CN113242790A - Adhesive resin composition, cured adhesive resin, adhesive sheet, and image display device laminate - Google Patents

Adhesive resin composition, cured adhesive resin, adhesive sheet, and image display device laminate Download PDF

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Publication number
CN113242790A
CN113242790A CN201980081863.7A CN201980081863A CN113242790A CN 113242790 A CN113242790 A CN 113242790A CN 201980081863 A CN201980081863 A CN 201980081863A CN 113242790 A CN113242790 A CN 113242790A
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meth
acrylate
resin composition
adhesive resin
pressure
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石井嘉穗儿
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Thermal Sciences (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

Provided are a pressure-sensitive adhesive resin composition which has excellent flexing resistance after curing and improved adhesion, and a pressure-sensitive adhesive resin cured product, a pressure-sensitive adhesive sheet and an image display device laminate obtained using the pressure-sensitive adhesive resin composition. The binder resin composition used is characterized by containing: the photocurable composition comprises a base polymer (A) comprising a (meth) acrylate copolymer, a photocurable compound (B), and a photoinitiator (C), wherein the glass transition temperature (TgB) of the photocurable compound (B) after photocuring is lower than the glass transition temperature (TgA) of the base polymer (A).

Description

Adhesive resin composition, cured adhesive resin, adhesive sheet, and image display device laminate
Technical Field
The present invention relates to a binder resin composition, and a cured binder resin obtained using the binder resin composition, a pressure-sensitive adhesive sheet, an image display device laminate, and the like.
Background
In recent years, in order to improve the visibility of an image Display device, a gap between an image Display Panel such as a Liquid Crystal Display (LCD, Liquid Crystal Display), a Plasma Display Panel (PDP, Plasma Display Panel), or electroluminescence (EL, Electro-Luminescence) and a protective Panel or a touch Panel member disposed on the front surface side (visible side) thereof is filled with an adhesive sheet, an adhesive agent, or the like, thereby suppressing the diffuse reflection that would occur in the case where the gap is not filled, that is, the diffuse reflection of incident light or outgoing light from a Display image at the air layer interface.
In this case, for example, when the protective panel is made of plastic, there is a possibility that gas is generated from the protective panel (referred to as outgassing), and therefore, if the adhesive or sheet does not have sufficient adhesive force and cohesive force to withstand the gas pressure, the gas remains in the adhesive or sheet and when the temperature is high, the remaining gas foams, and the visibility of the screen is reduced.
For this reason, for example, patent document 1 proposes a pressure-sensitive adhesive sheet that can be bonded so as not to foam in a high-temperature environment of about 80 ℃.
Patent documents 2 and 3 propose, as an adhesive sheet having both of the aforementioned foaming resistance under high-temperature environment and the concave-convex following property to an adherend, a so-called post-curing adhesive sheet in which the adhesive sheet is photocured after being bonded to an adherend to improve the cohesive force.
Recently, as a new generation of display, a flexible display capable of freely flexing is attracting attention. The flexible display mainly uses an organic electroluminescent (organic EL) display.
Since flexible displays use flexible thin glass substrates or plastic substrates, double-sided pressure-sensitive adhesive sheets used for bonding these members constituting the image display device are required to have optical properties and durability required for conventional flat display panels, and also to be free from breakage, peeling, and lifting even when subjected to a bending test.
For example, patent document 4 proposes an adhesive for an optical film that does not peel off or float even when a bonded film is held for a long period of time in a deformed state or a bending test is performed, which comprises a (meth) acrylate copolymer (A) having a glass transition temperature of-70 to-55 ℃ and a mass-average molecular weight of more than 100 ten thousand and not more than 250 ten thousand, the (meth) acrylate copolymer (A) is obtained by polymerizing (a1) 10 to 95 mass% of a structural unit derived from an alkyl (meth) acrylate monomer, (a2) 5 to 90 mass% of a structural unit derived from a (meth) acrylate monomer having an alkoxyalkyl group or an oxyalkylene group, and (a3) 0 to 20 mass% of a structural unit derived from a functional group-containing monomer which is a (meth) acrylate monomer having no plurality of radically polymerizable functional groups.
Further, patent document 5 proposes, as an adhesive sheet used for a flexible optical display device, an adhesive sheet which is formed from a monomer mixture containing a hydroxyl group-containing (meth) acrylate and an alkyl group-containing (meth) acrylate, contains a hydroxyl group-containing (meth) acrylic copolymer, and has a glass transition temperature of-35 ℃ or lower.
Further, patent document 6 proposes an adhesive composition that does not cause peeling or floating even when a buckling operation is performed under both high-temperature and low-temperature conditions, the adhesive composition including: the adhesive composition comprises a main agent (A) containing a curable compound, a crosslinking agent (B) and a photopolymerization initiator (C), wherein the main agent (A) comprises at least one of a substance (a-1) formed by combining a (meth) acrylate monomer (a-1-a) and a hydroxyl group-containing (meth) acrylic monomer (a-1-B), and a copolymer (a-2) comprising a structural unit (1) derived from the (meth) acrylate monomer (a-1-a) and a structural unit (2) derived from the hydroxyl group-containing (meth) acrylic monomer (a-1-B), the crosslinking agent (B) is an acrylic polymer having a urethane acrylate in a side chain, and the adhesive composition has a glass transition temperature of-57.5 ℃ or lower after curing.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2010/044229
Patent document 2: international publication No. 2012/032995
Patent document 3: international publication No. 2013/108565
Patent document 4: japanese patent laid-open publication No. 2016 and 108555
Patent document 5: U.S. patent application publication No. 2017/0306194
Patent document 6: international publication No. 2017/116079
Disclosure of Invention
Problems to be solved by the invention
As described above, in patent documents 4 to 6, in order to impart sufficient flexibility to a cured product of an adhesive composition at a low temperature and obtain folding resistance at a low temperature, a base polymer having a low glass transition temperature is used to provide the adhesive sheet with high-temperature and low-temperature flexibility resistance.
However, a base polymer having a low glass transition temperature is insufficient in adhesion and cohesion, and is inferior in resistance to moist-heat whitening.
Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive resin composition having excellent flexing resistance after curing and improved adhesion, and a cured pressure-sensitive adhesive resin obtained using the pressure-sensitive adhesive resin composition, a pressure-sensitive adhesive sheet, and an image display device laminate.
Means for solving the problems
The present invention provides an adhesive resin composition, characterized by containing: a base polymer (A) comprising a (meth) acrylate copolymer, a photocurable compound (B), and a photoinitiator (C),
the glass transition temperature (TgB) of the photocurable compound (B) after photocuring is lower than the glass transition temperature (TgA) of the base polymer (a).
The present invention also provides a binder resin composition comprising: a base polymer (A) comprising a (meth) acrylate copolymer, a photocurable compound (B), and a photoinitiator (C),
the photocurable compound (B) is a (meth) acrylate (B-1) having a diol skeleton.
The present invention also provides a cured adhesive resin obtained by curing the adhesive resin composition, and also provides an adhesive sheet having an adhesive layer formed from the adhesive resin composition.
The present invention also provides a laminate for image display device construction, which is characterized in that it has a structure in which 2 image display device constituent members are laminated via a pressure-sensitive adhesive layer containing 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 2 image display device-constituting members is an arbitrary 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.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive resin composition contains a base polymer (A) and a photocurable compound (B), and the photocurable compound (B) has a glass transition temperature (TgB) after photocuring that is lower than that of the base polymer (A). That is, it is designed that the addition of the photocurable compound (B) having a low glass transition temperature to the base polymer (a) having a high cohesive force can achieve both the buckling resistance and the adhesiveness (cohesive force) capable of resisting peeling and foaming. In this case, even when the photocurable compound (B) is a (meth) acrylate (B-1) having a diol skeleton, the photocurable compound (B) can have both flexibility resistance and adhesiveness (cohesive force) that can resist peeling and foaming.
