaming. be able to.
  • the pressure-sensitive adhesive resin composition proposed by the present invention can control the flexibility with the photocurable compound (B) having a low glass transition temperature, and therefore the base polymer (A) has flexibility (flexibility).
  • the low Tg component for ensuring the above) can be relatively reduced, and a large amount of the polarizable component (hydrophilic component) can be contained, so that there is an advantage that the wet heat whitening property is also improved.
  • the base polymer (A) can develop resistance to moist heat and whitening and adhesiveness (cohesive force) with a polar component (hydrophilic component) other than the acid component, the base polymer (A) contains an acid component that causes corrosion. Since it does not have to be present, there is also an advantage that corrosion resistance can be provided.
  • FIG. 1A is a diagram for explaining an evaluation test method of ITO corrosion resistance and Cu corrosion reliability performed in Examples described later, and FIG. 1A is a top view of an ITO pattern of an ITO glass substrate; (B) is a top view showing a state in which an adhesive sheet is coated on an ITO glass substrate for evaluating ITO corrosion reliability, or a state in which an adhesive sheet is coated on a copper glass substrate for evaluating Cu corrosion reliability.
  • the top view and FIG. 1C are cross-sectional views of the ITO corrosion resistance evaluation sample.
  • a pressure-sensitive adhesive resin composition according to an example of an embodiment of the present invention (hereinafter referred to as “present resin composition”) comprises a base polymer (A) composed of a (meth)acrylic acid ester copolymer, and a photocurable compound ( B) and a photoinitiator (C).
  • (meth)acryl means acryl and methacryl
  • (meth)acryloyl means acryloyl and methacryloyl
  • (meth)acrylate means acrylate and methacrylate.
  • base polymer means a resin having the highest content of the resin components contained in the present resin composition, preferably 50% by mass of the resin components contained in the present resin composition. A resin contained in excess.
  • bending resistance means durability against repeated bending (folding) tests and durability when a bent state is maintained, and specifically, described in Examples described below. Durability to bending test evaluated according to the method.
  • flexible means that it can be bent or bent, and “bendable or bendable” also includes a state of being bent or bent. Therefore, the flexible member preferably has a bendable or bendable radius of curvature of 10 mm or less, and more preferably a radius of curvature of 3 mm or less.
  • the (meth)acrylic acid ester copolymer preferably has a glass transition temperature (TgA) of ⁇ 30° C. or higher.
  • TgA glass transition temperature of the base polymer
  • the adhesive strength and cohesive strength of the resin composition and the pressure-sensitive adhesive sheet formed from the resin composition can be increased. Therefore, the glass transition temperature (TgA) of the (meth)acrylic acid ester copolymer is preferably ⁇ 30° C. or higher, and more preferably ⁇ 20° C. or higher.
  • the upper limit of the glass transition temperature (TgA) of the (meth)acrylic acid ester copolymer is ⁇ 10° C. or lower in consideration of practicality.
  • the glass transition temperature (Tg) means the glass transition temperature defined by the temperature at which the loss tangent (Tan ⁇ ) obtained by dynamic viscoelasticity measurement has a peak value.
  • the method for measuring the glass transition temperature is based on the method described in Examples below.
  • the (meth)acrylic acid ester copolymer is represented by the following formula 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched alkyl group having 4 to 18 carbon atoms). Of 50% by mass or more, preferably 55% by mass or more or 95% by mass or less, and more preferably 60% by mass or more or 90% by mass or less. More preferable.
  • Examples of the monomer (a) represented by the formula 2 include n-butyl(meth)acrylate, isobutyl(meth)acrylate, sec-butyl(meth)acrylate, t-butyl(meth)acrylate, pentyl(meth)acrylate.
  • the (meth)acrylic copolymer preferably contains a structural unit derived from "another monomer” other than the monomer (a).
  • the “constituent unit derived from a monomer” means a constituent unit as a result of a copolymerization reaction of the monomer, that is, a unit constituting a copolymer.
  • the “other monomer” is preferably contained in the (meth)acrylic copolymer (A) in a proportion of 1 to 30% by mass, and more preferably in a proportion of 5% by mass or more or 25% by mass or less. More preferably.
  • Examples of the "other monomer” include (i) hydroxyl group-containing monomer (hereinafter also referred to as “monomer (a-1)”) and (ii) carboxyl group-containing monomer (hereinafter also referred to as “monomer (a-2)”. .), (iii) amino group-containing monomer (hereinafter also referred to as “monomer (a-3)”), (iv) epoxy group-containing monomer (hereinafter also referred to as “monomer (a-4)”), (v).
  • Amide group-containing monomer hereinafter also referred to as “monomer (a-5)”), (vi) vinyl group-containing monomer (hereinafter also referred to as “monomer (a-6)”), (vii) 1 to 3 (meth)acrylate monomers (hereinafter also referred to as “monomer (a-7)”), (viii) macromonomers (hereinafter also referred to as “monomer (a-8)”), (ix) aromatic-containing Examples thereof include a monomer (hereinafter referred to as “monomer (a-9)”) and (x) other functional group-containing monomer (hereinafter also referred to as “monomer (a-10)”). These can be used alone or in combination of two or more.
  • Examples of the monomer (a-1) include hydroxyalkyl such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate.
  • Examples thereof include hydroxyl group-containing monomers such as (meth)acrylates. These may be used alone or in combination of two or more.
  • Examples of the monomer (a-2) include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypropyl (meth)acrylate, carboxybutyl (meth)acrylate, ⁇ -carboxypolycaprolactone mono (meth)acrylate, 2 -(Meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-( (Meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, Mention may be made of carboxyl
  • Examples of the monomer (a-3) include aminoalkyl (meth)acrylates such as aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, aminopropyl (meth)acrylate and aminoisopropyl (meth)acrylate, N-alkyl.
