WO2017138544A1 - 透明両面粘着シート及び粘着シート積層体 - Google Patents
透明両面粘着シート及び粘着シート積層体 Download PDFInfo
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- WO2017138544A1 WO2017138544A1 PCT/JP2017/004489 JP2017004489W WO2017138544A1 WO 2017138544 A1 WO2017138544 A1 WO 2017138544A1 JP 2017004489 W JP2017004489 W JP 2017004489W WO 2017138544 A1 WO2017138544 A1 WO 2017138544A1
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- meth
- adhesive sheet
- sensitive adhesive
- image display
- pressure
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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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
-
- 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
- C09J2301/312—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 parameters being the characterizing feature
-
- 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
Definitions
- the present invention relates to a transparent double-sided pressure-sensitive adhesive sheet that can be used as a member for constituting 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, and a pen tablet.
- 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, and a pen tablet.
- an image display panel such as a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), and a protection disposed on the front side (viewing side).
- Patent Document 1 As a method for filling the gap between the constituent members for an image display device with an adhesive, there is a method in which a liquid adhesive resin composition containing an ultraviolet curable resin is filled into the gap and then cured by irradiation with ultraviolet rays.
- Patent Document 1 a liquid adhesive resin composition containing an ultraviolet curable resin is filled into the gap and then cured by irradiation with ultraviolet rays.
- Patent Document 2 discloses a method in which a pressure-sensitive adhesive sheet that has undergone primary crosslinking with ultraviolet rays is bonded to an image display device constituent member, and then the adhesive sheet is irradiated with ultraviolet rays through the image display device constituent member to be secondarily cured.
- Patent Document 3 discloses a pressure-sensitive adhesive sheet comprising a hot-melt 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. And a method for filling a gap between constituent members for an image display device.
- the adhesive sheet which consists of an adhesive resin composition containing a base resin, a crosslinking agent, and an ultraviolet polymerization initiator
- two image display apparatus structural members are attached.
- UV light is irradiated from the outside of one image display device constituent member, and the pressure-sensitive adhesive sheet is UV-cured through the image display device constituent member and secondarily attached.
- the primary sticking can be performed while filling the unevenness of the adherend surface, and the adhesive reliability can be further improved by finally curing.
- the pressure-sensitive adhesive sheet when such an ultraviolet-sensitive pressure-sensitive adhesive sheet is exposed to ultraviolet rays for a long time, the pressure-sensitive adhesive sheet itself deteriorates, and a decomposition product may be generated to cause foaming or peeling.
- the image display device constituent members there are members that are easily deteriorated by ultraviolet rays. In such a case, the two image display device constituent members cannot be attached by the method described above. Further, when the image display device constituent member has ultraviolet absorptivity, the ultraviolet ray does not reach the adhesive sheet sufficiently even if the ultraviolet ray is irradiated through the member. Thus, the two image display device constituent members cannot be attached.
- image display device constituent members may be required to have an ultraviolet absorbing function, and the ultraviolet absorbing function is generally secured by a polarizing plate protective film. It was. However, along with the thinning of the image display device constituent member, the polarizing plate protective film has also been thinned, and it has become difficult to obtain a sufficient ultraviolet absorption function. Therefore, an ultraviolet ray absorbing function is also required for image display device constituent members other than the polarizing plate protective film, such as an adhesive and an adhesive sheet.
- the present invention is to provide a new transparent double-sided pressure-sensitive adhesive sheet that has an ultraviolet absorbing function and that can be further cured and secondarily stuck after first sticking using the pressure-sensitive adhesive sheet. is there.
- the present invention relates to a (meth) acrylic copolymer (A), a crosslinking agent (B), a photopolymerization initiator (C) having an absorption coefficient of 10 mL / (g ⁇ cm) or more at a wavelength of 405 nm, and an ultraviolet absorber. It is a transparent double-sided adhesive sheet which consists of an adhesive resin composition containing (D).
- the transparent double-sided pressure-sensitive adhesive sheet for image display of the present invention has an ultraviolet absorption function and is first attached using an adhesive sheet, it can be further photocured and secondarily attached. It is possible to achieve both the level difference absorbability when there is unevenness on the adherend surface and the anti-foaming reliability after bonding.
- the transparent double-sided PSA sheet has a (meth) acrylic copolymer (A), a crosslinking agent (B), and an extinction coefficient at a wavelength of 405 nm of 10 mL / (g ⁇ cm) or more.
- a transparent double-sided pressure-sensitive adhesive sheet (referred to as “this pressure-sensitive adhesive sheet”) comprising a pressure-sensitive adhesive resin composition (referred to as “this pressure-sensitive adhesive composition”) containing a photopolymerization initiator (C) and an ultraviolet absorber (D). .
- the (meth) acrylic polymer as the base polymer of the pressure-sensitive adhesive sheet has a glass transition temperature (Tg), etc., depending on the type, composition ratio, polymerization conditions, etc. of the acrylic monomer and methacrylic monomer used to polymerize the polymer. These characteristics can be adjusted as appropriate.
- the “base polymer” in the pressure-sensitive adhesive sheet means a resin that forms the main component of the pressure-sensitive adhesive sheet.
- the specific content is not specified. As a guide, it is a resin that occupies 50% by mass or more of the resin contained in the pressure-sensitive adhesive sheet, especially 65% by mass or more, of which 80% by mass (including 100% by mass) or more.
- the total amount thereof corresponds to the content.
- the (meth) acrylic (co) polymer (A) for example, in addition to a homopolymer of alkyl (meth) acrylate, a copolymer obtained by polymerizing this and a monomer component having copolymerizability More preferably, from alkyl (meth) acrylate and a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, an amide group-containing monomer and other vinyl monomers copolymerizable therewith.
- a copolymer containing any one or more selected monomers as a monomer component can be exemplified.
- a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain hereinafter also referred to as “copolymerizable monomer A”
- a carboxyl group-containing monomer hereinafter referred to as “copolymerizable monomer A”.
- copolymerizable monomer B vinyl monomer
- copolymerizable monomer C vinyl monomer
- copolymerizable monomer D (meth) acrylate having 1 to 3 carbon atoms in the side chain
- a copolymer composed of any one or more monomers selected from a hydroxyl group-containing monomer hereinafter “copolymerizable monomer E”).
- a copolymer composed of a monomer component containing a polymerizable monomer B and / or a copolymerizable monomer C and a copolymerizable monomer D and / or a copolymerizable monomer E can also be mentioned as a particularly preferred example.
- a copolymer of copolymerizable monomers A and B a copolymer of copolymerizable monomers A and C, a copolymer of copolymerizable monomers A, B and C, a copolymerizable monomer A, B And D copolymer, copolymerizable monomer A, B and E copolymer, copolymerizable monomer A, B, D and E copolymer, copolymerizable monomer A, C and D copolymer , Copolymers of copolymerizable monomers A, C and E, copolymers of copolymerizable monomers A, C, D and E, copolymers of copolymerizable monomers A, B, C and D, copolymerizable Mention may be made of copolymers of monomers A, B, C and E and copolymers of copolymerizable monomers A, B, C, D and E.
- Examples of the “copolymerizable monomer A” include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, and isopentyl.
- the copolymerizable monomer A is preferably contained in an amount of 30% by mass or more and 90% by mass or less, and particularly 35% by mass or 88% by mass, particularly 40% by mass or more. Or it is more preferable to contain in 85 mass% or less.
- Examples of the “copolymerizable monomer B” include (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) Acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, Examples include 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, and itaconic acid. These may be used alone or in combination of two or more. “(Meth) acryl” means to include acrylic and methacrylic. Similarly, “(meth) acryloyl” means
- Examples of the “copolymerizable monomer C” include compounds having a vinyl group in the molecule.
- examples of such compounds include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, functional monomers having a functional group such as a hydroxyl group, an amide group and an alkoxylalkyl group in the molecule; Polyalkylene glycol di (meth) acrylates and vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl laurate, and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene and other substituted styrenes Can be illustrated. These may be used alone or in combination of two or more.
- the copolymerizable monomer B and the copolymerizable monomer C are 1.2% by mass to 15% by mass or less in the total monomer components of the copolymer, and particularly 1.5% by mass or more from the viewpoint of obtaining excellent adhesive properties. Alternatively, it is preferably contained in an amount of 10% by mass or less, and more preferably 2% by mass or more or 8% by mass or less.
- copolymerizable monomer D examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate and the like. These may be used alone or in combination of two or more.
- the copolymerizable monomer D is preferably contained in the total monomer component of the copolymer in an amount of 0% by mass or more and 70% by mass or less, particularly 3% by mass or more or 65% by mass or less, and more preferably 5% by mass or more. More preferably, it is contained in the range of 60% by mass or less.
- Examples of the “copolymerizable monomer E” include hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Mention may be made of (meth) acrylates. These may be used alone or in combination of two or more.
- the copolymerizable monomer E is preferably contained in an amount of 0% by mass or more and 30% by mass or less in all monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less. More preferably, it is contained in the range of 20% by mass or less.
- acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, and epoxies such as glycidyl (meth) acrylate, glycidyl ⁇ -ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate Group-containing monomers, amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol Monomers containing amide groups such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, maleimide, vinylpyrrolidone, vinylpyridine, vinyl Heterocyclic basic
- (meth) acrylic (co) polymers include, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) ) Acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate and other monomer components (a), carboxyl group-containing (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthal Acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (Meth) acryloyloxypro
- the mass average molecular weight of the (meth) acrylic (co) polymer is preferably 100,000 to 1.5 million, more preferably 150,000 or more and 1.3 million or less, and particularly preferably 200,000 or more and 1,200,000 or less.
- the mass average molecular weight is 700,000 to 1,500,000, particularly 800,000 to 1,300,000 or less from the viewpoint of obtaining cohesive force by entanglement of molecular chains as the molecular weight increases. Is preferred.
- the mass average molecular weight is preferably 70,000 to 700,000, particularly 100,000 or more, or 600,000 or less.
- the mass average molecular weight of the acrylic copolymer is 70,000 to 700,000, particularly 100,000 or more.
- (Acrylic copolymer (A1)) As an example of a preferable base polymer of the pressure-sensitive adhesive sheet, a (meth) acrylic copolymer (A1) composed of a graft copolymer including a macromonomer as a branch component can be exemplified.
- this pressure-sensitive adhesive sheet is composed of the acrylic copolymer (A1) as a base resin
- the pressure-sensitive adhesive sheet can exhibit self-adhesion while maintaining a sheet shape at room temperature, and when heated in an uncrosslinked state It has a hot melt property that melts or flows, and can be photocured, and after photocuring, it exhibits excellent cohesive force and can be bonded. Therefore, if the acrylic copolymer (A1) is used as the base polymer of the pressure-sensitive adhesive sheet, it exhibits adhesiveness at room temperature (20 ° C.) and is softened or fluidized at 100 ° C. even in an uncrosslinked state. Or a property of softening or fluidizing when heated to a temperature of 50 to 90 ° C., more preferably 60 ° C. or higher or 80 ° C. or lower.
- the glass transition temperature of the copolymer constituting the trunk component of the acrylic copolymer (A1) 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 a polymer obtained by copolymerizing only the monomer component composing the trunk component of the acrylic copolymer (A1). .
- 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 (A1) is the flexibility of the pressure-sensitive adhesive sheet at room temperature, the wettability of the pressure-sensitive adhesive sheet to the adherend,
- the glass transition temperature is preferably ⁇ 70 ° C. to 0 ° C., in particular, ⁇ 65 ° C. in order for the pressure-sensitive adhesive sheet to have appropriate adhesion (tackiness) at room temperature because it affects the adhesion. Above, or ⁇ 5 ° C. or less, particularly preferably ⁇ 60 ° C. or more or ⁇ 10 ° C. or less.
- 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 (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth
- hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate having a hydrophilic group or an organic functional group
- hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate having a hydrophilic group or an organic functional group
- Acrylic acid 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalate Acid, 2- (
- Monomers containing amide group, vinyl pyrrolidone, vinyl pyridine can also be used heterocyclic basic monomers such as vinyl carbazole.
- styrene, t-butylstyrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl which can be copolymerized with the above acrylic monomers and methacrylic monomers.
- Various vinyl monomers such as vinyl monomers can also be used as appropriate.
- the trunk component of the acrylic copolymer (A1) contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units. If the trunk component of the acrylic copolymer (A1) 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 acrylic copolymer (A1) a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the terminal 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, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) ) Acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meta) ) Acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl
- hydrophilic (meth) acrylate monomer examples include methyl acrylate, (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate, hydroxyl-containing (meth) acrylate such as glycerol (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- Carboxyl group-containing mono
- the acrylic copolymer (A1) preferably contains a macromonomer-derived repeating unit by introducing a macromonomer as a branch component of the graft copolymer.
- 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 (A1). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the present adhesive sheet, the glass transition temperature (Tg) of the macromonomer is 30 ° C. to 120 ° C. Of these, 40 ° C. or higher or 110 ° C. or lower, and more preferably 50 ° C. or higher or 100 ° C. or lower among these. 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 around 50 ° C. to 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).
- the branch components are attracted to each other and can maintain a state where they are physically cross-linked as a pressure-sensitive adhesive composition, and the physical cross-linking is released by heating to an appropriate temperature.
- the macromonomer is preferably contained in the acrylic copolymer (A1) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or 25% by mass, and more preferably 8% by mass. It is preferable that the amount is 20% by mass or more.
- the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
- a generally produced one for example, a macromonomer manufactured by Toa Gosei Co., Ltd.
- the high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
- Examples of the high molecular weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
- Crosslinking agent (B) As the crosslinking agent (B), a crosslinking agent having at least double bond crosslinking is preferred.
- at least one crosslinkable functional group selected from (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, and amide group
- the crosslinking agent which has You may use 1 type or in combination of 2 or more types. Further, an embodiment in which the crosslinking agent (B) is chemically bonded to the (meth) acrylic copolymer (A) is also included.
- polyfunctional (meth) acrylate it is preferable to use polyfunctional (meth) acrylate.
- polyfunctional means what has two or more crosslinkable functional groups.
- the crosslinkable functional group may be protected with a deprotectable protecting group.
- polyfunctional (meth) acrylates examples include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polyalkoxydi (meth) ) Acrylate, bisphenol F polyalkoxydi (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ⁇ -caprolactone modified Lith (2-hydroxyethyl) isocyanurate
- polyfunctional (meth) acrylic acid ester monomers polar functional groups such as a hydroxyl group, a carboxyl group, and an amide group from the viewpoint of improving the adhesion to the adherend and the effect of suppressing wet heat whitening.
- Polyfunctional monomers or oligomers containing are preferred.
- it contains a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as the trunk component of the (meth) acrylic acid ester copolymer (A1), 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 0.1 to 20 with respect to 100 parts by mass of the (meth) acrylic copolymer (A) from the viewpoint of balancing the flexibility and cohesive force as the pressure-sensitive adhesive composition. It is preferable to contain it by the ratio of a mass part, and it is especially preferable that it is a ratio of 0.5 mass part or more or 15 mass parts or less, and especially the ratio of 1 mass part or more or 13 mass parts or less.
- the photopolymerization initiator (C) used in the pressure-sensitive adhesive sheet functions as a reaction initiation assistant in the crosslinking reaction of the crosslinking agent (B), and is capable of emitting visible light, for example, light in the wavelength region of 380 nm to 700 nm.
- Those that generate radicals by irradiation and serve as starting points for the polymerization reaction of the base resin are preferred.
- radicals may be generated only by irradiation with visible light, or radicals may be generated by irradiation with light in a wavelength region other than the visible light region.
- the photopolymerization initiator (C) has an extinction coefficient at a wavelength of 405 nm of 10 mL / (g ⁇ cm) or more, particularly 15 mL / (g ⁇ cm) or more, and more preferably 25 mL / (g ⁇ cm) or more. Some are particularly preferred.
- the upper limit of the extinction coefficient at a wavelength of 405 nm is preferably 1 ⁇ 10 4 mL / (g ⁇ cm) or less, and more preferably 1 ⁇ 10 3 mL / (g ⁇ cm) or less.
- the extinction coefficient in the present invention corresponds to the absorbance at an optical path length of 1 cm when the photopolymerization initiator (C) is a methanol solution having a concentration of 1 g / L.
- the extinction coefficient of the photopolymerization initiator (C) does not mean simply absorbing light of a specific wavelength, but means decomposition performance (radical generation ability) with light of a specific wavelength.
- the “absorption coefficient at a wavelength of 405 nm” means the decomposition performance (radical generation ability) of the photopolymerization initiator when irradiated with light having a wavelength of 405 nm.
- Examples of the photopolymerization initiator having an extinction coefficient at a wavelength of 405 nm of 10 mL / (g ⁇ cm) or more include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis ( ⁇ 5 -2,4-cyclopentadien-1-yl) -bis (2,6- Difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2, 4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine
- photopolymerization initiator (C) is chemically bonded to the (meth) acrylic copolymer (A) is also included. Any one of these or derivatives thereof may be used, or two or more of these may be used in combination. Moreover, you may use together with the photoinitiator whose extinction coefficient in wavelength 405nm is less than 10 mL / (g * cm).
- 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.
- the photopolymerization initiator (C) having an absorption wavelength in the visible light region
- the photoreaction is carried out after the pressure-sensitive adhesive sheet is cross-linked by light irradiation as compared with the case of using the hydrogen abstraction type.
- Photopolymerizable initiators are preferred because they are less likely to remain in the pressure-sensitive adhesive composition, and are unlikely to cause unexpected aging of the pressure-sensitive adhesive sheet, promotion of crosslinking, and promotion of decomposition.
- 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. Damage to the body can be reduced.
- cleavage type photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine is a cleavage-type photopolymerization initiator, and becomes a degradation product after the reaction and discolors.
- Acylphosphine oxide photoinitiators such as fin oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide are preferred.
- the content of the photopolymerization initiator (C) is not particularly limited. For example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic copolymer (A), especially 0.2 parts by weight or more and 5 parts by weight or less, and more preferably 0.5 parts by weight or more or 3 parts by weight. It is particularly preferred to contain it in a proportion of not more than parts. However, this range may be exceeded in balance with other elements.