Further, the binder resin composition proposed by the present invention has an advantage that the flexibility can be controlled by the photocurable compound (B) having a low glass transition temperature, and therefore the low Tg component for ensuring flexibility (flex resistance) can be relatively reduced in the base polymer (a), and a polar component (hydrophilic component) corresponding thereto can be contained in a large amount, and thus the wet heat whitening property is also improved.
Further, the base polymer (a) can exhibit resistance to wet whitening and adhesion (cohesive force) by a polar component (hydrophilic component) other than the acid component, and therefore, it is possible to have an advantage that it can have corrosion resistance because it does not contain an acid component which causes corrosion.
Drawings
Fig. 1 is a diagram for explaining a test method for evaluating ITO corrosion resistance reliability and Cu corrosion resistance reliability performed in examples described later, where fig. 1 (a) is a plan view of an ITO pattern of an ITO glass substrate, fig. 1 (B) is a plan view showing a state where an ITO glass substrate for ITO corrosion resistance reliability evaluation is covered with an adhesive sheet or a plan view showing a state where a copper glass substrate for Cu corrosion resistance reliability evaluation is covered with an adhesive sheet, and fig. 1 (C) is a cross-sectional view of a sample for ITO corrosion resistance reliability evaluation.
Detailed Description
Next, the present invention will be described based on embodiments. However, the present invention is not limited to the embodiments described below.
The resin composition
An adhesive resin composition (hereinafter referred to as "the present resin composition") according to an embodiment of the present invention includes: a base polymer (A) comprising a (meth) acrylate copolymer, a photocurable compound (B), and a photoinitiator (C).
In the present invention, "(meth) acrylic acid" means including acrylic acid and methacrylic acid, "(meth) acryloyl group" means including acryloyl group and methacryloyl group, and "(meth) acrylate" means including acrylate and methacrylate.
The term "base polymer" refers to a resin having the largest content of the resin components contained in the resin composition, and preferably to a resin contained in an amount exceeding 50 mass% of the resin components contained in the resin composition.
Further, in the present invention, "flex resistance" refers to durability against repeated bending (folding) tests and durability when the bent state is maintained, and specifically, refers to durability against bending tests evaluated according to the methods described in the following examples.
Further, "flexible" means bendable or bendable, and bendable or bendable includes a state of bending or bending.
Therefore, the flexible member is preferably bendable or bendable with a radius of curvature of 10mm or less, and preferably with a radius of curvature of 3mm or less.
< (meth) acrylate copolymer
The (meth) acrylate copolymer preferably has a glass transition temperature (TgA) of-30 ℃ or higher.
When the glass transition temperature (TgA) of the base polymer is-30 ℃ or higher, the adhesive strength and cohesive strength of the resin composition and the adhesive sheet formed therefrom can be improved.
Accordingly, the glass transition temperature (TgA) of the (meth) acrylate copolymer is preferably-30 ℃ or higher, and more preferably-20 ℃ or higher.
The upper limit of the glass transition temperature (TgA) of the (meth) acrylate copolymer is-10 ℃ or lower in view of practical use.
In the present invention, the glass transition temperature (Tg) is defined as a temperature at which a loss tangent (Tan δ) obtained by dynamic viscoelasticity measurement is a peak.
The method for measuring the glass transition temperature was as described in the following examples.
The (meth) acrylate copolymer preferably contains the following formula 2 (wherein R is1Represents a hydrogen atom or a methyl group, R2A linear or branched alkyl group having 4 to 18 carbon atoms), and the monomer component (a) is preferably contained by 50 mass% or more, more preferably 55 mass% or more or 95 mass% or less, and further preferably 60 mass% or more or 90 mass% or less.
CH2＝CH(R1)-COO(R2) (formula 2)
Examples of the monomer (a) represented by the formula 2 include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, and the like, Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, 3,5, 5-trimethylcyclohexane (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like. These may be 1 or a combination of 2 or more.
The (meth) acrylic copolymer preferably contains a structural unit derived from "another monomer" other than the monomer (a).
Here, the "structural unit derived from a monomer" refers to a structural unit that is a result of copolymerization of the monomer, that is, a unit constituting a copolymer.
The "other monomer" is preferably contained in the (meth) acrylic copolymer (a) at a ratio of 1 to 30% by mass, more preferably at a ratio of 5% by mass or more and 25% by mass or less.
Examples of the "other monomer" include (i) a hydroxyl group-containing monomer (hereinafter also referred to as "monomer (a-1)"), (ii) a carboxyl group-containing monomer (hereinafter also referred to as "monomer (a-2)"), (iii) an amino group-containing monomer (hereinafter also referred to as "monomer (a-3)"), (iv) an epoxy group-containing monomer (hereinafter also referred to as "monomer (a-4)"), (v) an amide group-containing monomer (hereinafter also referred to as "monomer (a-5)"), (vi) a vinyl group-containing monomer (hereinafter also referred to as "monomer (a-6)"), (vii) a (meth) acrylate monomer having 1 to 3 carbon atoms in the side chain (hereinafter also referred to as "monomer (a-7)"), (viii) a macromonomer (hereinafter also referred to as "monomer (a-8)"), and (ix) an aromatic group-containing monomer (hereinafter also referred to as "monomer (a-9)"), (iv) and (iv) in the above, (x) A monomer having another functional group (hereinafter also referred to as "monomer (a-10)"). These may be used in 1 kind or in combination of 2 or more kinds.
Examples of the monomer (a-1) include hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates including 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. These may be 1 or 2 or more in combination.
Examples of the monomer (a-2) include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypropyl (meth) acrylate, carboxybutyl (meth) acrylate, omega-carboxypolycaprolactone mono (meth) acrylate, ethyl 2- (meth) acryloyloxyhexahydrophthalate, propyl 2- (meth) acryloyloxyhexahydrophthalate, ethyl 2- (meth) acryloyloxyphthalate, propyl 2- (meth) acryloyloxyphthalate, ethyl 2- (meth) acryloyloxymaleate, propyl 2- (meth) acryloyloxymaleate, ethyl 2- (meth) acryloyloxysuccinate, propyl 2- (meth) acryloyloxysuccinate, crotonic acid, fumaric acid, maleic acid, and maleic acid, and maleic acid, Carboxyl group-containing monomers such as itaconic acid. These may be 1 or 2 or more in combination.
Examples of the monomer (a-3) include amino group-containing monomers such as aminoalkyl (meth) acrylates, e.g., aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, and aminoisopropyl (meth) acrylate, N-alkylaminoalkyl (meth) acrylates, N-dimethylaminoethyl (meth) acrylates, and N, N-dialkylaminoalkyl (meth) acrylates, e.g., N-dimethylaminopropyl (meth) acrylates. These may be 1 or 2 or more in combination.
Examples of the monomer (a-4) include epoxy group-containing monomers such as glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether. These may be 1 or 2 or more in combination.
Examples of the monomer (a-5) include amide group-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic amide, and maleimide. These may be 1 or 2 or more in combination.
Examples of the monomer (a-6) include compounds having a vinyl group in the molecule. Examples of such a compound include alkyl (meth) acrylates having an alkyl group of 1 to 12 carbon atoms, functional monomers having a functional group such as a hydroxyl group, an amide group, and an alkoxyalkyl group in a molecule, polyalkylene glycol di (meth) acrylates, vinyl ester monomers such as vinyl acetate, N-vinyl-2-pyrrolidone, vinyl propionate, and vinyl laurate, and vinyl group-containing monomers such as aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, α -methylstyrene, and other substituted styrenes. These may be 1 or 2 or more in combination.
Examples of the monomer (a-7) include (meth) acrylate monomers having 1 to 3 carbon atoms in the side chain, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and the like. These may be 1 or 2 or more in combination.
The macromonomer that is the monomer (a-8) is a polymer monomer having a terminal functional group and a high molecular weight skeleton component, and is preferably a monomer having a side chain of 20 or more carbon atoms when a (meth) acrylate copolymer is formed by polymerization.
