WO2015137178A1 - Method for manufacturing layered body used to constitute image display device - Google Patents

Method for manufacturing layered body used to constitute image display device Download PDF

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Publication number
WO2015137178A1
WO2015137178A1 PCT/JP2015/056079 JP2015056079W WO2015137178A1 WO 2015137178 A1 WO2015137178 A1 WO 2015137178A1 JP 2015056079 W JP2015056079 W JP 2015056079W WO 2015137178 A1 WO2015137178 A1 WO 2015137178A1
Authority
WO
WIPO (PCT)
Prior art keywords
image display
display device
sensitive adhesive
adhesive material
laminate
Prior art date
Application number
PCT/JP2015/056079
Other languages
French (fr)
Japanese (ja)
Inventor
かほる 新美
誠 稲永
Original Assignee
三菱樹脂株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN201580012808.4A priority Critical patent/CN106104658B/en
Priority to JP2016507456A priority patent/JP6388023B2/en
Priority to KR1020167027007A priority patent/KR101888984B1/en
Publication of WO2015137178A1 publication Critical patent/WO2015137178A1/en

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Classifications

    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2451/00—Presence of graft polymer

Definitions

  • the present invention relates to a transparent double-sided pressure-sensitive adhesive material excellent in followability to uneven surfaces and storage stability.
  • manufacture of a laminate for constituting an image display device that can be suitably used as a constituent member of an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, etc.
  • PDA mobile terminal
  • TV television
  • TV television
  • touch panel a touch panel
  • pen tablet etc.
  • an image display panel such as a liquid crystal display (LCD), a plasma display (PDP) or an electroluminescence display (ELD), and a protection disposed on the front side (viewing side) thereof.
  • LCD liquid crystal display
  • PDP plasma display
  • ELD electroluminescence display
  • a space between the panel and the touch panel member is filled with an adhesive sheet, a liquid adhesive, or the like to suppress reflection of incident light or outgoing light from a display image at the air layer interface.
  • Patent Document 1 As a method of filling the gap between the constituent members for an image display device with an adhesive, a method of filling the gap with a liquid adhesive resin composition containing an ultraviolet curable resin and then curing it by irradiating with ultraviolet rays. Is known (Patent Document 1).
  • Patent Document 2 discloses a pressure-sensitive adhesive sheet that is primarily cross-linked by ultraviolet rays as a method of manufacturing a laminated body for an image display device having a configuration in which an image display device constituent member is laminated on at least one side of a transparent double-sided pressure-sensitive adhesive sheet. Is disclosed in which a pressure-sensitive adhesive sheet is irradiated with ultraviolet rays through the image display device constituting member and then secondarily cured after being bonded to the image display device constituting member.
  • Patent Document 3 discloses a sheet using a hot melt type adhesive composition having a loss tangent at 25 ° C. of less than 1 based on urethane (meth) acrylate having a weight average molecular weight of 20,000 to 100,000. Is disclosed.
  • Patent Document 4 discloses a touch panel comprising a (meth) acrylic polymer obtained by copolymerizing a monomer containing a (meth) acrylic monomer having a crosslinkable functional group and a specific macromer, and a crosslinking agent.
  • a pressure-sensitive adhesive layer suitable for pasting is disclosed.
  • Patent Document 5 discloses a method for manufacturing an image display device constituting laminate having a structure in which image display device constituting members are laminated via a transparent double-sided pressure-sensitive adhesive sheet, and includes at least the following (1) and The manufacturing method of the laminated body for image display apparatus structures characterized by having the process of (2) is disclosed.
  • ultraviolet rays are irradiated from at least one image display device constituent member side, and the secondary material is passed through this member.
  • a black concealment portion is conventionally printed in a frame shape on the peripheral portion of the surface protection panel.
  • the frame concealment portion other than black is printed. Forming in color is starting to take place.
  • the concealment part is formed with a color other than black, the concealability is low with a color other than black, and therefore the height of the concealment part, that is, the printing part tends to be higher than that of black.
  • the pressure-sensitive adhesive sheet for laminating components having such a printing unit is required to have a print level followability that can fill up every corner following a large print level.
  • the surface protection panel on which the printing unit is formed is bonded to another image display device constituent member via the adhesive sheet, it can be filled to every corner following the printing step, If the surface of the pressure-sensitive adhesive sheet is not smooth, the pressure-sensitive adhesive sheet is distorted or deformed. Therefore, the pressure-sensitive adhesive sheet is required to have fluidity.
  • the hot melt type sheet in the prior art is generally a sheet having no tackiness using an adhesive composition having a certain degree of rigidity in a room temperature region in order to obtain storage stability. .
  • the hot-melt type sheet needs to preheat the adherend from the positioning stage when pasting, and the work is complicated compared to the pressure-sensitive adhesive sheet that can be stuck at room temperature only by pressure bonding Was holding.
  • the present invention can maintain a sheet-like shape in a normal state, that is, a room temperature state, and has a peelable adhesiveness (referred to as “tackiness”). Like the pressure-sensitive adhesive sheet, it can be attached at room temperature. Furthermore, after the image display device constituent members are laminated via the pressure-sensitive adhesive sheet, the image display device constituent members can be bonded by cross-linking. It is intended to provide a method for manufacturing a laminated body for device configuration.
  • the present invention relates to a method for producing a laminate for constituting an image display device having a constitution in which image display device constituting members are laminated via a transparent double-sided adhesive material, and includes at least the following (1) to (3):
  • the manufacturing method of the laminated body for image display apparatus structures characterized by having a process.
  • a pressure-sensitive adhesive resin composition comprising an acrylic copolymer (A) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B), and a photopolymerization initiator (C). And forming a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition into a sheet.
  • the transparent double-sided pressure-sensitive adhesive material obtained in step (1) does not have a chemical cross-linked structure, but has a physical cross-linked structure by aggregating macromonomers constituting the branch components of the base polymer. Thus, the flow in a normal state, that is, at room temperature is suppressed, and the sheet shape can be maintained. Moreover, the transparent double-sided pressure-sensitive adhesive material obtained in the step (1) has an adhesive property (“ (Referred to as “tackiness”). Moreover, when the said adhesive material is heated, the said aggregation of macromonomer will be dissolved, a physical crosslinked structure will be eliminated, and high fluidity
  • adherends can be firmly bonded to each other by irradiating light rays, that is, active energy rays.
  • it is a transparent double-sided pressure-sensitive adhesive material having the advantages of a pressure-sensitive adhesive sheet and a hot melt sheet. Therefore, using such a transparent double-sided adhesive material obtained in step (1), the following steps (2) to (3) can be realized to produce a laminate for constituting an image display device.
  • the “chemically crosslinked structure” means a structure that is crosslinked through a chemical bond, and the “physical crosslinked structure” does not involve a chemical bond and aggregates by a physical action. It means the state.
  • step (2) two image display device components can be attached via the transparent double-sided adhesive material while maintaining the sheet shape, so positioning is easy when attaching and it is very convenient for work. It is.
  • the adhesive layer can be cured by irradiating active energy to the uncrosslinked transparent double-sided pressure-sensitive adhesive material via the image display device constituent member. can do. Therefore, for example, the adhesive force and the cohesive force that can sufficiently counter the gas pressure of the outgas generated from the protective panel or the like can be provided.
  • the laminate obtained in the step (2) is heated to a temperature capable of being heated and melted (hot melt), it has fluidity and there is a large printing step on the bonding surface. However, it is possible to fill up every corner by arbitrarily following the stepped portion of the bonding surface.
  • a method for producing a laminate for constituting an image display device is a predetermined adhesive resin composition (“present adhesive”).
  • present adhesive A transparent double-sided pressure-sensitive adhesive material from the resin composition ”, two image display device constituent members are laminated via the transparent double-sided adhesive material, and the two image display device constituent members are attached.
  • This is a method for manufacturing a laminate for constituting an image display device (referred to as “the laminate for constituting an image display device”).
  • the laminate for constituting an image display device First, the “adhesive resin composition” used in the method for producing a laminate for constituting an image display device will be described.
  • This pressure-sensitive adhesive resin composition is a pressure-sensitive adhesive resin composition containing an acrylic copolymer (A), a crosslinking agent (B), and a photopolymerization initiator (C).
  • the acrylic copolymer (A) is a graft copolymer having a macromonomer as a branch component.
  • the trunk component of the acrylic copolymer (A) is preferably composed of a copolymer component containing a repeating unit derived from (meth) acrylic acid ester.
  • the glass transition temperature of the copolymer constituting the trunk component of the acrylic copolymer (A) is preferably ⁇ 70 to 0 ° C.
  • the glass transition temperature of the copolymer component constituting the trunk component refers to the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the trunk component of the acrylic copolymer (A). .
  • it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
  • the calculation formula of Fox is a calculation value calculated
  • the glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (A) is the flexibility of the pressure-sensitive adhesive resin composition at room temperature and the pressure-sensitive adhesive resin composition to the adherend.
  • the glass transition temperature is ⁇ 70 ° C. to 0 ° C. in order for the pressure-sensitive adhesive resin composition to obtain appropriate adhesiveness (tackiness) at room temperature because it affects the wettability of an object, that is, adhesiveness.
  • ⁇ 65 ° C. or higher or ⁇ 5 ° C. or lower is preferable, and among them, ⁇ 60 ° C. or higher or ⁇ 10 ° C. or lower is particularly preferable.
  • the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
  • Examples of the (meth) acrylic acid ester monomer contained in the main component of the acrylic copolymer (A) include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, and methyl methacrylate. And methyl acrylate.
  • Various vinyl monomers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether that can be copolymerized with the acrylic monomer or methacryl monomer can also be used as appropriate.
  • the trunk component of the acrylic copolymer (A) contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units. If the trunk component of the acrylic copolymer (A) is composed only of a hydrophobic monomer, a tendency to wet-heat whitening is recognized. Therefore, it is preferable to introduce a hydrophilic monomer into the trunk component to prevent wet-heat whitening. .
  • the backbone component of the acrylic copolymer (A) a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the end of the macromonomer are included.
  • the copolymer component formed by random copolymerization can be mentioned.
  • examples of the hydrophobic (meth) acrylate monomer include n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n -Decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (
  • hydrophilic (meth) acrylate monomer examples include methyl acrylate, (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- (Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, N, N-dimethylacrylamide, hydroxyethylacrylamide, etc. Can do.
  • the acrylic copolymer (A) is important for the acrylic copolymer (A) to introduce a macromonomer as a branch component of the graft copolymer and to contain a repeating unit derived from the macromonomer.
  • the macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
  • the glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (A). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heat melting temperature (hot melt temperature) of the present adhesive resin composition, the glass transition temperature (Tg) of the macromonomer is 30 ° C. to 120 ° C. Preferably, the temperature is 40 ° C. or higher or 110 ° C. or lower, more preferably 50 ° C. or higher or 100 ° C. or lower.
  • the glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC).
  • the branch components are attracted to each other and can maintain a state where they are physically cross-linked as an adhesive resin composition, and the physical cross-linking is released by heating to an appropriate temperature.
  • the macromonomer is preferably contained in the acrylic copolymer (A) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or more and 25% by mass or less, of which 8% by mass. It is preferable that the amount is 20% by mass or more.
  • the component constituting the high molecular weight skeleton of the macromonomer is preferably composed of an acrylic monomer or a vinyl monomer, and more preferably a hydrophobic monomer.
  • Examples of the component constituting the high molecular weight skeleton of the macromonomer include styrene, acrylonitrile, t-butylstyrene, ⁇ -methylstyrene, vinyltoluene, methyl methacrylate, 2-phenoxyethyl methacrylate, 3,5,5-trimethylcyclohexane acrylate.
  • P-cumylphenol EO modified acrylate isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl methacrylate, stearyl acrylate, stearyl methacrylate, cetyl acrylate, cetyl methacrylate, phenoxyethyl methacrylate, behenyl Examples include acrylate, behenyl methacrylate, and benzyl methacrylate.
  • a monomer having a glass transition temperature of 30 ° C. to 120 ° C. when the component constituting the high molecular weight skeleton of the macromonomer is a homopolymer is more preferable.
  • examples of the monomer include methyl methacrylate, 3,5,5-trimethylcyclohexane acrylate, isobornyl acrylate, and dicyclopentanyl acrylate.
  • the monomer when the component constituting the high molecular weight skeleton of the macromonomer has crystallinity, the monomer has a crystal melting temperature of 30 ° C. to 120 ° C. when the component is a homopolymer. Is more preferable.
  • examples of the monomer include stearyl acrylate, stearyl methacrylate, cetyl acrylate, cetyl methacrylate, behenyl acrylate, and behenyl methacrylate.
  • one of these monomers may be polymerized and used alone, or a plurality of these monomers may be copolymerized and used.
  • Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
  • the acrylic copolymer (A) preferably has a complex viscosity of 100 to 800 Pa ⁇ s, more preferably 150 to 700 Pa ⁇ s, more preferably 170 to 600 Pa ⁇ s at a temperature of 130 ° C. and a frequency of 0.02 Hz. preferable.
  • the complex viscosity at a temperature of 130 ° C. of the acrylic copolymer (A) affects the fluidity of the pressure-sensitive adhesive resin composition when the transparent double-sided pressure-sensitive adhesive material is hot-melted. If it is ⁇ 800 Pa ⁇ s, excellent hot melt suitability can be imparted.
  • the glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (A) is mentioned. It is done.
  • the viscosity is adjusted to ⁇ 70 ° C. to 0 ° C., particularly ⁇ 65 ° C. or higher or ⁇ 5 ° C. or lower, and in particular, ⁇ 60 ° C. or higher or ⁇ 10 ° C. or lower, and the molecular weight of the copolymer component is adjusted to improve viscoelasticity.
  • the method of adjusting can be mentioned. However, it is not limited to this method.
  • Cross-linking agent (B) After the image display device constituent members are bonded and integrated, the cross-linking agent (B) is cross-linked in the adhesive material, so that the sheet exhibits high cohesion in a high temperature environment instead of losing hot melt properties. Excellent foaming reliability can be obtained.
  • crosslinking agent (B) for example, an epoxy crosslinking agent, an isocyanate crosslinking agent, an oxetane compound, a silane compound, an acrylic compound, or the like can be appropriately selected.
  • the polyfunctional (meth) acrylate which has 3 or more of (meth) acryloyl groups is preferable at the point of reactivity or the intensity
  • polyfunctional (meth) acrylates examples include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group is preferable from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the heat and whitening.
  • polyfunctional (meth) acrylic acid ester having a hydroxyl group it is preferable to use polyfunctional (meth) acrylic acid ester having a hydroxyl group. Therefore, from the viewpoint of preventing wet heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a backbone component of the acrylic copolymer (A), that is, the graft copolymer.
  • a polyfunctional (meth) acrylic acid ester having a hydroxyl group as the crosslinking agent (B).
  • the content of the crosslinking agent (B) is not particularly limited.
  • the ratio of 0.5 to 20 parts by weight, particularly 1 part or more or 15 parts by weight or less, particularly 2 parts or more or 10 parts by weight or less based on 100 parts by weight of the acrylic copolymer (A). is preferred.
  • a crosslinking agent (B) in the said range, the shape stability of this adhesive material in an uncrosslinked state and the anti-foaming reliability in the adhesive material after bridge
  • the photopolymerization initiator (C) functions as a reaction initiation assistant in the crosslinking reaction of the aforementioned crosslinking agent (B).
  • the photopolymerization initiator those currently known can be used as appropriate.
  • a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. This is useful in that damage to the body can be reduced.
  • cleavage type photoinitiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy-2 -Methyl-propionyl) benzyl ⁇ phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic Methyl acid, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2- (dimethylamino
  • Examples of the hydrogen abstraction type photoinitiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2-benzoylbenzoic acid.
  • the photopolymerization initiator is not limited to the substances listed above. In the present adhesive resin composition, any one of a cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator may be used, or a combination of both may be used.
  • the content of the photopolymerization initiator (C) is not particularly limited. As a guideline, 0.1 to 10 parts by weight, particularly 0.5 parts by weight or more and 5 parts by weight or less, and 1 part by weight or more or 3 parts by weight or less based on 100 parts by weight of the acrylic copolymer (A). It is preferable to contain in the ratio. By setting the content of the photopolymerization initiator (C) in the above range, an appropriate reaction sensitivity with respect to the active energy ray can be obtained.
  • This adhesive resin composition may contain the well-known component mix
  • various additives such as a tackifier resin, an antioxidant, a light stabilizer, a metal deactivator, an anti-aging agent, and a hygroscopic agent can be appropriately contained.
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • This method for producing a laminate for constituting an image display device is a production method characterized by having at least the following steps (1) to (3).
  • the present pressure-sensitive adhesive resin composition is prepared, and a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material (referred to as “the present pressure-sensitive adhesive material”) having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition is formed into a sheet.
  • the step of forming into (referred to as “step (1)”).
  • step (2) A step of attaching and laminating two image display device constituent members via the present adhesive material (referred to as “step (2)”).
  • step (3) A step of irradiating the adhesive layer of the present adhesive material with active energy rays from the outside of at least one of the image display device constituent members, cross-linking the adhesive layer, and bonding the two image display device constituent members ( (Referred to as “step (3)”).
  • the manufacturing method of the laminate for constituting the image display device only needs to include at least the following steps (1) to (3), other steps are added or other steps are performed between the steps. It is possible to insert.
  • step (1) the pressure-sensitive adhesive resin composition is prepared, and a single-layer or multilayer uncrosslinked transparent double-sided pressure-sensitive adhesive material (this pressure-sensitive adhesive material) provided with a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition is formed into a sheet.
  • a method for forming the pressure-sensitive adhesive resin composition into a sheet a currently known method can be arbitrarily adopted.
  • the pressure-sensitive adhesive resin composition is formed into a single-layer or multilayer sheet on the release film to produce a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material having an adhesive layer. Good.
  • the pressure-sensitive adhesive resin composition is molded into a single-layer or multilayer sheet on the image display device constituent member, and the single-layer or multi-layer transparent provided with the adhesive layer on the image display device constituent member. You may make it produce a double-sided adhesive material.
  • the adhesive material is a multilayer transparent double-sided adhesive material
  • the outermost layer has both uneven followability and foam resistance reliability as in the case of the single layer. It is preferable to mold using an adhesive resin composition.
  • the intermediate layer does not contribute to adhesion with the image display device constituent member, it does not impair the transparency, and has a light transmittance that does not hinder the secondary curing reaction of the outermost layer, and has a cutting property. In addition, it preferably has a property of improving handling properties.
  • middle layer is transparent resin, it will not specifically limit.
  • the base polymer forming the intermediate layer may be the same resin as the base polymer of the outermost layer or a different resin. Among these, it is preferable to use the same acrylic resin as the base polymer of the outermost layer from the viewpoints of ensuring transparency and ease of production, and preventing light refraction at the lamination boundary surface.
  • the intermediate layer and other resin layers may or may not have active energy ray curability.
  • it may be formed so as to be cured by ultraviolet crosslinking or may be formed so as to be cured by heat. Further, it may be formed so as not to be post-cured.
  • it is preferably formed so as to be post-cured, and particularly preferably formed so as to be UV-crosslinked. In that case, since light transmittance will fall, if content of a crosslinking initiator increases, it is preferable to contain a ultraviolet-ray crosslinking agent by the content rate lower than the content rate in the outer layer of the crosslinking initiator in an intermediate
  • the present adhesive material is a multi-layer transparent double-sided adhesive material, as a laminated structure, specifically, a two-type two-layer structure in which the present adhesive resin composition and another adhesive resin composition are laminated, Two kinds of three-layer structure in which the present adhesive resin composition is arranged on the front and back through an intermediate resin layer, the present adhesive resin composition, an intermediate resin composition, and another adhesive resin composition are laminated in this order. 3 types, 3 layers structure etc. which are formed can be mentioned. Further, the pressure-sensitive adhesive resin composition and another pressure-sensitive adhesive resin composition are formed into a sheet shape on different release films or image display device constituent members, and the pressure-sensitive adhesive material is obtained by laminating both pressure-sensitive adhesive surfaces.