- a photoinitiator can be used 1 type or in combination of 2 or more types.
- the ultraviolet absorber (D) may be any substance that can absorb ultraviolet rays.
- the absorbance at a wavelength of 380 nm of the transparent double-sided PSA sheet can be increased to 0.3 mL / (g ⁇ cm) or more, preferably 0.5 mL / (g ⁇ cm) or more, and more preferably 1.0 mL / (g ⁇ cm) or more.
- the light absorbency in wavelength 380nm is calculated
- a 380 -Log (T 380/ 100)
- a 380 Absorbance at a wavelength of 380 nm T 380 ; Transmittance (%) at 380 nm of a transparent double-sided PSA sheet
- Examples of the ultraviolet absorber (D) include one or more structures selected from the group consisting of a benzotriazole structure, a benzophenone structure, a triazine structure, a benzoate structure, an oxalanilide structure, a salicylate structure, and a cyanoacrylate structure. What has is preferable. Among these, those having one or two or more structures selected from the group consisting of a benzotriazole structure, a triazine structure and a benzophenone structure are preferable from the viewpoint of ultraviolet absorption.
- the content of the ultraviolet absorber (D) is not particularly limited.
- 0.01 to 10 parts by weight especially 0.1 parts by weight or more and 5 parts by weight or less, among which 0.2 parts by weight or more or 3 parts by weight. It is particularly preferable to contain it in a proportion of not more than parts. However, this range may be exceeded in balance with other elements.
- the ratio of the ultraviolet absorber (D) to 100 parts by mass of the photopolymerization initiator (C) is 25 to 400 parts by mass. However, it is particularly preferably 50 parts by mass or more and 300 parts by mass or less, and particularly preferably 80 parts by mass or more or 250 parts by mass or less.
- An ultraviolet absorber can be used 1 type or in combination of 2 or more types.
- This adhesive sheet may contain the well-known component mix
- tackifying resins, antioxidants, light stabilizers, metal deactivators, rust inhibitors, anti-aging agents, hygroscopic agents, hydrolysis inhibitors, sensitizers, antistatic agents, antifoaming agents, Various additives such as inorganic particles can be appropriately contained.
- the (meth) acrylic copolymer (A) contains an acrylic copolymer composed of a graft copolymer having a macromonomer as a branch component, and is crosslinked. It contains a polyfunctional (meth) acrylic acid ester compound such as bifunctional and trifunctional as the agent (B), a cleavage type photopolymerization initiator as the photopolymerization initiator (C), and an ultraviolet absorber (D ), Examples of compositions containing an ultraviolet absorber having a benzotriazole structure or a benzophenone structure can be given. However, the composition is not limited to the above.
- the pressure-sensitive adhesive sheet may be a single-layer sheet or a multilayer sheet in which two or more layers are laminated.
- the pressure-sensitive adhesive sheet is a multilayer pressure-sensitive adhesive sheet, that is, when a pressure-sensitive adhesive sheet having a laminated structure including an intermediate layer and an outermost layer is formed, the outermost layer is formed from the pressure-sensitive adhesive composition. It is preferable.
- 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. Is more preferable. 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 composition that is, a (meth) acrylic copolymer (A), a crosslinking agent (B), and an extinction coefficient at a wavelength of 405 nm is 10 mL / (g ⁇ cm )
- An intermediate layer ( ⁇ layer) comprising a pressure-sensitive adhesive resin composition containing the photopolymerization initiator (C) and the ultraviolet absorber (D), a (meth) acrylic copolymer (A), and a crosslinking agent.
- the multilayer structure provided with the surface layer ((beta) layer) which contains (B) and does not contain a ultraviolet absorber (D) can be mentioned.
- the laminated structure examples include ⁇ layer / ⁇ layer / ⁇ layer, ⁇ layer / ⁇ layer / ⁇ layer / ⁇ layer / ⁇ layer, and the like. Among them, the two types / three layers of ⁇ layer / ⁇ layer / ⁇ layer are more preferable. If necessary, other layers such as an outgas barrier layer may be interposed between the ⁇ layer and the ⁇ layer.
- ⁇ layer containing the (meth) acrylic copolymer (A) and the crosslinking agent (B) and not containing the ultraviolet absorber (D)
- the ultraviolet absorber (D in the ⁇ layer) Can be suppressed from bleeding out.
- the photopolymerization initiator (C), the decomposition product thereof, or the ultraviolet absorber (D) is contained in the resin composition forming the ⁇ layer, for example, the ⁇ layer (intermediate layer) and the ⁇ layer (
- the ⁇ layer which is the surface layer, absorbs light and cuts the light reaching the ⁇ layer, which is the intermediate layer, or the ultraviolet absorber (D) is
- the layer may shift to a layer and inhibit the photocuring of the ⁇ layer.
- the ⁇ layer preferably does not have photocurability, and more preferably has thermosetting properties.
- the ⁇ layer is more preferably a resin composition that does not contain the photopolymerization initiator (C) and the ultraviolet absorber (D).
- the cross-linking agent (B) used for the ⁇ layer is a polar group such as a hydroxyl group or a carboxyl group from the viewpoint of improving the adhesion to the ⁇ layer and the effect of suppressing wet heat whitening.
- Polyfunctional monomers or oligomers containing functional groups are preferred. Among these, it is more preferable to use a polyfunctional (meth) acrylic monomer having a hydroxyl group.
- the content of the cross-linking agent (B) in the ⁇ layer is 0.5 to 50 parts by mass, particularly 1 to 40 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A) in the ⁇ layer.
- the ratio is preferably 5 parts by mass or more or 30 parts by mass or less.
- the crosslinking agent (B) used for the ⁇ layer has an organic functional group selected from a (meth) acryloyl group, an epoxy group, an isocyanate group, a melamine group, a glycol group, a siloxane group and an amino group from the viewpoint of thermosetting.
- a crosslinking agent containing at least one is preferred.
- the content of the cross-linking agent (B) in the ⁇ layer is 0.1 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A) in the ⁇ layer, particularly 0.2 parts by mass or more and 10 parts by mass or less.
- the ratio is By containing the cross-linking agent (B) within the above range, the curing reaction proceeds sufficiently in a short time.
- tackiness and reliability, foam resistance, step absorbability (foreign matter biting property) ), Flexibility, processability when forming into a sheet, and the like are easily balanced.
- more crosslinking agent (B) is added to the ⁇ layer than to the ⁇ layer. It is possible to impart high elasticity to the ⁇ layer after curing to exhibit the function as a core material and to impart excellent handling properties to the pressure-sensitive adhesive sheet.
- the ⁇ layer absorbs ultraviolet rays and starts photopolymerization in the visible light region excluding the ultraviolet rays.
- the ultraviolet absorber (D) is preferably contained in an amount of 25 to 400 parts by mass, more preferably 50 parts by mass or more and 300 parts by mass or less, and more preferably 80 parts by mass or more and 250 parts by mass with respect to 100 parts by mass. The following is more preferable.
- the procedure for laminating the ⁇ layer and the ⁇ layer and the procedure for curing are not particularly limited. Specifically, the following lamination methods can be exemplified.
- Method I A method of curing the ⁇ layer and the ⁇ layer by irradiating light or heat after laminating the uncured ⁇ layer and the ⁇ layer.
- Method II A method in which a ⁇ layer cured by heat or the like is laminated on an uncured ⁇ layer, and then the ⁇ layer is cured by light irradiation.
- Method III A method in which an uncured ⁇ layer is laminated on an ⁇ layer cured by light irradiation, and then the ⁇ layer is cured by heat or the like.
- Method IV A method in which an ⁇ layer and a ⁇ layer which are separately molded and cured are superposed. Among them, the method II is more preferable because it has a strong interlayer adhesion, is excellent in heat-and-moisture resistance and reliability, and can suppress bleeding out of the ultraviolet absorber.
- the ⁇ layer is preferably thermoset.
- the heating temperature for curing the ⁇ layer is not particularly limited, and can be appropriately adjusted according to the type and amount of the crosslinking agent (B) contained in the ⁇ layer. In consideration of the handling properties of the resin composition before curing, the heat resistance of the resin, etc., specifically, it is preferably 40 to 200 ° C., more preferably 50 ° C. or more and 180 ° C. or less, especially 60 ° C. or more and 150 ° C. or less. Is more preferable.
- the ⁇ layer is preferably photocured.
- amount of light irradiation for curing the ⁇ layer, at the wavelength 405nm reference preferably 100 ⁇ 8000mJ / cm 2, inter alia 500 mJ / cm 2 or more, or 5000 mJ / cm 2 or less is more preferable, and among them 1000 mJ / cm 2 or more or 4000mJ / Cm 2 or less is more preferable.
- the light source that emits light include a high-pressure mercury lamp, a metal halide lamp, and an LED lamp.
- the pressure-sensitive adhesive sheet may be photocrosslinked by irradiating the pressure-sensitive adhesive sheet with light that does not substantially contain light having a wavelength of 380 nm or less, preferably visible light.
- a light beam that does not substantially include light having a wavelength of less than 380 nm means that the light transmittance of light having a wavelength of less than 380 nm is less than 10%.
- a light source that emits only visible light that does not include light in the ultraviolet region may be used, or light having a wavelength in the ultraviolet region may not be transmitted. You may make it irradiate through a filter.