By using the monomer (a-8) as a graft component of the graft copolymer and introducing a macromonomer, the (meth) acrylate copolymer can be formed into a graft copolymer. For example, the (meth) acrylate copolymer (a) including a graft copolymer having a macromonomer as a branch component can be formed.
Therefore, the characteristics of the main chain and the side chain of the graft copolymer can be changed by the selection and the compounding ratio of the monomer (a-8) and other monomers.
The backbone component of the macromonomer is preferably composed of an acrylate polymer or a vinyl polymer. Examples of the alkyl ester include a linear or branched alkyl (meth) acrylate having a side chain of 4 to 18 carbon atoms, the monomer (a-1), the monomer (a-2), and the monomer (a-7), and 1 kind of the alkyl ester may be used alone or 2 or more kinds may be used in combination.
Examples of the monomer (a-9) include aromatic group-containing monomers such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and EO-modified nonylphenol (meth) acrylate. These may be 1 or 2 or more in combination.
Examples of the monomer (a-10) include functional group-containing monomers such as (meth) acrylic acid-modified siloxane, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, and fluorine-containing monomers such as 1H, 2H-tridecafluorooctyl (meth) acrylate. These may be 1 or 2 or more in combination.
Among the above, the (meth) acrylate copolymer preferably contains a structural unit derived from the monomer (a-1) from the viewpoint of improving the moist heat whitening property.
As described above, the "structural unit derived from the monomer (a-1)" refers to a structural unit which is a result of copolymerization of the monomer (a-1), that is, a unit constituting a copolymer.
On the other hand, from the viewpoint of metal corrosion resistance, the (meth) acrylate copolymer preferably does not contain a structural unit derived from the monomer (a-2), i.e., a carboxyl group-containing monomer.
In this case, the meaning of "not containing a structural unit derived from the monomer (a-2)" is "not substantially contained", and is not only the meaning that it is not completely contained, but also the meaning that it is contained in the (meth) acrylate copolymer to a small extent, that is, less than 0.5 mass%, preferably less than 0.1 mass%, of a structural unit derived from the monomer (a-2).
From the above, it is preferable that the (meth) acrylate 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 does not contain a structural unit derived from the monomer (a-2) (referred to as "preferred embodiment 1 of the base polymer").
In this case, the content of the structural unit derived from the monomer (a-1) in the (meth) acrylate copolymer is preferably 5 to 30% by mass, more preferably 7% by mass or more or 28% by mass or less, and further preferably 10% by mass or more or 25% by mass or less.
In particular, the (meth) acrylate copolymer preferably contains a structural unit derived from the monomer (a) represented by the above formula 2, a structural unit derived from the monomer (a-1), and a structural unit derived from the monomer (a-5), and does not contain a structural unit derived from the monomer (a-2) (referred to as "preferred embodiment 2 of the base polymer").
Further, the (meth) acrylate copolymer preferably contains a structural unit derived from the monomer (a) represented by the above formula 2, a structural unit derived from the monomer (a-1), a structural unit derived from the monomer (a-5), a structural unit derived from the monomer (a-7), and no structural unit derived from the monomer (a-2) (referred to as "preferred embodiment 3 of the base polymer").
In addition, preferred embodiments 1 to 3 of the base polymer each preferably contain, as the monomer (a), at least one selected from the group consisting of 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, and isobornyl (meth) acrylate.
< Photocurable Compound (B) >)
The photocurable compound (B) is a compound having a property of being cured by light irradiation, and is preferably a compound having a glass transition temperature (TgB) after photocuring lower than the glass transition temperature (TgA) of the base polymer (a).
By blending a compound having a lower glass transition temperature (TgA) than the base polymer (A), the glass transition temperature of the resin composition can be lowered, and flexibility at a low temperature (for example, -30 ℃) can be improved to make folding resistance at that temperature excellent.
Further, the glass transition temperature (TgB) of the photocurable compound (B) after photocuring is preferably-40 ℃ or lower, more preferably-45 ℃ or lower.
Since the photocurable compound (B) has a glass transition temperature in the above range, the glass transition temperature (TgA) of the base polymer (a) can be set to be relatively high, and thus a pressure-sensitive adhesive sheet can be obtained which has both flexibility capable of resisting buckling at the time of bending deformation and flexibility capable of ensuring adhesion.
In the present invention, "photocurable" means generally reactive (curable) with respect to radiation. Specifically, the curable composition has a property of being cured by light having a wavelength in a range of 200nm to 780nm, and is particularly preferably used from the viewpoint of having reactivity (curability) with ultraviolet rays.
A glass obtained by photocuring the photocurable compound (B)The glass transition temperature (TgB) means that the resin composition is formed by adding 1 part by mass of a photoinitiator to 100 parts by mass of the compound (B) and the cumulative amount of light having a wavelength of 365nm is 3000mJ/cm2The glass transition temperature of the photocurable compound (B) after curing the photocurable compound (B) by irradiation with ultraviolet rays.
The photocurable compound (B) is preferably a compound having 1 or more ethylenically unsaturated groups in the molecule from the viewpoint of forming a crosslinked structure.
Among the above, the photocurable compound (B) is preferably a (meth) acrylate (B-1) having a diol skeleton.
The (meth) acrylate (b-1) having a diol skeleton is easy to lower the glass transition temperature (TgB) after photocuring, and flexibility and the like can be provided by adjusting the molecular weight of the skeleton component.
Examples of the diol skeleton include an ethylene glycol skeleton, a propylene glycol skeleton, a diethylene glycol skeleton, a butanediol skeleton, a hexanediol skeleton, a1, 4-cyclohexanedimethanol skeleton, a glycolic acid skeleton, and a polyglycolic acid skeleton. Among them, a polyethylene glycol skeleton and/or a polypropylene glycol skeleton are particularly more preferable.
The (meth) acrylate (b-1) having a diol skeleton preferably has 2 or more peaks of loss tangent (Tan δ) obtained by dynamic viscoelasticity measurement.
More specifically, there may be mentioned: a photocurable compound having a peak (b1) derived from polymerization of a terminal (meth) acryloyl group and a peak (b2) derived from a diol skeleton.
In this case, the peak temperature of the peak (b1) is preferably-40 ℃ or lower, wherein-65 ℃ or higher or-45 ℃ or lower, wherein-60 ℃ or higher or-50 ℃ or lower, and the peak temperature of the peak (b2) is preferably 0 ℃ or lower, wherein-50 ℃ or higher or-5 ℃ or lower, wherein-45 ℃ or higher or-10 ℃ or lower.
By thus having 2 peak temperatures of loss tangent (Tan δ) of dynamic viscoelasticity of the photocurable compound (B), TgB of the compound (B) can be reduced.
Further, the (meth) acrylate (b-1) having a diol skeleton is preferably a (meth) acrylate having a mass average molecular weight (Mw) of 5000 or more, more preferably 7000 or more, and still more preferably 9000 or more, and particularly preferably a urethane (meth) acrylate having a diol skeleton having a mass average molecular weight of 5000 or more, more preferably 7000 or more, and still more preferably 9000 or more.
When the photocurable compound (B) is such a urethane (meth) acrylate having a diol skeleton, the linear structure is bonded to a longer length, and thus the resin composition having such a diol skeleton can more effectively lower the glass transition temperature, and can impart good wettability to an adherend and high flexibility.
Examples of the urethane (meth) acrylate having a diol skeleton include urethane acrylates having a polytetramethylene glycol skeleton, urethane acrylates having a polypropylene glycol skeleton, and urethane acrylates having a polyethylene glycol skeleton.
From the viewpoint of imparting high flexibility, the photocurable compound (B) is preferably a monofunctional urethane acrylate oligomer represented by the following formula 1. Among them, the monofunctional urethane acrylate oligomer having a polypropylene glycol skeleton represented by the following formula 1 is most preferable.
Figure BDA0003110068330000131
Wherein R1 in formula 1 represents hydrogen or methyl, X represents a urethane linkage, R2, R3 and R4 represent alkyl groups, and n is an integer of 2 or more.
The photocurable compound (B) is preferably contained in a ratio 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 the above ratio, the adhesive strength and the flex resistance of the adhesive sheet formed from the present resin composition can be combined in a well-balanced manner.