  • the pressure-sensitive adhesive resin composition, the intermediate resin composition, and the pressure-sensitive adhesive resin composition may be coextruded in this order to obtain a two-kind three-layer pressure-sensitive adhesive material.
  • the pressure-sensitive adhesive material may be obtained by laminating the pressure-sensitive adhesive resin composition or another pressure-sensitive adhesive resin composition on the front and back surfaces of the intermediate resin layer. However, it is not limited to these manufacturing methods.
  • the transparent double-sided pressure-sensitive adhesive material is in an uncrosslinked state.
  • the total thickness of the present adhesive material is preferably 50 ⁇ m to 1 mm, more preferably 75 ⁇ m or more or 500 ⁇ m or less. If the total thickness of the pressure-sensitive adhesive material is 50 ⁇ m or more, it is possible to follow unevenness such as a high printing level difference, and if it is 1 mm or less, the demand for thinning can be met. Furthermore, the printing thickness of the peripheral concealing layer in the conventional image display device is higher, specifically, from the viewpoint of filling up to a level difference of about 80 ⁇ m, the total thickness of the present adhesive material is more preferably 75 ⁇ m or more. More preferably, it is 100 ⁇ m or more. On the other hand, from the viewpoint of meeting the demand for thinning, it is preferably 500 ⁇ m or less, more preferably 350 ⁇ m or less.
  • the ratio of the thickness of each outermost layer to the thickness of the intermediate layer is preferably 1: 1 to 1:20, and more preferably 1: 2 to 1:10. If the thickness of the intermediate layer is within the above range, the contribution of the thickness of the pressure-sensitive adhesive layer in the laminate is not too large, and it is preferable that the workability relating to cutting and handling is not deteriorated because it is too flexible. In addition, if the outermost layer is in the above range, it is preferable because the adhesion to the adherend and the wettability can be maintained without being inferior in conformity to unevenness and a bent surface.
  • the present pressure-sensitive adhesive material both of a single layer and a multilayer structure, is transparent, can maintain a shape in a sheet shape in a normal state, and has adhesiveness.
  • by heating the pressure-sensitive adhesive material and fluidizing the pressure-sensitive adhesive layer it is possible to fill in every corner following the stepped portion of the bonding surface without leaving any distortion in the pressure-sensitive adhesive material.
  • By cross-linking it is possible to maintain foam resistance under high temperature and high humidity environment. Therefore, using this pressure-sensitive adhesive material, the following steps (2) to (3) can be realized to produce the laminate for constituting the image display device.
  • Transparency of the adhesive material is determined by shaping the adhesive resin composition into a 150 ⁇ m thick sheet between soda lime glass (0.5 mm thickness) and a cycloolefin polymer film (100 ⁇ m thickness).
  • the haze (JIS K7136) of the sandwiched laminate can be made less than 10%, especially 5% or less, especially 2% or less.
  • the pressure-sensitive adhesive resin composition is shaped into a sheet having a thickness of 150 ⁇ m, soda lime glass (0.5 mm thickness) and cycloolefin polymer film (100 ⁇ m thickness).
  • the laminate sandwiched between the layers was stored in a moist heat environment of 65 ° C. and 90% RH for 100 hours, and then stored for 2 hours in a room temperature environment of 23 ° C. and 50% RH.
  • Haze JIS K7136
  • this adhesive material was bonded to a SUS plate with an area of 20 mm ⁇ 20 mm in a holding power measurement according to JIS-Z-0237 (ISO 29863), and a load of 500 gf was applied in an atmosphere of 40 ° C.
  • the drop time can be 20 minutes or more, and the drop time when a load of 500 gf is applied in an atmosphere at 70 ° C. can be less than 5 minutes.
  • the dropping time in an atmosphere of 40 ° C. is more preferably 40 minutes or longer, and more preferably 60 minutes or longer.
  • the dropping time in an atmosphere at 70 ° C. is more preferably 3 minutes or less, and more preferably 2 minutes or less.
  • Step (2) two image display device constituent members can be adhered and laminated through the present adhesive material.
  • the acrylic copolymer (A) that is the base polymer of the present adhesive material is a graft copolymer containing a macromonomer as a branch component, the macromonomer aggregates in a normal state, that is, at room temperature. A physical cross-linked structure can be formed, and excellent storage stability and cutting processability can be imparted to the present adhesive material.
  • the acrylic copolymer (A) has a complex viscosity of 100 to 800 Pa ⁇ s at a temperature of 130 ° C. and a frequency of 0.02 Hz, it enjoys excellent workability when used as a hot melt sheet during bonding. be able to.
  • step (2) two image display device constituent members can be adhered and laminated through the present adhesive material.
  • an image display device constituent member for laminating the present adhesive material formed on a release film It can also be cut in advance according to the dimensions.
  • the cutting method at this time is generally punched with a Thomson blade, cut with a super cutter or laser, and half-cuts leaving either the front or back release film in a frame shape so that the release film can be easily peeled off. Is more preferable.
  • the present adhesive material that is, the transparent double-sided adhesive material is in an uncrosslinked state.
  • step (3) the adhesive layer of the present adhesive material is irradiated with active energy rays from the outside of at least one of the image display device constituent members, the adhesive layer is crosslinked, and the two image display device constituent members are bonded.
  • the laminate for constituting the image display device can be manufactured.
  • the adhesive layer of the present adhesive material is irradiated with active energy rays, and the adhesive layer is crosslinked and cured.
  • the two image display device constituent members can be firmly attached.
  • an energy ray that sensitizes the polymerization initiator such as a heat ray, an X-ray, an electron beam, an ultraviolet ray, or a visible ray
  • a heat ray such as a heat ray, an X-ray, an electron beam, an ultraviolet ray, or a visible ray
  • ultraviolet rays particularly ultraviolet rays having a wavelength of 380 nm or less, from the viewpoints of suppressing damage to the image display device constituent members and facilitating reaction control.
  • the UV irradiation conditions There are no particular restrictions on the UV irradiation conditions. For example, it is preferable to irradiate such that the cumulative amount of ultraviolet light reaching the adhesive material is 500 to 5000 mJ / cm 2 at a wavelength of 365 nm.
  • the type of energy rays to which the adhesive material is sensitive in accordance with the interposed member is the type of polymerization initiator. It is preferable to adjust as appropriate.
  • the pressure-sensitive adhesive layer after irradiation of the pressure-sensitive adhesive layer is measured in holding power according to JIS-Z-0237 (ISO 29863).
  • the deviation length after 30 minutes when a load of 500 gf is applied in an atmosphere of 40 ° C. and 70 ° C. can be made less than 1 mm.
  • the shift length is more preferably 0.8 mm or less, and more preferably 0.5 mm or less.
  • a step of heating and melting the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive material by heating the laminate obtained in the step (2) may be inserted. That is, the adhesive layer of the present adhesive material may be heated and melted (hot melted) by heating the laminate adhered in the step (2).
  • the adhesive When the adhesive is heated, the aggregation of the macromonomers is released, the physical cross-linking structure is eliminated, and high fluidity can be exhibited. Therefore, if there are irregularities such as printing steps on the wearing surface, when laminating two image display device components, this adhesive material is heated to flow (hot melt) to follow the irregularities of the adhesive material. And wettability to the adherend are increased, and the members can be more firmly integrated without leaving any distortion.
  • the hot melt temperature is preferably 60 to 100 ° C., more preferably 62 ° C. or more and 95 ° C. or less, and particularly preferably 65 ° C. or more and 90 ° C. or less.
  • the laminate for constituting the image display device examples include a plane using an image display panel such as an LCD, PDP, or EL, such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet.
  • mold image display apparatus can be mentioned.
  • a configuration in which a surface protection panel is laminated on a functional film such as a touch panel film via a sheet-like adhesive material is employed.
  • a concealing printing portion thickness of about 5 ⁇ m to 80 ⁇ m
  • the adhesive is provided even in the corner of the step portion formed at the edge of the concealing printing portion. If the liquid does not enter sufficiently, bubbles remain and the visibility of the screen decreases.
  • the film member may be bent in the vicinity of the step, resulting in poor appearance, or residual strain due to the bending of the film may be a starting point, and foaming or peeling may occur between the stacked members.
  • This pressure-sensitive adhesive material can be stuck without filling up every corner of the step and leaving bubbles even if there is a step of about 30 to 80 ⁇ m as well as a step of about 5 to 30 ⁇ m.
  • one of the adherends is a flexible film member, it is possible to smooth the surface without distortion by hot-melting the adhesive material.
  • the members can be bonded and integrated without causing deformation.
  • cross-linking the adhesive material after bonding the adhesive material can maintain high cohesive force without flowing even under a high temperature environment of, for example, about 85 ° C., so that foaming reliability can be obtained.
  • sheet refers to a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width.
  • film is compared to the length and width. It is a thin flat product whose thickness is extremely small and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900).
  • sheet refers to a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width.
  • film is compared to the length and width. It is a thin flat product whose thickness is extremely small and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900).
  • Japanese Industrial Standard JIS K6900 Japanese Industrial Standard JIS K6900
  • the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet, and a film.
  • “sticking” refers to a state in which the adherend is fixed by the self-adhesive property of the adhesive material, that is, the adhesive material is in an uncrosslinked state, for example, temporarily fixing the adherend. It includes a state and a state where the adherend is fixed so as to be peelable.
  • “adhesion” refers to a state in which the adherend is fixed in a state where the pressure-sensitive adhesive is chemically or physically changed by crosslinking the pressure-sensitive adhesive. For example, it is high at the interface with the adherend. This includes a state in which a bonding force is expressed and a case where the adherend is fixed in a state in which peeling is difficult.
  • X to Y (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included. Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case, unless otherwise specified, the meaning of “preferably smaller than Y” is also included.
  • Example 1 As the acrylic copolymer (A), an acrylic ester copolymer obtained by random copolymerization of 15 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 2400, 81 parts by weight of butyl acrylate, and 4 parts by weight of acrylic acid.
  • A-1) 1 kg (weight average molecular weight 230,000), 100 g of trimethylolpropane epoxy acrylate (EA5321 Shin-Nakamura Chemical Co., Ltd.) (B-1) as a crosslinking agent (B), a photopolymerization initiator ( Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (manufactured by Omnirad TPO IGM) (C-1) (C-1) as C) was uniformly mixed to prepare an adhesive resin composition.
  • a laminator was sandwiched between two polyethylene terephthalate films (referred to as “release films”) from which the above composition was peeled off (Diafoil MLV-V06, Mitsubishi Plastics, Inc., 100 ⁇ m thick / Diafoil MRQ, Mitsubishi Plastics, 75 ⁇ m thick) It was shaped into a sheet shape so as to have a thickness of 150 ⁇ m, and an adhesive material 1 was produced.
  • release films polyethylene terephthalate films
  • Evaluation glass with white printing (total light transmittance of 0%) with a width of 10 mm and a thickness of 40 ⁇ m on the periphery of soda lime glass of 60 mm ⁇ 90 mm ⁇ thickness 0.5 mm, and a printing step of 40 ⁇ m on the periphery A substrate was produced.
  • This glass substrate for evaluation is a substitute for an image display device constituent member having a stepped portion and a flat surface portion on the bonding surface.
  • a polarizing plate (“NWF-KDSEGHC-ST22” manufactured by Nitto Denko Corporation) as an image display device constituent member is previously placed on a glass plate (60 ⁇ 90 mm ⁇ What was bonded to the whole surface on one side (t0.5 mm) was produced.
  • One release film of the pressure-sensitive adhesive material 1 was peeled off, and the exposed pressure-sensitive adhesive surface was stuck with a hand roller so as to cover the printing step portion of the glass substrate. Next, the remaining release film is peeled off, and untreated soda lime glass is press bonded under reduced pressure (absolute pressure 5 kPa) to the exposed adhesive surface, followed by autoclaving (60 ° C., gauge pressure 0.2 MPa, 20 minutes).
  • the adhesive material 1 was irradiated with ultraviolet rays and cross-linked so that the cumulative amount of light at a wavelength of 365 nm was 2000 mJ / cm 2 from the soda lime glass surface, and a laminate for constituting an image display device was produced. .
  • the acrylic ester copolymer (A-1) comprises a polymethyl methacrylate macromonomer as a branch component, and butyl acrylate, acrylic acid, and a polymerizable functional group at the end of the macromonomer as a trunk component. It is a graft copolymer provided with a copolymerization component formed by random copolymerization with a methacryloyl group.
  • the glass transition temperature of the copolymer component constituting the backbone component of the acrylate copolymer (A-1) (the glass transition temperature determined from the theoretical value of the polymer obtained by polymerizing the copolymer component) is ⁇ It was 50 ° C.
  • the number average molecular weight of the polymethyl methacrylate macromonomer constituting the branch component of the acrylic ester copolymer (A-1) is 2400, the glass transition temperature of the macromonomer is 60 ° C., The acrylate copolymer (A-1) contained 15% by mass.
  • the acrylic copolymer (A) had a complex viscosity of 260 Pa ⁇ s at a temperature of 130 ° C. and a frequency of 0.02 Hz.
  • Example 2 A sheet-like pressure-sensitive adhesive material 2 having a thickness of 150 ⁇ m was prepared in the same manner as the pressure-sensitive adhesive material 1 except that 100 g of glycerin dimethacrylate (G101P manufactured by Kyoeisha Chemical Co., Ltd.) (B-2) was used as the crosslinking agent (B). And the laminated body for image display apparatus structure was produced similarly to Example 1 using this adhesive material 2.
  • G101P manufactured by Kyoeisha Chemical Co., Ltd.
  • An adhesive material 3 was prepared using an acrylic copolymer having no macromonomer. That is, an acrylic ester copolymer (A-2) obtained by random copolymerization of 20 parts by weight of methyl methacrylate and 80 parts by weight of butyl acrylate as the acrylic copolymer (A) (weight average molecular weight 400,000)
  • a sheet-like pressure-sensitive adhesive material 3 having a thickness of 150 ⁇ m was produced in the same manner as the pressure-sensitive adhesive material 1 except that.
  • the laminated body for image display apparatus structure was produced like Example 1 using this adhesive material 3.
  • An adhesive material 4 was produced according to Example 3 of Japanese Patent No. 4971529. That is, an acrylic ester copolymer obtained by random copolymerization of 75 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate and 5 parts by mass of acrylic acid, into 1 kg of the acrylic ester copolymer (A-3), Nonanediol diacrylate (Biscoat 260 manufactured by Osaka Organic Chemical Co., Ltd.) (B-3) 50 g as a crosslinking agent (B) and 10 g of 4-methylbenzophenone (C-3) as a photopolymerization initiator (C) were mixed and added. An agent resin composition was prepared.
  • an adhesive material 5 was produced. That is, as an acrylic copolymer (A), 10 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 6000, 16 parts by weight of butyl acrylate, 70 parts by weight of methoxyethyl acrylate, and 4 parts by weight of 2-hydroxyethyl acrylate are randomly added.
  • acrylic copolymer (A) 10 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 6000, 16 parts by weight of butyl acrylate, 70 parts by weight of methoxyethyl acrylate, and 4 parts by weight of 2-hydroxyethyl acrylate are randomly added.
  • Copolymerized acrylic ester copolymer (A-4) (weight average molecular weight 300,000) 1 kg, xylylene diisocyanate trimethylolpropane adduct (TD-75, manufactured by Soken Chemical Co., Ltd.) as a crosslinking agent (B) )
  • a pressure-sensitive adhesive resin composition consisting of 4 g (B-4) was prepared.
  • the pressure-sensitive adhesive resin composition was diluted with ethyl acetate to give a 50% solid concentration diluted solution, and the release-treated polyethylene terephthalate film (Diafoil MRV-V06, 100 ⁇ m thick, manufactured by Mitsubishi Plastics) had a thickness after drying.
  • the polyethylene terephthalate film (Diafoil MRQ thickness 75 ⁇ m, manufactured by Mitsubishi Plastics) was coated on the adhesive surface and cured at 23 ° C. and 40% humidity for 1 week. Then, the crosslinking reaction was advanced to produce a sheet-like adhesive material 5 having a thickness of 150 ⁇ m. And using this adhesive material 5, the laminated body for image display apparatus structure was produced similarly to Example 1 except not irradiating an ultraviolet-ray.
  • a weight of 500 gf (4.9 N) was attached to the test piece in a vertical direction and left standing, and then the falling time (minute) of the weight was determined. It was measured. About what did not fall within 30 minutes, the length (mm) that the sticking position of SUS and a test piece shifted
  • a laminate of a SUS plate and a test piece was prepared in the same manner as in the holding force measurement. After curing for 15 minutes in an atmosphere of 70 ° C., a weight of 500 gf (4.9 N) was attached to the test piece in the vertical direction and allowed to stand for 30 minutes, and then the falling time (minute) of the weight was measured. About what did not fall within 30 minutes, the length (mm) that the sticking position of SUS and a test piece shifted
  • Adhesive strength One release film of adhesives 1 to 5 was peeled off, and a 50 ⁇ m PET film (Mitsubishi Resin Diafoil T100 thickness 50 ⁇ m) was bonded as a backing film. After the laminated product was cut to a length of 150 mm and a width of 10 mm, the remaining release film was peeled off and the exposed adhesive surface was roll-bonded to soda lime glass. After the autoclave treatment (80 ° C., gauge pressure 0.2 MPa, 20 minutes) is applied to the pasted product and the final product is pasted, the accumulated light quantity of 365 nm of the adhesive materials 1 to 4 becomes 2000 mJ / cm 2.
  • the adhesive material was cured by irradiation and cured at 23 ° C. and 50% RH for 15 hours to obtain a peel force measurement sample.
  • a post-curing treatment such as ultraviolet irradiation was not performed, and the sample was used as it was as a peeling force measurement sample.
  • the remaining release film is peeled off and a ZEONOR film (manufactured by Nippon Zeon Co., Ltd., 100 ⁇ m thickness) is press-bonded, then subjected to autoclaving (80 ° C., gauge pressure 0.2 MPa, 20 minutes), and finally bonded, and the laminate 1 To 5 were produced.
  • Visual observation of the produced laminates 1 to 5 indicates that the adhesive material does not follow in the vicinity of the printing step and bubbles remain, and “x” indicates that the film is bent near the step and unevenness due to distortion is visible. “B” and those smoothly bonded without bubbles were judged as “B”.
  • the sheet-like pressure-sensitive adhesive materials of the examples show that the macromonomer in the acrylate copolymer contributes as an aggregating component, and as a result, exhibits high holding power even in an uncrosslinked state, and is excellent in workability and storage stability. there were.
  • the adhesive materials of the examples exhibit high fluidity by heating, by heating and melting at the time of bonding, not only the followability to the uneven surface is excellent, but one of the adherends is a film Even if the material has a low rigidity, it was not bent near the step, and a smooth laminate could be obtained.
  • the adhesive is cured by irradiating with ultraviolet rays after forming the laminate, thereby obtaining a highly reliable laminate that does not peel, foam or deform even under severe environmental tests such as high temperature and high humidity. I was able to.
  • Comparative Example 1 is a sheet-like adhesive material using an acrylate copolymer that does not contain a macromonomer, the cohesive force as an adhesive is low, and processability and storage stability cannot be obtained. It was. Comparative Example 2 is excellent in storage stability and cutting processability because the pressure-sensitive adhesive resin composition is partially cross-linked by ultraviolet irradiation. However, when laminating the printed stepped glass and the film, the printed step is formed on the film side. As a result, not only was the unevenness caused by the transfer transferred and a smooth laminate could not be obtained, but in the vicinity of the corner where the printing steps crossed, some of the adhesive could not be filled and bubbles remained.