  • Amino group-containing monomers such as N,N-dialkylaminoalkyl (meth)acrylates such as aminoalkyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate Can be mentioned. These may be used alone or in combination of two or more.
  • Examples of the monomer (a-4) include epoxy groups such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Mention may be made of included monomers. These may be used alone or in combination of two or more.
  • Examples of the monomer (a-5) include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide.
  • Examples thereof include amide group-containing monomers such as N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, maleic acid amide, and maleimide. These may be used alone or in combination of two or more.
  • Examples of the monomer (a-6) include compounds having a vinyl group in the molecule.
  • Examples of such a compound include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, functional monomers having a functional group such as a hydroxyl group, an amide group and an alkoxyl alkyl group in the molecule, and Polyalkylene glycol di(meth)acrylates and vinyl ester monomers such as vinyl acetate, N-vinyl-2-pyrrolidone, vinyl propionate and vinyl laurate, and styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene and other Examples thereof include vinyl group-containing monomers such as aromatic vinyl monomers such as substituted styrene. These may be used alone or in combination of two or more.
  • methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate and the like have 1 to 10 carbon atoms in the side chain.
  • the (meth)acrylate monomer which is 3 can be mentioned. These may be used alone or in combination of two or more.
  • the macromonomer as the monomer (a-8) is a high molecular monomer having a terminal functional group and a high molecular weight skeleton component, and when the (meth)acrylic acid ester copolymer is formed by polymerization, It is preferable that the monomer has 20 or more carbon atoms in the chain.
  • a macromonomer can be introduced as a branch component of the graft copolymer, and the (meth)acrylic acid ester copolymer can be made into a graft copolymer.
  • a (meth)acrylic acid ester copolymer (a) made of a graft copolymer having a macromonomer as a branch component can be used. Therefore, the characteristics of the main chain and the side chains of the graft copolymer can be changed by selecting the monomer (a-8) and the other monomer and mixing ratio.
  • the skeleton component of the macromonomer is preferably composed of an acrylic acid ester polymer or a vinyl polymer.
  • examples thereof include linear or branched alkyl (meth)acrylates having 4 to 18 carbon atoms in the side chain, the monomer (a-1), the monomer (a-2), the monomer (a-7) and the like. These can be used alone or in combination of two or more.
  • Examples of the monomer (a-9) include aromatic-containing monomers such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and nonylphenol EO-modified (meth)acrylate. Can be mentioned. These may be used alone or in combination of two or more.
  • Examples of the monomer (a-10) include (meth)acryl-modified silicone, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2 , 2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-tridecafluoro-n-octyl (meth)acrylate, etc.
  • Examples thereof include functional group-containing monomers such as fluorine-containing monomers. These may be used alone or in combination of two or more.
  • the (meth)acrylic acid ester copolymer is preferably one containing a structural unit derived from the monomer (a-1) from the viewpoint of improving the wet heat whitening property.
  • the “structural unit derived from the monomer (a-1)” means a structural unit as a result of the copolymerization reaction of the monomer (a-1), that is, a unit constituting the copolymer. is there.
  • the (meth)acrylic acid ester copolymer preferably does not include a monomer (a-2), that is, a structural unit derived from a carboxyl group-containing monomer.
  • a-2 a structural unit derived from a carboxyl group-containing monomer.
  • the phrase “does not contain a constitutional unit derived from the monomer (a-2)” means “not substantially contain”, and not only when it does not completely contain but also when the (meth)acrylic acid ester It is also acceptable that the polymer contains a small amount of the structural unit derived from the monomer (a-2), that is, less than 0.5% by mass, preferably less than 0.1% by mass.
  • the (meth)acrylic acid ester copolymer contains a structural unit derived from the monomer (a) represented by the above formula 2 and a structural unit derived from the monomer (a-1), and It is preferable that the constitutional unit derived from (a-2) is not included (referred to as “preferred form 1 of base polymer”).
  • the content of the structural unit derived from the monomer (a-1) in the (meth)acrylic acid ester copolymer is preferably 5 to 30% by mass, and more preferably 7% by mass or more or 28% by mass or less. Of these, more preferably 10% by mass or more or 25% by mass or less.
  • the (meth)acrylic acid ester copolymer has a constitutional unit derived from the monomer (a) represented by the above formula 2, a constitutional unit derived from the monomer (a-1), and a monomer (a-5). And a structural unit derived from the monomer (a-2) is not included (referred to as “preferred form 2 of the base polymer”). Further, the (meth)acrylic acid ester copolymer has a constitutional unit derived from the monomer (a) represented by the above formula 2, a constitutional unit derived from the monomer (a-1), and a monomer (a-5). It is preferable that the constitutional unit derived from (1) and the constitutional unit derived from the monomer (a-7) are contained and the constitutional unit derived from the monomer (a-2) is not contained (“Preferred form 3 of base polymer”). Called)).
  • the monomer (a) may be 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isostearyl (meth)acrylate and isobornyl (meth)acrylate. It is preferable to include any one or more selected from the group consisting of
  • the photocurable compound (B) is a compound having a property of being cured by light irradiation, and has a glass transition temperature (TgB) after photocuring lower than the glass transition temperature (TgA) of the base polymer (A). Is preferred.
  • TgB glass transition temperature
  • the glass transition temperature of the present resin composition can be lowered and the flexibility at low temperature (eg -30°C) can be obtained. It is possible to improve the folding resistance at that temperature by making it higher.
  • the photocurable compound (B) has a glass transition temperature (TgB) after photocuring of preferably ⁇ 40° C. or lower, more preferably ⁇ 45° C. or lower. Since the photocurable compound (B) has a glass transition temperature in such a range, the glass transition temperature (TgA) of the base polymer (A) can be set relatively high, so that the adhesiveness is secured. Meanwhile, it is possible to obtain a pressure-sensitive adhesive sheet that has flexibility to endure buckling during bending deformation and also has bending resistance.