From the above viewpoint, the photocurable compound (B) is preferably contained in a ratio of more than 15 parts by mass and less than 75 parts by mass, more preferably 20 parts by mass or more and 70 parts by mass or less, and further preferably 30 parts by mass or more and 65 parts by mass or less, based on 100 parts by mass of the base polymer (a).
< photoinitiator (C) >
The photoinitiator (C) is preferably a compound which generates active radical species by irradiation with light such as ultraviolet light or visible light, more specifically, light having a wavelength of 200 to 780 nm.
As the photoinitiator (C), either one of the cleavage type photoinitiator (C-1) and the hydrogen abstraction type initiator (C-2) may be used, or both of them may be used in combination.
Examples of the cleavage type photoinitiator (C-1) include 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl 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, and oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone ) Methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, (2,4, 6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) 2,4, 4-trimethylpentylphosphine oxide, or a derivative thereof.
The use of the cleavage type photoinitiator (C-1) is preferable because the photoinitiator structure changes and is deactivated after the completion of the photoreaction, and therefore, the photoinitiator does not remain as an active species in the present resin composition after the completion of the curing reaction, and does not cause unexpected photodegradation or the like to the present resin composition.
Examples of the hydrogen abstraction photoinitiator (C-2) include benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 3' -dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2-phenyl-2-oxoacetic acid) oxydiene, 4- (1, 3-acryloyl-1, 4,7,10, 13-pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2, 4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, and mixtures thereof, 2-tert-butylanthraquinone, 2-aminoanthraquinone, or derivatives thereof.
The use of the hydrogen abstraction photoinitiator (C-2) is preferable because the photoinitiator can also undergo a hydrogen abstraction reaction from the base polymer (a) because the base polymer (a) can form a complex network structure in addition to the photocurable compound (B) and the base polymer (a) in the present resin composition after curing.
Further, the hydrogen abstraction photoinitiator (C-2) is capable of repeatedly functioning as an active species by irradiation with light again even after being used for a single photocuring reaction, and therefore, when the present resin is used as a so-called post cure (post cure) type described later, it is preferable from the viewpoint of being able to form a starting point of the photocuring reaction at the time of post curing.
The lower limit of the content of the initiator (C) is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and most preferably 0.05 part by mass or more, based on 100 parts by mass of the base polymer (a).
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, per 100 parts by mass of the base polymer (a).
< other ingredients >
The resin composition may further contain, in addition to the base polymer (a), the photocurable compound (B), and the photoinitiator (C), any one or more of a crosslinking agent (D), a rust inhibitor (E), and a silane coupling agent (F), as necessary.
In addition to the above, various additives such as a tackifier resin, an antioxidant, a light stabilizer, a metal deactivator, an antiaging agent, a moisture absorbent, a polymerization inhibitor, an ultraviolet absorber, and inorganic particles may be appropriately contained as necessary.
(crosslinking agent (D))
In the present resin composition, the crosslinking agent (D) may be any component as required. The present resin composition containing the crosslinking agent (D) can be formed without the crosslinking agent (D), and on the other hand, from the viewpoint of obtaining high reliability against foaming after curing, it is preferable to cure the present resin composition containing the crosslinking agent (D), and among these, the polyfunctional (meth) acrylate (D-1) described below is particularly preferably used as the crosslinking agent (D).
The crosslinking agent (D) may include, in addition to the polyfunctional monomer, isocyanate-based crosslinking agents such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4, 4-diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate and the like isocyanate-based compounds such as these isocyanate-based compounds and polyol compounds such as trimethylolpropane and the like adduct thereof, biuret compounds, isocyanurate compounds and the like of these polyisocyanate compounds, isocyanate-based crosslinking agents such as the isocyanurate compounds, the like, the polyisocyanate compounds, the like, Epoxy crosslinking agents such as polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, melamine resin crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, urea crosslinking agents, metal salt crosslinking agents, metal chelate crosslinking agents, amino resin crosslinking agents, metal alkoxide crosslinking agents, and peroxide crosslinking agents. These crosslinking agents (D) may be used in 1 kind or in combination of 2 or more kinds.
Further, a (meth) acrylate monomer having an organic functional group such as a glycidyl group, a hydroxyl group, or an isocyanate group may be used so that a crosslinked structure formed by different crosslinkable reactive groups may coexist.
Among the above, the polyfunctional monomer (d-1) is preferred.
Examples of the polyfunctional monomer (d-1) include 1, 4-butanediol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol 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 polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane triethoxy (meth) acrylate, epsilon-caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and mixtures thereof, Pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, di (meth) acrylate of the epsilon-caprolactone adduct of hydroxypivalic acid neopentyl glycol, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, polyethylene glycol di (meth) acrylate, and mixtures thereof, Ultraviolet-curable polyfunctional (meth) acrylic monomers such as trimethylolpropane polyethoxy tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, and polyfunctional (meth) acrylic oligomers such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and polyether (meth) acrylate. These may be used in 1 kind or in combination of 2 or more kinds.
The content of the crosslinking agent (D) is preferably 10 parts by mass or less, more preferably 0.05 parts by mass or more or 5 parts by mass or less, and further preferably 0.1 parts by mass or more or 3 parts by mass or less, based on 100 parts by mass of the base polymer (a).
(Rust preventive (E))
The resin composition may contain a rust inhibitor (E) if necessary for improving the property of not promoting the corrosion of metals
The rust inhibitor (E) is preferably a triazole-based compound. Among them, a mixture of 1 or 2 or more selected from benzotriazole, 1,2, 3-triazole and 1,2, 4-triazole is particularly preferable.
Examples of the benzotriazole include substituted or unsubstituted benzotriazoles, for example, alkylbenzotriazoles such as 1,2, 3-benzotriazole and methyl-1H-benzotriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, 5-aminobenzotriazole, 5-phenylthiobenzotriazole, 5-methoxybenzotriazole, nitrobenzotriazole, chlorobenzotriazole, bromobenzotriazole and fluorobenzotriazole, halogenated benzotriazoles such as copper benzotriazole, silver benzotriazole and benzotriazole silane compounds. Among them, from the viewpoint of dispersibility in the resin composition, ease of addition, and effect of preventing corrosion of metals, 1 or 2 or more selected from the group consisting of 1,2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole, and 2, 2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol are preferable.
Further, 1,2, 4-triazole is a solid having a melting point of about 120 ℃ and 1,2, 3-triazole has a melting point of about 20 ℃ and is substantially in a liquid state at room temperature. Thus, 1,2, 3-triazole is excellent in dispersibility when mixed into the present resin composition, can be uniformly mixed, and has excellent advantages such as easy masterbatching.
The content of the rust inhibitor (E) is preferably 0.01 to 5 parts by mass, more preferably 0.1 part by mass or more or 1 part by mass or less, and still more preferably 0.2 part by mass or more or 0.5 part by mass or less, based on 100 parts by mass of the base polymer (a).
(silane coupling agent (F))
The present resin composition may contain a silane coupling agent (F) as necessary from the viewpoint of improvement in durability and adhesion to glass.
Examples of the silane coupling agent (F) include epoxy-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, amino-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine and N-phenyl-gamma-aminopropyltrimethoxysilane, (meth) acryloyl-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane, and the like, And isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.
Examples of commercially available silane coupling agents (F) include KBM-303, KBM-403, KBE-402, KBE-403, KBE-502, KBE-503, KBM-5103, KBM-573, KBM-802, KBM-803, KBE-846, and KBE-9007 (manufactured by shin-Etsu chemical Co., Ltd.).
These may be used in 1 kind or in combination of 2 or more kinds.
The content of the silane coupling agent (F) is preferably 0.001 part by mass or more and 5 parts by mass or less, more preferably 0.01 part by mass or more and 1 part by mass or less, and most preferably 0.02 part by mass or more and 1 part by mass or less, based on 100 parts by mass of the base polymer (a).