  • an acrylic copolymer (A) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B),
  • B crosslinking agent
  • C photopolymerization initiator

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Abstract

　Provided is a novel method for manufacturing a layered article used to constitute an image display device, in which a sheet-form configuration can be maintained at room temperature, adhesiveness can be provided to a degree that allows separation, and constituent members of the image display device can be securely bonded together through final crosslinking upon flow properties being retained by hot melting. Proposed is a method for manufacturing a layered body used to configure an image display device, the method being characterized in having the following steps (1) to (3) at a minimum. (1) Preparing an adhesive resin composition containing an acrylic copolymer (A) comprising a graft copolymer provided with a macromonomer as a branch component, a crosslinking agent (B), and a photopolymerization initiator (C); and molding a single-layer or multilayer transparent double-sided adhesive material into the form of a sheet, the material being provided with adhesive layers comprising the adhesive resin composition. (2) Affixing and layering two image-display-device-constituting members interposed by the transparent double-sided adhesive material. (3) Irradiating the adhesive layer of the transparent double-sided adhesive material with active energy rays from the outer side of at least one of the image-display-device-constituting members, and crosslinking the adhesive layer so as to bond the two image display device constituent members.

Description

画像表示装置構成用積層体の製造方法Manufacturing method of laminate for constituting image display device
　本発明は、凹凸面への追従性並びに保管安定性に優れた透明両面粘着材に関する。特にパソコン、モバイル端末（ＰＤＡ）、ゲーム機、テレビ（ＴＶ）、カーナビ、タッチパネル、ペンタブレットなどのような画像表示装置の構成部材として好適に使用することができる画像表示装置構成用積層体の製造方法に関する。 The present invention relates to a transparent double-sided pressure-sensitive adhesive material excellent in followability to uneven surfaces and storage stability. In particular, manufacture of a laminate for constituting an image display device that can be suitably used as a constituent member of an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, etc. Regarding the method.
　近年、画像表示装置の視認性を向上させるために、液晶ディスプレイ（ＬＣＤ）、プラズマディスプレイ（ＰＤＰ）又はエレクトロルミネッセンスディスプレイ（ＥＬＤ）等の画像表示パネルと、その前面側（視認側）に配置する保護パネルやタッチパネル部材との間の空隙を、粘着シートや液状の接着剤等で充填し、入射光や表示画像からの出射光の空気層界面での反射を抑えることが行われている。 In recent years, in order to improve the visibility of an image display device, an image display panel such as a liquid crystal display (LCD), a plasma display (PDP) or an electroluminescence display (ELD), and a protection disposed on the front side (viewing side) thereof. A space between the panel and the touch panel member is filled with an adhesive sheet, a liquid adhesive, or the like to suppress reflection of incident light or outgoing light from a display image at the air layer interface.
　このような画像表示装置用構成部材間の空隙に粘着剤を用いて充填する方法として、紫外線硬化性樹脂を含む液状の接着樹脂組成物を該空隙に充填した後、紫外線を照射し硬化せしめる方法が知られている（特許文献１）。 As a method of filling the gap between the constituent members for an image display device with an adhesive, a method of filling the gap with a liquid adhesive resin composition containing an ultraviolet curable resin and then curing it by irradiating with ultraviolet rays. Is known (Patent Document 1).
　また、画像表示装置用構成部材間の空隙を、粘着シートを用いて充填する方法も知られている。例えば特許文献２には、透明両面粘着シートの少なくとも片側に、画像表示装置構成部材が積層してなる構成を備えた画像表示装置構成用積層体の製造方法として、紫外線によって１次架橋した粘着シートを画像表示装置構成部材に貼合後、画像表示装置構成部材を介して粘着シートに紫外線照射し２次硬化させる方法が開示されている。 Also known is a method of filling a gap between component members for an image display device using an adhesive sheet. For example, Patent Document 2 discloses a pressure-sensitive adhesive sheet that is primarily cross-linked by ultraviolet rays as a method of manufacturing a laminated body for an image display device having a configuration in which an image display device constituent member is laminated on at least one side of a transparent double-sided pressure-sensitive adhesive sheet. Is disclosed in which a pressure-sensitive adhesive sheet is irradiated with ultraviolet rays through the image display device constituting member and then secondarily cured after being bonded to the image display device constituting member.
　また、特許文献３には重量平均分子量が２万から１０万であるウレタン（メタ）アクリレートを主成分とした、２５℃における損失正接が１未満であるホットメルトタイプの接着組成物をもちいたシートが開示されている。 Patent Document 3 discloses a sheet using a hot melt type adhesive composition having a loss tangent at 25 ° C. of less than 1 based on urethane (meth) acrylate having a weight average molecular weight of 20,000 to 100,000. Is disclosed.
　さらに特許文献４には、架橋性官能基を有する（メタ）アクリル系モノマーおよび特定のマクロマーを含むモノマーを共重合させて得られる、（メタ）アクリル系ポリマーと、架橋剤とを含む、タッチパネルの貼合に好適な粘着剤層が開示されている。 Further, Patent Document 4 discloses a touch panel comprising a (meth) acrylic polymer obtained by copolymerizing a monomer containing a (meth) acrylic monomer having a crosslinkable functional group and a specific macromer, and a crosslinking agent. A pressure-sensitive adhesive layer suitable for pasting is disclosed.
　また、特許文献５には、透明両面粘着シートを介して画像表示装置構成部材が積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、少なくとも次の（１）及び（２）の工程を有することを特徴とする画像表示装置構成用積層体の製造方法が開示されている。
（１）　粘着剤組成物を単層又は多層のシート状に形成し、これを紫外線架橋して１次硬化させることにより２次硬化前透明両面粘着シートを形成する工程。
（２）　２次硬化前透明両面粘着シートを介して２つの画像表示装置構成部材を積層した後、少なくとも一方の画像表示装置構成部材側から紫外線を照射し、この部材を介して、前記２次硬化前透明両面粘着シートを紫外線架橋して２次硬化させる工程。 Patent Document 5 discloses a method for manufacturing an image display device constituting laminate having a structure in which image display device constituting members are laminated via a transparent double-sided pressure-sensitive adhesive sheet, and includes at least the following (1) and The manufacturing method of the laminated body for image display apparatus structures characterized by having the process of (2) is disclosed.
(1) A step of forming a transparent double-sided pressure-sensitive adhesive sheet before secondary curing by forming the pressure-sensitive adhesive composition into a single-layer or multi-layered sheet, UV-crosslinking this and performing primary curing.
(2) After the two image display device constituent members are laminated via the transparent double-sided adhesive sheet before secondary curing, ultraviolet rays are irradiated from at least one image display device constituent member side, and the secondary material is passed through this member. A step of subjecting the transparent double-sided PSA sheet before curing to UV-curing by secondary crosslinking.
国際公開２０１０／０２７０４１号公報International Publication No. 2010/027041 特許第４９７１５２９号公報Japanese Patent No. 4971529 国際公開２０１０／０３８３６６号公報International Publication No. 2010/038366 特開２０１３－１８２２７号公報JP 2013-18227 A 特開２０１２－１８４４２３号公報JP 2012-184423 A
　粘着シートを使用して画像表示装置構成部材を貼着する際、通常状態、すなわち室温において、適度な接着性、例えば、剥離可能な程度の接着性（“タック性”と称する）を備えていれば、貼着する際の位置決めを行いやすく、作業上とても便利である。 When sticking an image display device component using an adhesive sheet, it should have adequate adhesiveness in a normal state, that is, at room temperature, for example, adhesive enough to be peeled off (referred to as “tackiness”). It is easy to perform positioning when sticking and is very convenient for work.
　また、携帯電話や携帯端末などを中心に画像表示装置の分野では、薄肉化、高精密化に加えて、デザインの多様化が進んでおり、それに伴って新たな課題が生じてきている。例えば、表面保護パネルの周縁部には、枠状に黒色の隠蔽部を印刷するのが従来は一般的であったが、デザインの多様化に伴って、この枠状の隠蔽部を黒色以外の色で形成することが行われ始めている。黒色以外の色で隠蔽部を形成する場合、黒色以外の色では隠蔽性が低いため、黒色に比べて隠蔽部、すなわち印刷部の高さが高くなる傾向がある。そのため、そのような印刷部を備えた構成部材を貼り合わせるための粘着シートには、大きな印刷段差に追従して隅々まで充填することができる印刷段差追従性が求められる。
　中でも、粘着シートを介して、例えば印刷部が形成された表面保護パネルを、他の画像表示装置構成部材を貼り合わせる場合には、印刷段差に追従して隅々まで充填することができると共に、粘着シートの表面が平滑にならないと、粘着シートに歪や変形が生じるため、当該粘着シートには流動性が求められる。 In addition, in the field of image display devices, mainly mobile phones and portable terminals, in addition to thinning and high precision, design diversification is progressing, and new problems have arisen accordingly. For example, a black concealment portion is conventionally printed in a frame shape on the peripheral portion of the surface protection panel. However, with the diversification of the design, the frame concealment portion other than black is printed. Forming in color is starting to take place. When the concealment part is formed with a color other than black, the concealability is low with a color other than black, and therefore the height of the concealment part, that is, the printing part tends to be higher than that of black. For this reason, the pressure-sensitive adhesive sheet for laminating components having such a printing unit is required to have a print level followability that can fill up every corner following a large print level.
Among them, for example, when the surface protection panel on which the printing unit is formed is bonded to another image display device constituent member via the adhesive sheet, it can be filled to every corner following the printing step, If the surface of the pressure-sensitive adhesive sheet is not smooth, the pressure-sensitive adhesive sheet is distorted or deformed. Therefore, the pressure-sensitive adhesive sheet is required to have fluidity.
　その一方で、通常状態、すなわち室温において、粘着シートが流動すると、シートとしての形状を保持できないようになり、粘着シートの保管安定性や取り回し時の作業性が損なわれることになってしまう。
　そのため、従来技術におけるホットメルトタイプのシートは、保管安定性を得るために、室温域においてある程度の剛性を備えた接着性組成物を用いた、タック性をもたないシートが一般的であった。このため、ホットメルトタイプのシートは、貼合せする際に位置決めの段階から被着体を予熱する必要があり、圧着のみで常温貼付可能な粘着シートと比して、作業が煩雑であるという課題を抱えていた。 On the other hand, when the pressure-sensitive adhesive sheet flows in a normal state, that is, at room temperature, the shape as a sheet cannot be maintained, and the storage stability of the pressure-sensitive adhesive sheet and the workability during handling are impaired.
Therefore, the hot melt type sheet in the prior art is generally a sheet having no tackiness using an adhesive composition having a certain degree of rigidity in a room temperature region in order to obtain storage stability. . For this reason, the hot-melt type sheet needs to preheat the adherend from the positioning stage when pasting, and the work is complicated compared to the pressure-sensitive adhesive sheet that can be stuck at room temperature only by pressure bonding Was holding.
　そこで本発明は、通常状態、すなわち、室温状態では、シート状の形状を保持することができ、しかも、剥離可能な程度の接着性（“タック性”と称する）を備えているため、通常の粘着シート同様、室温で貼着でき、さらには、画像表示装置構成部材を、粘着シートを介して積層した後は、架橋させて画像表示装置構成部材同士を接着することができる、新たな画像表示装置構成用積層体の製造方法を提供せんとするものである。 Therefore, the present invention can maintain a sheet-like shape in a normal state, that is, a room temperature state, and has a peelable adhesiveness (referred to as “tackiness”). Like the pressure-sensitive adhesive sheet, it can be attached at room temperature. Furthermore, after the image display device constituent members are laminated via the pressure-sensitive adhesive sheet, the image display device constituent members can be bonded by cross-linking. It is intended to provide a method for manufacturing a laminated body for device configuration.
　本発明は、透明両面粘着材を介して画像表示装置構成部材が積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、少なくとも次の（１）～（３）の工程を有することを特徴とする画像表示装置構成用積層体の製造方法。
（１）　枝成分としてマクロモノマーを備えたグラフト共重合体からなるアクリル系共重合体（Ａ）と、架橋剤（Ｂ）と、光重合開始剤（Ｃ）とを含有する粘着剤樹脂組成物を作製して、該粘着剤樹脂組成物からなる粘着層を備えた単層又は多層の透明両面粘着材をシート状に成形する工程。
（２）　前記透明両面粘着材を介して２つの画像表示装置構成部材を貼着して積層する工程。
（３）　少なくとも一方の画像表示装置構成部材の外側から、活性エネルギー線を透明両面粘着材の前記粘着層に照射し、当該粘着層を架橋させて、２つの画像表示装置構成部材を接着させる工程。 The present invention relates to a method for producing a laminate for constituting an image display device having a constitution in which image display device constituting members are laminated via a transparent double-sided adhesive material, and includes at least the following (1) to (3): The manufacturing method of the laminated body for image display apparatus structures characterized by having a process.
(1) A pressure-sensitive adhesive resin composition comprising an acrylic copolymer (A) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B), and a photopolymerization initiator (C). And forming a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition into a sheet.
(2) The process of sticking and laminating | stacking two image display apparatus structural members through the said transparent double-sided adhesive material.
(3) A step of irradiating the adhesive layer of the transparent double-sided pressure-sensitive adhesive material from the outside of at least one of the image display device constituent members, crosslinking the adhesive layer, and bonding the two image display device constituent members .
　工程（１）で得られる透明両面粘着材は、化学的な架橋構造を有していない代わりに、ベースポリマーの枝成分を構成するマクロモノマー同士が凝集して物理的な架橋構造を有しており、これにより、通常状態、すなわち室温における流動が抑えられ、シート形状を保持することができる。しかも、工程（１）で得られる透明両面粘着材は、ベースポリマーの幹成分を構成する部分が粘着性を有しているため、共重合から室温状態において、剥離可能な程度の接着性（“タック性”と称する）を備えることもできる。また、当該粘着材を加熱すると、マクロモノマー同士の前記凝集が解れて物理的な架橋構造が解消して高い流動性を発現させることができる。さらには、光線、すなわち活性エネルギー線を照射することにより、被着体同士を強固に接着させることができる。このように、粘着シートとホットメルトシートの長所を兼ね備えた透明両面粘着材である。
　よって、工程（１）で得られるこのような透明両面粘着材を用いて、次の工程（２）～（３）を実現して画像表示装置構成用積層体を製造することができる。
　なお、上記「化学的な架橋構造」とは、化学結合を介して架橋している構造を意味し、上記「物理的な架橋構造」とは、化学結合を介さず、物理的作用によって凝集している状態を意味するものである。 The transparent double-sided pressure-sensitive adhesive material obtained in step (1) does not have a chemical cross-linked structure, but has a physical cross-linked structure by aggregating macromonomers constituting the branch components of the base polymer. Thus, the flow in a normal state, that is, at room temperature is suppressed, and the sheet shape can be maintained. Moreover, the transparent double-sided pressure-sensitive adhesive material obtained in the step (1) has an adhesive property (“ (Referred to as “tackiness”). Moreover, when the said adhesive material is heated, the said aggregation of macromonomer will be dissolved, a physical crosslinked structure will be eliminated, and high fluidity | liquidity can be expressed. Furthermore, adherends can be firmly bonded to each other by irradiating light rays, that is, active energy rays. Thus, it is a transparent double-sided pressure-sensitive adhesive material having the advantages of a pressure-sensitive adhesive sheet and a hot melt sheet.
Therefore, using such a transparent double-sided adhesive material obtained in step (1), the following steps (2) to (3) can be realized to produce a laminate for constituting an image display device.
The “chemically crosslinked structure” means a structure that is crosslinked through a chemical bond, and the “physical crosslinked structure” does not involve a chemical bond and aggregates by a physical action. It means the state.
　工程（２）では、シート形状を保持しつつ、透明両面粘着材を介して２つの画像表示装置構成部材を貼着することができるから、貼着する際の位置決めを行いやすく、作業上とても便利である。
　そして、工程（３）では、画像表示装置構成部材を介して、未架橋状態の透明両面粘着材に活性エネルギーを照射して粘着層を硬化させることができるから、画像表示装置構成部材同士を接着することができる。よって、例えば保護パネル等から発生するアウトガスのガス圧に対して十分に対抗できるだけの接着力と凝集力を持たせることができる。
　また、前記工程（２）で得られた積層物を、加熱して加熱溶融（ホットメルト）可能な温度に加熱すると、流動性を持つようになり、貼合面に大きな印刷段差があった場合でも、貼合面の段差部へ任意に追従して隅々まで充填することができる。 In step (2), two image display device components can be attached via the transparent double-sided adhesive material while maintaining the sheet shape, so positioning is easy when attaching and it is very convenient for work. It is.
In the step (3), the adhesive layer can be cured by irradiating active energy to the uncrosslinked transparent double-sided pressure-sensitive adhesive material via the image display device constituent member. can do. Therefore, for example, the adhesive force and the cohesive force that can sufficiently counter the gas pressure of the outgas generated from the protective panel or the like can be provided.
In addition, when the laminate obtained in the step (2) is heated to a temperature capable of being heated and melted (hot melt), it has fluidity and there is a large printing step on the bonding surface. However, it is possible to fill up every corner by arbitrarily following the stepped portion of the bonding surface.
　以下、本発明の実施形態の一例について説明する。但し、本発明が下記実施形態の例に制限されるものではない。 Hereinafter, an example of an embodiment of the present invention will be described. However, the present invention is not limited to the following embodiments.
　本発明の実施形態の一例に係る画像表示装置構成用積層体の製造方法（「本画像表示装置構成用積層体の製造方法」と称する）は、所定の粘着剤樹脂組成物（「本粘着剤樹脂組成物」と称する）から透明両面粘着材を作製し、前記透明両面粘着材を介して２つの画像表示装置構成部材を積層し、２つの画像表示装置構成部材を貼着する工程を備えた画像表示装置構成用積層体（「本画像表示装置構成用積層体」と称する）の製造方法である。
　そこで先ずは、本画像表示装置構成用積層体の製造方法で使用する「本粘着剤樹脂組成物」について説明する。 A method for producing a laminate for constituting an image display device according to an example of an embodiment of the present invention (referred to as “a method for producing a laminate for constituting an image display device”) is a predetermined adhesive resin composition (“present adhesive”). A transparent double-sided pressure-sensitive adhesive material from the resin composition ”, two image display device constituent members are laminated via the transparent double-sided adhesive material, and the two image display device constituent members are attached. This is a method for manufacturing a laminate for constituting an image display device (referred to as “the laminate for constituting an image display device”).
First, the “adhesive resin composition” used in the method for producing a laminate for constituting an image display device will be described.
≪本粘着剤樹脂組成物≫
　本粘着剤樹脂組成物は、アクリル系共重合体（Ａ）と、架橋剤（Ｂ）と、光重合開始剤（Ｃ）とを含有する粘着剤樹脂組成物である。 ≪This adhesive resin composition≫
This pressure-sensitive adhesive resin composition is a pressure-sensitive adhesive resin composition containing an acrylic copolymer (A), a crosslinking agent (B), and a photopolymerization initiator (C).
＜アクリル系共重合体（Ａ）＞
　前記アクリル系共重合体（Ａ）は、枝成分としてマクロモノマーを備えたグラフト共重合体である。 <Acrylic copolymer (A)>
The acrylic copolymer (A) is a graft copolymer having a macromonomer as a branch component.
（幹成分）
　前記アクリル系共重合体（Ａ）の幹成分は、（メタ）アクリル酸エステル由来の繰り返し単位を含有する共重合体成分から構成されるのが好ましい。 (Stem component)
The trunk component of the acrylic copolymer (A) is preferably composed of a copolymer component containing a repeating unit derived from (meth) acrylic acid ester.