  • TgB glass transition temperature after photocuring of preferably ⁇ 40° C. or lower, more preferably ⁇ 45° C. or lower. Since the photocurable compound (B) has a glass transition temperature in such a range, the glass transition temperature (TgA) of the base polymer (A) can be set relatively high, so that the adhesiveness is secured. Meanwhile, it is possible to obtain a pressure-sensitive adhesive sheet that has flexibility to endure buckling during bending deformation and also has bending resistance
  • photocurable means reactivity (curability) with respect to general radiation. Specifically, it means that it has the property of being cured by light in the wavelength range of 200 nm to 780 nm, and it is particularly preferably used because it has reactivity (curability) with respect to ultraviolet rays.
  • TgB glass transition temperature of the photocurable compound (B) after photocuring
  • 1 part by mass of a photoinitiator is added to 100 parts by mass of the compound (B) to form the resin composition, and the wavelength is 365 nm.
  • the photocurable compound (B) is preferably a compound having at least one ethylenically unsaturated group in the molecule, from the viewpoint of forming a crosslinked structure.
  • the photocurable compound (B) is preferably (meth)acrylate (b-1) having a glycol skeleton.
  • the (meth)acrylate (b-1) having the glycol skeleton easily lowers the glass transition temperature (TgB) after photocuring, and flexibility and the like can be imparted by adjusting the molecular weight of the skeleton component. ..
  • glycol skeleton examples include ethylene glycol skeleton, propylene glycol skeleton, diethylene glycol skeleton, butanediol skeleton, hexanediol skeleton, 1,4-cyclohexanedimethanol skeleton, glycolic acid skeleton and polyglycolic acid skeleton.
  • a polyethylene glycol skeleton and/or a polypropylene glycol skeleton is more preferable.
  • the (meth)acrylate (b-1) having a glycol skeleton more preferably has two or more loss tangent (Tan ⁇ ) peaks obtained by dynamic viscoelasticity measurement. More specifically, a photocurable compound having a peak (b1) derived from the polymerization of a terminal (meth)acryloyl group and a peak (b2) derived from a glycol skeleton can be mentioned.
  • the peak temperature of the peak (b1) is preferably ⁇ 40° C. or lower, more preferably ⁇ 65° C. or higher or ⁇ 45° C. or lower, especially ⁇ 60° C. or higher or ⁇ 50° C. or lower, and the peak (b2) is preferable. It is preferable that the peak temperature is 0° C.
  • TgB of the compound (B) can be lowered.
  • the (meth)acrylate (b-1) having a glycol skeleton is a (meth)acrylate having a mass average molecular weight (Mw) of 5,000 or more, more preferably 7,000 or more, and further preferably 9,000 or more. It is preferable that the urethane (meth)acrylate has a glycol skeleton having a weight average molecular weight of 5,000 or more, more preferably 7,000 or more, and further preferably 9,000 or more. If the photocurable compound (B) is a urethane (meth)acrylate having such a glycol skeleton, the linear structure is long-bonded. The temperature can be lowered more effectively, and good adherence to the adherend and high flexibility can be imparted.
  • Mw mass average molecular weight
  • Examples of the urethane (meth)acrylate having a glycol skeleton include polytetramethylene glycol skeleton-containing urethane acrylate, polypropylene glycol skeleton-containing urethane acrylate, and polyethylene glycol skeleton-containing urethane acrylate.
  • the photocurable compound (B) is preferably a monofunctional urethane acrylate oligomer represented by the following formula 1.
  • a monofunctional urethane acrylate oligomer having a polypropylene glycol skeleton represented by the following formula 1 is most preferable.
  • R1 represents hydrogen or a methyl group
  • X represents a urethane bond
  • R2, R3 and R4 each represent an alkyl group
  • n is an integer of 2 or more.
  • the photocurable compound (B) is preferably contained in a proportion of more than 15 parts by mass and less than 75 parts by mass with respect to 100 parts by mass of the base polymer (A). By containing the photocurable compound (B) in such a ratio, the adhesive strength and flex resistance of the pressure-sensitive adhesive sheet formed from the resin composition can be well balanced. From this viewpoint, the photocurable compound (B) is preferably contained in a proportion of more than 15 parts by mass and less than 75 parts by mass with respect to 100 parts by mass of the base polymer (A), and particularly 20 parts by mass or more. Alternatively, it is more preferably contained in an amount of 70 parts by mass or less, and more preferably 30 parts by mass or more or 65 parts by mass or less.
  • Photoinitiator (C) Preferred examples of the photoinitiator (C) include compounds that generate active radical species upon irradiation with light such as ultraviolet rays and visible light, more specifically, light with a wavelength of 200 nm to 780 nm. it can.
  • the photoinitiator (C) both a cleavage type photoinitiator (C-1) and a hydrogen abstraction type initiator (C-2) can be used, or both can be used in combination. is there.
  • Examples of the cleavage type photoinitiator (C-1) include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl. -Propan-1-one, 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4- ⁇ 4-( 2-Hydroxy-2-methyl-propionyl)benzyl ⁇ phenyl]-2-methyl-propan-1-one, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone) , Methyl phenylglyoxylic acid, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpho Linopropan-1-one, 2-(dimethyla
  • the photoinitiator undergoes a structural change after the photoreaction and is deactivated, so that it remains as an active species in the present resin composition after the completion of the curing reaction. It is preferable because it does not occur and there is no possibility of causing unexpected photodegradation or the like in the resin composition.
  • Examples of the hydrogen abstraction type photoinitiator (C-2) include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyloxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, 4-(1,3-acryloyl-1,4,7, 10,13-Pentaoxotridecyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-amino Examples thereof include anthraquinone and derivatives thereof.