- the thickness of the ⁇ layer is preferably 10 to 400 ⁇ m, more preferably 20 ⁇ m or more and 300 ⁇ m or less, and particularly preferably 30 ⁇ m or more and 200 ⁇ m or less.
- the thickness of the ⁇ layer is preferably 1 to 60 ⁇ m, more preferably 3 ⁇ m or more and 40 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 25 ⁇ m or less.
- the ratio of the ⁇ layer thickness to the ⁇ layer thickness is preferably 1: 1 to 1:20, more preferably 1: 2 to 1:15.
- the thickness of the ⁇ layer (intermediate layer) is in the above range, it is easy to obtain the ultraviolet absorption performance, and it is easy to achieve the photocuring performance of the ⁇ layer. Moreover, it is preferable because it is too flexible and the workability related to cutting and handling is not deteriorated. If the thickness of the ⁇ layer (surface layer) is in the above range, it is preferable because the followability to unevenness and a bent surface is not inferior, and the adhesive force and wettability to the adherend can be maintained.
- the thickness of this adhesive sheet is preferably 20 to 500 ⁇ m, more preferably 25 ⁇ m or more and 350 ⁇ m or less, and particularly preferably 50 ⁇ m or more and 250 ⁇ m or less.
- the ultraviolet transmittance (JIS K7361-1) of the pressure-sensitive adhesive sheet is preferably 50% or less at a wavelength of 380 nm, more preferably 30% or less, and even more preferably 10% or less.
- the light transmittance at a wavelength of 420 nm which is a visible light region is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more.
- the transparent double-sided pressure-sensitive adhesive sheet of the present invention preferably has a viscosity at 100 ° C. of 50 Pa ⁇ s to 5000 Pa ⁇ s, particularly 100 Pa ⁇ s or more or 3000 Pa ⁇ s or less, of which 150 Pa ⁇ s or more or 2500 Pa ⁇ s or less. More preferably.
- This pressure-sensitive adhesive sheet can be used alone as it is. Moreover, it is also possible to use it by laminating with other members.
- a pressure-sensitive adhesive sheet laminate (referred to as “the pressure-sensitive adhesive sheet laminate”) is formed by laminating a film such as a release film, a protective film, or a film formed by laminating these on one side or both sides of the pressure-sensitive adhesive sheet. It is possible.
- the release film on one side or both sides is a release film having a light transmittance of 40% or less at a wavelength of 410 nm or less
- the release sheet is laminated on the adhesive sheet, whereby the adhesive sheet has an extinction coefficient at a wavelength of 405 nm.
- the photopolymerization initiator (C) is 10 mL / (g ⁇ cm) or more, the photopolymerization can be effectively prevented from proceeding by irradiation with visible light.
- it is preferable that one or both of the release films have a light transmittance of 40% or less at a wavelength of 410 nm or less, more preferably 30% or less, and more preferably 20% or less.
- a release film having a light transmittance of 40% or less at a wavelength of 410 nm or less that is, a release film having a function of partially blocking transmission of visible light and ultraviolet light
- an ultraviolet absorber for example, an ultraviolet absorber is used.
- examples thereof include those obtained by applying a silicone resin to a cast film or a stretched film made of a blended polyester-based, polypropylene-based, or polyethylene-based resin and performing a release treatment.
- a multilayer cast film or stretched film formed by molding a layer made of a resin not containing an ultraviolet absorber on one or both sides of a layer made of a polyester, polypropylene, or polyethylene resin containing an ultraviolet absorber.
- One surface may be a silicone resin-coated mold release treatment.
- a UV-absorbing layer is provided on one side of a cast film or stretched film made of a polyester, polypropylene, or polyethylene resin, and a UV-absorbing layer is provided, and a silicone resin is formed on the UV-absorbing layer.
- coated and mold-released can be mentioned.
- a paint film containing a UV absorber is applied to one side of a cast film or stretched film made of polyester, polypropylene, or polyethylene resin to provide an UV absorbing layer, and a silicone resin is applied to the other side. Examples of the mold release treatment can be given.
- the other side of a resin film made of polyester, polypropylene, or polyethylene resin having a release treatment on one surface and a resin film that has not been subjected to a release treatment separately prepared are bonded with an ultraviolet absorber.
- or the adhesion layer can be mentioned.
- the said release film may have other layers, such as an antistatic layer, a hard-coat layer, and an anchor layer, as needed. If the thickness of the release film is too thick, the cutting processability is inferior, and if it is too thin, the handling property is inferior, and there is a possibility that the adhesive sheet is likely to have a dent. From this viewpoint, the thickness of the release film is preferably 20 ⁇ m or more and 300 ⁇ m or less, more preferably 25 ⁇ m or more and 250 ⁇ m or less, and particularly preferably 38 ⁇ m or more or 200 ⁇ m or less. When it is set as the structure which laminated
- the film on one side or both sides is a film having a light transmittance of 40% or less at a wavelength of 380 nm or more and 410 nm or less, such as a release film, a protective film, or the like.
- a film which can be illustrated is a film which can be illustrated.
- a transparent double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive resin composition containing one or both sides, a film having a light transmittance of 40% or less at a wavelength of 380 nm to 410 nm is laminated at least to a wavelength of 405 nm.
- the film on one side or both sides in the pressure-sensitive adhesive sheet laminate has a light transmittance of 40% or less, particularly 30% or less, of which 20% or less, of which 10%. More preferably, it is as follows.
- surface or both surfaces of this adhesive sheet laminated body is mentioned.
- the pressure-sensitive adhesive sheet has a light absorption coefficient of 10 mL / (at a wavelength of 405 nm.
- the surface protective film laminated on one or both surfaces of the pressure-sensitive adhesive sheet laminate preferably has a light transmittance of 40% or less at a wavelength of 410 nm or less, particularly 30% or less, of which 20 % Or less is more preferable.
- a surface protective film having a light transmittance of 40% or less at a wavelength of 410 nm or less that is, a surface protective film having a function of partially blocking transmission of visible light and ultraviolet light
- a surface protective film having a function of partially blocking transmission of visible light and ultraviolet light for example, polyester-based, polypropylene Laminate with an ultraviolet absorbing layer formed by applying a re-peelable fine-adhesive resin to one side of a polyethylene-based or polyethylene-based cast film or stretched film, and applying a paint containing an ultraviolet absorber to the other side A film can be mentioned.
- blended the ultraviolet absorber to one side of a polypropylene-type and a polyethylene-type cast film and a stretched film can be mentioned.
- blended the ultraviolet absorber can be mentioned.
- a multilayer cast film or stretched film formed by molding a layer made of a resin not containing an ultraviolet absorber on one or both sides of a layer made of a polyester, polypropylene, or polyethylene resin containing an ultraviolet absorber.
- One surface may be one in which a slightly adhesive resin having removability is applied.
- a UV-absorbing layer is applied to one side of a cast film or stretched film made of polyester, polypropylene, or polyethylene resin, and an ultraviolet absorbing layer is provided.
- coated the slightly adhesive resin which has property can be mentioned.
- a cast film or stretched film made of polyester, polypropylene, or polyethylene resin is coated on one side with a paint containing an ultraviolet absorber to provide an ultraviolet absorption layer, and the other side has a removability.
- coated the adhesive resin can be mentioned.
- the other side of a resin film made of polyester-based, polypropylene-based, or polyethylene-based resin coated with a slightly peelable resin having removability on one side is bonded to a separately prepared resin film containing an ultraviolet absorber.
- a resin film made of polyester-based, polypropylene-based, or polyethylene-based resin coated with a slightly peelable resin having removability on one side is bonded to a separately prepared resin film containing an ultraviolet absorber. Examples thereof include those laminated through a layer or an adhesive layer.
- the surface protective film may have other layers as necessary, such as an antistatic layer, a hard coat layer, and an anchor layer.
- image display device configuration laminate (Laminated body for configuring the present image display device) It is also possible to form an image display device configuration laminate (referred to as “image display device configuration laminate”) by laminating two image display device components via the adhesive sheet. .
- examples of the two constituent members for the image display device include any one of a group consisting of a touch sensor, an image display panel, a surface protection panel, and a polarizing film, or a combination of two or more kinds.
- the laminate for constituting the present image display device include, for example, a release sheet / this adhesive sheet / touch panel, a release sheet / this adhesive sheet / protective panel, a release sheet / this adhesive sheet / image display panel, and an image display.
- the touch panel includes a structure in which a touch panel function is included in a protective panel and a structure in which a touch panel function is included in an image display panel.
- At least one of the two image display device constituting members may have an ultraviolet absorbing performance, for example, an ultraviolet absorbent. Since this pressure-sensitive adhesive sheet is not cured by ultraviolet rays but is cured by visible light, even if the image display device constituent member has ultraviolet absorption performance, the visible light is irradiated through the image display device constituent member. By this, this adhesive sheet can be hardened.
- An image display device (referred to as “present image display device”) can be configured using the present adhesive sheet or the laminate for constituting the present image display device.
- image display apparatuses such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, and a micro electro mechanical system (MEMS) display, can be comprised, for example.