　前記アクリル系共重合体（Ａ）の幹成分を構成する共重合体のガラス転移温度は－７０～０℃であるのが好ましい。
　この際、幹成分を構成する共重合体成分のガラス転移温度とは、アクリル系共重合体（Ａ）の幹成分を組成するモノマー成分のみを共重合して得られるポリマーのガラス転移温度をさす。具体的には、当該共重合体各成分のホモポリマーから得られるポリマーのガラス転移温度と構成比率から、Ｆｏｘの計算式によって算出される値を意味する。
　なお、Ｆｏｘの計算式とは、以下の式により求められる計算値であり、ポリマーハンドブック〔Ｐｏｌｙｍｅｒ　ＨａｎｄＢｏｏｋ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｉｎｔｅｒｓｃｉｅｎｃｅ，１９８９〕に記載されている値を用いて求めることができる。
　　　１／（２７３＋Ｔｇ）＝Σ（Ｗｉ／（２７３＋Ｔｇｉ））
　［式中、Ｗｉはモノマーｉの重量分率、ＴｇｉはモノマーｉのホモポリマーのＴｇ（℃）を示す。］ The glass transition temperature of the copolymer constituting the trunk component of the acrylic copolymer (A) is preferably −70 to 0 ° C.
In this case, the glass transition temperature of the copolymer component constituting the trunk component refers to the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the trunk component of the acrylic copolymer (A). . Specifically, it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
In addition, the calculation formula of Fox is a calculation value calculated | required by the following formula | equation, Polymer handbook [Polymer HandBook, J.M. Brandrup, Interscience, 1989].
1 / (273 + Tg) = Σ (Wi / (273 + Tgi))
[Wherein Wi represents the weight fraction of monomer i, and Tgi represents Tg (° C.) of the homopolymer of monomer i. ]
　前記アクリル系共重合体（Ａ）の幹成分を構成する共重合体成分のガラス転移温度は、室温状態での本粘着剤樹脂組成物の柔軟性や、被着体への本粘着剤樹脂組成物の濡れ性、すなわち接着性に影響するため、本粘着剤樹脂組成物が室温状態で適度な接着性（タック性）を得るためには、当該ガラス転移温度は、－７０℃～０℃であるのが好ましく、中でも－６５℃以上或いは－５℃以下、その中でも－６０℃以上或いは－１０℃以下であるのが特に好ましい。 The glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (A) is the flexibility of the pressure-sensitive adhesive resin composition at room temperature and the pressure-sensitive adhesive resin composition to the adherend. The glass transition temperature is −70 ° C. to 0 ° C. in order for the pressure-sensitive adhesive resin composition to obtain appropriate adhesiveness (tackiness) at room temperature because it affects the wettability of an object, that is, adhesiveness. Of these, −65 ° C. or higher or −5 ° C. or lower is preferable, and among them, −60 ° C. or higher or −10 ° C. or lower is particularly preferable.
　但し、当該共重合体成分のガラス転移温度が同じ温度であったとしても、分子量を調整することにより粘弾性を調整することができる。例えば共重合体成分の分子量を小さくすることにより、より柔軟化させることができる。 However, even if the glass transition temperature of the copolymer component is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
　前記アクリル系共重合体（Ａ）の幹成分が含有する(メタ)アクリル酸エステルモノマーとしては、例えば２－エチルヘキシルアクリレート、ｎ－オクチルアクリート、イソオクチルアクリレート、ｎ－ブチルアクリレート、エチルアクリレート、メチルメタクリレート、メチルアクリレート等を挙げることができる。これらに、親水基や有機官能基などをもつヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、アクリル酸、メタクリル酸、グリシジルアクリレート、アクリルアミド、Ｎ、Ｎ-ジメチルアクリルアミド、アクリルニトリル、メタクリロニトリル等を用いることもできる。
　また、上記アクリルモノマーやメタクリルモノマーと共重合可能な酢酸ビニルやアルキルビニルエーテル、ヒドロキシアルキルビニルエーテル等の各種ビニルモノマーも適宜用いることができる。 Examples of the (meth) acrylic acid ester monomer contained in the main component of the acrylic copolymer (A) include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, and methyl methacrylate. And methyl acrylate. These include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, acrylamide, N, N-dimethylacrylamide, acrylonitrile, methacrylate having hydrophilic groups and organic functional groups. Ronitrile and the like can also be used.
Various vinyl monomers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether that can be copolymerized with the acrylic monomer or methacryl monomer can also be used as appropriate.
　また、アクリル系共重合体（Ａ）の幹成分は、疎水性の（メタ）アクリレートモノマーと、親水性の（メタ）アクリレートモノマーとを構成単位として含有するのが好ましい。
　アクリル系共重合体（Ａ）の幹成分が、疎水性モノマーのみから構成されると、湿熱白化する傾向が認められるため、親水性モノマーも幹成分に導入して湿熱白化を防止するのが好ましい。
　具体的には、上記アクリル系共重合体（Ａ）の幹成分として、疎水性の（メタ）アクリレートモノマーと、親水性の（メタ）アクリレートモノマーと、マクロモノマーの末端の重合性官能基とがランダム共重合してなる共重合体成分を挙げることができる。 Moreover, it is preferable that the trunk component of the acrylic copolymer (A) contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units.
If the trunk component of the acrylic copolymer (A) is composed only of a hydrophobic monomer, a tendency to wet-heat whitening is recognized. Therefore, it is preferable to introduce a hydrophilic monomer into the trunk component to prevent wet-heat whitening. .
Specifically, as the backbone component of the acrylic copolymer (A), a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the end of the macromonomer are included. The copolymer component formed by random copolymerization can be mentioned.
　ここで、上記の疎水性の（メタ）アクリレートモノマーとしては、例えばｎ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－メチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、t－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレ－ト、メチルメタクリレート、酢酸ビニルなどを挙げることができる。 Here, examples of the hydrophobic (meth) acrylate monomer include n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n -Decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyloxyethyl Examples include ru (meth) acrylate, methyl methacrylate, and vinyl acetate.
　上記の親水性の（メタ）アクリレートモノマーとしては、例えばメチルアクリレート、（メタ）アクリル酸、テトラヒドロフルフリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、Ｎ，Ｎ－ジメチルアクリルアミド、ヒドロキシエチルアクリルアミドなどを挙げることができる。 Examples of the hydrophilic (meth) acrylate monomer include methyl acrylate, (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- (Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, N, N-dimethylacrylamide, hydroxyethylacrylamide, etc. Can do.
（枝成分：マクロモノマー）
　アクリル系共重合体（Ａ）は、グラフト共重合体の枝成分として、マクロモノマーを導入し、マクロモノマー由来の繰り返し単位を含有することが重要である。
　マクロモノマーとは、末端の重合性官能基と高分子量骨格成分とを有する高分子単量体である。 (Branch component: macromonomer)
It is important for the acrylic copolymer (A) to introduce a macromonomer as a branch component of the graft copolymer and to contain a repeating unit derived from the macromonomer.
The macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
　マクロモノマーのガラス転移温度（Ｔｇ）は、上記アクリル系共重合体（Ａ）を構成する共重合体成分のガラス転移温度よりも高いことが好ましい。
　具体的には、マクロモノマーのガラス転移温度（Ｔｇ）は、本粘着剤樹脂組成物の加熱溶融温度（ホットメルト温度）に影響するため、マクロモノマーのガラス転移温度（Ｔｇ）は３０℃～１２０℃であるのが好ましく、中でも４０℃以上或いは１１０℃以下、その中でも５０℃以上或いは１００℃以下であるのがさらに好ましい。
　このようなガラス転移温度（Ｔｇ）であれば、分子量を調整することにより、優れた加工性や保管安定性を保持できると共に、８０℃付近でホットメルトするように調整することができる。
　マクロモノマーのガラス転移温度とは、当該マクロモノマー自体のガラス転移温度をさし、示差走査熱量計（ＤＳＣ）で測定することができる。 The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (A).
Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heat melting temperature (hot melt temperature) of the present adhesive resin composition, the glass transition temperature (Tg) of the macromonomer is 30 ° C. to 120 ° C. Preferably, the temperature is 40 ° C. or higher or 110 ° C. or lower, more preferably 50 ° C. or higher or 100 ° C. or lower.
With such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and to adjust so as to hot-melt near 80 ° C.
The glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC).
　また、室温状態では、枝成分同士が引き寄せ合って粘着剤樹脂組成物として物理的架橋をしたような状態を維持することができ、しかも、適度な温度に加熱することで前記物理的架橋が解れて流動性を得ることができるようにするためには、マクロモノマーの含有量を調整することも好ましいことである。
　かかる観点から、マクロモノマーは、アクリル系共重合体（Ａ）中に５質量％～３０質量％の割合で含有することが好ましく、中でも６質量％以上或いは２５質量％以下、その中でも８質量％以上或いは２０質量％以下であるのが好ましい。 Further, at room temperature, the branch components are attracted to each other and can maintain a state where they are physically cross-linked as an adhesive resin composition, and the physical cross-linking is released by heating to an appropriate temperature. In order to obtain fluidity, it is also preferable to adjust the content of the macromonomer.
From this viewpoint, the macromonomer is preferably contained in the acrylic copolymer (A) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or more and 25% by mass or less, of which 8% by mass. It is preferable that the amount is 20% by mass or more.
　マクロモノマーの高分子量骨格を構成する成分は、アクリル系モノマーまたはビニル系モノマーから構成されるのが好ましく、中でも疎水性のモノマーがより好ましい。
　前記マクロモノマーの高分子量骨格を構成する成分としては、例えばスチレン、アクリロニトリル、ｔ－ブチルスチレン、α－メチルスチレン、ビニルトルエン、メチルメタクリレート、２－フェノキシエチルメタクリレート、３，５，５－トリメチルシクロヘキサンアクリレート、ｐ－クミルフェノールＥＯ変性アクリレート、イソボルニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニルオキシエチルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート、セチルアクリート、セチルメタクリレート、フェノキシエチルメタクリレート、ベヘニルアクリレート、ベヘニルメタクリレート、ベンジルメタクリレートなどを挙げることができる。
　前記成分の中でも、マクロモノマーの高分子量骨格を構成する前記成分をホモポリマーとした時のガラス転移温度が３０℃～１２０℃であるモノマーであるのがさらに好ましい。具体的には、当該モノマーとして、例えばメチルメタクリレート、３，５，５－トリメチルシクロヘキサンアクリレート、イソボルニルアクリレート、ジシクロペンタニルアクリレートなどを挙げることができる。
　また、前記成分の中でも、マクロモノマーの高分子量骨格を構成する前記成分が結晶性を有する場合、当該前記成分をホモポリマーとした時の結晶融解温度が３０℃～１２０℃であるモノマーであるのがさらに好ましい。具体的には、当該モノマーとして、例えばステアリルアクリレート、ステアリルメタクリレート、セチルアクリート、セチルメタクリレート、ベヘニルアクリレート、ベヘニルメタクリレートなどを挙げることができる。
　なお、マクロモノマーの高分子量骨格を構成する際、これらのモノマーの一つを単独で重合して使用してもよいし、これら複数のモノマーを共重合させて使用してもよい。 The component constituting the high molecular weight skeleton of the macromonomer is preferably composed of an acrylic monomer or a vinyl monomer, and more preferably a hydrophobic monomer.
Examples of the component constituting the high molecular weight skeleton of the macromonomer include styrene, acrylonitrile, t-butylstyrene, α-methylstyrene, vinyltoluene, methyl methacrylate, 2-phenoxyethyl methacrylate, 3,5,5-trimethylcyclohexane acrylate. P-cumylphenol EO modified acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl methacrylate, stearyl acrylate, stearyl methacrylate, cetyl acrylate, cetyl methacrylate, phenoxyethyl methacrylate, behenyl Examples include acrylate, behenyl methacrylate, and benzyl methacrylate.
Among the components, a monomer having a glass transition temperature of 30 ° C. to 120 ° C. when the component constituting the high molecular weight skeleton of the macromonomer is a homopolymer is more preferable. Specifically, examples of the monomer include methyl methacrylate, 3,5,5-trimethylcyclohexane acrylate, isobornyl acrylate, and dicyclopentanyl acrylate.
Further, among the components, when the component constituting the high molecular weight skeleton of the macromonomer has crystallinity, the monomer has a crystal melting temperature of 30 ° C. to 120 ° C. when the component is a homopolymer. Is more preferable. Specifically, examples of the monomer include stearyl acrylate, stearyl methacrylate, cetyl acrylate, cetyl methacrylate, behenyl acrylate, and behenyl methacrylate.
When constituting the high molecular weight skeleton of the macromonomer, one of these monomers may be polymerized and used alone, or a plurality of these monomers may be copolymerized and used.
　前記マクロモノマーの末端重合性官能基としては、例えば、メタクリロイル基、アクリロイル基、ビニル基などを挙げることができる。 Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
（アクリル系共重合体（Ａ）の物性）
　前記アクリル系共重合体（Ａ）は、温度１３０℃、周波数０．０２Ｈｚにおける複素粘度が１００～８００Ｐａ・ｓであることが好ましく、１５０～７００Ｐａ・ｓがより好ましく、１７０～６００Ｐａ・ｓがさらに好ましい。
　前記アクリル系共重合体（Ａ）の温度１３０℃における複素粘度は、当該透明両面粘着材をホットメルトさせて使用するときの粘着剤樹脂組成物の流動性に影響するため、かかる複素粘度が１００～８００Ｐａ・ｓであれば、優れたホットメルト適性を持たせることができる。 (Physical properties of acrylic copolymer (A))
The acrylic copolymer (A) preferably has a complex viscosity of 100 to 800 Pa · s, more preferably 150 to 700 Pa · s, more preferably 170 to 600 Pa · s at a temperature of 130 ° C. and a frequency of 0.02 Hz. preferable.
The complex viscosity at a temperature of 130 ° C. of the acrylic copolymer (A) affects the fluidity of the pressure-sensitive adhesive resin composition when the transparent double-sided pressure-sensitive adhesive material is hot-melted. If it is ˜800 Pa · s, excellent hot melt suitability can be imparted.
　前記アクリル系共重合体（Ａ）の複素粘度を前記範囲に調整するには、例えばアクリル系共重合体（Ａ）の幹成分を構成する共重合体成分のガラス転移温度を調整することが挙げられる。好ましくは－７０℃～０℃、中でも－６５℃以上或いは－５℃以下、その中でも－６０℃以上或いは－１０℃以下に調整すると共に、当該共重合体成分の分子量を調整して粘弾性を調整する方法を挙げることができる。但し、この方法に限定するものではない。 In order to adjust the complex viscosity of the acrylic copolymer (A) to the above range, for example, adjusting the glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (A) is mentioned. It is done. Preferably, the viscosity is adjusted to −70 ° C. to 0 ° C., particularly −65 ° C. or higher or −5 ° C. or lower, and in particular, −60 ° C. or higher or −10 ° C. or lower, and the molecular weight of the copolymer component is adjusted to improve viscoelasticity. The method of adjusting can be mentioned. However, it is not limited to this method.
＜架橋剤（Ｂ）＞
　画像表示装置構成部材を貼合一体化させた後、架橋剤（Ｂ）を粘着材中で架橋することで、当該シートはホットメルト性を失う代わりに、高温環境下における高い凝集力を発現し、優れた耐発泡信頼性を得ることができる。 <Crosslinking agent (B)>
After the image display device constituent members are bonded and integrated, the cross-linking agent (B) is cross-linked in the adhesive material, so that the sheet exhibits high cohesion in a high temperature environment instead of losing hot melt properties. Excellent foaming reliability can be obtained.
　このような架橋剤（Ｂ）としては、例えばエポキシ架橋剤やイソシアネート架橋剤、オキセタン化合物、シラン化合物、アクリル化合物等からなる架橋剤を適宜選択可能である。中でも、反応性や得られる硬化物の強度の点で、（メタ）アクリロイル基を３個以上有する多官能（メタ）アクリレートが好ましい。 As such a crosslinking agent (B), for example, an epoxy crosslinking agent, an isocyanate crosslinking agent, an oxetane compound, a silane compound, an acrylic compound, or the like can be appropriately selected. Especially, the polyfunctional (meth) acrylate which has 3 or more of (meth) acryloyl groups is preferable at the point of reactivity or the intensity | strength of the hardened | cured material obtained.
　このような多官能（メタ）アクリレートとしては、例えば１，４－ブタンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、グリセリングリシジルエーテルジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ビスフェノールＡポリエトキシジ（メタ）アクリレート、ビスフェノールＡポリプロポキシジ（メタ）アクリレート、ビスフェノールＦポリエトキシジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、ε-カプロラクトン変性トリス（２-ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロポキシ化ペンタエリスリトールトリ（メタ）アクリレート、エトキシ化ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、プロポキシ化ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、ヒドロキシビバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ヒドロキシビバリン酸ネオペングリコールのε－カプロラクトン付加物のジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等の紫外線硬化型の多官能モノマー類のほか、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエーテル（メタ）アクリレート等の多官能アクリルオリゴマー類を挙げることができる。 Examples of such polyfunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. ) Acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxydi (meth) Acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ε-caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxy Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (me ) Acrylate, tripentaerythritol penta (meth) acrylate, hydroxybivalic acid neopentyl glycol di (meth) acrylate, di- (meth) acrylate of ε-caprolactone adduct of hydroxybivalic acid neopentglycol, trimethylolpropane tri ( In addition to UV-curable polyfunctional monomers such as (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane ( Mention may be made of polyfunctional acrylic oligomers such as (meth) acrylates and polyether (meth) acrylates.
　上記に挙げた中でも、被着体への密着性や湿熱白化抑制の効果を向上させる観点から、水酸基等の極性官能基を含有する多官能モノマーもしくはオリゴマーが、好ましい。
　その中でも、水酸基を有する多官能（メタ）アクリル酸エステルを用いるのが好ましい。
　よって、湿熱白化を防止する観点からは、前記アクリル系共重合体（Ａ）、すなわちグラフト共重合体の幹成分として、疎水性のアクリレートモノマーと、親水性のアクリレートモノマーとを含有するのが好ましく、さらには、架橋剤（Ｂ）として、水酸基を有する多官能（メタ）アクリル酸エステルを用いるのが好ましい。 Among the examples mentioned above, a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group is preferable from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the heat and whitening.
Among these, it is preferable to use polyfunctional (meth) acrylic acid ester having a hydroxyl group.
Therefore, from the viewpoint of preventing wet heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a backbone component of the acrylic copolymer (A), that is, the graft copolymer. Furthermore, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group as the crosslinking agent (B).
　架橋剤（Ｂ）の含有量は、特に制限されるものではない。目安としては、アクリル系共重合体（Ａ）１００質量部に対して０．５～２０質量部、中でも１質量部以上或いは１５質量部以下、その中でも２質量部以上或いは１０質量部以下の割合であるのが好ましい。
　架橋剤（Ｂ）を上記範囲で含有することで、未架橋状態における本粘着材の形状安定性と、架橋後の粘着材における耐発泡信頼性とを両立させることができる。但し、他の要素とのバランスでこの範囲を超えてもよい。 The content of the crosslinking agent (B) is not particularly limited. As a guideline, the ratio of 0.5 to 20 parts by weight, particularly 1 part or more or 15 parts by weight or less, particularly 2 parts or more or 10 parts by weight or less based on 100 parts by weight of the acrylic copolymer (A). Is preferred.
By containing a crosslinking agent (B) in the said range, the shape stability of this adhesive material in an uncrosslinked state and the anti-foaming reliability in the adhesive material after bridge | crosslinking can be made compatible. However, this range may be exceeded in balance with other elements.