< method for producing the resin composition >
The resin composition can be obtained by mixing the base polymer (a), the photocurable compound (B), the photoinitiator (C), if necessary, the crosslinking agent (D), if necessary, the rust inhibitor (E), if necessary, the silane coupling agent (F), and if necessary, other components in predetermined amounts.
The method of mixing these components is not particularly limited, and the order of mixing the components is not particularly limited.
In addition, a heat treatment step may be added at the time of production of the present resin composition.
In this case, it is preferable to mix the components of the present resin composition in advance and then perform heat treatment. A master batch obtained by concentrating and masterbatching various mixed components may be used.
The apparatus for mixing is not particularly limited, and examples thereof include a universal mixer, a planetary mixer, a banbury mixer, a kneader, a gate mixer, a pressure kneader, a three-roll mill, and a two-roll mill. If necessary, a solvent may be used for mixing.
The resin composition can be used as a solvent-free system containing no solvent.
By using the resin as a solvent-free system, the resin has advantages of no solvent residue and improved heat resistance and light resistance.
(ii) the cured product
A binder resin cured product (hereinafter referred to as "present cured product") according to an embodiment of the present invention is obtained by photocuring the present resin composition.
The cured product may be used as a so-called post cure (post cure) type in which the cured product is subjected to light irradiation after being bonded to an adhesive member to be cured and is finally cured.
Further, the present invention can be used as a so-called non-curing type which is used without light irradiation after the members are bonded. The use of the non-curable type is advantageous in that it is not necessary to perform post-curing after the bonding of the adhesive members, and it can be applied to a structure in which members not transmitting light or members incapable of being irradiated with light due to light deterioration are stacked.
The value of loss tangent (Tan. delta.) at-40 ℃ of the cured product is preferably 0.1 or more and less than 0.6, more preferably 0.11 or more or 0.55 or less, further preferably 0.15 or more or 0.5 or less.
Meanwhile, the value of loss tangent (Tan. delta.) at 100 ℃ of the cured product is preferably 0.3 or more and less than 1, more preferably 0.35 or more or 0.95 or less, and still more preferably 0.38 or more or 0.92 or less.
The cured product has the above properties, and thus has advantages such as excellent flex resistance.
In order for the present cured product to have the above properties, it is sufficient to cure the present resin composition.
The glass transition temperature (TgA) of the base polymer (a) forming the cured product and the glass transition temperature (TgB) of the photocurable compound can be determined by the following FOX formula.
FOX formula: 1/Tg-W1/T1 + W2/T2+ … Wn/Tn
Wherein, Tg: for the theoretical glass transition temperature (K), W1 and W2 … … Wn are the mass fractions of the respective monomers, and T1 and T2 … … Tn are the actually measured glass transition temperatures (K) of the respective monomers.
In the present resin composition and the present cured product, the crosslinking agent (D) is an arbitrary component.
The present resin composition containing the crosslinking agent (D) can be used as the present cured product, but from the viewpoint of obtaining high reliability against foaming after curing, the present resin composition containing the crosslinking agent (D) is preferably used for curing, and among them, the polyfunctional (meth) acrylate (D-1) is particularly preferably used as the crosslinking agent (D).
The form of the cured product is arbitrary, and the cured product is sheet-like, layer-like, film-like, block-like, or the like.
(adhesive sheet)
A pressure-sensitive adhesive sheet (hereinafter referred to as "the present pressure-sensitive adhesive sheet") according to an embodiment of the present invention has a pressure-sensitive adhesive layer (referred to as "the present pressure-sensitive adhesive layer") formed from the present resin composition.
The present pressure-sensitive adhesive layer in the present pressure-sensitive adhesive sheet may be a single layer or a plurality of layers, and in the case of a plurality of layers, another layer such as a so-called base layer may be interposed.
In the case where the adhesive layer has a multilayer structure having other layers, the surface layer of the adhesive sheet is preferably the adhesive layer formed of the resin composition.
The pressure-sensitive adhesive layer may be of a so-called post cure (post cure) type used by further performing light irradiation to main cure the pressure-sensitive adhesive layer after the members to be bonded are bonded.
Further, the present invention can be used as a so-called non-curing type which is used without light irradiation after the members are bonded. By using the adhesive as a non-curing type, there is an advantage that post-curing after bonding by an adhesive member is not required.
The loss tangent (Tan. delta.) at-40 ℃ is preferably 0.1 or more and less than 0.6, more preferably 0.11 or more or 0.55 or less, and still more preferably 0.15 or more or 0.5 or less.
Meanwhile, the value of loss tangent (Tan δ) at 100 ℃ of the adhesive sheet is preferably 0.3 or more and less than 1, more preferably 0.35 or more or 0.95 or less, and still more preferably 0.38 or more or 0.92 or less.
The pressure-sensitive adhesive sheet has the above properties and is advantageous in that excellent flexibility resistance is obtained.
In order for the adhesive sheet to have the above properties, the resin composition may be cured.
In the present invention, the present resin composition may be used to form the psa layer so that the psa sheet has the above properties.
As described above, the present resin composition contains the crosslinking agent (D) as an optional component, and the present resin composition containing no crosslinking agent (D) can be used as the present cured product, but the present resin composition containing the crosslinking agent (D) is preferably used to form the pressure-sensitive adhesive layer from the viewpoint of obtaining high reliability against foaming after curing, and in particular, the polyfunctional (meth) acrylate (D-1) is preferably used as the crosslinking agent (D).
The thickness of the adhesive sheet is preferably 10 μm to 500. mu.m, more preferably 15 μm or more or 400 μm or less, particularly preferably 20 μm or more or 350 μm or less.
< use form of the adhesive sheet >
The adhesive sheet can also be used alone as an adhesive sheet. For example, the adhesive sheet can be used by directly applying the resin composition to an adherend to form a sheet, directly extruding the resin composition, or injecting the resin composition into a mold.
Further, the adhesive sheet may be used by directly filling the resin composition between members such as conductive members.
On the other hand, the present adhesive sheet can also be used as an adhesive sheet having an adhesive layer formed from the present resin composition. For example, the present resin composition may be formed into a release film-equipped adhesive sheet by molding the resin composition in a single-layer or multi-layer sheet form on a release film.
Examples of the material of the release film include a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, and a fluororesin film. Among them, polyester films and polyolefin films are particularly preferable.
The thickness of the release film is not particularly limited, and is preferably 25 μm to 500 μm, more preferably 38 μm or more or 250 μm or less, and further preferably 50 μm or more or 200 μm or less, from the viewpoint of processability and workability, for example.
(the laminate)
The laminate for image display device construction (hereinafter referred to as "the present laminate") according to the embodiment of the present invention has a structure in which any one of the pressure-sensitive adhesive layer containing the present cured product and the present pressure-sensitive adhesive sheet (hereinafter collectively referred to as "the present pressure-sensitive adhesive sheets") is interposed between 2 image display device constituent members.
In this case, at least one of the 2 image display device constituent members may be any one 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.
Specific examples of the laminate include laminates having a structure such as a release film, the pressure-sensitive adhesive sheet, a touch panel, an image display panel, the pressure-sensitive adhesive sheet, the touch panel, the pressure-sensitive adhesive sheet, a protective panel, a polarizing film, the pressure-sensitive adhesive sheet, the touch panel, the polarizing film, the pressure-sensitive adhesive sheet, the protective panel, and the like.
The touch panel may include a structure in which a touch panel function is provided inside a protective panel, and a structure in which a touch panel function is provided inside an image display panel.
Thus, the laminate can have a structure of, for example, a release film, the pressure-sensitive adhesive sheet, a protective panel, a release film, the pressure-sensitive adhesive sheet, an image display panel, the pressure-sensitive adhesive sheet, a protective panel, or the like.
In addition, the above-described structure may be any structure in which the conductive layer is inserted between the pressure-sensitive adhesive sheet and a member adjacent thereto, such as a touch panel, a protective panel, an image display panel, or a polarizing film. However, the present invention is not limited to these examples.