- MEMS micro electro mechanical system
- At least one of the image display device constituent members constituting the image display device may have an ultraviolet absorption performance, for example, an ultraviolet absorber. Since this pressure-sensitive adhesive sheet is not cured by ultraviolet rays but is cured by visible light, even if the image display device constituent member has ultraviolet absorption performance, the visible light is irradiated through the image display device constituent member. By this, this adhesive sheet can be hardened.
- This pressure-sensitive adhesive sheet has an ultraviolet absorbing function and curability that is cured by irradiation with light having a wavelength other than the ultraviolet region, particularly visible light.
- a laminate for constituting an image display device can be produced as follows.
- this pressure-sensitive adhesive composition After forming this pressure-sensitive adhesive composition into a sheet (sheet preparation step), two image display device constituent members are laminated through this pressure-sensitive adhesive sheet before photocuring (primary sticking step), and then at least wavelength
- the pressure-sensitive adhesive sheet is photocrosslinked and cured (secondary attaching step), thereby producing a laminate for constituting an image display device. can do.
- the light including light rays having a wavelength in the visible light region may include light in the ultraviolet region, that is, a wavelength of 380 nm or less.
- This pressure-sensitive adhesive composition can be formed into a sheet to produce this pressure-sensitive adhesive sheet.
- a method for forming the present pressure-sensitive adhesive resin composition into a sheet a currently known method can be arbitrarily employed.
- this adhesive sheet by forming this adhesive resin composition into a sheet form on the said release film.
- the pressure-sensitive adhesive resin composition may be formed into a sheet on an image display device constituent member and the pressure-sensitive adhesive sheet may be laminated on the image display device constituent member.
- this pressure-sensitive adhesive sheet is provided with self-adhesiveness (tackiness), it is possible to perform primary adhesion simply by overlapping two image display device constituent members via this pressure-sensitive adhesive sheet.
- this pressure-sensitive adhesive sheet is based on an acrylic copolymer (A1) made of a graft copolymer having a macromonomer as a branch component, it is self-attached while maintaining the sheet shape at room temperature.
- an appropriate adhesive property for example, a peelable adhesive property (referred to as “tackiness”). It is possible to facilitate positioning and the like when sticking.
- the pressure-sensitive adhesive can be filled following uneven portions such as printing steps, and filling is performed without generating bubbles. be able to.
- a well-known apparatus can be used for the bonding apparatus used when laminating.
- an electrothermal press machine provided with a heating plate, a diaphragm type laminator, a roll laminator, a vacuum bonding machine, a hand roll, and the like can be given.
- this pressure-sensitive adhesive sheet uses an acrylic copolymer (A1) comprising a graft copolymer having a macromonomer as a branch component as a base polymer, excellent storage stability in a normal state, that is, at room temperature. And cutting processability can be imparted. Moreover, since it has self-adhesiveness (tackiness), it is possible to obtain adhesiveness to the extent that it can be easily attached by simply pressing the adhesive sheet against the adherend, so positioning for adhering adhesive material can be achieved. It is easy to do and very convenient for work.
- the pressure-sensitive adhesive sheet molded on the release film can be made to the dimensions of the components constituting the image display device to be laminated. It can also be cut in advance.
- 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 pressure-sensitive adhesive sheet has a hot melt property, that is, a property of being softened or fluidized by heating, it is preferable to heat the pressure-sensitive adhesive sheet and laminate two image display device constituent members.
- a heating means of this pressure-sensitive adhesive sheet for example, various thermostats, a hot plate, an electromagnetic heating device, a heating roll, or the like can be used.
- an electrothermal press, a diaphragm type laminator, a roll laminator, or the like is preferably used. Under the present circumstances, this adhesive sheet can also be heated by heating one or both of the image display apparatus structural members.
- the softening temperature of the pressure-sensitive adhesive sheet is 50 ° C. or higher, the processing characteristics and the storage characteristics at room temperature can be made sufficient.
- the softening temperature of the pressure-sensitive adhesive sheet is 100 ° C. or less, not only can the thermal damage to the image display panel or the front panel be suppressed, but also the pressure-sensitive adhesive sheet can be prevented from flowing too much. it can.
- the softening temperature of the present pressure-sensitive adhesive sheet is preferably 50 to 100 ° C., more preferably 55 ° C. or more and 95 ° C. or less, and particularly preferably 60 ° C. or more and 90 ° C. or less.
- the pressure-sensitive adhesive sheet When heating the pressure-sensitive adhesive sheet, it is preferable to heat the laminated body under a reduced pressure environment after two image display device constituent members are stacked and stacked via the pressure-sensitive adhesive sheet. By heating the laminate in a reduced pressure environment, it is possible to prevent air bubbles from being mixed into the pressure-sensitive adhesive sheet after the pasting or foreign matters from being mixed in.
- the image display device constituting member is formed from the outside of at least one image display device constituting member with respect to a laminate formed by laminating two image display device constituting members via the adhesive sheet. Then, the pressure-sensitive adhesive sheet is irradiated with light having a wavelength of at least 405 nm, for example, light containing light having a wavelength in the visible light region, that is, visible light, and the pressure-sensitive adhesive sheet is photocrosslinked and cured.
- this pressure-sensitive adhesive sheet can be firmly cross-linked by photocrosslinking in this way, for example, an adhesive force that can sufficiently counteract the gas pressure of outgas generated from image display device constituent members such as a protective panel. It can have cohesive strength. And since this adhesive sheet has ultraviolet absorptivity, deterioration by the ultraviolet-ray of adhesive sheet itself and an image display apparatus structural member can be suppressed.
- the light having a wavelength of at least 405 nm can be irradiated from a light source composed of at least one or a combination of two or more selected from, for example, the sun, a fluorescent lamp, an LED, an organic EL, an inorganic EL, and a light emitting module for an image display device.
- a light source composed of at least one or a combination of two or more selected from, for example, the sun, a fluorescent lamp, an LED, an organic EL, an inorganic EL, and a light emitting module for an image display device.
- a light source composed of at least one or a combination of two or more selected from, for example, the sun, a fluorescent lamp, an LED, an organic EL, an inorganic EL, and a light emitting module for an image display device.
- the pressure-sensitive adhesive sheet is irradiated with light having a wavelength of at least 405 nm, for example, light having a wavelength in the visible light region and not substantially including light having a wavelength of 380 nm or less, and the pressure-sensitive adhesive sheet is photocrosslinked and cured. It is preferable to do so.
- substantially free of light having a wavelength of 380 nm or less means that the emission intensity of light having a wavelength of 380 nm or less is 5 mW / cm 2 or less, preferably 1 mW / cm 2 or less.
- a light source that emits only visible light that does not include light having a wavelength in the ultraviolet region may be used.
- a light source composed of at least one kind selected from the sun, a fluorescent lamp, an LED, an organic EL, an inorganic EL, and a light emitting module for an image display device, or a combination of two or more kinds can be used.
- the light transmittance at a wavelength of 380 nm is less than 10%.
- a method of irradiating the adhesive composition with visible light through a filter having a light transmittance of 60% or more at a wavelength of 405 nm can be mentioned.
- the filter may be a release film constituting the pressure-sensitive adhesive sheet laminate or a surface protective film used by being laminated on the surface of the pressure-sensitive adhesive sheet laminate.
- the visible light is partially blocked by irradiating visible light through the filter. It is also possible to adjust the degree of crosslinking.
- 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).
- the term “sheet” is included and the term “sheet” is used.
- film is included.
- the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet, and a film.
- 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.
- the integrated light quantity at a wavelength of 405 nm and a wavelength of 365 nm measured in this example was measured using an integrated light quantity meter (UIT-250, manufactured by USHIO INC.).
- Example 1-1 (Meth) acrylic copolymer (A) comprising 15 parts by mass of polymethyl methacrylate macromonomer (Tg 80 ° C.) having a number average molecular weight of 3000, 81 parts by mass of butyl acrylate, and 4 parts by mass of acrylic acid (A-1, mass average molecular weight 300,000) 1 kg, 100 g of glycerin dimethacrylate (Blenmer GMR, manufactured by NOF Corporation) (B-1) as a crosslinking agent (B), and Ezacure KTO46 as a photopolymerization initiator (C) (C-1) 15 g (manufactured by Lanberti), 2,6-diphenyl-4- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine (BASF) as UV absorber (D) Manufactured, Tinuvin 1577) (D-1) was added and mixed uniformly to obtain an adhesive composition 1.
- the pressure-sensitive adhesive composition 1 was formed into a sheet shape having a thickness of 100 ⁇ m on a polyethylene terephthalate film (Mitsubishi Resin Co., Ltd., Diafoil MRV, thickness 100 ⁇ m) subjected to a release treatment, and then the release-treated polyethylene.
- a terephthalate film manufactured by Mitsubishi Plastics, Diafoil MRQ, thickness 75 ⁇ m was coated to prepare an adhesive sheet laminate 1.