  • the photoinitiator can also carry out hydrogen abstraction reaction from the base polymer (A). Therefore, in the present resin composition after curing, the photocurable compound ( Not only B) but also the base polymer (A) can form a network structure incorporated into a crosslinked structure, which is preferable. Further, the hydrogen abstraction type photoinitiator (C-2) can repeatedly function as an active species by being irradiated again with light even after being used for the photocuring reaction once.
  • the present resin is used as the (post-cure) type, it is preferable because it can serve as a starting point of photoreaction during post-curing.
  • the lower limit of the content of the initiator (C) is preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the base polymer (A). It is most preferably 0.05 part by mass or more. Further, the upper limit thereof is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and most preferably 2 parts by mass or less with respect to 100 parts by mass of the base polymer (A). preferable.
  • the present resin composition contains a crosslinking agent (D), a rust preventive agent (E) and a silane cup, if necessary.
  • a tackifying resin, an antioxidant, a light stabilizer, a metal deactivator, an antiaging agent, a hygroscopic agent, a polymerization inhibitor, an ultraviolet absorber, an inorganic particle it is possible to appropriately contain various additives such as
  • the cross-linking agent (D) is an optional component that may be contained as necessary. While the present resin composition containing no cross-linking agent (D) can be used, the present resin composition containing the cross-linking agent (D) is used from the viewpoint of obtaining high foaming reliability after curing. It is preferable to cure, and it is particularly preferable to use a polyfunctional (meth)acrylate (d-1) described later as the crosslinking agent (D).
  • crosslinking agent (D) examples include polyfunctional monomers, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene.
  • a (meth)acrylate monomer having an organic functional group such as a glycidyl group, a hydroxyl group or an isocyanate group may be used to allow a crosslinked structure formed by different crosslinkable reactive groups to coexist.
  • the polyfunctional monomer (d-1) is preferable.
  • the polyfunctional monomer (d-1) include 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, glyceryl glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethacrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, bisphenol F polyethoxydi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane trioxyethyl(me)acrylate
  • polyester (meth)acrylate In addition to functional (meth)acrylic monomers, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyether (meth)acrylate, and other multifunctional (meth)acrylic Gomer can be mentioned. These may be used alone or in combination of two or more.
  • the content of the cross-linking agent (D) is preferably 10 parts by mass or less with respect to 100 parts by mass of the base polymer (A), and more preferably 0.05 parts by mass or more or 5 parts by mass or less, and even more preferably 0. It is more preferable that the proportion is 1 part by mass or more or 3 parts by mass or less.
  • the resin composition may contain a rust preventive agent (E), if necessary, in order to enhance the property of not promoting metal corrosion.
  • the rust preventive agent (E) is preferably a triazole compound. Among them, one kind or a mixture of two or more kinds selected from benzotriazole, 1,2,3-triazole and 1,2,4-triazole is particularly preferable.
  • the benzotriazole may be substituted or unsubstituted benzotriazole, and examples thereof include alkylbenzotriazole such as 1,2,3-benzotriazole and methyl-1H-benzotriazole, carboxybenzotriazole, and 1-hydroxy.
  • alkylbenzotriazole such as 1,2,3-benzotriazole and methyl-1H-benzotriazole, carboxybenzotriazole, and 1-hydroxy.
  • 1,2,3-benzotriazole 1-[N,N-bis(2-ethylhexyl)aminomethyl, from the viewpoints of dispersibility in the resin composition, ease of addition, and effect of preventing metal corrosion.
  • benzotriazole 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol Any one kind or a mixture of two or more kinds selected from the group consisting of is preferable.
  • 1,2,4-triazole is a solid having a melting point of about 120° C.
  • 1,2,3-triazole has a melting point of about 20° C. and is in a substantially liquid state at room temperature. Therefore, 1,2,3-triazole has excellent advantages that it has excellent dispersibility when mixed in the present resin composition, can be uniformly mixed, and is easily master-batched.
  • the content of the rust preventive agent (E) is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the base polymer (A), and more preferably 0.1 part by mass or more or 1 part by mass or less. It is more preferable that the amount is 0.2 parts by mass or more or 0.5 parts by mass or less.
  • the present resin composition may contain a silane coupling agent (F), if necessary, from the viewpoint of improving durability and improving adhesion to glass.
  • a silane coupling agent (F) examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane and other epoxy group-containing silane coupling agents, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- Amino group-containing silane coupling agents such as (1,3-dimethylbutylidene)propylamine and N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropy
  • silane coupling agents (F) examples include KBM-303, KBM-403, KBE-402, KBE-403, KBE-502, KBE-503, KBM-5103, KBM-573, KBM-802, Examples thereof include KBM-803, KBE-846, KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.
  • the content of the silane coupling agent (F) is preferably 0.001 part by mass or more and 5 parts by mass or less, and particularly 0.01 part by mass or more or 1 part by mass, relative to 100 parts by mass of the base polymer (A). It is more preferably not more than mass part, and most preferably not less than 0.02 mass part or not more than 1 mass part.
  • the resin composition comprises the base polymer (A), the photocurable compound (B) and the photoinitiator (C), a crosslinking agent (D) if necessary, and a rust preventive agent (E) if necessary. It can be obtained by mixing a silane coupling agent (F), if necessary, and a predetermined amount of other components, if necessary.
  • the method of mixing these is not particularly limited, and the order of mixing the respective components is also not particularly limited.
  • a heat treatment step may be added at the time of producing the present resin composition. In this case, it is desirable that the respective components of the resin composition are mixed in advance and then the heat treatment is performed. You may use what concentrated the various mixed components and master-batch.
  • the device for mixing is not particularly limited, and for example, a universal kneader, a planetary mixer, a Banbury mixer, a kneader, a gate mixer, a pressure kneader, a triple roll, or a double roll can be used.