The touch panel may be of a resistive type, a capacitive type, an electromagnetic induction type, or the like. Among them, the electrostatic capacitance system is preferable.
The protective panel may be made of glass, or plastic such as alicyclic polyolefin resin such as acrylic resin, polycarbonate resin, or cycloolefin polymer, styrene resin, polyvinyl chloride resin, phenol resin, melamine resin, or epoxy resin.
The image display panel is composed of other optical films such as a polarizing film and a retardation film, a liquid crystal material, and a backlight system (in general, the surface of the pressure-sensitive adhesive resin composition or the pressure-sensitive adhesive article to be bonded to the image display panel is an optical film), and there are an STN system, a VA system, an IPS system, and the like depending on the control system of the liquid crystal material, and any of them is possible.
The laminate can be used as a component 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 Micro Electro Mechanical System (MEMS) display.
Since the adhesive sheets have flexibility resistance, the 2 image display device constituting members are preferably flexible members that can be bent or curved.
< method for producing laminate of the present invention >
The laminate can be produced by bonding any image display device constituting 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 to the adhesive sheet.
The present pressure-sensitive adhesive sheets in the present laminate may further have photocurability (post cure property).
When the present pressure-sensitive adhesive sheet has such photocurability (post-curing property), the present pressure-sensitive adhesive sheet can be produced by bonding the image display device constituting member to the present pressure-sensitive adhesive sheet, and then irradiating light from the outside of the image display device constituting member via the image display device constituting member to cure the present pressure-sensitive adhesive sheet to bond 2 image display device constituting members to each other, thereby achieving both excellent reliability against foaming.
The pressure-sensitive adhesive sheets of the present invention can be used as a non-curable type without further post-curing by light irradiation after the bonding of the members to be bonded as described above, and have an advantage that curing after the bonding of the members to be bonded is not required when used in this form.
From the viewpoint of obtaining excellent buckling resistance, the pressure-sensitive adhesive sheets used in the laminate preferably have a loss tangent (Tan δ) value of 0.1 or more and less than 0.6 at a temperature of-40 ℃ and a loss tangent (Tan δ) value of 0.3 or more and less than 1 at a temperature of 100 ℃.
The display device
An image display device (hereinafter referred to as "the present display device") according to an embodiment of the present invention includes the present 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 Micro Electro Mechanical System (MEMS) display, each of which includes the laminate.
Description of "statement
In the present invention, when "X to Y" (X, Y is an arbitrary number) are expressed, unless otherwise specified, the meaning of "X or more and Y or less" is included, and the meaning of "preferably more than X" or "preferably less than Y" is also included.
In addition, the expression "X is equal to or greater than (X is an arbitrary number) or" Y is equal to or less than (Y is an arbitrary number), the intention of "preferably being greater than X" or "preferably being less than Y" is also included.
Examples
Hereinafter, examples and comparative examples will be described in more detail. However, the present invention is not limited to these examples.
[ example 1]
1kg of an acrylic graft copolymer (A-1, mass average molecular weight: 44 ten thousand) as a (meth) acrylic copolymer obtained by randomly copolymerizing 64 parts by mass of 2-ethylhexyl acrylate, 19 parts by mass of methyl acrylate and 17 parts by mass of hydroxyethyl acrylate was uniformly mixed with 300g of monofunctional urethane acrylate (B-1, PEM-X264, manufactured by AGC Co., Ltd., mass average molecular weight (Mw): 10000) containing a propylene glycol skeleton as a photocurable compound and 10g of a mixture (C-1, Esacure TZT, manufactured by IGM Co., Ltd.) of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone as a photoinitiator to obtain an adhesive resin composition 1.
The photocurable compound (B-1) had 2 or more peaks of loss tangent (Tan. delta.) obtained by measuring the dynamic viscoelasticity of the cured product, and the peak (B1) derived from the polymerization of the terminal acryloyl group was-53 ℃ and the peak (B2) derived from the diol skeleton was-24 ℃.
Next, the adhesive resin composition 1 was sandwiched between 2 sheets of polyethylene terephthalate film (DIAFOIL MRV (V03) manufactured by Mitsubishi Chemical Corporation, DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 100. mu.m, DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 75 μm) whose surface was subjected to a peeling treatment, and the resultant was hot-melt molded into a sheet shape having a thickness of 100 μm, and then a high-pressure mercury lamp was used to sandwich the release film so that the cumulative light amount at a wavelength of 365nm was 3000mJ/cm2By irradiating ultraviolet rays to cure the adhesive resin composition 1, thereby obtainingTo a double-sided adhesive sheet laminate 1 comprising a release film/adhesive sheet/release film.
[ example 2]
To 1kg of the acrylic graft copolymer (A-1), 300g of a propylene glycol skeleton-containing urethane acrylate (B-1) as a photocurable compound and 10g of a mixture of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone ("Esacure TZT" manufactured by IGM Co., Ltd.) as a photoinitiator were added, and 5g of a silane coupling agent ("KBM-403" manufactured by Shin-Etsu Silicones) was further uniformly mixed to obtain an adhesive resin composition 2.
Next, the adhesive resin composition 2 was sandwiched between 2 sheets of polyethylene terephthalate film (DIAFOIL MRV (V03) manufactured by Mitsubishi Chemical Corporation, DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 100. mu.m, DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 75 μm) whose surface was subjected to a peeling treatment, and the resultant was hot-melt molded into a sheet shape having a thickness of 100 μm, and then a high-pressure mercury lamp was used to sandwich the release film so that the cumulative light amount at a wavelength of 365nm was 3000mJ/cm2The adhesive resin composition 2 is cured by irradiation with ultraviolet rays, thereby obtaining a double-sided adhesive sheet laminate 2 including a release film/an adhesive sheet/a release film.
[ example 3]
An adhesive resin composition 3 and a double-sided adhesive sheet laminate 3 were obtained in the same manner as in example 1 except that 500g of a propylene glycol skeleton-containing urethane acrylate (B-1) was added as the photocurable compound.
Comparative example 1
To 1kg of the acrylic graft copolymer (A-1), 45g of a mixture of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone (C-1, "Escapure TZT" manufactured by IGM Co.) as a photoinitiator was added and uniformly mixed to obtain an adhesive resin composition 4.
Next, the adhesive resin composition 4 was sandwiched between 2 sheets of polyethylene terephthalate film (DIAFOIL MRV (V03) manufactured by Mitsubishi Chemical Corporation, "DIAFOIL MRQ (V03)" manufactured by Mitsubishi Chemical Corporation, thickness 100 μm, "DIAFOIL MRQ" manufactured by Mitsubishi Chemical Corporation, thickness 75 μm) having a surface subjected to a peeling treatment, i.e., 2 sheets of release film, and heatedAfter melt-molding into a sheet having a thickness of 100 μm, a cumulative light quantity at a wavelength of 365nm was 3000mJ/cm through the release film using a high-pressure mercury lamp2The adhesive resin composition 4 is cured by irradiation with ultraviolet rays, thereby obtaining a double-sided adhesive sheet laminate 4 including a release film/an adhesive sheet/a release film.
Comparative example 2
An acrylic graft copolymer (A-2, mass average molecular weight: 47 ten thousand) 1kg as a (meth) acrylic copolymer obtained by random copolymerization of 71 parts by mass of butyl acrylate, 26.2 parts by mass of 2-ethylhexyl acrylate and 2.8 parts by mass of acrylamide was uniformly mixed with 60g of nonanediol diacrylate (B-2, "Viscoat 260" manufactured by Osaka organic chemical Co., Ltd., mass average molecular weight (Mw): 268) as a photocurable compound and 15g of a mixture of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone (C-1, "Esacure TZT" manufactured by IGM Co., Ltd.) as a photoinitiator to obtain an adhesive resin composition 5.