- Example 1-2 As the (meth) acrylic copolymer (A), 10 parts by mass of a polymethyl methacrylate macromonomer having a number average molecular weight of 1400 (Tg 55 ° C.) and 90 parts by mass of 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) 1 kg of polymerized acrylic graft copolymer (A-2) (weight average molecular weight: 230,000) and tricyclodecane dimethacrylate (product name: DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent (B) ( B-2) 50 g, Irgacure 369 (C-2) (manufactured by BASF) as photopolymerization initiator (C), and 2- (2H-benzotriazol-2-yl) -4 as UV absorber (D) , 6-Di-tert-pentylphenol (JF-80, JF-80) (D-
- the pressure-sensitive adhesive composition 4 was applied on a polyethylene terephthalate film (Mitsubishi Resin, Diafoil MRV, thickness 100 ⁇ m) subjected to a release treatment so as to have a thickness of 100 ⁇ m, and then the release-treated polyethylene terephthalate film (Mitsubishi). Resin Co., Ltd., Diafoil MRQ, thickness 75 ⁇ m) was coated to prepare an adhesive sheet laminate 2.
- the extinction coefficient at 405 nm of the photopolymerization initiator (C-2) was 1.6 ⁇ 10 2 (mL / (g ⁇ cm)).
- Example 1-3 As the (meth) acrylic copolymer (A), a copolymer comprising 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 4 parts by mass of acrylic acid (A-3, mass average molecular weight 400,000)
- A-3 mass average molecular weight 400,000
- propoxylated pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., ATM-4P
- B-3 propoxylated pentaerythritol tetraacrylate
- B-3 200 g as a crosslinking agent
- Irgacure 819 C-3
- C photopolymerization initiator
- D-3 as an ultraviolet absorber
- the adhesive resin composition 3 is sandwiched between two peeled polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Mitsubishi Resin, Diafoil MRT, thickness 38 ⁇ m), and the thickness is 100 ⁇ m.
- the sheet was formed into a sheet shape so as to form an intermediate layer sheet ( ⁇ ).
- L as an isocyanate-based crosslinking agent for 1 kg of a pressure-sensitive adhesive solution (manufactured by Soken Chemical Co., Ltd., SK Dyne 1882, solid content concentration: about 17%) made of a commercially available acrylic copolymer (A-4, mass average molecular weight 1.3 million) 1.85 g of -45 (B-5) (manufactured by Soken Chemical Co., Ltd.) and 0.5 g of E-5XM (B-6) (manufactured by Soken Chemical Co., Ltd.) as an epoxy-based cross-linking agent were added.
- A-4 mass average molecular weight 1.3 million
- the PET films on both sides of the intermediate layer resin sheet ( ⁇ ) are sequentially peeled and removed, and the adhesive surfaces of the adhesive layer resin sheets ( ⁇ ) and ( ⁇ ′) are sequentially applied to both surfaces of the intermediate layer sheet ( ⁇ ).
- a laminate (thickness 150 ⁇ m) composed of ( ⁇ ) / ( ⁇ ) / ( ⁇ ′) was produced.
- the pressure-sensitive adhesive sheet laminate 3 was prepared by irradiating and photocrosslinking the intermediate layer resin sheet ( ⁇ ).
- Example 1-4 Example 1 except that a release film obtained by applying a silicone release agent to a PET film (thickness 100 ⁇ m) containing an ultraviolet absorber instead of the polyethylene terephthalate film (diafoil MRV, thickness 100 ⁇ m) subjected to the release treatment was used.
- a pressure-sensitive adhesive sheet laminate 4 was prepared in the same manner as in -1.
- Example 1-5 From the surface of the polyethylene terephthalate film (diafoil MRV, thickness 100 ⁇ m) of the pressure-sensitive adhesive sheet laminate prepared in Example 1-1, from a slightly adhesive layer (5 ⁇ m) / polyethylene terephthalate film (25 ⁇ m) / ultraviolet absorption layer (3 ⁇ m). The surface of the surface protective film was adhered to the surface of the slightly adhesive layer, and a pressure-sensitive adhesive sheet laminate 5 having a structure of release film / adhesive sheet / release film / surface protective film was prepared.
- Example 1-1 An adhesive sheet laminate 6 was prepared in the same manner as in Example 1-1 except that 15 g of Ezacure TZT (C-5) was added as a photopolymerization initiator instead of Ezacure KTO46 (C-1).
- the extinction coefficient at 405 nm of the photopolymerization initiator (C-5) was less than 10 (mL / (g ⁇ cm)), and was too low to be measured.
- Example 1-2 A pressure-sensitive adhesive sheet laminate 7 was prepared in the same manner as in Example 1-2 except that the ultraviolet absorbent (D-2) was not added.
- the pressure-sensitive adhesive composition was applied so that the thickness after drying was 50 ⁇ m, and then at 80 ° C. It was dried for 5 minutes to obtain a sheet-like pressure-sensitive adhesive composition 7 having a thickness of 50 ⁇ m.
- the film was applied to a peeled polyethylene terephthalate film (manufactured by Mitsubishi Plastics, Diafoil MRQ, thickness 75 ⁇ m) so that the thickness after drying was 50 ⁇ m, and then dried at 80 ° C. for 5 minutes. A 50 ⁇ m sheet-like pressure-sensitive adhesive composition 7 was obtained.
- a release-treated polyethylene terephthalate film manufactured by Mitsubishi Plastics, Diafoil MRQ, thickness 75 ⁇ m was coated. This was cured for 7 days at room temperature (23 ° C.) to react with the cross-linking agent, and the pressure-sensitive adhesive sheet laminate 8 was prepared.
- the light transmittance in the wavelength range of 360 to 430 nm of the prepared test piece was measured with a spectrophotometer (manufactured by Shimadzu Corporation; instrument name “UV2450”).
- a sample having a light transmittance of less than 50% at 380 nm was determined as “UV (good)”, and a sample having 50% or more was determined as “UV (poor)”.
- the results are shown in Table 1.
- a glass plate 1 with a printed level difference of 58 mm ⁇ 110 mm ⁇ 0.8 mm thick is printed on the peripheral edge of the glass (long side 3 mm, short side 15 mm) and the opening is 52 mm ⁇ 80 mm. did. Further, a glass plate 2 with a printed step having a printing height of 10 ⁇ m and an opening of 52 mm ⁇ 80 mm is applied to the peripheral part (long side 3 mm, short side 15 mm) of glass 58 mm ⁇ 110 mm ⁇ 0.8 mm thick. Prepared.
- One release film of the pressure-sensitive adhesive sheet laminate was peeled off and roll-bonded to soda lime glass having a thickness of 54 mm ⁇ 82 mm and a thickness of 0.5 mm.
- the remaining release film is peeled off and press-bonded to the printing surface of the glass plates 1 and 2 with a printing step using a vacuum press so that the four sides of the adhesive surface are on the printing step (absolute pressure 5 kPa, temperature 70 ° C., press pressure 0.04 MPa), autoclave treatment (70 ° C., gauge pressure 0.2 MPa, 20 minutes) was applied and finished.
- the integrated light quantity at a wavelength of 405 nm is 3000 mJ / cm 2 .
- the sample for evaluation was created by irradiating with light.
- the sample for evaluation was cured at 85 ° C. for 6 hours, and the one having no change in appearance without foaming or the like was heat-resistant “ ⁇ (good)”, and the one having foaming or peeling was heat-resistant “ ⁇ ( poor) ”.
- the results are shown in Table 1.
- the sample for evaluation was irradiated with ultraviolet rays for 24 hours using a xenon light resistance tester (Suntest CPS, manufactured by Atlas Co., Ltd.), and the pressure-sensitive adhesive sheet was not lifted. Those with floating or peeling were judged as light resistance “ ⁇ (poor)”. The results are shown in Table 1.
- Example 1-1 The polyethylene terephthalate film (Mitsubishi Resin Co., Ltd., Diafoil MRV, thickness 100 ⁇ m) used in Example 1-1 and the PET film containing the UV absorber used in Example 1-4 (thickness 100 ⁇ m) were used.
- the release film coated with the silicone release agent and the surface protective film used in Example 1-5 the light transmittance in the wavelength range of 380 to 450 nm was measured with a spectrophotometer (manufactured by Shimadzu Corporation; device name “UV2450”) ). The results are shown in Table 2.
- the polyethylene terephthalate film (Mitsubishi resin company make, Diafoil MRV, thickness 100micrometer) which carried out the peeling process, the ultraviolet-ray used in Example 1-4, respectively.
- the release film with the silicone release agent applied to the PET film (thickness 100 ⁇ m) containing the absorbent and the surface protective film side were left to stand.
- a fluorescent lamp (illuminance 1100 Lx) was irradiated from the film side for 7 days.
- the integrated light amount of the irradiated light at a wavelength of 405 nm was about 43 J / cm 2
- the integrated light amount at a wavelength of 365 nm was about 1 mJ / cm 2 or less and was not measurable.
- the gel fraction of the pressure-sensitive adhesive material was determined by the following method. The results are shown in Table 2.
- the pressure-sensitive adhesive sheet laminates of Examples 1-1 to 1-5 have not only excellent ultraviolet absorption performance, but also excellent quality that satisfies both the unevenness absorbability at the time of bonding and the reliability after member bonding. It was a thing.
- Comparative Example 1-1 used a photopolymerization initiator having an extinction coefficient at a wavelength of 405 nm of less than 10 mL / (g ⁇ cm), that is, an extinction coefficient at a wavelength of 405 nm of 10 mL / (g ⁇ cm) or more. Since the photopolymerization initiator was not used, the pressure-sensitive adhesive material was not cured even when irradiated with light, and the adhesive strength after the secondary sticking and the reliability after the sticking were not obtained.