  • the resin composition can be used as a solvent-free system containing no solvent. By using it as a solvent-free system, it is possible to provide the advantage that the solvent does not remain and the heat resistance and light resistance are improved.
  • a pressure-sensitive adhesive resin cured product (hereinafter referred to as “main cured product”) according to an example of an embodiment of the present invention is obtained by photocuring the above-described present resin composition.
  • the main cured product can also be used as a so-called post-curing type in which the main cured product is used by being further irradiated with light after being adhered to the adherend member to be main cured. Further, it can be used as a so-called non-cure type which is used without light irradiation after the members are bonded.
  • the cured product preferably has a loss tangent (Tan ⁇ ) value of 0.1 or more and less than 0.6 at a temperature of ⁇ 40° C., of which 0.11 or more or 0.55 or less, of which 0.15 or more. Alternatively, it is more preferably 0.5 or less.
  • the main cured product preferably has a loss tangent (Tan ⁇ ) value of 0.3 or more and less than 1 at a temperature of 100° C., among which 0.35 or more or 0.95 or less, and among them 0.38 or more or It is more preferably 0.92 or less.
  • the main cured product having such properties has advantages such as excellent flex resistance.
  • the present resin composition may be used for curing.
  • the glass transition temperature (TgB) of the base polymer (A) and the glass transition temperature (TgB) of the photocurable compound forming the main cured product can be determined using the following FOX equation.
  • FOX formula: 1/Tg W1/T1+W2/T2+... Wn/Tn
  • Tg theoretical glass transition temperature (K)
  • W1, W2... Wn are mass fractions of each monomer
  • T1, T2... Tn are measured glass transition temperatures (K) of each monomer. Is.
  • the crosslinking agent (D) is an optional component.
  • the present resin composition containing no crosslinking agent (D) can be used, while from the viewpoint of obtaining high foaming reliability after curing, the present resin containing the crosslinking agent (D). It is preferable to use the composition for curing, and it is particularly preferable to use the polyfunctional (meth)acrylate (d-1) as the crosslinking agent (D).
  • the form of the main cured product is arbitrary, such as a sheet, a layer, a film, or a block.
  • a pressure-sensitive adhesive sheet (hereinafter referred to as “present pressure-sensitive adhesive sheet”) according to an example of an embodiment of the present invention has a pressure-sensitive adhesive layer (hereinafter referred to as “present pressure-sensitive adhesive layer”) formed from the present resin composition described above. is there.
  • the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet may be a single layer or a multilayer, and in the case of a multilayer, another layer such as a so-called base material layer may be interposed.
  • the surface layer of the pressure-sensitive adhesive sheet is preferably the pressure-sensitive adhesive layer formed from the resin composition.
  • the pressure-sensitive adhesive layer can also be used as a so-called post-curing type in which the pressure-sensitive adhesive layer is used after being light-irradiated after the bonding of the adherend members to perform main curing. Further, it can be used as a so-called non-cure type which is used without light irradiation after the members are bonded. By using the non-cure type, there is an advantage that post-curing is not required after bonding the adherend members.
  • the pressure-sensitive adhesive sheet preferably has a loss tangent (Tan ⁇ ) value of 0.1 or more and less than 0.6 at a temperature of ⁇ 40° C., more preferably 0.11 or more or 0.55 or less, and even more preferably 0.15 or more. Alternatively, it is more preferably 0.5 or less.
  • the pressure-sensitive adhesive sheet preferably has a loss tangent (Tan ⁇ ) value of 0.3 or more and less than 1 at a temperature of 100° C., among which 0.35 or more or 0.95 or less, and among them, 0.38 or more or It is more preferably 0.92 or less.
  • the present pressure-sensitive adhesive sheet having such properties has advantages such as excellent flex resistance.
  • the present resin composition may be used for curing.
  • the present resin composition may be used to form the present pressure-sensitive adhesive layer.
  • the crosslinking agent (D) is an optional component, and the present cured product can use the present resin composition containing no crosslinking agent (D). From the viewpoint of obtaining high anti-foaming reliability after curing, it is preferable to form the present pressure-sensitive adhesive layer using the present resin composition containing the cross-linking agent (D). Above all, as the cross-linking agent (D), It is particularly preferable to use a polyfunctional (meth)acrylate (d-1).
  • the thickness of the present pressure-sensitive adhesive sheet is preferably 10 ⁇ m to 500 ⁇ m, more preferably 15 ⁇ m or more or 400 ⁇ m or less, and particularly preferably 20 ⁇ m or more or 350 ⁇ m or less.
  • the present pressure-sensitive adhesive sheet can also be used as a single pressure-sensitive adhesive sheet.
  • the present adhesive sheet can be used by directly applying the present resin composition to an adherend to form a sheet, or by directly extruding the present resin composition or injecting it into a mold. ..
  • the present pressure-sensitive adhesive sheet can be used by directly filling the resin composition between members such as a conductive member.
  • the present pressure-sensitive adhesive sheet can also be used as a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer formed from the present resin composition.
  • the present resin composition may be in the form of a pressure-sensitive adhesive sheet with a release film, which is obtained by molding a single layer or a multi-layer sheet on the release film.
  • polyester film examples include polyester film, polyolefin film, polycarbonate film, polystyrene film, acrylic film, triacetyl cellulose film, fluororesin film and the like.
  • polyester film and polyolefin film are particularly preferable.
  • the thickness of the release film is not particularly limited.
  • the thickness of the release film is preferably 25 ⁇ m to 500 ⁇ m, of which 38 ⁇ m or more or 250 ⁇ m or less, and more preferably 50 ⁇ m or more or 200 ⁇ m or less.