Next, the adhesive resin composition 5 was sandwiched between 2 sheets of polyethylene terephthalate film (DIAFOIL MRV (V03) manufactured by Mitsubishi Chemical Corporation, DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 100. mu.m, DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 75 μm) whose surface was subjected to a peeling treatment, and the resultant was hot-melt molded into a sheet shape having a thickness of 100 μm, and then a high-pressure mercury lamp was used to give a cumulative light amount of 1000mJ/cm at a wavelength of 365nm through the release film2The adhesive resin composition 5 is cured by irradiation with ultraviolet rays, thereby obtaining a double-sided adhesive sheet laminate 5 including a release film/an adhesive sheet/a release film.
Comparative example 3
An adhesive resin composition 6 and a double-sided adhesive sheet laminate 6 were obtained in the same manner as in comparative example 2 except that an acrylic graft copolymer (a-3, mass average molecular weight: 42 ten thousand) as a (meth) acrylic copolymer obtained by randomly copolymerizing 72 parts by mass of butyl acrylate, 26 parts by mass of 2-ethylhexyl acrylate, and 2 parts by mass of acrylic acid was used.
Comparative example 4
1kg of urethane acrylate (B-1) having a propylene glycol skeleton as a photocurable compound was added with 10g of a mixture of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone (C-1, Esacure TZT, manufactured by IGM Co.) as a photoinitiator, and the mixture was uniformly mixed to obtain an adhesive resin composition 7.
Subsequently, the adhesive resin composition 7 was applied in a sheet form having a thickness of 100 μm to a release film, which is a polyethylene terephthalate film (DIAFOIL MRV (V03) manufactured by Mitsubishi Chemical Corporation, thickness 100 μm) having a surface subjected to a peeling treatment, and the coated surface was covered with a release film, which is a polyethylene terephthalate film (DIAFOIL MRQ manufactured by Mitsubishi Chemical Corporation, thickness 75 μm) having a surface subjected to a peeling treatment. A high-pressure mercury lamp was used, and the cumulative quantity of light having a wavelength of 365nm was 3000mJ/cm through the release film2The adhesive resin composition 7 is cured by irradiation with ultraviolet rays, thereby obtaining a double-sided adhesive sheet laminate 7 including a release film/an adhesive sheet/a release film.
[ evaluation ]
The double-sided adhesive sheet laminates produced in the examples and comparative examples were subjected to the following various measurements and evaluations. The evaluation results are shown in Table 1.
< measurement of viscoelasticity >
The release films of the adhesive sheet laminates 1 to 7 prepared in examples and comparative examples were peeled off, and the adhesive sheets were stacked to have a thickness of 1mm or more. Next, using a rheometer ("MARS" manufactured by british herbal and fine industries), the bonding jig: Φ 20mm parallel plate, strain: 0.5%, frequency 1Hz, temperature rise rate: 3 ℃/min, measurement temperature: the dynamic viscoelasticity was measured at-70 ℃ to 130 ℃.
From the obtained viscoelasticity curve, the peak temperature of Tan δ was read as the glass transition temperature (Tg). In addition, Tan.delta.values at-40 ℃ and 100 ℃ were read. The results are shown in the table.
The glass transition temperature of the photocurable compound after photocuring was measured as follows.
To 100g of the photocurable compound, 1g of a mixture of 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone ("Esacure TZT" manufactured by IGM Co.) as a photoinitiator was added, and the mixture was uniformly mixed, and the uniform mixture was coated on a release film, which was a polyethylene terephthalate film whose surface was subjected to a peeling treatment ("DIAFOIL MRV (V03)" manufactured by Mitsubishi Chemical Corporation, and then, the coated surface was covered with a polyethylene terephthalate film whose surface was subjected to a peeling treatment ("DIAFOIL MRQ" manufactured by Mitsubishi Chemical Corporation, having a thickness of 75 μm).
A high-pressure mercury lamp was used, and the cumulative quantity of light having a wavelength of 365nm was 3000mJ/cm through the release film2The method (3) is a method of irradiating ultraviolet rays to photocure the photocurable compound.
Subsequently, the cured photocurable compounds are stacked to a thickness of 1mm or more.
Next, using a rheometer (MARS, manufactured by british herbal medicine), the bonding jig: Φ 20mm parallel plate, strain: 0.5%, frequency 1Hz, temperature rise rate: 3 ℃/min, measurement temperature: the dynamic viscoelasticity is measured at-70 ℃ to 100 ℃.
From the obtained viscoelasticity curve, the peak temperature of Tan δ was read as the glass transition temperature of the photocurable compound. The glass transition temperature of each photocurable compound after photocuring is shown in the following table.
< glass adhesion >
The adhesive sheet laminates 1 to 7 produced in examples and comparative examples were peeled off from one side of the release film, and a polyethylene terephthalate film (made by Toyo Boseki Kaisha, COSMOSHINE A4300, 100 μm thick) as a backing film was pressure-bonded by a hand roller. The sheet was cut into a long strip having a width of 10mm × 150mm, the remaining release film was peeled off, the exposed pressure-sensitive adhesive surface roller was stuck to soda-lime glass by a hand roller to prepare a laminate including a glass/pressure-sensitive adhesive sheet/liner film, and the laminate was subjected to autoclave treatment (60 ℃, gauge pressure of 0.2MPa, 20 minutes) and finish-stuck to prepare a glass adhesion force measurement sample.
The liner film was peeled from the glass while stretching at a peeling speed of 60 mm/min at an angle of 180 °, and the tensile strength was measured with a load cell to measure the 180 ° peel strength (N/cm) of the adhesive sheet before photocuring with respect to the glass.
< wet heat haze >
One release film was peeled off from each of the adhesive sheet laminates 1 to 7 produced in examples and comparative examples, and a COP film (ZF-14 manufactured by Zeon Corporation, thickness 100 μm) was pressure-bonded to the exposed adhesive surface by a hand roller.
The remaining release film was peeled off, and soda-lime glass having a thickness of 82mm × 53mm and a thickness of 0.55mm was bonded to the exposed adhesive surface using a hand roll, and then autoclave treatment was performed at 60 ℃ and 0.2MPa for 20 minutes to prepare a sample for wet haze evaluation including a glass/adhesive sheet/COP film.
After the wet hot haze evaluation sample was stored at 65 ℃ for 90% RH for 300 hours, the haze value of the wet hot haze evaluation sample was measured according to JIS K7136 using a haze meter ("NDH 5000", manufactured by Nippon Denshoku industries Co., Ltd.).
< Corrosion resistance >
(1) Resistance to ITO substrate corrosion
On a glass substrate (60 mm. times.45 mm), in thickness
Figure BDA0003110068330000291
A round-trip line of indium oxide (ITO) was formed so that the line width was 70 μm, the line length was 46mm, and the line interval was 30 μm, and 10.5 round trips were made, and a 2mm square made of ITO was formed at both ends of the round-trip line to form an ITO pattern (length: about 97cm), thereby producing an ITO glass substrate for corrosion resistance evaluation (see fig. 1 (a)).
The release films on one side of the adhesive sheet laminates 1 to 7 produced in the examples and comparative examples were peeled off, and a PET film (product name "COSMOSHINE a 4100", 125 μm, manufactured by toyobo co., ltd.) was pressure-bonded to the exposed surface by a hand roller. Next, the adhesive sheet with the PET film was cut out to 52mm × 45mm, and then the remaining release film was peeled off, and as shown in fig. 1 (B), the adhesive sheet was attached to an ITO glass substrate for corrosion resistance evaluation by a hand roller so as to cover the reciprocating line of ITO, to prepare a sample for corrosion resistance evaluation (ITO wiring with adhesive sheet) (see fig. 1 (C)).
The resistance value (Ω 0) of the ITO wiring at room temperature in the sample for corrosion resistance evaluation (ITO wiring with adhesive sheet) was measured in advance.
On the other hand, the sample for corrosion resistance evaluation (ITO wiring with adhesive sheet) was stored at 65 ℃. 90% RH for 500 hours, and after storage, the resistance value (Ω) of the ITO wiring in the sample for corrosion resistance evaluation (ITO wiring with adhesive sheet) was measured.
The ITO resistance value, that is, the rate of change in resistance value (%) between the line ends [ ((Ω/Ω 0) -1) × 100], was calculated and shown as "resistance value change" in the table.