＜光重合開始剤（Ｃ）＞
　光重合開始剤（Ｃ）は、前述の架橋剤（Ｂ）の架橋反応における反応開始助剤としての機能を果たす。光重合開始剤は、現在公知のものを適宜使用することができる。中でも、波長３８０ｎｍ以下の紫外線に感応する光重合開始剤が、架橋反応の制御のしやすさの観点から好ましい。 <Photopolymerization initiator (C)>
The photopolymerization initiator (C) functions as a reaction initiation assistant in the crosslinking reaction of the aforementioned crosslinking agent (B). As the photopolymerization initiator, those currently known can be used as appropriate. Among these, a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
　光重合開始剤は、ラジカル発生機構によって大きく２つに分類され、光重合性開始剤自身の単結合を開裂分解してラジカルを発生させることができる開裂型光重合開始剤と、光励起した開始剤と系中の水素供与体とが励起錯体を形成し、水素供与体の水素を転移させることができる水素引抜型光重合開始剤と、に大別される。 Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
　これらのうちの開裂型光重合開始剤は、光照射によってラジカルを発生する際に分解して別の化合物となり、一度励起されると反応開始剤としての機能をもたなくなる。このため、架橋反応が終了した後の粘着材中に活性種として残存することがなく、粘着材に予期せぬ光劣化等をもたらす可能性がないため、好ましい。
　他方、水素引抜型の光重合開始剤は、紫外線などの活性エネルギー線照射によるラジカル発生反応時に、開裂型光重合開始剤のような分解物を生じないので、反応終了後に揮発成分となりにくく、被着体へのダメージを低減させることができる点で有用である。 Among these, the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
On the other hand, a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. This is useful in that damage to the body can be reduced.
　前記開裂型光開始剤としては、例えば２,２-ジメトキシ-１,２-ジフェニルエタン-１-オン、１-ヒドロキシシクロヘキシルフェニルケトン、２-ヒドロキシ-２-メチル-１-フェニル-プロパン-１-オン、１-（４-（２-ヒドロキシエトキシ）フェニル）-２-ヒドロキシ-２-メチル-１-プロパン-１-オン、２-ヒロドキシ-１-［４-｛４-（２-ヒドロキシ-２-メチル-プロピオニル）ベンジル｝フェニル］-２-メチル-プロパン-１-オン、オリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）、フェニルグリオキシリック酸メチル、２-ベンジル-２-ジメチルアミノ-１-（４-モルフォリノフェニル）ブタン-１-オン、２-メチル-１-［４-（メチルチオ）フェニル］-２-モルフォリノプロパン-１-オン、２-(ジメチルアミノ)-２-[(４-メチルフェニル)メチル]-１-[４-(４-モルホリニル)フェニル]-１-ブタノン、ビス（２，４，６-トリメチルベンゾイル）-フェニルフォスフィンオキサイド、２，４，６-トリメチルベンゾイルジフェニルフォスフィンオキサイドや、それらの誘導体などを挙げることができる。 Examples of the cleavage type photoinitiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy-2 -Methyl-propionyl) benzyl} phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic Methyl acid, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2- (dimethylamino) -2-[( 4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide and derivatives thereof.
　前記水素引抜型光開始剤としては、例えばベンゾフェノン、４-メチル-ベンゾフェノン、２，４，６-トリメチルベンゾフェノン、４-フェニルベンゾフェノン、３，３‘-ジメチル-４-メトキシベンゾフェノン、２－ベンゾイル安息香酸メチル、ベンゾイルぎ酸メチル、ビス（２‐フェニル‐２‐オキソ酢酸）オキシビスエチレン、４-（１，３-アクリロイル-１，４，７，１０，１３-ペンタオキソトリデシル）ベンゾフェノン、チオキサントン、２-クロロチオキサントン、３-メチルチオキサントン、２，４-ジメチルチオキサントン、２-メチルアントラキノン、２-エチルアントラキノン、２-ｔｅｒｔ-ブチルアントラキノン、２-アミノアントラキノンやその誘導体などを挙げることができる。
　但し、光重合開始剤として前記に挙げた物質に限定するものではない。本粘着剤樹脂組成物は、開裂型光重合開始剤及び水素引抜型光重合開始剤のいずれか一種を使用してもよいし、両者を組み合わせて使用してもよい。 Examples of the hydrogen abstraction type photoinitiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2-benzoylbenzoic acid. Methyl, methyl benzoylformate, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone, Examples thereof include 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and derivatives thereof.
However, the photopolymerization initiator is not limited to the substances listed above. In the present adhesive resin composition, any one of a cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator may be used, or a combination of both may be used.
　光重合開始剤（Ｃ）の含有量は特に制限されるものではない。目安としては、アクリル系共重合体（Ａ）１００質量部に対して０．１～１０質量部、中でも０．５質量部以上或いは５質量部以下、その中でも１質量部以上或いは３質量部以下の割合で含有するのが好ましい。
　光重合開始剤（Ｃ）の含有量を上記範囲とすることで、活性エネルギー線に対する適度な反応感度を得ることができる。 The content of the photopolymerization initiator (C) is not particularly limited. As a guideline, 0.1 to 10 parts by weight, particularly 0.5 parts by weight or more and 5 parts by weight or less, and 1 part by weight or more or 3 parts by weight or less based on 100 parts by weight of the acrylic copolymer (A). It is preferable to contain in the ratio.
By setting the content of the photopolymerization initiator (C) in the above range, an appropriate reaction sensitivity with respect to the active energy ray can be obtained.
＜その他の成分（Ｄ）＞
　本粘着剤樹脂組成物は、上記以外の成分として、通常の粘着剤樹脂組成物に配合されている公知の成分を含有してもよい。例えば、必要に応じて、粘着付与樹脂や、酸化防止剤、光安定化剤、金属不活性化剤、老化防止剤、吸湿剤などの各種の添加剤を適宜含有させることが可能である。
　また、必要に応じて反応触媒（三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物など）を適宜含有してもよい。 <Other components (D)>
This adhesive resin composition may contain the well-known component mix | blended with the normal adhesive resin composition as components other than the above. For example, as necessary, various additives such as a tackifier resin, an antioxidant, a light stabilizer, a metal deactivator, an anti-aging agent, and a hygroscopic agent can be appropriately contained.
Moreover, you may contain reaction catalyst (A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.) suitably as needed.
＜本画像表示装置構成用積層体の製造方法＞
　本画像表示装置構成用積層体の製造方法は、少なくとも次の（１）～（３）の工程を有することを特徴とする製造方法である。
（１）　上記の本粘着剤樹脂組成物を作製して、該粘着剤樹脂組成物からなる粘着層を備えた単層又は多層の透明両面粘着材（「本粘着材」と称する）をシート状に成形する工程（「工程（１）」と称する）。
（２）　前記本粘着材を介して２つの画像表示装置構成部材を貼着して積層する工程（「工程（２）」と称する）。
（３）　少なくとも一方の画像表示装置構成部材の外側から、活性エネルギー線を本粘着材の前記粘着層に照射し、当該粘着層を架橋させて、２つの画像表示装置構成部材を接着させる工程（「工程（３）」と称する）。 <Method for Producing Laminate for Configuring Image Display Device>
This method for producing a laminate for constituting an image display device is a production method characterized by having at least the following steps (1) to (3).
(1) The present pressure-sensitive adhesive resin composition is prepared, and a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material (referred to as “the present pressure-sensitive adhesive material”) having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition is formed into a sheet. The step of forming into (referred to as “step (1)”).
(2) A step of attaching and laminating two image display device constituent members via the present adhesive material (referred to as “step (2)”).
(3) A step of irradiating the adhesive layer of the present adhesive material with active energy rays from the outside of at least one of the image display device constituent members, cross-linking the adhesive layer, and bonding the two image display device constituent members ( (Referred to as “step (3)”).
　なお、本画像表示装置構成用積層体の製造方法は、少なくとも次の（１）～（３）の工程を有すればよいから、他の工程を追加したり、各工程の間に他の工程を挿入したりすることは可能である。 In addition, since the manufacturing method of the laminate for constituting the image display device only needs to include at least the following steps (1) to (3), other steps are added or other steps are performed between the steps. It is possible to insert.
＜工程（１）＞
　工程（１）では、本粘着剤樹脂組成物を作製して、該粘着剤樹脂組成物からなる粘着層を備えた単層又は多層の未架橋状態の透明両面粘着材（本粘着材）をシート状に成形する。
　本粘着剤樹脂組成物をシート状に成形する方法は、現在公知の方法を任意に採用することができる。
　この際、本粘着剤樹脂組成物を、離型フィルムの上に単層又は多層のシート状に成形して、粘着層を備えた単層又は多層の透明両面粘着材を作製するようにしてもよい。
　また、本粘着剤樹脂組成物を、画像表示装置構成部材の上に単層又は多層のシート状に成形して、当該画像表示装置構成部材上に、粘着層を備えた単層又は多層の透明両面粘着材を作製するようにしてもよい。 <Step (1)>
In step (1), the pressure-sensitive adhesive resin composition is prepared, and a single-layer or multilayer uncrosslinked transparent double-sided pressure-sensitive adhesive material (this pressure-sensitive adhesive material) provided with a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition is formed into a sheet. To form.
As a method for forming the pressure-sensitive adhesive resin composition into a sheet, a currently known method can be arbitrarily adopted.
At this time, the pressure-sensitive adhesive resin composition is formed into a single-layer or multilayer sheet on the release film to produce a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material having an adhesive layer. Good.
Further, the pressure-sensitive adhesive resin composition is molded into a single-layer or multilayer sheet on the image display device constituent member, and the single-layer or multi-layer transparent provided with the adhesive layer on the image display device constituent member. You may make it produce a double-sided adhesive material.
　本粘着材を多層の透明両面粘着材とする場合には、最外層は、上記単層の場合と同様に、凹凸追随性と耐発泡信頼性とを兼ね備えているのが好ましいから、上記の本粘着剤樹脂組成物を用いて成形するのが好ましい。 When the adhesive material is a multilayer transparent double-sided adhesive material, it is preferable that the outermost layer has both uneven followability and foam resistance reliability as in the case of the single layer. It is preferable to mold using an adhesive resin composition.
　他方、中間層は、画像表示装置構成部材との粘着には寄与しないため、透明性を損なわず、かつ最外層の２次硬化反応を阻害しない程度の光透過性を有し、かつ、カット性及びハンドリング性を高める性質を有しているのが好ましい。
　中間層を形成するベースポリマーの種類は、透明樹脂であれば、特に限定するものではない。中間層を形成するベースポリマーは、最外層のベースポリマーと同一の樹脂であっても異なる樹脂であってもよい。中でも、透明性の確保や作製し易さ、さらには積層境界面での光の屈折を防ぐ観点から、最外層のベースポリマーと同一のアクリル系樹脂を用いるのが好ましい。
　中間層及び他の樹脂層は、活性エネルギー線硬化性を有していてもいなくてもよい。例えば紫外線架橋によって硬化するように形成してもよいし、熱によって硬化するように形成してもよい。また、特に後硬化しないように形成してもよい。但し、最外層との密着性等を考慮すると、後硬化するように形成するのが好ましく、特に紫外線架橋するように形成するのが好ましい。
　その際、架橋開始剤の含有量が多くなると光透過率が低下するため、中間層における架橋開始剤の外層における含有率よりも低い含有率で紫外線架橋剤を含むのが好ましい。 On the other hand, since the intermediate layer does not contribute to adhesion with the image display device constituent member, it does not impair the transparency, and has a light transmittance that does not hinder the secondary curing reaction of the outermost layer, and has a cutting property. In addition, it preferably has a property of improving handling properties.
If the kind of base polymer which forms an intermediate | middle layer is transparent resin, it will not specifically limit. The base polymer forming the intermediate layer may be the same resin as the base polymer of the outermost layer or a different resin. Among these, it is preferable to use the same acrylic resin as the base polymer of the outermost layer from the viewpoints of ensuring transparency and ease of production, and preventing light refraction at the lamination boundary surface.
The intermediate layer and other resin layers may or may not have active energy ray curability. For example, it may be formed so as to be cured by ultraviolet crosslinking or may be formed so as to be cured by heat. Further, it may be formed so as not to be post-cured. However, in consideration of adhesion to the outermost layer, etc., it is preferably formed so as to be post-cured, and particularly preferably formed so as to be UV-crosslinked.
In that case, since light transmittance will fall, if content of a crosslinking initiator increases, it is preferable to contain a ultraviolet-ray crosslinking agent by the content rate lower than the content rate in the outer layer of the crosslinking initiator in an intermediate | middle layer.
　本粘着材を多層の透明両面粘着材とする場合、積層構成としては、具体的には、本粘着剤樹脂組成物と、他の粘着剤樹脂組成物とを積層した２種２層構成や、中間樹脂層を介して表裏に本粘着剤樹脂組成物を配した２種３層構成や、本粘着剤樹脂組成物と、中間樹脂組成物と、他の粘着剤樹脂組成物とをこの順に積層してなる３種３層構成などを挙げることができる。
　また、本粘着剤樹脂組成物と他の粘着剤樹脂組成物とを、それぞれ異なる離型フィルム乃至画像表示装置構成部材上にシート状に成形し、両粘着面を積層して本粘着材を得るようにしてもよいし、また、本粘着剤樹脂組成物と、中間樹脂組成物と、粘着剤樹脂組成物とを、この順に共押出して２種３層の本粘着材を得るようにしてもよいし、また、中間樹脂層の表裏面に本粘着剤樹脂組成物又は他の粘着剤樹脂組成物を積層して本粘着材を得るようにしてもよい。
　但し、これらの製法に限定するものではない。
　工程（１）において、透明両面粘着材は未架橋状態である。 When the present adhesive material is a multi-layer transparent double-sided adhesive material, as a laminated structure, specifically, a two-type two-layer structure in which the present adhesive resin composition and another adhesive resin composition are laminated, Two kinds of three-layer structure in which the present adhesive resin composition is arranged on the front and back through an intermediate resin layer, the present adhesive resin composition, an intermediate resin composition, and another adhesive resin composition are laminated in this order. 3 types, 3 layers structure etc. which are formed can be mentioned.
Further, the pressure-sensitive adhesive resin composition and another pressure-sensitive adhesive resin composition are formed into a sheet shape on different release films or image display device constituent members, and the pressure-sensitive adhesive material is obtained by laminating both pressure-sensitive adhesive surfaces. Alternatively, the pressure-sensitive adhesive resin composition, the intermediate resin composition, and the pressure-sensitive adhesive resin composition may be coextruded in this order to obtain a two-kind three-layer pressure-sensitive adhesive material. Alternatively, the pressure-sensitive adhesive material may be obtained by laminating the pressure-sensitive adhesive resin composition or another pressure-sensitive adhesive resin composition on the front and back surfaces of the intermediate resin layer.
However, it is not limited to these manufacturing methods.
In the step (1), the transparent double-sided pressure-sensitive adhesive material is in an uncrosslinked state.
（厚さ）
　本粘着材の総厚さは、５０μｍ～１ｍｍであるのが好ましく、より好ましくは７５μｍ以上或いは５００μｍ以下である。
　本粘着材の総厚さが５０μｍ以上であれば、高印刷段差等の凹凸への追従することが可能であり、１ｍｍ以下であれば、薄肉化の要求にこたえることができる。
　さらに、従来の画像表示装置における周縁の隠蔽層の印刷高さがより高く、具体的には８０μｍ程度の段差までをも埋める観点から、本粘着材の総厚さは７５μｍ以上がより好ましく、特に１００μｍ以上であるのがさらに好ましい。他方、薄肉化の要求にこたえる観点からは、５００μｍ以下であるのが好ましく、特に３５０μｍ以下であるのがさらに好ましい。 (thickness)
The total thickness of the present adhesive material is preferably 50 μm to 1 mm, more preferably 75 μm or more or 500 μm or less.
If the total thickness of the pressure-sensitive adhesive material is 50 μm or more, it is possible to follow unevenness such as a high printing level difference, and if it is 1 mm or less, the demand for thinning can be met.
Furthermore, the printing thickness of the peripheral concealing layer in the conventional image display device is higher, specifically, from the viewpoint of filling up to a level difference of about 80 μm, the total thickness of the present adhesive material is more preferably 75 μm or more. More preferably, it is 100 μm or more. On the other hand, from the viewpoint of meeting the demand for thinning, it is preferably 500 μm or less, more preferably 350 μm or less.
　多層構成とする場合には、各最外層の厚さと中間層の厚さの比率は１：１～１：２０であるのが好ましく、中でも１：２～１：１０であるのがさらに好ましい。
　中間層の厚みが、上記範囲であれば、積層体における粘着材層の厚みの寄与が大きくなりすぎず、柔軟すぎて裁断や取回しに係る作業性が劣るようになることがなく好ましい。
　また、最外層が上記範囲であれば、凹凸や屈曲した面への追随性に劣ることがなく、被着体への接着力や濡れ性を維持することができて、好ましい。 In the case of a multilayer structure, the ratio of the thickness of each outermost layer to the thickness of the intermediate layer is preferably 1: 1 to 1:20, and more preferably 1: 2 to 1:10.
If the thickness of the intermediate layer is within the above range, the contribution of the thickness of the pressure-sensitive adhesive layer in the laminate is not too large, and it is preferable that the workability relating to cutting and handling is not deteriorated because it is too flexible.
In addition, if the outermost layer is in the above range, it is preferable because the adhesion to the adherend and the wettability can be maintained without being inferior in conformity to unevenness and a bent surface.
（本粘着材の特徴）
　本粘着材は、単層のものも多層構成のものもいずれも、透明で、通常状態でシート状に形状を保持できており、かつ接着性を備えている。また、本粘着材を加熱して粘着層を流動化させることによって、粘着材内に歪みを残すことなく、貼合面の段差部に追従して隅々まで充填することができ、さらには、架橋することによって高温や高湿環境下での耐発泡性を維持することができる。
　よって、本粘着材を用いて、次の工程（２）～（３）を実現して本画像表示装置構成用積層体を製造することができる。 (Features of this adhesive)
The present pressure-sensitive adhesive material, both of a single layer and a multilayer structure, is transparent, can maintain a shape in a sheet shape in a normal state, and has adhesiveness. In addition, by heating the pressure-sensitive adhesive material and fluidizing the pressure-sensitive adhesive layer, it is possible to fill in every corner following the stepped portion of the bonding surface without leaving any distortion in the pressure-sensitive adhesive material. By cross-linking, it is possible to maintain foam resistance under high temperature and high humidity environment.
Therefore, using this pressure-sensitive adhesive material, the following steps (2) to (3) can be realized to produce the laminate for constituting the image display device.
　本粘着材の透明性は、本粘着剤樹脂組成物を、厚さ１５０μｍのシート状に賦形して、ソーダライムガラス（０．５ｍｍ厚）とシクロオレフィンポリマーフィルム（１００μｍ厚）との間に挟んだ積層体のヘイズ（ＪＩＳ　Ｋ７１３６）を１０％未満、中でも５％以下、中でも２％以下とすることができる。 Transparency of the adhesive material is determined by shaping the adhesive resin composition into a 150 μm thick sheet between soda lime glass (0.5 mm thickness) and a cycloolefin polymer film (100 μm thickness). The haze (JIS K7136) of the sandwiched laminate can be made less than 10%, especially 5% or less, especially 2% or less.
　また、湿熱保管後の透明性については、本粘着剤樹脂組成物を厚さ１５０μｍのシート状に賦形して、ソーダライムガラス（０．５ｍｍ厚）とシクロオレフィンポリマーフィルム（１００μｍ厚）との間に挟んだ積層体を、紫外線照射して硬化した後に６５℃、９０％ＲＨの湿熱環境下にて１００時間保管した後、２３℃、５０％ＲＨの室温環境下にて２時間保管した後のヘイズ（ＪＩＳ　Ｋ７１３６）を１０％未満、中でも５％以下、中でも２％以下とすることができる。 For transparency after wet heat storage, the pressure-sensitive adhesive resin composition is shaped into a sheet having a thickness of 150 μm, soda lime glass (0.5 mm thickness) and cycloolefin polymer film (100 μm thickness). After being cured by irradiating with ultraviolet rays, the laminate sandwiched between the layers was stored in a moist heat environment of 65 ° C. and 90% RH for 100 hours, and then stored for 2 hours in a room temperature environment of 23 ° C. and 50% RH. Haze (JIS K7136) can be less than 10%, especially 5% or less, especially 2% or less.