  • An image display device-constituting laminate according to an example of an embodiment of the present invention (hereinafter referred to as “main laminate”) is an adhesive composed of the above-described cured product between two image display device constituting members. It is provided with a structure in which either a layer or the present pressure-sensitive adhesive sheet (hereinafter collectively referred to as “the present pressure-sensitive adhesive sheet”) is interposed. At this time, at least one of the two image display device constituent members is a polarizing plate, a polarizing film, a retardation film, an image display panel, an organic EL display panel, a plasma display panel, a touch panel, a protection panel and a touch sensor. Any of the group consisting of
  • the present laminate include, for example, release film/adhesive sheet/touch panel, image display panel/adhesive sheet/touch panel, image display panel/adhesive sheet/touch panel/adhesive sheet/protection panel. , A polarizing film/present adhesive sheet/touch panel, a polarizing film/present adhesive sheet/touch panel/present adhesive sheet/protective panel, and the like.
  • the touch panel includes a structure in which a touch panel function is incorporated in a protection panel and a structure in which a touch panel function is incorporated in an image display panel. Therefore, the present laminate has a constitution of, for example, release film/main adhesive sheet/protective panel, release film/main adhesive sheet/image display panel, image display panel/main adhesive sheet/protective panel, etc. Good. Further, in the above-mentioned structure, all the structures in which the conductive layer is interposed between the present adhesive sheet and a member such as a touch panel, a protection panel, an image display panel, a polarizing film and the like adjacent thereto can be mentioned. .. However, it is not limited to these laminated examples.
  • the touch panel may be of a resistive film type, an electrostatic capacitance type, an electromagnetic induction type, or the like. Of these, the capacitance method is preferable.
  • acrylic resin polycarbonate resin
  • alicyclic polyolefin resin such as cycloolefin polymer, styrene resin, polyvinyl chloride resin, phenol resin, melamine resin
  • It may be a plastic such as an epoxy resin.
  • the image display panel is composed of another optical film such as a polarizing film or other retardation film, a liquid crystal material, and a backlight system (usually, the adhered surface of the adhesive resin composition or the adhesive article to the image display panel is an optical film.
  • a polarizing film or other retardation film such as a liquid crystal material
  • a backlight system usually, the adhered surface of the adhesive resin composition or the adhesive article to the image display panel is an optical film.
  • STN method STN method, VA method, IPS method, etc. depending on the control method of the liquid crystal material, and any method may be used.
  • the laminate can be used as a constituent member of an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display.
  • an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display.
  • MEMS microelectromechanical system
  • the above-mentioned two component members for the image display device are flexible members that can be bent or curved.
  • the present laminate is any image display device constituent member selected from the group consisting of a polarizing plate, a polarizing film, a retardation film, an image display panel, an organic EL display panel, a plasma display panel, a touch panel, a protective panel and a touch sensor.
  • the present pressure-sensitive adhesive sheets can be bonded together to manufacture.
  • the present pressure-sensitive adhesive sheets in the present laminate may have further photocurability (post-curing).
  • the present pressure-sensitive adhesive sheets have the photo-curability (post-curability)
  • the image display device constituent member and the present pressure-sensitive adhesive sheet are bonded together, and then the image display is performed from the outside of the image display device constituent member.
  • This laminate can be manufactured by irradiating light through the device constitution member, main curing the present pressure sensitive adhesive sheets, and adhering the two image display device constitution members together. It is possible to combine reliability.
  • the present pressure-sensitive adhesive sheets can be used as a non-cure type form in which post-curing is not performed by further light irradiation after bonding the adherend members. There are advantages such as no need for curing after the attachment of the attachment members.
  • the present pressure-sensitive adhesive sheets used for the present laminate have a loss tangent (Tan ⁇ ) value at a temperature of ⁇ 40° C. of 0.1 or more and less than 0.6, and
  • the value of loss tangent (Tan ⁇ ) at a temperature of 100° C. is preferably 0.3 or more and less than 1.
  • An image display device (hereinafter referred to as “main display device”) according to an example of an embodiment of the present invention includes the above-described main laminate.
  • Specific examples of the image display device include a liquid crystal display, an organic EL (electroluminescence) display, an inorganic EL display, electronic paper, a plasma display, and a microelectromechanical system (MEMS) display including the laminate. ..
  • the photocurable compound (B-1) is a compound having two or more loss tangent (Tan ⁇ ) peaks obtained by dynamic viscoelasticity measurement of a cured product, and the peak (b1) derived from the polymerization of the terminal acryloyl group. ) was ⁇ 53° C., and the peak (b2) derived from the glycol skeleton was ⁇ 24° C.
  • the above-mentioned pressure-sensitive adhesive resin composition 1 was treated with two polyethylene terephthalate films (“Diafoil MRV (V03)” manufactured by Mitsubishi Chemical Co., Ltd., thickness: 100 ⁇ m, “Diafoil” manufactured by Mitsubishi Chemical Co., Ltd. (MRQ", thickness 75 ⁇ m), that is, sandwiched between two release films and hot-melt molded into a sheet having a thickness of 100 ⁇ m.
  • the pressure-sensitive adhesive resin composition 1 was cured by irradiating with ultraviolet rays so that the integrated light amount would be 3000 mJ/cm 2 , to obtain a double-sided pressure-sensitive adhesive sheet laminate 1 composed of release film/adhesive sheet/release film.
  • Example 2 To 1 kg of the acrylic graft copolymer (A-1), 300 g of a propylene glycol skeleton-containing urethane acrylate (B-1) as a photocurable compound and 2,4,6-trimethylbenzophenone and 4 as a photoinitiator 10 g of a mixture of methylbenzophenone (C-1, "Esacure TZT” manufactured by IGM Co., Ltd.) and 5 g of a silane coupling agent ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.) were uniformly mixed to obtain an adhesive. Resin composition 2 was obtained.
  • B-1 propylene glycol skeleton-containing urethane acrylate
  • C-1 a mixture of methylbenzophenone
  • KBM-403 silane coupling agent manufactured by Shin-Etsu Silicone Co., Ltd.