- Comparative Example 1-2 did not contain the ultraviolet absorber (D), and no ultraviolet absorption performance was obtained. For this reason, foaming of the adhesive sheet was observed in the light resistance test, and the bonding reliability was inferior.
- Comparative Example 1-3 is a pressure-sensitive adhesive sheet obtained by crosslinking a pressure-sensitive adhesive composition by thermal crosslinking. Since it did not have a photocurable layer, it was inferior to the uneven
- a PET film containing an ultraviolet absorber is used as a release film. Thereby, before bonding to a member, it was able to suppress that the photocuring reaction of an adhesive material composition advances, and it was able to be set as the adhesive sheet laminated body excellent in storage stability.
- Example 1-5 a surface protective film having an ultraviolet absorbing layer is laminated on the surface of the release film. Thereby, before bonding to a member, it was able to suppress that the photocuring reaction of an adhesive material composition advances, and it was able to be set as the adhesive sheet laminated body excellent in storage stability.
- Example 2-1 As the (meth) acrylic copolymer (2-A), a copolymer composed of 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 4 parts by mass of acrylic acid (2-A-1, having a mass average molecular weight of 40 1) 1 kg of propoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., ATM-4P) (2-B-1) as a crosslinking agent (2-B), photopolymerization initiator (2-C) ) 8 g of Irgacure 369 (2-C-1) (manufactured by BASF), and 2,2′-dihydroxy-4-methoxybenzophenone (manufactured by Chemipro Kasei Co., Ltd., Chemisorb 111) (2- D-1) 10 g was added and mixed uniformly to obtain an adhesive resin composition 2-1.
- the extinction coefficient at 405 nm of the photopolymerization initiator (2-C-1) was 1.6 ⁇ 10 2 mL / (g ⁇ cm).
- the adhesive resin composition 2-1 is sandwiched between two exfoliated polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Mitsubishi Resin, Diafoil MRT, thickness 38 ⁇ m).
- An intermediate layer sheet ( ⁇ -1) was prepared by forming into a sheet shape to 110 ⁇ m.
- Isocyanate-based crosslinking agent for 1 kg of a pressure-sensitive adhesive solution (manufactured by Soken Chemical Co., Ltd., SK Dyne 1882, solid content concentration: about 17%) made of a commercially available acrylic copolymer (2-A-2, weight average molecular weight 1.3 million)
- a pressure-sensitive adhesive solution manufactured by Soken Chemical Co., Ltd., SK Dyne 1882, solid content concentration: about 17%
- the polyethylene terephthalate film (Mitsubishi Resin Co., Ltd., Diafoil MRV, thickness 100 ⁇ m) subjected to the release treatment, after applying the above adhesive layer coating solution so that the thickness after drying becomes 20 ⁇ m, 80 The ⁇ layer was thermally cured by drying at 5 ° C. for 5 minutes to prepare a surface layer sheet ( ⁇ -1). Furthermore, after coating the polyethylene resin terephthalate film (Mitsubishi Resin Co., Ltd., Diafoil MRQ, thickness 75 ⁇ m) on the peel-treated polyethylene adhesive terephthalate film 2 so that the thickness after drying is 20 ⁇ m, The ⁇ layer was thermally cured by drying at 80 ° C.
- a surface layer sheet ( ⁇ ′-1) For 5 minutes to prepare a surface layer sheet ( ⁇ ′-1).
- the PET films on both sides of the intermediate layer sheet ( ⁇ -1) are peeled and removed sequentially, and the adhesive surfaces of the surface layer sheets ( ⁇ -1) and ( ⁇ ′-1) are sequentially bonded to both surfaces, and ( ⁇ -1) / ( ⁇ -1) / ( ⁇ '-1) was produced.
- Irradiation is performed using a high-pressure mercury lamp through a PET film remaining on the surface of ( ⁇ -1) and ( ⁇ ′-1) using a high-pressure mercury lamp so that the accumulated light amount at a wavelength of 405 nm is 1500 mJ / cm 2, and the ⁇ layer is cured.
- a transparent double-sided PSA sheet laminate 2-1 was produced.
- Example 2-2 For 1 kg of (meth) acrylic copolymer (2-A-1), 200 g of crosslinking agent (2-B-1) and Ezacure KTO46 (2-C-2) as a photopolymerization initiator (2-C) ) (Manufactured by Lanberti) and 20 g of UV absorber (2-D-1) were added and mixed uniformly to obtain an adhesive resin composition 2-3.
- the extinction coefficient at 405 nm of the photopolymerization initiator (2-C-2) was 7.4 ⁇ 10 1 mL / (g ⁇ cm).
- the adhesive resin composition 2-3 is sandwiched between two peeled polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Mitsubishi Resin, Diafoil MRT, thickness 38 ⁇ m).
- An intermediate layer sheet ( ⁇ -2) was prepared by forming into a sheet shape to 60 ⁇ m.
- the PET films on both sides of the intermediate layer sheet ( ⁇ -2) were sequentially peeled and removed, and the adhesive layers of the surface layer sheets ( ⁇ -1) and ( ⁇ ′-1) were formed on both surfaces. Were laminated in order to produce a laminate composed of ( ⁇ -1) / ( ⁇ -2) / ( ⁇ '-1).
- Irradiation is performed using a high-pressure mercury lamp through a PET film remaining on the surfaces of ( ⁇ -1) and ( ⁇ ′-1) using a high-pressure mercury lamp so that the integrated light quantity at a wavelength of 405 nm is 3000 mJ / cm 2, and the ⁇ layer is cured.
- a transparent double-sided PSA sheet laminate 2-2 (thickness: 100 ⁇ m) was produced.
- Example 2-3 For 1 kg of (meth) acrylic copolymer (2-A-1), 200 g of crosslinking agent (2-B-1), 8 g of photopolymerization initiator (2-C-2), UV absorber ( 20 g of 2-D-1) was added and mixed uniformly to obtain an adhesive resin composition 2-4.
- the adhesive resin composition 2-4 is sandwiched between two peeled polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Mitsubishi Resin, Diafoil MRT, thickness 38 ⁇ m).
- An intermediate layer sheet ( ⁇ -3) was prepared by forming into a sheet shape to 60 ⁇ m.
- Example 2-1 the PET films on both sides of the intermediate layer sheet ( ⁇ -3) were sequentially peeled and removed, and the adhesive surfaces of the surface layer sheets ( ⁇ -1) and ( ⁇ ′-1) were provided on both sides.
- Lamination was sequentially performed to prepare a laminate composed of ( ⁇ -1) / ( ⁇ -3) / ( ⁇ '-1). Irradiation is performed using a high-pressure mercury lamp through a PET film remaining on the surfaces of ( ⁇ -1) and ( ⁇ ′-1) using a high-pressure mercury lamp so that the integrated light quantity at a wavelength of 405 nm is 3000 mJ / cm 2, and the ⁇ layer is cured.
- a transparent double-sided PSA sheet laminate 2-3 (thickness: 100 ⁇ m) was prepared.
- the adhesive resin composition 2-5 is sandwiched between two exfoliated polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Mitsubishi Resin, Diafoil MRT, thickness 38 ⁇ m).
- An intermediate layer sheet ( ⁇ -4) was prepared by forming into a sheet shape so as to be 110 ⁇ m.
- the PET films on both sides of the intermediate layer sheet ( ⁇ -4) were sequentially peeled and removed, and the adhesive layers of the surface layer sheets ( ⁇ -1) and ( ⁇ ′-1) were formed on both surfaces. Were laminated in order to produce a laminate composed of ( ⁇ -1) / ( ⁇ -4) / ( ⁇ '-1).
- Irradiation is performed using a high-pressure mercury lamp through a PET film remaining on the surface of ( ⁇ -1) and ( ⁇ ′-1) using a high-pressure mercury lamp so that the accumulated light amount at a wavelength of 405 nm is 1500 mJ / cm 2, and the ⁇ layer is cured.
- a transparent double-sided PSA sheet laminate 2-4 (thickness: 100 ⁇ m) was produced.
- Example 2-1 the PET films on both sides of the intermediate layer sheet ( ⁇ -5) were sequentially peeled and removed, and the adhesive surfaces of the surface layer sheets ( ⁇ -1) and ( ⁇ ′-1) were both removed.
- the laminate was sequentially laminated on the surface to prepare a laminate composed of ( ⁇ -1) / ( ⁇ -5) / ( ⁇ '-1). Irradiation is performed using a high-pressure mercury lamp through a PET film remaining on the surface of ( ⁇ -1) and ( ⁇ ′-1) using a high-pressure mercury lamp so that the accumulated light amount at a wavelength of 405 nm is 1500 mJ / cm 2, and the ⁇ layer is cured.
- a transparent double-sided PSA sheet laminate 2-5 was produced.
- the remaining release film was peeled off, and the test piece was attached to the SUS plate (thickness 120 mm, 5 mm ⁇ 1.5 mm) erected vertically by a hand roller so as to overlap the length of 20 mm. .
- the sticking area of the transparent double-sided PSA sheet and the SUS plate is 25 mm ⁇ 20 mm.