　また、本粘着材は、ＪＩＳ－Ｚ－０２３７（ＩＳＯ　２９８６３）に準じた保持力測定において、ＳＵＳ板に面積２０ｍｍ×２０ｍｍで貼着させ、４０℃の雰囲気下で５００ｇｆの荷重をかけた時の落下時間が２０分以上であり、且つ、７０℃の雰囲気下で５００ｇｆの荷重をかけた時の落下時間が５分未満であるものとすることができる。
　この際、４０℃の雰囲気下での当該落下時間は４０分以上であるのがさらに好ましく、中でも６０分以上であるのさらに好ましい。
　他方、７０℃の雰囲気下での当該落下時間は３分以下であるのがさらに好ましく、中でも２分以下であるのさらに好ましい。 In addition, this adhesive material was bonded to a SUS plate with an area of 20 mm × 20 mm in a holding power measurement according to JIS-Z-0237 (ISO 29863), and a load of 500 gf was applied in an atmosphere of 40 ° C. The drop time can be 20 minutes or more, and the drop time when a load of 500 gf is applied in an atmosphere at 70 ° C. can be less than 5 minutes.
At this time, the dropping time in an atmosphere of 40 ° C. is more preferably 40 minutes or longer, and more preferably 60 minutes or longer.
On the other hand, the dropping time in an atmosphere at 70 ° C. is more preferably 3 minutes or less, and more preferably 2 minutes or less.
＜工程（２）＞
　工程（２）では、前記本粘着材を介して２つの画像表示装置構成部材を貼着して積層することができる。 <Step (2)>
In the step (2), two image display device constituent members can be adhered and laminated through the present adhesive material.
　本粘着材のベースポリマーであるアクリル系共重合体（Ａ）は、マクロモノマーを枝成分として含有するグラフト共重合体であるから、通常状態、すなわち室温状態で、当該マクロモノマー同士が凝集して物理的架橋構造を形成し、本粘着材に優れた保管安定性や裁断加工性を付与することができる。
　また、アクリル系共重合体（Ａ）は、温度１３０℃、周波数０．０２Ｈｚにおける複素粘度が１００～８００Ｐａ・ｓであるから、貼合時にホットメルトシートとして用いる際、優れた作業性を享受することができる。 Since the acrylic copolymer (A) that is the base polymer of the present adhesive material is a graft copolymer containing a macromonomer as a branch component, the macromonomer aggregates in a normal state, that is, at room temperature. A physical cross-linked structure can be formed, and excellent storage stability and cutting processability can be imparted to the present adhesive material.
In addition, since the acrylic copolymer (A) has a complex viscosity of 100 to 800 Pa · s at a temperature of 130 ° C. and a frequency of 0.02 Hz, it enjoys excellent workability when used as a hot melt sheet during bonding. be able to.
　このように工程（２）では、本粘着材を介して２つの画像表示装置構成部材を貼着して積層することができる。このようにすれば、本粘着材を被着体に押し付けるだけで簡単に貼りつく程度の粘着性を得ることができるから、粘着材を貼着する位置決めがしやすく、作業上とても便利である。 Thus, in the step (2), two image display device constituent members can be adhered and laminated through the present adhesive material. In this way, it is possible to obtain a degree of adhesiveness that can be easily attached by simply pressing the present adhesive material against the adherend. Therefore, it is easy to position the adhesive material and it is very convenient for work.
　また、本粘着材は、形状保持性に優れ、事前に任意の形状に加工しておくことが可能であることから、離型フィルム上に成形した本粘着材を、積層する画像表示装置構成部材の寸法に合わせて予めカットしておくこともできる。
　この際のカット方法は、トムソン刃による打ち抜き、スーパーカッターやレーザーでのカットが一般的であり、離型フィルムを剥がし易いように表裏どちらか一方の離型フィルムを額縁状に残してハーフカットするのがより好ましい。
　工程（２）においても、本粘着材、すなわち透明両面粘着材は未架橋状態である。 In addition, since the present adhesive material is excellent in shape retention and can be processed into an arbitrary shape in advance, an image display device constituent member for laminating the present adhesive material formed on a release film It can also be cut in advance according to the dimensions.
The cutting method at this time is generally punched with a Thomson blade, cut with a super cutter or laser, and half-cuts leaving either the front or back release film in a frame shape so that the release film can be easily peeled off. Is more preferable.
Also in the step (2), the present adhesive material, that is, the transparent double-sided adhesive material is in an uncrosslinked state.
＜工程（３）＞
　工程（３）では、少なくとも一方の画像表示装置構成部材の外側から、活性エネルギー線を本粘着材の前記粘着層に照射し、当該粘着層を架橋させて、２つの画像表示装置構成部材を接着させて、本画像表示装置構成用積層体を製造することができる。 <Step (3)>
In step (3), the adhesive layer of the present adhesive material is irradiated with active energy rays from the outside of at least one of the image display device constituent members, the adhesive layer is crosslinked, and the two image display device constituent members are bonded. Thus, the laminate for constituting the image display device can be manufactured.
　本粘着材は、架橋剤（Ｂ）及び光重合開始剤（Ｃ）を含有しているから、活性エネルギー線を本粘着材の前記粘着層に照射し、当該粘着層を架橋させて硬化させることができ、２つの画像表示装置構成部材をしっかりと貼着することができる。 Since the present adhesive material contains a crosslinking agent (B) and a photopolymerization initiator (C), the adhesive layer of the present adhesive material is irradiated with active energy rays, and the adhesive layer is crosslinked and cured. The two image display device constituent members can be firmly attached.
　この際、活性エネルギー線としては、熱線、Ｘ線、電子線、紫外線、可視光線等の、重合開始剤を感応せしめるエネルギー線を照射すればよい。中でも、画像表示装置構成部材へのダメージ抑制や、反応制御のしやすさの観点から、紫外線、とくに波長３８０ｎｍ以下の紫外線を照射するのが好ましい。
　紫外線照射条件について特に制約はない。例えば、粘着材に到達する紫外線の積算光量が、波長３６５ｎｍにおいて５００～５０００ｍＪ/ｃｍ２となるよう照射するのが好ましい。作業性を保持しつつ、十分に架橋反応を進行させる観点からである。
　但し、紫外線を照射する際に介在する画像表示装置構成部材が、上記波長の光線を遮断する場合は、介在する部材に合わせて、粘着材が感応するエネルギー線の種類を、重合開始剤の種類によって適宜調整するのが好ましい。 In this case, as the active energy ray, an energy ray that sensitizes the polymerization initiator, such as a heat ray, an X-ray, an electron beam, an ultraviolet ray, or a visible ray, may be irradiated. Among them, it is preferable to irradiate ultraviolet rays, particularly ultraviolet rays having a wavelength of 380 nm or less, from the viewpoints of suppressing damage to the image display device constituent members and facilitating reaction control.
There are no particular restrictions on the UV irradiation conditions. For example, it is preferable to irradiate such that the cumulative amount of ultraviolet light reaching the adhesive material is 500 to 5000 mJ / cm 2 at a wavelength of 365 nm. This is from the viewpoint of sufficiently promoting the crosslinking reaction while maintaining workability.
However, when the constituent elements of the image display device that are interposed when irradiating ultraviolet rays block the light beam having the above wavelength, the type of energy rays to which the adhesive material is sensitive in accordance with the interposed member is the type of polymerization initiator. It is preferable to adjust as appropriate.
　本工程（３）において、前記粘着層に照射して架橋させた後の粘着層すなわち該粘着層を形成する透明両面粘着材は、ＪＩＳ－Ｚ－０２３７（ＩＳＯ　２９８６３）に準じた保持力測定において、ＳＵＳ板に面積２０ｍｍ×２０ｍｍで貼着させ、４０℃および７０℃の雰囲気下で５００ｇｆの荷重をかけた時の３０分後のズレ長さが１ｍｍ未満とすることができる。
　この際、前記ズレ長さを０．８ｍｍ以下とするのがさらに好ましく、中でも０．５ｍｍ以下とするのがさらに好ましい。 In this step (3), the pressure-sensitive adhesive layer after irradiation of the pressure-sensitive adhesive layer, that is, the transparent double-sided pressure-sensitive adhesive material that forms the pressure-sensitive adhesive layer, is measured in holding power according to JIS-Z-0237 (ISO 29863). The deviation length after 30 minutes when a load of 500 gf is applied in an atmosphere of 40 ° C. and 70 ° C. can be made less than 1 mm.
At this time, the shift length is more preferably 0.8 mm or less, and more preferably 0.5 mm or less.
＜他の工程＞
　前記工程（２）と前記工程（３）の間に、前記工程（２）で得られた積層物を加熱して透明両面粘着材の粘着層を加熱溶融させる工程を挿入するようにしてもよい。すなわち、工程（２）で貼着した積層物を加熱して本粘着材の粘着層を加熱溶融（ホットメルト）させるようにしてもよい。 <Other processes>
Between the step (2) and the step (3), a step of heating and melting the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive material by heating the laminate obtained in the step (2) may be inserted. . That is, the adhesive layer of the present adhesive material may be heated and melted (hot melted) by heating the laminate adhered in the step (2).
　本粘着材は、加熱すると、マクロモノマー同士の前記凝集が解れて物理的架橋構造が解消して高い流動性を発現させることができる。よって、着面に印刷段差等の凹凸がある場合には、２つの画像表示装置構成部材を積層する際に、本粘着材を加熱して流動（ホットメルト）させることで、粘着材の凹凸追従性や被着体への濡れ性が高まり、歪みを残さず、部材同士をより強固に一体化させることができる。 When the adhesive is heated, the aggregation of the macromonomers is released, the physical cross-linking structure is eliminated, and high fluidity can be exhibited. Therefore, if there are irregularities such as printing steps on the wearing surface, when laminating two image display device components, this adhesive material is heated to flow (hot melt) to follow the irregularities of the adhesive material. And wettability to the adherend are increased, and the members can be more firmly integrated without leaving any distortion.
　この際、６０～１００℃に加熱してホットメルトさせるのが好ましい。６０℃以上であれば、粘着材の流動性を十分に付与することができ、凹凸部へ十分に粘着剤樹脂組成物を充填させることができる。他方、１００℃以下であれば、被着体たる画像表示装置構成部材に熱ダメージを与えるのを抑えることができるばかりか、粘着材が流動し過ぎて粘着剤樹脂組成物のはみだしや潰れが生じることを防ぐこともできる。
　このような観点から、ホットメルト温度は、６０～１００℃であるのが好ましく、中でも６２℃以上或いは９５℃以下、その中でも６５℃以上或いは９０℃以下であるのがさらに好ましい。 At this time, it is preferable to perform hot melt by heating to 60 to 100 ° C. If it is 60 degreeC or more, the fluidity | liquidity of an adhesive material can fully be provided and an adhesive resin composition can fully be filled to an uneven | corrugated | grooved part. On the other hand, if it is 100 ° C. or less, not only can the thermal damage to the image display device constituting member to be adhered be suppressed, but also the adhesive material flows too much and the adhesive resin composition is protruded and crushed. Can also be prevented.
From such a viewpoint, the hot melt temperature is preferably 60 to 100 ° C., more preferably 62 ° C. or more and 95 ° C. or less, and particularly preferably 65 ° C. or more and 90 ° C. or less.
＜本画像表示装置構成用積層体＞
　本画像表示装置構成用積層体としては、例えばパソコン、モバイル端末（ＰＤＡ）、ゲーム機、テレビ（ＴＶ）、カーナビ、タッチパネル、ペンタブレットなど、ＬＣＤ、ＰＤＰ又はＥＬなどの画像表示パネルを用いた平面型画像表示装置の構成部材を挙げることができる。
　中でも、これら画像表示パネルと、保護パネルやタッチパネル等の透明パネル乃至フィルム部材とを粘着材を介して貼り合わせてなる構成を備えた画像表示装置構成用積層体を挙げることができる。 <Laminated body for configuring the present image display device>
Examples of the laminate for constituting the image display device include a plane using an image display panel such as an LCD, PDP, or EL, such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet. The structural member of a type | mold image display apparatus can be mentioned.
Among them, there can be mentioned a laminate for constituting an image display device having a construction in which these image display panels and a transparent panel or a film member such as a protective panel or a touch panel are bonded together with an adhesive material.
　例えば、携帯電話の表示画面などでは、タッチパネルフィルム等の機能性フィルム上にシート状の粘着材を介して表面保護パネルを積層する構成が採用されている。この際、該保護パネルの裏面には、周縁部に隠蔽用印刷部（厚さ５μｍ～８０μｍ程度）が付設され、隠蔽用印刷部の縁に形成される段差部の入隅部内にまで粘着剤が十分に入り込まないと、気泡が残留して画面の視認性が低下することになる。また、段差近傍でフィルム部材が屈曲して外観不良となったり、フィルムの屈曲による残留歪が起点となって、積層した部材間に発泡や剥離が起こったりするおそれがあった。
　本粘着材は、このような５μｍ～３０μｍ程度の段差はもちろん、３０～８０μｍ程度の段差があっても、段差の隅々まで充填して気泡を残留させることなく貼着することができる。しかも、たとえ被着体の一方が屈曲性をもつフィルム部材であったとしても、当該粘着材をホットメルトさせることで、表面を歪みなく平滑に均す事が可能であるため、フィルム部材に歪や変形を生じさせずに、部材を貼合一体化することができる。さらには、貼合後に粘着材を架橋することで、例えば８５℃程度の高温環境下においても、粘着材は流動せずに高凝集力を維持できることから、耐発泡信頼性を得ることができる。 For example, in a display screen of a mobile phone, a configuration in which a surface protection panel is laminated on a functional film such as a touch panel film via a sheet-like adhesive material is employed. At this time, a concealing printing portion (thickness of about 5 μm to 80 μm) is attached to the back surface of the protective panel, and the adhesive is provided even in the corner of the step portion formed at the edge of the concealing printing portion. If the liquid does not enter sufficiently, bubbles remain and the visibility of the screen decreases. In addition, the film member may be bent in the vicinity of the step, resulting in poor appearance, or residual strain due to the bending of the film may be a starting point, and foaming or peeling may occur between the stacked members.
This pressure-sensitive adhesive material can be stuck without filling up every corner of the step and leaving bubbles even if there is a step of about 30 to 80 μm as well as a step of about 5 to 30 μm. Moreover, even if one of the adherends is a flexible film member, it is possible to smooth the surface without distortion by hot-melting the adhesive material. The members can be bonded and integrated without causing deformation. Furthermore, by cross-linking the adhesive material after bonding, the adhesive material can maintain high cohesive force without flowing even under a high temperature environment of, for example, about 85 ° C., so that foaming reliability can be obtained.
　なお、一般的に「シート」とは、ＪＩＳにおける定義上、薄く、その厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう（日本工業規格ＪＩＳ　Ｋ６９００）。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
　また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シートおよびフィルムを包含するものである。
　また、本発明において、「貼着」とは、粘着材が有する自己粘着性によって、すなわち粘着材が未架橋状態で被着体を固定する状態を示し、例えば一時的に被着体を固定する状態や剥離可能に被着体を固定する状態などを包含する。他方、「接着」とは、粘着剤を架橋することによって、該粘着剤を化学的もしくは物理的に変化させた状態で被着体を固定する状態を示し、例えば被着体との界面に高い接合力を発現せしめた状態や、被着体を剥離困難な状態に固定するなどを包含する。 In general, “sheet” refers to a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width. In general, “film” is compared to the length and width. It is a thin flat product whose thickness is extremely small and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
In addition, the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet, and a film.
Further, in the present invention, “sticking” refers to a state in which the adherend is fixed by the self-adhesive property of the adhesive material, that is, the adhesive material is in an uncrosslinked state, for example, temporarily fixing the adherend. It includes a state and a state where the adherend is fixed so as to be peelable. On the other hand, “adhesion” refers to a state in which the adherend is fixed in a state where the pressure-sensitive adhesive is chemically or physically changed by crosslinking the pressure-sensitive adhesive. For example, it is high at the interface with the adherend. This includes a state in which a bonding force is expressed and a case where the adherend is fixed in a state in which peeling is difficult.
　本明細書において、「Ｘ～Ｙ」（Ｘ，Ｙは任意の数字）と記載した場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含するものである。
　また、「Ｘ以上」（Ｘは任意の数字）と記載した場合、特にことわらない限り「好ましくはＸより大きい」の意を包含し、「Ｙ以下」（Ｙは任意の数字）と記載した場合、特にことわらない限り「好ましくはＹより小さい」の意も包含するものである。 In the present specification, when “X to Y” (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included.
Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case, unless otherwise specified, the meaning of “preferably smaller than Y” is also included.
　以下、実施例及び比較例によりさらに詳しく説明する。但し、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these.
［実施例１］
　アクリル系共重合体（Ａ）として、数平均分子量２４００のポリメタクリル酸メチルマクロモノマー１５重量部とブチルアクリレート８１重量部とアクリル酸４重量部とがランダム共重合してなるアクリル酸エステル共重合体（Ａ－１）（重量平均分子量２３万）１ｋｇに対し、架橋剤（Ｂ）として、トリメチロールプロパンエポキシアクリレート（ＥＡ５３２１　新中村化学工業社製）（Ｂ－１）１００ｇと、光重合開始剤（Ｃ）としてのジフェニル－２，４，６－トリメチルベンゾイルホスフィンオキサイド（オムニラッドＴＰＯ　ＩＧＭ社製）（Ｃ－１）１５ｇを均一混合し、粘着剤樹脂組成物を作製した。
　前記組成物を剥離処理した２枚のポリエチレンテレフタレートフィルム（「剥離フィルム」と称する。三菱樹脂社製　ダイアホイルＭＲＶ－Ｖ０６　厚さ１００μｍ／三菱樹脂社製　ダイアホイルＭＲＱ　厚さ７５μｍ）で挟み、ラミネータを用いて厚さ１５０μｍとなるようシート状に賦形して、粘着材１を作製した。 [Example 1]
As the acrylic copolymer (A), an acrylic ester copolymer obtained by random copolymerization of 15 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 2400, 81 parts by weight of butyl acrylate, and 4 parts by weight of acrylic acid. (A-1) 1 kg (weight average molecular weight 230,000), 100 g of trimethylolpropane epoxy acrylate (EA5321 Shin-Nakamura Chemical Co., Ltd.) (B-1) as a crosslinking agent (B), a photopolymerization initiator ( Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (manufactured by Omnirad TPO IGM) (C-1) (C-1) as C) was uniformly mixed to prepare an adhesive resin composition.
A laminator was sandwiched between two polyethylene terephthalate films (referred to as “release films”) from which the above composition was peeled off (Diafoil MLV-V06, Mitsubishi Plastics, Inc., 100 μm thick / Diafoil MRQ, Mitsubishi Plastics, 75 μm thick) It was shaped into a sheet shape so as to have a thickness of 150 μm, and an adhesive material 1 was produced.
　６０ｍｍ×９０ｍｍ×厚さ０．５ｍｍのソーダライムガラスの周縁部に、幅１０ｍｍ、厚み４０μｍの白色の印刷（全光線透過率０％）を施し、周縁部に４０μｍの印刷段差をもつ評価用ガラス基板を作製した。この評価用ガラス基板は、段差部及び平坦面部を貼合面に有する画像表示装置構成部材の代替品である。
　この評価用ガラス基板に貼合する試験用被着体として、画像表示装置構成部材としての偏光板（日東電工株式会社製「ＮＷＦ－ＫＤＳＥＧＨＣ－ＳＴ２２」）を、予めガラス板上（６０×９０ｍｍ×ｔ０．５ｍｍ）の片面に全面貼合したものを作製した。 Evaluation glass with white printing (total light transmittance of 0%) with a width of 10 mm and a thickness of 40 μm on the periphery of soda lime glass of 60 mm × 90 mm × thickness 0.5 mm, and a printing step of 40 μm on the periphery A substrate was produced. This glass substrate for evaluation is a substitute for an image display device constituent member having a stepped portion and a flat surface portion on the bonding surface.
As a test adherend to be bonded to the glass substrate for evaluation, a polarizing plate (“NWF-KDSEGHC-ST22” manufactured by Nitto Denko Corporation) as an image display device constituent member is previously placed on a glass plate (60 × 90 mm × What was bonded to the whole surface on one side (t0.5 mm) was produced.