  • the pressure-sensitive adhesive resin composition 2 was treated with two pieces of polyethylene terephthalate film (“Diafoil MRV (V03)” manufactured by Mitsubishi Chemical Co., Ltd., thickness: 100 ⁇ m, “Diafoil foil” manufactured by Mitsubishi Chemical Co., Ltd. (MRQ", thickness 75 ⁇ m), that is, sandwiched between two release films and hot-melt molded into a sheet having a thickness of 100 ⁇ m.
  • the pressure-sensitive adhesive resin composition 2 was cured by irradiating with ultraviolet rays so that the integrated light amount was 3000 mJ/cm 2 , to obtain a double-sided pressure-sensitive adhesive sheet laminate 2 composed of release film/adhesive sheet/release film.
  • Example 3 A pressure-sensitive adhesive resin composition 3 and a double-sided pressure-sensitive adhesive sheet laminate 3 were obtained in the same manner as in Example 1 except that 500 g of a propylene glycol skeleton-containing urethane acrylate (B-1) was added as a photocurable compound.
  • the pressure-sensitive adhesive resin composition 4 was treated with two polyethylene terephthalate films (“Diafoil MRV (V03)” manufactured by Mitsubishi Chemical Co., Ltd., thickness: 100 ⁇ m, “Diafoil” manufactured by Mitsubishi Chemical Co., Ltd. (MRQ", thickness 75 ⁇ m), that is, sandwiched between two release films and hot-melt molded into a sheet having a thickness of 100 ⁇ m.
  • the pressure-sensitive adhesive resin composition 5 was cured by irradiating it with ultraviolet rays so that the integrated light amount would be 3000 mJ/cm 2 , to obtain a double-sided pressure-sensitive adhesive sheet laminate 4 composed of release film/adhesive sheet/release film.
  • the pressure-sensitive adhesive resin composition 5 was treated with two sheets of polyethylene terephthalate film (“Diafoil MRV (V03)” manufactured by Mitsubishi Chemical Co., Ltd., thickness: 100 ⁇ m, “Diafoil manufactured by Mitsubishi Chemical Co., Ltd.” (MRQ", thickness 75 ⁇ m), that is, sandwiched between two release films and hot-melt molded into a sheet having a thickness of 100 ⁇ m.
  • the pressure-sensitive adhesive resin composition 6 was cured by irradiating with ultraviolet rays so that the integrated light amount would be 1000 mJ/cm 2 , to obtain a double-sided pressure-sensitive adhesive sheet laminate 5 composed of release film/adhesive sheet/release film.
  • the pressure-sensitive adhesive resin composition 7 was applied to a polyethylene terephthalate film (“DIAFOIL MRV (V03)” manufactured by Mitsubishi Chemical Co., thickness 100 ⁇ m), the surface of which was subjected to a release treatment, that is, a release film, to a thickness of 100 ⁇ m. Then, the coated surface was coated with a polyethylene terephthalate film (“Diafoil MRQ” manufactured by Mitsubishi Chemical Corporation, thickness 75 ⁇ m), that is, a release film, on the coated surface.
  • DIAFOIL MRV (V03) manufactured by Mitsubishi Chemical Co., thickness 100 ⁇ m
  • a release treatment that is, a release film
  • the pressure-sensitive adhesive resin composition 7 is cured by irradiating with ultraviolet rays through the release film so that the integrated light amount at a wavelength of 365 nm becomes 3000 mJ/cm 2, and the release film/adhesive sheet/release A double-sided pressure-sensitive adhesive sheet laminate 7 made of a mold film was obtained.
  • the glass transition temperature of the photocurable compound after photocuring was measured as follows. To 100 g of the photocurable compound, 1 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (“Esacure TZT” manufactured by IGM Co.) was added as a photoinitiator, and the mixture was uniformly mixed.
  • Release-treated polyethylene terephthalate film (“Diafoil MRV (V03)” manufactured by Mitsubishi Chemical Co., Ltd., that is, a polyethylene terephthalate film whose release surface has been subjected to release treatment after coating on a release film (“Mitsubishi foil manufactured by Mitsubishi Chemical” DIAFOIL MRQ", thickness 75 ⁇ m).
  • the photocurable compound was photocured by irradiating with ultraviolet rays through the release film so that the integrated light amount at a wavelength of 365 nm was 3000 mJ/cm 2 . Then, the cured photocurable compound was laminated to have a thickness of 1 mm or more.
  • a rheometer (“MARS” manufactured by Eiko Seiki Co., Ltd.), adhesive jig: ⁇ 20 mm parallel plate, strain: 0.5%, frequency 1 Hz, temperature rising rate: 3° C./min, measurement temperature: ⁇
  • the dynamic viscoelasticity measurement was performed under the condition of 70°C to 100°C.
  • the peak temperature of Tan ⁇ was read from the obtained viscoelastic curve and used as the glass transition temperature of the photocurable compound.
  • the glass transition temperatures of the photocurable compounds after photohardening are shown in the table below.
  • This is cut into a strip shape having a width of 10 mm and a length of 150 mm, the remaining release film is peeled off, and the exposed adhesive surface is roll-attached to soda lime glass using a hand roller to release film/adhesive sheet/
  • a laminated body made of a backing film was prepared, and the laminated body was subjected to autoclave treatment (60° C., gauge pressure 0.2 MPa, 20 minutes) and finish-bonded to prepare a glass adhesive strength measurement sample.
  • ⁇ Moist heat haze> One of the release films was peeled off from the pressure-sensitive adhesive sheet laminates 1 to 7 produced in Examples and Comparative Examples, and a COP film (“ZF-14” manufactured by Zeon Corporation, thickness 100 ⁇ m) was handrolled on the exposed pressure-sensitive adhesive surface. It was crimped with. After peeling off the remaining release film, 82 mm ⁇ 53 mm and 0.55 mm thick soda lime glass was pasted on the exposed adhesive surface with a hand roller, and then autoclaved at 60°C, 0.2 MPa, 20 min. , A glass/adhesive sheet/COP film were used as a sample for moist heat haze evaluation. After storing the sample for moist heat haze evaluation in an environment of 65° C.