< bending test >
(1) Dynamic bending test
The adhesive surfaces exposed by peeling the release films of the adhesive sheet laminates 1 to 7 prepared in examples and comparative examples were laminated with a PET film (made by Mitsubishi Chemical Corporation, "DIAFOIL S-100", thickness 38 μm, made by toyobo textile Corporation, "COSMOSHINE a 4300", 100 μm) by roll bonding to prepare a laminate comprising the release film/adhesive sheet/release film, and then cut to 50mm × 100mm to prepare an evaluation sample for a dynamic bending test.
The prepared evaluation sample was mounted on a bending tester (YUASA SYSTEM co., ltd. "DLDMLH-FS") with the bonding surface of 38 μmet facing inward, and subjected to a bending test under the following test conditions at 24 ℃ (room temperature) and-20 ℃ (low temperature).
Test temperature: 24 ℃ (normal temperature), -20 ℃ (low temperature)
Radius of curvature r: 3mm
Test speed: 60rpm
Number of trials: 30 ten thousand times
The samples for evaluation after the test in the test environment of 24 ℃ (normal temperature) and-20 ℃ (low temperature) were visually observed, and the case where the pressure-sensitive adhesive sheet was creased and the case where the interface between the adherend and the pressure-sensitive adhesive sheet was peeled was judged as "poor" and the case where no change was observed visually was judged as "good".
(2) Static bending test
The adhesive surfaces exposed by peeling the release films of the adhesive sheet laminates 1 to 7 prepared in examples and comparative examples were laminated with a PET film (made by Mitsubishi Chemical Corporation, "DIAFOIL S-100", thickness 38 μm, made by toyobo textile Corporation, "COSMOSHINE a 4300", 100 μm) by roll bonding to prepare a laminate comprising the release film/adhesive sheet/release film, and then cut to 40mm × 100mm to prepare an evaluation sample for static bending test.
The prepared evaluation sample was mounted on the inner side of the 38 μmet bonding surface, and the curvature radius r: the plate was bent to a length of 3mm, fixed, and stored at 65 ℃ and 90% RH for 48 hours.
The evaluation samples after the test were visually observed, and the cases where the pressure-sensitive adhesive sheet was creased and where the interface between the adherend and the pressure-sensitive adhesive sheet was peeled were judged to be "poor" (good), and the case where no change was observed visually was judged to be "good".
< comprehensive evaluation >
The overall evaluation was performed by the following criteria.
The glass adhesion was 2N/cm or more, and the case where no change was observed by visual observation in all bending tests (dynamic bending test: 30 ten thousand at 24 ℃ and 30 ten thousand at-20 ℃ and static bending test: 90% at 65 ℃ for 48 hours) was judged as "very good" and the case where the glass adhesion was less than 2N/cm and/or the case where there was a crease or peeling in the dynamic bending test at normal temperature or the static bending test at high temperature was judged as "poor" (por).
[ Table 1]
Figure BDA0003110068330000321
(evaluation results)
The pressure-sensitive adhesive sheets obtained in examples 1 to 3 were pressure-sensitive adhesive resin compositions containing a base polymer (a) containing a (meth) acrylate copolymer having a glass transition temperature (TgA) of-30 ℃ or higher, a photoinitiator (C), and a photocurable compound (B) having a lower glass transition temperature than the base polymer (a), and containing a predetermined amount of the compound (B) in the compositions, and were found to be excellent in adhesive properties, optical properties, and flex resistance.
It is clear that comparative example 1 has insufficient static bending test and low-temperature flex resistance because it does not contain a photocurable compound.
It is clear that comparative examples 2 and 3 have insufficient flex resistance in the static bending test because a photocurable compound having a higher glass transition temperature than the base polymer (a) is used.
It is understood that comparative example 4 does not contain the base polymer (a) containing a (meth) acrylate and therefore does not adhere to an adherend, and results of peeling in a bending test are obtained.
Industrial applicability
The adhesive resin composition of the present invention is excellent in adhesion properties and flex resistance, and an adhesive resin cured product, an adhesive sheet and an image display device laminate formed from the composition can be suitably used for applications as a void-filling layer for improving visibility of an image display device, and particularly can be suitably used for an image display device having a flexible member.

Claims (15)

1. An adhesive resin composition characterized by comprising: a base polymer (A) comprising a (meth) acrylate copolymer, a photocurable compound (B), and a photoinitiator (C),
the glass transition temperature (TgB) of the photocurable compound (B) after photocuring is lower than the glass transition temperature (TgA) of the base polymer (a).
2. An adhesive resin composition characterized by comprising: a base polymer (A) comprising a (meth) acrylate copolymer, a photocurable compound (B), and a photoinitiator (C),
the photocurable compound (B) is a (meth) acrylate (B-1) having a diol skeleton.
3. The adhesive resin composition according to claim 2, wherein the (meth) acrylate (b-1) is a urethane (meth) acrylate having a mass average molecular weight (Mw) of 5000 or more.
4. The binder resin composition according to claim 3, wherein the urethane (meth) acrylate is a monofunctional urethane acrylate oligomer represented by the following formula 2,
CH2＝CH(R1)-COO(R2) (formula 2)
Wherein R1 in formula 2 represents hydrogen or methyl, X represents a urethane linkage, R2, R3 and R4 represent alkyl groups, and n is an integer of 2 or more.
5. The adhesive resin composition according to any one of claims 1 to 4, wherein the photocurable compound is contained at a ratio 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.
6. The adhesive resin composition according to any one of claims 1 to 5, wherein the glass transition temperature (TgB) of the photocurable compound after photocuring is-40 ℃ or lower.
7. The adhesive resin composition according to any one of claims 1 to 6, wherein the glass transition temperature (TgA) of the base polymer (A) is-30 ℃ or higher.
8. The adhesive resin composition according to any one of claims 1 to 7, wherein the base polymer (A) is a copolymer containing at least a structural unit derived from a hydroxyl group-containing monomer (a-1) and not containing a structural unit derived from a carboxyl group-containing monomer (a-2), and the content of the structural unit derived from the hydroxyl group-containing monomer (a-1) in the copolymer is 5 to 30% by mass.
9. A cured adhesive resin obtained by curing the adhesive resin composition according to any one of claims 1 to 8.
10. The cured adhesive resin according to claim 9, wherein the value of loss tangent (Tan δ) at a temperature of-40 ℃ is 0.1 or more and less than 0.6, and the value of loss tangent (Tan δ) at a temperature of 100 ℃ is 0.3 or more and less than 1.
11. An adhesive sheet having an adhesive layer formed from the adhesive resin composition according to any one of claims 1 to 8.
12. The adhesive sheet according to claim 11, wherein the value of loss tangent (Tan δ) at a temperature of-40 ℃ is 0.1 or more and less than 0.6, and the value of loss tangent (Tan δ) at a temperature of 100 ℃ is 0.3 or more and less than 1.
13. A laminate for constituting an image display device, which is characterized by having a structure in which 2 constituent members for an image display device are laminated via a pressure-sensitive adhesive layer comprising the cured pressure-sensitive adhesive resin according to claim 9 or the pressure-sensitive adhesive sheet according to claim 11 having the pressure-sensitive adhesive layer,
at least one of the 2 image display device-constituting members is any 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.
14. The laminate for constituting an image display device according to claim 13, wherein the pressure-sensitive adhesive layer or the pressure-sensitive adhesive sheet has a loss tangent (Tan δ) value at a temperature of-40 ℃ of 0.1 or more and less than 0.6, and a loss tangent (Tan δ) value at a temperature of 100 ℃ of 0.3 or more and less than 1.
15. The laminate for image display device formation according to claim 13 or 14, wherein each of the 2 image display device-forming members is a flexible member that can be flexed or bent.
CN201980081863.7A 2018-12-14 2019-12-13 Adhesive resin composition, cured adhesive resin, adhesive sheet, and image display device laminate Pending CN113242790A (en)

Applications Claiming Priority (3)

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