　前記粘着材１の一方の剥離フィルムを剥がし、露出した粘着面を上記ガラス基板の印刷段差部を覆うようにハンドローラにて貼着した。次いで、残る剥離フィルムを剥がし、露出した粘着面に未処理のソーダライムガラスを減圧下（絶対圧５ｋＰa）にてプレス貼合した後、オートクレーブ処理（６０℃、ゲージ圧０．２ＭＰａ、２０分）を施して仕上げ貼着し、ソーダライムガラス面から、波長３６５ｎｍの積算光量が２０００ｍＪ／ｃｍ２となるように粘着材１に紫外線を照射して架橋させ、画像表示装置構成用積層体を作製した。 One release film of the pressure-sensitive adhesive material 1 was peeled off, and the exposed pressure-sensitive adhesive surface was stuck with a hand roller so as to cover the printing step portion of the glass substrate. Next, the remaining release film is peeled off, and untreated soda lime glass is press bonded under reduced pressure (absolute pressure 5 kPa) to the exposed adhesive surface, followed by autoclaving (60 ° C., gauge pressure 0.2 MPa, 20 minutes). The adhesive material 1 was irradiated with ultraviolet rays and cross-linked so that the cumulative amount of light at a wavelength of 365 nm was 2000 mJ / cm 2 from the soda lime glass surface, and a laminate for constituting an image display device was produced. .
　なお、アクリル酸エステル共重合体（Ａ－１）は、枝成分としてポリメタクリル酸メチルマクロモノマーを備え、幹成分として、ブチルアクリレートと、アクリル酸と、マクロモノマーの末端の重合性官能基であるメタクリロイル基とがランダム共重合してなる共重合成分を備えたグラフト共重合体である。
　アクリル酸エステル共重合体（Ａ－１）の幹成分を構成する共重合体成分のガラス転移温度（当該共重合体成分をポリマー化して得られるポリマーの理論値で求められるガラス転移温度）は－５０℃であった。
　アクリル酸エステル共重合体（Ａ－１）の枝成分を構成するポリメタクリル酸メチルマクロモノマーの数平均分子量は２４００であり、該マクロモノマーのガラス転移温度は６０℃であり、該マクロモノマーは、アクリル酸エステル共重合体（Ａ－１）中に１５質量％の割合で含有されていた。
　アクリル系共重合体（Ａ）は、温度１３０℃、周波数０．０２Ｈｚにおける複素粘度が２６０Ｐａ・ｓであった。 The acrylic ester copolymer (A-1) comprises a polymethyl methacrylate macromonomer as a branch component, and butyl acrylate, acrylic acid, and a polymerizable functional group at the end of the macromonomer as a trunk component. It is a graft copolymer provided with a copolymerization component formed by random copolymerization with a methacryloyl group.
The glass transition temperature of the copolymer component constituting the backbone component of the acrylate copolymer (A-1) (the glass transition temperature determined from the theoretical value of the polymer obtained by polymerizing the copolymer component) is − It was 50 ° C.
The number average molecular weight of the polymethyl methacrylate macromonomer constituting the branch component of the acrylic ester copolymer (A-1) is 2400, the glass transition temperature of the macromonomer is 60 ° C., The acrylate copolymer (A-1) contained 15% by mass.
The acrylic copolymer (A) had a complex viscosity of 260 Pa · s at a temperature of 130 ° C. and a frequency of 0.02 Hz.
［実施例２］
　架橋剤（Ｂ）としてグリセリンジメタクリレート（Ｇ１０１Ｐ　共栄社化学社製）（Ｂ－２）１００ｇを用いる以外は、粘着材１と同様にして厚さ１５０μｍのシート状の粘着材２を作製した。
　そして、この粘着材２を用いて実施例１と同様に画像表示装置構成用積層体を作製した。 [Example 2]
A sheet-like pressure-sensitive adhesive material 2 having a thickness of 150 μm was prepared in the same manner as the pressure-sensitive adhesive material 1 except that 100 g of glycerin dimethacrylate (G101P manufactured by Kyoeisha Chemical Co., Ltd.) (B-2) was used as the crosslinking agent (B).
And the laminated body for image display apparatus structure was produced similarly to Example 1 using this adhesive material 2. FIG.
［比較例１］
　マクロモノマーを有さないアクリル系共重合体を用いて粘着材３を作製した。すなわち、アクリル系共重合体（Ａ）として、メタクリル酸メチル２０重量部とブチルアクリレート８０重量部とをランダム共重合してなるアクリル酸エステル共重合体（Ａ－２）（重量平均分子量４０万）を用いる以外は、粘着材１と同様にして厚さ１５０μｍのシート状の粘着材３を作製した。
　そして、この粘着材３を用いて実施例１と同様に画像表示装置構成用積層体を作製した。 [Comparative Example 1]
An adhesive material 3 was prepared using an acrylic copolymer having no macromonomer. That is, an acrylic ester copolymer (A-2) obtained by random copolymerization of 20 parts by weight of methyl methacrylate and 80 parts by weight of butyl acrylate as the acrylic copolymer (A) (weight average molecular weight 400,000) A sheet-like pressure-sensitive adhesive material 3 having a thickness of 150 μm was produced in the same manner as the pressure-sensitive adhesive material 1 except that.
And the laminated body for image display apparatus structure was produced like Example 1 using this adhesive material 3. FIG.
［比較例２］
　特許４９７１５２９号公報の実施例３に準じて粘着材４を作製した。
　すなわち、２－エチルヘキシルアクリレート７５質量部と酢酸ビニル２０質量部とアクリル酸５質量部とをランダム共重合してなるアクリル酸エステル共重合体前記アクリル酸エステル共重合体（Ａ－３）１ｋｇに、架橋剤（Ｂ）としてノナンジオールジアクリレート（ビスコート２６０　大阪有機化学社製）（Ｂ－３）５０ｇ及び光重合開始剤（Ｃ）として４－メチルベンゾフェノン（Ｃ－３）１０ｇを混合添加して粘着剤樹脂組成物を調製した。
　前記粘着剤樹脂組成物を剥離処理した２枚のポリエチレンテレフタレートフィルム（三菱樹脂社製　ダイアホイルＭＲＶ－Ｖ０６　厚さ１００μｍ／三菱樹脂社製　ダイアホイルＭＲＱ　厚さ７５μｍ）で挟み、ラミネータを用いて厚さ１５０μｍとなるようシート状に賦形した。続いて、ポリエチレンテレフタレートフィルムを介して、粘着層に波長３６５ｎｍの紫外線が１０００ｍＪ／ｃｍ２到達するよう紫外線を照射し、架橋剤を一部反応させて、粘着材４（厚さ１５０μｍ）を作製した。
　そして、この粘着材４を用いて実施例１と同様に画像表示装置構成用積層体を作製した。 [Comparative Example 2]
An adhesive material 4 was produced according to Example 3 of Japanese Patent No. 4971529.
That is, an acrylic ester copolymer obtained by random copolymerization of 75 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate and 5 parts by mass of acrylic acid, into 1 kg of the acrylic ester copolymer (A-3), Nonanediol diacrylate (Biscoat 260 manufactured by Osaka Organic Chemical Co., Ltd.) (B-3) 50 g as a crosslinking agent (B) and 10 g of 4-methylbenzophenone (C-3) as a photopolymerization initiator (C) were mixed and added. An agent resin composition was prepared.
It is sandwiched between two polyethylene terephthalate films (Diafoil MLV-V06, manufactured by Mitsubishi Plastics Co., Ltd., 100 μm thick / Diafoil MRQ, manufactured by Mitsubishi Plastics Co., Ltd., 75 μm thick), and the thickness is obtained using a laminator It was shaped into a sheet so as to be 150 μm. Subsequently, UV light was irradiated to the adhesive layer through the polyethylene terephthalate film so that UV light having a wavelength of 365 nm reached 1000 mJ / cm 2 , and the cross-linking agent was partially reacted to prepare an adhesive material 4 (thickness 150 μm). .
And the laminated body for image display apparatus structure was produced similarly to Example 1 using this adhesive material 4. FIG.
［比較例３］　
　特開２０１３－１８２２７号公報の実施例１に準じて粘着材５を作製した。
　すなわち、アクリル系共重合体（Ａ）として、数平均分子量６０００のポリメタクリル酸メチルマクロモノマー１０重量部とブチルアクリレート１６重量部とメトキシエチルアクリレート７０重量部と２－ヒドロキシエチルアクリレート４重量部をランダム共重合してなるアクリル酸エステル共重合体（Ａ－４）（重量平均分子量３０万）１ｋｇに対し、架橋剤（Ｂ）としてキシリレンジイソシアネートのトリメチロールプロパン付加体（ＴＤ－７５　綜研化学社製）４ｇ（Ｂ－４）からなる、粘着剤樹脂組成物を作製した。
　前記粘着剤樹脂組成物を酢酸エチルで希釈した固形分濃度５０％希釈溶液とし、剥離処理したポリエチエレンテレフタレートフィルム（三菱樹脂社製　ダイアホイルＭＲＶ－Ｖ０６　厚さ１００μｍ）上に、乾燥後の厚みが１５０μｍとなるように塗布し、乾燥させた後、剥離処理したポリエチエレンテレフタレートフィルム（三菱樹脂社製　ダイアホイルＭＲＱ　厚さ７５μｍ）を粘着面に被覆し、２３℃湿度４０％にて１週間養生して架橋反応を進行させ、厚さ１５０μｍのシート状の粘着材５を作製した。
　そして、この粘着材５を用いて、紫外線を照射しない事以外は実施例１と同様に画像表示装置構成用積層体を作製した。 [Comparative Example 3]
According to Example 1 of JP2013-18227A, an adhesive material 5 was produced.
That is, as an acrylic copolymer (A), 10 parts by weight of a polymethyl methacrylate macromonomer having a number average molecular weight of 6000, 16 parts by weight of butyl acrylate, 70 parts by weight of methoxyethyl acrylate, and 4 parts by weight of 2-hydroxyethyl acrylate are randomly added. Copolymerized acrylic ester copolymer (A-4) (weight average molecular weight 300,000) 1 kg, xylylene diisocyanate trimethylolpropane adduct (TD-75, manufactured by Soken Chemical Co., Ltd.) as a crosslinking agent (B) ) A pressure-sensitive adhesive resin composition consisting of 4 g (B-4) was prepared.
The pressure-sensitive adhesive resin composition was diluted with ethyl acetate to give a 50% solid concentration diluted solution, and the release-treated polyethylene terephthalate film (Diafoil MRV-V06, 100 μm thick, manufactured by Mitsubishi Plastics) had a thickness after drying. After coating and drying to 150 μm, the polyethylene terephthalate film (Diafoil MRQ thickness 75 μm, manufactured by Mitsubishi Plastics) was coated on the adhesive surface and cured at 23 ° C. and 40% humidity for 1 week. Then, the crosslinking reaction was advanced to produce a sheet-like adhesive material 5 having a thickness of 150 μm.
And using this adhesive material 5, the laminated body for image display apparatus structure was produced similarly to Example 1 except not irradiating an ultraviolet-ray.
［評価］
（架橋前の粘着材の保持力）
　実施例及び比較例で作製した粘着材１～５を４０ｍｍ×５０ｍｍに裁断して片面の離型フィルムを剥がし、裏打用のＰＥＴフィルム（三菱樹脂製ダイアホイルＳ－１００、厚さ３８μｍ）をハンドローラで背貼りした後、これを巾２５ｍｍ×長さ１００ｍｍの短冊状に裁断して試験片とした。次に、残る離型フィルムを剥がして、ＳＵＳ板（１２０ｍｍ×５０ｍｍ×厚さ１．２ｍｍ）に対して、貼着面積が２０ｍｍ×２０ｍｍとなるようハンドローラで貼着した。その後、試験片を４０℃の雰囲気下で１５分養生させた後、試験片に５００ｇｆ（４．９Ｎ）の錘を垂直方向に取り付けて掛けて静置した後、錘の落下時間（分）を測定した。３０分以内に落下しなかったものについては、ＳＵＳと試験片との貼着位置が下方にズレた長さ（ｍｍ）、すなわちズレ量を測定した。この時、錘の落下時間が２０分以上であれば十分な保持力を有しており、加工性および保管安定性が優れていることを示唆している。なお、表中の「＜０．５ｍｍ」はズレ長さが０．５ｍｍ未満で、ほとんどズレのない状態を意味している。 [Evaluation]
(Retention force of adhesive material before crosslinking)
The adhesive materials 1 to 5 produced in the examples and comparative examples were cut into 40 mm × 50 mm, the release film on one side was peeled off, and the PET film (Mitsubishi Resin Diafoil S-100, thickness 38 μm) for backing was handed After back-attaching with a roller, this was cut into a strip shape having a width of 25 mm and a length of 100 mm to obtain a test piece. Next, the remaining release film was peeled off and attached to a SUS plate (120 mm × 50 mm × thickness 1.2 mm) with a hand roller so that the application area was 20 mm × 20 mm. Then, after the test piece was cured for 15 minutes in an atmosphere of 40 ° C., a weight of 500 gf (4.9 N) was attached to the test piece in a vertical direction and left standing, and then the falling time (minute) of the weight was determined. It was measured. About what did not fall within 30 minutes, the length (mm) that the sticking position of SUS and a test piece shifted | deviated below, ie, the gap | deviation amount, was measured. At this time, if the falling time of the weight is 20 minutes or more, it has sufficient holding power, suggesting that the workability and storage stability are excellent. In the table, “<0.5 mm” means that the deviation length is less than 0.5 mm and there is almost no deviation.
　また、実施例及び比較例で作製した粘着材１～５について、上記保持力測定と同様にして、ＳＵＳ板と試験片との積層体を作成した。７０℃の雰囲気下で１５分養生させた後、試験片に５００ｇｆ（４．９Ｎ）の錘を垂直方向に取り付けて掛けて３０分間静置した後、錘の落下時間（分）を測定した。３０分以内に落下しなかったものについては、ＳＵＳと試験片との貼着位置が下方にズレた長さ（ｍｍ）、すなわちズレ量を測定した。
　この時、落下時間が５分未満であれば、加熱によって高い流動性を発現し、凹凸追従性や被着体への濡れ性が高められることを示唆している。 Further, for the adhesive materials 1 to 5 produced in the examples and comparative examples, a laminate of a SUS plate and a test piece was prepared in the same manner as in the holding force measurement. After curing for 15 minutes in an atmosphere of 70 ° C., a weight of 500 gf (4.9 N) was attached to the test piece in the vertical direction and allowed to stand for 30 minutes, and then the falling time (minute) of the weight was measured. About what did not fall within 30 minutes, the length (mm) that the sticking position of SUS and a test piece shifted | deviated below, ie, the gap | deviation amount, was measured.
At this time, if the drop time is less than 5 minutes, high fluidity is expressed by heating, suggesting that the unevenness followability and the wettability to the adherend are enhanced.
（架橋後の粘着材の保持力）
　実施例及び比較例で作製した粘着材１～５について、上記保持力測定と同様にして、ＳＵＳと試験片との積層体を作成した後、波長３６５ｎｍの紫外線が粘着シートに２０００ｍＪ／ｃｍ２到達するよう、光量計（ウシオ電機社製、ＵＮＩＭＥＴＥＲ  ＵＩＴ２５０／センサー：ＵＶＤ－Ｃ３６５）で積算光量を確認しながら裏打用のＰＥＴフィルム側から高圧水銀ランプを用いて紫外線照射し、工程（３）における光硬化後の透明両面粘着シートに相当する試験片を作製した。
　その後、試験片を４０℃および７０℃の雰囲気下で１５分養生させた後、試験片に４．９Ｎの錘を垂直方向に取り付けて掛けて３０分間静置した後、ＳＵＳと試験片との貼着位置が下方にズレた長さ（ｍｍ）を測定した。試験片が殆ど動かず、ズレ長さが０．５ｍｍ未満のものについては、表中「＜０．５ｍｍ」と表記した。
　この時、試験片が殆ど動かなければ、粘着材が高い凝集力を有しており、耐発泡信頼性に優れていることを示唆している。 (Holding power of adhesive material after crosslinking)
For adhesive materials 1 to 5 prepared in Examples and Comparative Examples, a laminate of SUS and a test piece was prepared in the same manner as in the above holding force measurement, and then an ultraviolet ray having a wavelength of 365 nm reached 2000 mJ / cm 2 on the adhesive sheet. The UV light was irradiated from the backing PET film side using a high-pressure mercury lamp while confirming the integrated light quantity with a light meter (USHIO Corporation, UNIMETER UIT250 / sensor: UVD-C365), and the light in step (3) A test piece corresponding to the cured transparent double-sided pressure-sensitive adhesive sheet was prepared.
Thereafter, the test piece was allowed to cure for 15 minutes in an atmosphere of 40 ° C. and 70 ° C., then a 4.9 N weight was attached to the test piece in a vertical direction, and the test piece was allowed to stand for 30 minutes. The length (mm) by which the sticking position was shifted downward was measured. For specimens where the test piece hardly moved and the deviation length was less than 0.5 mm, it was indicated as “<0.5 mm” in the table.
At this time, if the test piece hardly moves, the adhesive material has a high cohesive force, suggesting that the foaming reliability is excellent.
（ヘイズ）　
　粘着材１～５の一方の離型フィルムを剥がして露出した粘着面を、ソーダライムガラス（８２ｍｍ×５３ｍｍ×０．５ｍｍ厚）にロール圧着した。次いで残る離型フィルムを剥がし、ゼオノアフィルム（日本ゼオン製、１００μｍ厚）をロール貼合した後、オートクレーブ処理（８０℃、ゲージ圧０．２ＭＰａ、２０分）を施して仕上げ貼着し、積層体を作製した。
　前記積層体について、ヘイズメーター（日本電色工業株式会社製　ＮＤＨ５０００）を用いて、初期ヘイズ並びに６５℃９０％ＲＨの湿熱環境下にて１００時間保管した後のヘイズ値（表の「湿熱試験後ヘイズ」）をＪＩＳ　Ｋ７１３６に準じて測定した。 (Haze)
The pressure-sensitive adhesive surface exposed by peeling off one release film of the pressure-sensitive adhesive materials 1 to 5 was roll-bonded to soda lime glass (82 mm × 53 mm × 0.5 mm thickness). Next, the remaining release film is peeled off, a ZEONOR film (manufactured by ZEON Corporation, 100 μm thickness) is roll-bonded, and then autoclave treatment (80 ° C., gauge pressure 0.2 MPa, 20 minutes) is applied to finish and laminate. Was made.
About the said laminated body, using the haze meter (Nippon Denshoku Industries Co., Ltd. NDH5000), the haze value after 100-hour storage in the initial heat haze and the moist heat environment of 65 degreeC90% RH ("After a moist heat test of a table | surface) Haze ") was measured according to JIS K7136.
（加工適性）
　粘着材１～５を、離型フィルムを積層したままトムソン打抜機を用いて５０ｍｍ×８０ｍｍのトムソン刃で１００枚カットし、端部の形状を観察した。端部の潰れや糊はみだし、離型フィルムの浮きが２０枚以上みられたものを「×」と評価し、２０枚以上無かったものを「○」と判定した。 (Processability)
100 sheets of adhesives 1 to 5 were cut with a Thomson cutting machine with a 50 mm × 80 mm Thomson blade while the release film was laminated, and the shape of the edge was observed. Edge crushing and glue squeezed out, and 20 or more release film floats were evaluated as “x”, and 20 or more release films were evaluated as “◯”.