  • Corrosion resistance of ITO substrate On a glass substrate (60 mm ⁇ 45 mm), a thickness of 150 to 200 ⁇ , a line width of 70 ⁇ m, a line length of 46 mm, and a line interval of 30 ⁇ m were used to make 10.5 reciprocations of indium oxide (ITO). While forming a round trip line, a square of 2 mm square made of ITO was formed on both ends of the round trip line to form an ITO pattern (about 97 cm in length), and an ITO glass substrate for corrosion resistance evaluation was prepared (Fig. 1 (A)).
  • ITO indium oxide
  • the release film on one side of each of the pressure-sensitive adhesive sheet laminates 1 to 7 produced in the above Examples and Comparative Examples was peeled off, and a PET film (trade name “Cosmo Shine A4100”, 125 ⁇ m, manufactured by Toyobo Co., Ltd., 125 ⁇ m) was used as a hand roller on the exposed surface. Crimped. Next, after cutting the pressure-sensitive adhesive sheet with PET film into 52 mm ⁇ 45 mm, the remaining release film was peeled off, and as shown in FIG. The pressure-sensitive adhesive sheet was attached to an ITO glass substrate with a hand roller to prepare a sample for corrosion resistance evaluation (ITO wiring with pressure-sensitive adhesive sheet) (see FIG. 1(C)).
  • a PET film trade name “Cosmo Shine A4100”, 125 ⁇ m, manufactured by Toyobo Co., Ltd., 125 ⁇ m
  • the resistance value ( ⁇ 0) of the ITO wiring in this corrosion resistance evaluation sample (ITO wiring with adhesive sheet) at room temperature was measured in advance.
  • the corrosion resistance evaluation sample (ITO wiring with adhesive sheet) is stored in a 65° C./90% RH environment for 500 hours, and after storage, ITO in the corrosion resistance evaluation sample (ITO wiring with adhesive sheet) The resistance value ( ⁇ ) of the wiring was measured. Then, the change rate (%) [(( ⁇ / ⁇ 0) ⁇ 1) ⁇ 100] of the ITO resistance value, that is, the resistance value between the line ends was calculated and shown in the table as “change in resistance value”.
  • the prepared evaluation sample was set in a bending tester (“DLDMLH-FS” manufactured by Yuasa System Co., Ltd.) so that the 38 ⁇ m PET bonding surface was on the inside, and the test environment was 24° C. (normal temperature) and ⁇ 20° C. (low temperature).
  • a bending test was performed under the following test conditions. ⁇ Test temperature: 24°C (normal temperature), -20°C (low temperature) ⁇ Radius of curvature r: 3 mm ⁇ Test speed: 60 rpm ⁇ Number of tests: 300,000 times
  • the pressure-sensitive adhesive sheets obtained in Examples 1 to 3 had a base polymer (A) made of a (meth)acrylic acid ester copolymer having a glass transition temperature (TgA) of ⁇ 30° C. or higher, and a photoinitiator (C). And a photocurable compound (B) having a glass transition temperature lower than that of the base polymer (A), and a predetermined amount of the compound (B) in the composition. It was found that the characteristics and flex resistance were excellent.
  • TgA glass transition temperature
  • C photoinitiator
  • Comparative Example 1 does not contain a photocurable compound, it was found that the static bending test and the bending resistance at low temperature were poor.
  • Comparative Examples 2 and 3 use the photocurable compound having a glass transition temperature higher than that of the base polymer (A), it was found that the bending resistance in the static bending test was poor. Since Comparative Example 4 did not contain the base polymer (A) composed of (meth)acrylic acid ester, it was found that it did not adhere to the adherend, resulting in peeling in the bending test.
  • the pressure-sensitive adhesive resin composition of the present invention is excellent in adhesive properties and flex resistance, and a pressure-sensitive adhesive resin cured product, a pressure-sensitive adhesive sheet and an image display device laminate formed from the composition are visually recognizable in an image display device.
  • the present invention can be applied to a use as a void-filling layer for improving the property, and in particular, can be suitably used for an image display device having a flexible member.

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  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

Cette invention concerne : une composition de résine d'agent adhésif ayant une excellente résistance à la flexion après durcissement et ayant également une force d'adhésion améliorée ; et un article durci de résine d'agent adhésif, une feuille adhésive et un empilement de dispositif d'affichage d'image, chacun d'entre eux étant fabriqué à l'aide de la composition de résine d'agent adhésif. Plus particulièrement, l'invention concerne une composition de résine d'agent, comprenant un polymère de base (A) comprenant un copolymère d'ester d'acide (méth)acrylique, un composé photodurcissable (B) et un photo-initiateur (C), la composition de résine d'agent adhésif étant caractérisée en ce que la température de transition vitreuse après photo-durcissement (TgB) du composé photodurcissable (B) est inférieure à la température de transition vitreuse (TgA) du polymère de base (A).
PCT/JP2019/048943 2018-12-14 2019-12-13 Composition de résine d'agent adhésif, article durci de résine d'agent adhésif, feuille adhésive et empilement de dispositif d'affichage d'image WO2020122229A1 (fr)

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CN201980081863.7A CN113242790A (zh) 2018-12-14 2019-12-13 粘合剂树脂组合物、粘合剂树脂固化物、粘合片及图像显示装置层叠体
KR1020217010242A KR20210104019A (ko) 2018-12-14 2019-12-13 점착제 수지 조성물, 점착제 수지 경화물, 점착 시트 및 화상 표시 장치 적층체

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