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 PDFInfo
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- 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
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- WIPO (PCT)
- Prior art keywords
- image display
- display device
- sensitive adhesive
- adhesive material
- laminate
- Prior art date
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Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
Description
(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.
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.
(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 .
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.
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.
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).
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.
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.
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. ]
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.
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.
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.
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).
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.
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.
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.
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)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)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.
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.
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.
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)”).
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.
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.
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.
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.
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.
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)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.
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)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.
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.
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.
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).
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
(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.
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.
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.
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.
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 “◯”.
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 “◎”.
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.
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”.
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 “◯”.
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.
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.
Claims (15)
- 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 . - 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.
- 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.
- 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. .
- 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.
- 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 .
- 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.
- 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.
- 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.
- 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.
- 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.
- 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:
- 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).
- 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. - 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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Also Published As
Publication number | Publication date |
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JP6388023B2 (en) | 2018-09-12 |
TW201542378A (en) | 2015-11-16 |
KR101888984B1 (en) | 2018-08-16 |
KR20160128379A (en) | 2016-11-07 |
TWI674198B (en) | 2019-10-11 |
JPWO2015137178A1 (en) | 2017-04-06 |
CN106104658B (en) | 2019-11-29 |
CN106104658A (en) | 2016-11-09 |
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