（粘着材の保管安定性）
　上記加工適性評価で作製した粘着材１～５の裁断品を１００ｍｍ×１００ｍｍ×３ｍｍのガラス板間に挟むように積層し、天面のガラス板に１ｋｇの錘を乗せて４０℃で６５時間静置した。
　養生後に粘着材がつぶれ、糊はみ出しが顕著に見られたものを「×」、糊はみだしがわずかに見られたが、実用性に問題ないものを「○」、糊はみ出しが見られなかったものを「◎」と判定した。 (Storage stability of adhesive material)
The cut pieces of the adhesive materials 1 to 5 produced by the above processability evaluation are laminated so as to be sandwiched between 100 mm × 100 mm × 3 mm glass plates, and a 1 kg weight is placed on the top glass plate and allowed to stand at 40 ° C. for 65 hours. I put it.
After curing, the adhesive material was crushed, and “×” indicates that the paste protruded noticeably, “S” indicates that the adhesive protruded slightly, but “○” indicates that there was no problem with practicality, and no adhesive protruded. Was judged as “◎”.
（接着力）
　粘着材１～５の一方の離型フィルムを剥がし、裏打ちフィルムとして５０μｍのＰＥＴフィルム（三菱樹脂製ダイアホイルＴ１００　厚さ５０μｍ）を貼合した。
　上記積層品を長さ１５０ｍｍ、巾１０ｍｍに裁断した後、残る離型フィルムを剥がして露出した粘着面をソーダライムガラスにロール圧着した。貼合品にオートクレーブ処理（８０℃，ゲージ圧０．２ＭＰａ，２０分）を施して仕上げ貼着した後、粘着材１～４の試料については紫外線を３６５ｎｍの積算光量が２０００ｍＪ／ｃｍ2となるよう照射して粘着材を硬化し、２３℃、５０％ＲＨで１５時間養生して、剥離力測定試料とした。
　粘着材５については、架橋反応がすでに終了しているため、紫外線照射等の後硬化処理を行わず、そのまま剥離力測定試料とした。
　上記剥離力測定試料を、２３℃４０％ＲＨの環境下にて剥離角１８０°、剥離速度６０ｍｍ／分で引き剥がしたときのガラスへの剥離力（Ｎ／ｃｍ）を測定した。 (Adhesive strength)
One release film of adhesives 1 to 5 was peeled off, and a 50 μm PET film (Mitsubishi Resin Diafoil T100 thickness 50 μm) was bonded as a backing film.
After the laminated product was cut to a length of 150 mm and a width of 10 mm, the remaining release film was peeled off and the exposed adhesive surface was roll-bonded to soda lime glass. After the autoclave treatment (80 ° C., gauge pressure 0.2 MPa, 20 minutes) is applied to the pasted product and the final product is pasted, the accumulated light quantity of 365 nm of the adhesive materials 1 to 4 becomes 2000 mJ / cm 2. The adhesive material was cured by irradiation and cured at 23 ° C. and 50% RH for 15 hours to obtain a peel force measurement sample.
For the adhesive material 5, since the crosslinking reaction has already been completed, a post-curing treatment such as ultraviolet irradiation was not performed, and the sample was used as it was as a peeling force measurement sample.
The peeling force (N / cm) to the glass when the peeling force measurement sample was peeled at a peeling angle of 180 ° and a peeling speed of 60 mm / min in an environment of 23 ° C. and 40% RH was measured.
（貼合性）
　加工性評価にて裁断した粘着材１～５の一方の離型フィルムを剥がして露出した粘着面を、周縁部５ｍｍに厚さ８０μｍの印刷を施したソーダライムガラス（８２ｍｍ×５３ｍｍ×０．５ｍｍ厚）の印刷面に、粘着材の４辺が印刷段差にかかるようにして真空プレスを用いてプレス圧着した（絶対圧５ｋＰａ、温度８０℃、プレス圧０．０４ＭＰａ）。次いで残る離型フィルムを剥がし、ゼオノアフィルム（日本ゼオン製　１００μｍ厚）をプレス貼合した後、オートクレーブ処理（８０℃、ゲージ圧０．２ＭＰａ、２０分）を施して仕上げ貼着し、積層体１～５を作製した。
　作製した積層体１～５を目視観察し、印刷段差近傍で粘着材が追従せず気泡が残ったものを「×」、フィルムが段差近傍で屈曲し、歪むことによる凹凸ムラが見えたものを「△」、気泡なく平滑に貼合されたものを「○」と判定した。 (Pasteability)
Soda lime glass (82 mm x 53 mm x 0.5 mm) with an adhesive surface exposed by peeling off one of the release films of the adhesive materials 1 to 5 cut in the processability evaluation and printed with a thickness of 80 µm on the periphery 5 mm. The pressure side of the adhesive material was press-pressed using a vacuum press (absolute pressure 5 kPa, temperature 80 ° C., press pressure 0.04 MPa) so that the four sides of the adhesive material were on the printing step. Next, the remaining release film is peeled off and a ZEONOR film (manufactured by Nippon Zeon Co., Ltd., 100 μm thickness) is press-bonded, then subjected to autoclaving (80 ° C., gauge pressure 0.2 MPa, 20 minutes), and finally bonded, and the laminate 1 To 5 were produced.
Visual observation of the produced laminates 1 to 5 indicates that the adhesive material does not follow in the vicinity of the printing step and bubbles remain, and “x” indicates that the film is bent near the step and unevenness due to distortion is visible. “B” and those smoothly bonded without bubbles were judged as “B”.
（耐発泡信頼性）
　実施例及び比較例にて作製した積層体１～５について、８５℃、８５％ＲＨの環境下で１００時間保管した後の外観を目視観察し、環境試験後に粘着材の変形や発泡、剥離が生じたものを「×」、なきものを「○」と判定した。 (Foam resistance)
The laminates 1 to 5 produced in the examples and comparative examples were visually observed after storage for 100 hours in an environment of 85 ° C. and 85% RH, and the adhesive material was deformed, foamed and peeled after the environmental test. Those that occurred were judged as “x”, and those that did not were judged as “◯”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（考察）
　実施例のシート状の粘着材は、アクリル酸エステル共重合体中のマクロモノマーが凝集成分として寄与する結果、未架橋状態においても高い保持力を示し、加工性や保管安定性に優れたものであった。また、実施例の粘着材は、加熱により高い流動性を発現することから、貼合時に加熱し溶融させることで、凹凸面への追従性に優れるばかりか、被着体の一方がフィルムのような剛性の低い素材であっても段差近傍で屈曲を生じず、平滑な積層体を得ることができた。さらには、積層体とした後に紫外線照射し粘着材を硬化させることで、高温高湿下等の苛酷な環境試験下においても剥離や発泡、変形を生じず、高い信頼性をもつ積層体を得ることができた。 (Discussion)
The sheet-like pressure-sensitive adhesive materials of the examples show that the macromonomer in the acrylate copolymer contributes as an aggregating component, and as a result, exhibits high holding power even in an uncrosslinked state, and is excellent in workability and storage stability. there were. In addition, since the adhesive materials of the examples exhibit high fluidity by heating, by heating and melting at the time of bonding, not only the followability to the uneven surface is excellent, but one of the adherends is a film Even if the material has a low rigidity, it was not bent near the step, and a smooth laminate could be obtained. In addition, the adhesive is cured by irradiating with ultraviolet rays after forming the laminate, thereby obtaining a highly reliable laminate that does not peel, foam or deform even under severe environmental tests such as high temperature and high humidity. I was able to.
　これに対し、比較例１は、マクロモノマーを含まないアクリル酸エステル共重合体を用いたシート状の粘着材であるため粘着剤としての凝集力が低く、加工性や保管安定性が得られなかった。
　比較例２は、紫外線照射によって粘着剤樹脂組成物が一部架橋しているため保管安定性や裁断加工性には優れるものの、印刷段差尽きガラスとフィルムとを積層する際、フィルム側に印刷段差による凹凸が転写し平滑な積層体が得られないばかりか、印刷段差が交差する角部付近では一部粘着剤が充填しきれず気泡が残る結果となった。また、段差近傍の粘着材の歪みをきっかけに高温高湿試験下で発泡し、保管安定性に劣るものであった。
　比較例３は、粘着剤樹脂組成物の架橋反応が、部材へ貼合する前段階で既に完了しているため、粘着材単独での加工性や保管安定性には優れるものの、貼合面の段差部を平滑に埋められるものではなかった。 On the other hand, since Comparative Example 1 is a sheet-like adhesive material using an acrylate copolymer that does not contain a macromonomer, the cohesive force as an adhesive is low, and processability and storage stability cannot be obtained. It was.
Comparative Example 2 is excellent in storage stability and cutting processability because the pressure-sensitive adhesive resin composition is partially cross-linked by ultraviolet irradiation. However, when laminating the printed stepped glass and the film, the printed step is formed on the film side. As a result, not only was the unevenness caused by the transfer transferred and a smooth laminate could not be obtained, but in the vicinity of the corner where the printing steps crossed, some of the adhesive could not be filled and bubbles remained. In addition, the foaming under the high temperature and high humidity test was triggered by the distortion of the adhesive material in the vicinity of the step, resulting in poor storage stability.
In Comparative Example 3, since the crosslinking reaction of the pressure-sensitive adhesive resin composition has already been completed in the previous stage of bonding to the member, the pressure-sensitive adhesive material alone has excellent processability and storage stability, The stepped portion was not filled smoothly.
　以上の実施例の結果並びにこれまで発明者が行ってきた試験結果から、枝成分としてマクロモノマーを備えたグラフト共重合体からなるアクリル系共重合体（Ａ）と、架橋剤（Ｂ）と、光重合開始剤（Ｃ）とを含有する粘着剤樹脂組成物から成形した単層又は多層の透明両面粘着材を用いれば、実施例同様に２つの画像表示装置構成部材を接着させることができるものと考えることができる。 From the results of the above examples as well as the test results conducted by the inventors so far, an acrylic copolymer (A) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B), When a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material molded from a pressure-sensitive adhesive resin composition containing a photopolymerization initiator (C) is used, two image display device constituent members can be bonded in the same manner as in the examples. Can be considered.

Claims (15)

  1. 　透明両面粘着材を介して画像表示装置構成部材が積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、少なくとも次の（１）～（３）の工程を有することを特徴とする画像表示装置構成用積層体の製造方法。
    （１） 枝成分としてマクロモノマーを備えたグラフト共重合体からなるアクリル系共重合体（Ａ）と、架橋剤（Ｂ）と、光重合開始剤（Ｃ）とを含有する粘着剤樹脂組成物を作製して、該粘着剤樹脂組成物からなる粘着層を備えた単層又は多層の透明両面粘着材をシート状に成形する工程。
    （２） 前記透明両面粘着材を介して２つの画像表示装置構成部材を貼着して積層する工程。
    （３） 少なくとも一方の画像表示装置構成部材の外側から、活性エネルギー線を透明両面粘着材の前記粘着層に照射し、当該粘着層を架橋させて、２つの画像表示装置構成部材を接着させる工程。     A method of manufacturing a laminate for constituting an image display device comprising a structure in which image display device constituting members are laminated via a transparent double-sided adhesive material, comprising at least the following steps (1) to (3): A method for producing a laminate for constituting an image display device.
    (1) A pressure-sensitive adhesive resin composition comprising an acrylic copolymer (A) comprising a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B), and a photopolymerization initiator (C). And forming a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition into a sheet.
    (2) The process of sticking and laminating | stacking two image display apparatus structural members through the said transparent double-sided adhesive material.
    (3) A step of irradiating the adhesive layer of the transparent double-sided pressure-sensitive adhesive material from the outside of at least one of the image display device constituent members, crosslinking the adhesive layer, and bonding the two image display device constituent members .
  2. 　前記工程（２）と前記工程（３）の間に、前記工程（２）で得られた積層物を加熱して透明両面粘着材の粘着層を加熱溶融させる工程をさらに有することを特徴とする請求項１に記載の画像表示装置構成用積層体の製造方法。 Between the process (2) and the process (3), the laminate obtained in the process (2) is further heated to heat and melt the adhesive layer of the transparent double-sided pressure-sensitive adhesive material. The manufacturing method of the laminated body for image display apparatus structures of Claim 1.
  3. 　前記粘着層を加熱溶融させる工程では、積層物を６０～１００℃の温度範囲に加熱して透明両面粘着材の粘着層を加熱溶融（ホットメルト）させることを特徴とする請求項２に記載の画像表示装置構成用積層体の製造方法。 3. The step of heating and melting the pressure-sensitive adhesive layer comprises heating the laminate to a temperature range of 60 to 100 ° C. to heat and melt (hot-melt) the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive material. A method for producing a laminate for constituting an image display device.
  4. 　前記工程（１）および前記工程（２）における前記透明両面粘着材は、未架橋状態であることを特徴とする請求項１～３の何れかに記載の画像表示装置構成用積層体の製造方法。 The method for producing a laminate for constituting an image display device according to any one of claims 1 to 3, wherein the transparent double-sided pressure-sensitive adhesive material in the step (1) and the step (2) is in an uncrosslinked state. .
  5. 　前記工程（１）及び前記工程（２）における前記透明両面粘着材は、ＪＩＳ－Ｚ－０２３７（ＩＳＯ　２９８６３）に準じた保持力測定において、ＳＵＳ板に面積２０ｍｍ×２０ｍｍで貼着させ、４０℃の雰囲気下で５００ｇｆの荷重をかけた時の落下時間が２０分以上であり、且つ、７０℃の雰囲気下で５００ｇｆの荷重をかけた時の落下時間が５分未満であることを特徴とする請求項１～４の何れかに記載の画像表示装置構成用積層体の製造方法。 In the step (1) and the step (2), the transparent double-sided pressure-sensitive adhesive material is bonded to an SUS plate at an area of 20 mm × 20 mm in a holding power measurement according to JIS-Z-0237 (ISO 29863), and 40 ° C. The drop time when a load of 500 gf is applied in an atmosphere of 5 is 20 minutes or more, and the drop time when a load of 500 gf is applied in an atmosphere of 70 ° C. is less than 5 minutes. The method for producing a laminate for constituting an image display device according to any one of claims 1 to 4.
  6. 　前記工程（３）において、架橋後の透明両面粘着材は、ＪＩＳ－Ｚ－０２３７（ＩＳＯ　２９８６３）に準じた保持力測定において、ＳＵＳ板に面積２０ｍｍ×２０ｍｍで貼着させ、４０℃および７０℃の雰囲気下で５００ｇｆの荷重をかけた時の３０分後のズレ長さが１ｍｍ未満であることを特徴とする請求項１～５の何れかに記載の画像表示装置構成用積層体の製造方法。 In the step (3), the transparent double-sided pressure-sensitive adhesive material after cross-linking is adhered to an SUS plate at an area of 20 mm × 20 mm in a holding power measurement according to JIS-Z-0237 (ISO 29863), and 40 ° C. and 70 ° C. The method for producing a laminate for constituting an image display device according to any one of claims 1 to 5, wherein a shift length after 30 minutes when a load of 500 gf is applied in an atmosphere of less than 1 mm .
  7. 　前記アクリル系共重合体（Ａ）は、前記マクロモノマーを５～３０質量％の割合で含有することを特徴とする請求項１～６の何れかに記載の画像表示装置構成用積層体の製造方法。 The production of a laminate for constituting an image display device according to any one of claims 1 to 6, wherein the acrylic copolymer (A) contains the macromonomer in a proportion of 5 to 30% by mass. Method.
  8. 　前記アクリル系共重合体（Ａ）の枝成分としてのマクロモノマーのガラス転移温度は、上記アクリル系共重合体（Ａ）の幹成分を構成する共重合体成分のガラス転移温度よりも高いことを特徴とする請求項１～７の何れかに記載の画像表示装置構成用積層体の製造方法。 The glass transition temperature of the macromonomer as a branch component of the acrylic copolymer (A) is higher than the glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (A). The method for producing a laminate for constituting an image display device according to any one of claims 1 to 7.
  9. 　前記マクロモノマーのガラス転移温度は３０℃～１２０℃であることを特徴とする請求項１～８の何れかに記載の画像表示装置構成用積層体の製造方法。 The method for producing a laminate for constituting an image display device according to any one of claims 1 to 8, wherein the macromonomer has a glass transition temperature of 30 ° C to 120 ° C.
  10. 　前記アクリル系共重合体（Ａ）の幹成分を構成する共重合体成分のガラス転移温度は－７０～０℃であることを特徴とする請求項１～９の何れかに記載の画像表示装置構成用積層体の製造方法。 The image display device according to any one of claims 1 to 9, wherein the glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (A) is -70 to 0 ° C. A method for producing a structural laminate.
  11. 　前記アクリル系共重合体（Ａ）は、幹成分として、疎水性のアクリレートモノマーと、親水性のアクリレートモノマーとを含有することを特徴とする請求項１～１０の何れかに記載の画像表示装置構成用積層体の製造方法。 11. The image display device according to claim 1, wherein the acrylic copolymer (A) contains a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as trunk components. A method for producing a structural laminate.
  12. 　前記アクリル系共重合体（Ａ）は、幹成分として、疎水性のアクリレートモノマーと、親水性のアクリレートモノマーと、マクロモノマーの末端の重合性官能基とがランダム共重合してなる構成を備えていることを特徴とする請求項１～１１の何れかに記載の画像表示装置構成用積層体の製造方法。 The acrylic copolymer (A) has a structure in which a hydrophobic acrylate monomer, a hydrophilic acrylate monomer, and a polymerizable functional group at the end of a macromonomer are randomly copolymerized as a trunk component. The method for producing a laminate for constituting an image display device according to any one of claims 1 to 11, wherein:
  13. 　前記架橋剤（Ｂ）として、極性官能基を含有する多官能モノマー若しくはオリゴマーを用いることを特徴とする請求項１～１２の何れかに記載の画像表示装置構成用積層体の製造方法。 The method for producing a laminate for constituting an image display device according to any one of claims 1 to 12, wherein a polyfunctional monomer or oligomer containing a polar functional group is used as the crosslinking agent (B).
  14. 　前記工程（１）の代わりに、
    　枝成分としてマクロモノマーを備えたグラフト共重合体からなるアクリル系共重合体（Ａ）、架橋剤（Ｂ）及び光重合開始剤（Ｃ）を含有する粘着剤樹脂組成物を、離型フィルムの上に単層又は多層のシート状に成形して、粘着層を備えた単層又は多層の透明両面粘着材を作製すると共に、
    　前記工程（２）の代わりに、
    　前記離型フィルムを剥がして、前記透明両面粘着材を介して２つの画像表示装置構成部材を貼着して積層する、ことを特徴とする請求項１～１３の何れかに記載の画像表示装置構成用積層体の製造方法。     Instead of the step (1),
    A pressure-sensitive adhesive resin composition containing an acrylic copolymer (A) composed of a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B), and a photopolymerization initiator (C) is used as a release film. A single layer or multilayer transparent double-sided pressure-sensitive adhesive material provided with an adhesive layer is formed on a single-layer or multilayer sheet, and
    Instead of the step (2),
    The image display device according to any one of claims 1 to 13, wherein the release film is peeled off, and two image display device constituent members are laminated by way of the transparent double-sided adhesive material. A method for producing a structural laminate.
  15. 　前記工程（１）の代わりに、
    　枝成分としてマクロモノマーを備えたグラフト共重合体からなるアクリル系共重合体（Ａ）と、架橋剤（Ｂ）と、光重合開始剤（Ｃ）とを含有する粘着剤樹脂組成物を、画像表示装置構成部材の上に単層又は多層のシート状に成形して、当該画像表示装置構成部材上に、粘着層を備えた単層又は多層の透明両面粘着材を作製する、ことを特徴とする請求項１～１４の何れかに記載の画像表示装置構成用積層体の製造方法。

          Instead of the step (1),
    An adhesive resin composition containing an acrylic copolymer (A) composed of a graft copolymer having a macromonomer as a branch component, a crosslinking agent (B), and a photopolymerization initiator (C) is imaged. A single-layer or multi-layer transparent double-sided pressure-sensitive adhesive material having an adhesive layer is formed on the image display device constituent member by forming it into a single-layer or multilayer sheet on the display device constituent member. The method for producing a laminate for constituting an image display device according to any one of claims 1 to 14.

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