- a weight with a load of 500 g was attached to the test piece in the vertical direction and left to stand for 30 minutes, and then the SUS and the test piece were adhered to each other. The deviation length (mm) was measured downward.
- a deviation length of less than 1 mm is indicated by “ ⁇ (Excellent)”
- a deviation length of 1 mm or more and less than 2 mm is indicated by “ ⁇ (Good)”
- a deviation length of 2 mm or more is indicated by “ ⁇ (poor)”.
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Abstract
Description
しかし、かかる紫外線感応性を有する粘着シートは、長期間紫外線に曝されると粘着シート自身の劣化が進行し、分解物を生じて発泡や剥離を生ずる可能性がある。
また、画像表示装置構成部材の中には、紫外線劣化しやすい部材があるため、このような場合には、上記のような方法で2つの画像表示装置構成部材を貼着することはできない。
さらに、画像表示装置構成部材が紫外線吸収性をもつ場合は、当該部材を介して紫外線を照射しても粘着シートまで紫外線が十分に到達しないため、このような場合においても、上記のような方法で2つの画像表示装置構成部材を貼着することはできない。
本発明の実施形態の一例にかかる透明両面粘着シートは、(メタ)アクリル系共重合体(A)、架橋剤(B)、波長405nmでの吸光係数が10mL/(g・cm)以上である光重合開始剤(C)及び紫外線吸収剤(D)を含有する粘着剤樹脂組成物(「本粘着剤組成物」と称する)からなる透明両面粘着シート(「本粘着シート」と称する)である。
本粘着シートのベースポリマーとしての(メタ)アクリル系重合体は、これを重合するために用いられるアクリルモノマーやメタクリルモノマーの種類、組成比率、さらには重合条件等によって、ガラス転移温度(Tg)等の特性を適宜調整することが可能である。
上記共重合性モノマーDは、共重合体の全モノマー成分中に0質量%以上70質量%以下含有するのが好ましく、中でも3質量%以上或いは65質量%以下、その中でも特に5質量%以上或いは60質量%以下の範囲で含有するのがさらに好ましい。
本粘着シートの好ましいベースポリマーの一例として、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(メタ)アクリル系共重合体(A1)を挙げることができる。
よって、本粘着シートのベースポリマーとしてアクリル系共重合体(A1)を使用すれば、未架橋状態であっても、室温(20℃)において粘着性を示し、且つ、100℃で軟化乃至流動化する性質、又は、50~90℃、より好ましくは60℃以上或いは80℃以下の温度に加熱すると軟化乃至流動化する性質を備えることができる。
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(A1)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指す。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。]
但し、当該共重合体成分のガラス転移温度が同じ温度であったとしても、分子量を調整することにより粘弾性を調整することができる。例えば共重合体成分の分子量を小さくすることにより、より柔軟化させることができる。
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、スチレン、t-ブチルスチレン、α-メチルスチレン、ビニルトルエン、アクリロニトリル、メタクリロニトニル、酢酸ビニル、プロピオン酸ビニル、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、アルキルビニルモノマー等の各種ビニルモノマーも適宜用いることができる。
アクリル系共重合体(A1)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。
また、疎水性のビニルモノマーとしては酢酸ビニル、スチレン、t-ブチルスチレン、α-メチルスチレン、ビニルトルエン、アルキルビニルモノマーなどを挙げることができる。
アクリル系共重合体(A1)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好ましい。
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。
具体的には、マクロモノマーのガラス転移温度(Tg)は、本粘着シートの加熱溶融温度(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、50℃から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。
かかる観点から、マクロモノマーは、アクリル系共重合体(A1)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。
また、マクロモノマーの数平均分子量は500以上8000未満であることが好ましく、中でも800以上或いは7500未満、その中でも1000以上或いは7000未満であるのが好ましい。
マクロモノマーは、一般に製造されているもの(例えば、東亜合成社製マクロモノマーなど)を適宜使用することができる。
前記マクロモノマーの高分子量骨格成分としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、ネオペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、2-エチルヘキシルアクリレート、n-オクチルアクリート、イソオクチルアクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、t-ブチルシクロヘキシル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、セチル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、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(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、(メタ)アクリル酸、グリシジル(メタ)アクリレート、(メタ)アクリルアミド、N、N-ジメチル(メタ)アクリルアミド、(メタ)アクリルニトリル、アルコキシアルキル(メタ)アクリレート、アルコキシポリアルキレングリコール(メタ)アクリレート等の(メタ)アクリレートモノマーや、スチレン、t-ブチルスチレン、α-メチルスチレン、ビニルトルエン、アルキルビニルモノマー、アルキルビニルエステル、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が挙げられ、これらは単独で又は2種類以上を組み合わせて使用することができる。
架橋剤(B)としては、少なくとも二重結合架橋を有する架橋剤が好ましい。例えば(メタ)アクリロイル基、エポキシ基、イソシアネート基、カルボキシル基、ヒドロキシル基、カルボジイミド基、オキサゾリン基、アジリジン基、ビニル基、アミノ基、イミノ基、アミド基から選ばれる少なくとも1種の架橋性官能基を有する架橋剤を挙げることができ、1種又は2種以上を組み合わせて使用してもよい。また、架橋剤(B)が(メタ)アクリル系共重合体(A)と化学結合した態様も包含される。
中でも、多官能(メタ)アクリレートを用いるのが好ましい。ここで、多官能は2つ以上の架橋性官能基を有するものを指す。なお、必要に応じて3つ以上、4つ以上の架橋性官能基を有してもよい。
なお、上記架橋性官能基は、脱保護可能な保護基で保護されていてもよい。
湿熱白化を防止する観点からは、前記(メタ)アクリル酸エステル共重合体(A1)、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。
また、密着性や耐湿熱性、耐熱性等の効果を調整するために、架橋剤(B)と反応する、単官能又は多官能の(メタ)アクリル酸エステルを、更に加えてもよい。
本粘着シートに用いられる光重合開始剤(C)は、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ものであり、可視光線、例えば380nm~700nmの波長領域の光線の照射によって、ラジカルを発生させてベース樹脂の重合反応の起点となるものが好ましい。但し、可視光線の照射のみによってラジカルを発生させるものであってもよいし、また、可視光領域以外の波長領域の光線の照射によってもラジカルを発生させるものであってもよい。
本発明における吸光係数は、光重合開始剤(C)を濃度1g/Lのメタノール溶液としたときの、光路長1cmにおける吸光度に相当する。なお、光重合開始剤(C)の吸光係数は、単に特定波長の光を吸収するという意味ではなく、特定波長の光での分解性能(ラジカル発生能)を意味する。具体的には、「波長405nmでの吸光係数」は、波長405nmの光を照射した際の光重合開始剤の分解性能(ラジカル発生能)を意味するものである。
これらは、これらのうちの何れか一種またはその誘導体を用いてもよいし、又、これらのうちの二種類以上を組み合わせて用いてもよい。また、波長405nmでの吸光係数が10mL/(g・cm)未満の光重合開始剤と併用してもよい。
これらのうちの開裂型光重合開始剤は、光照射によってラジカルを発生する際に分解して別の化合物となり、一度励起されると反応開始剤としての機能をもたなくなる。このため、可視光線域に吸収波長をもつ光重合開始剤(C)として該分子内開裂型を用いると、水素引抜型を用いる場合に比べて、光線照射によって粘着シートを架橋した後、光線反応性の光重合性開始剤が本粘着剤組成物中に残りにくく、粘着シートの予期せぬ経時変化や架橋の促進、分解の促進を招く可能性が低いため好ましい。また、光重合性開始剤特有の着色については、従来は粘着剤に可視光線を照射して硬化させる光重合開始剤を添加する場合、着色のおそれがあったが、反応分解物の可視光線域の吸収がなくなり、消色するものを適宜選択することが好ましい。
他方、水素引抜型の光重合開始剤は、紫外線などの活性エネルギー線照射によるラジカル発生反応時に、開裂型光重合開始剤のような分解物を生じないので、反応終了後に揮発成分となりにくく、被着体へのダメージを低減させることができる。
さらに、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との相性からは、光重合開始剤(C)として2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、(2,4,6-トリメチルベンゾイル)エトキシフェニルホスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)2,4,4-トリメチルペンチルフォスフィンオキサイドなどを用いるのが好ましい。
紫外線吸収剤(D)は、紫外線を吸収できる物質であればよく、目安としては、紫外線吸収剤(D)の添加によって、透明両面粘着シートの波長380nmでの吸光度を0.3mL/(g・cm)以上、中でも0.5mL/(g・cm)以上、その中でも1.0mL/(g・cm)以上とすることができる物質であるのが好ましい。
A380=-Log(T380/100)
A380:波長380nmでの吸光度
T380;透明両面粘着シートの380nmにおける透過率(%)
中でも、紫外線吸収性の観点から、ベンゾトリアゾール構造、トリアジン構造及びベンゾフェノン構造からなる群より選択される1つ又は2つ以上の構造を有するものが好ましい。
また、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との相性の観点からは、紫外線吸収剤(D)としてベンゾトリアゾール構造又はベンゾフェノン構造などを用いるのが好ましい。
本粘着シートは、上記以外の成分として、通常の粘着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、粘着付与樹脂や、酸化防止剤、光安定化剤、金属不活性化剤、防錆剤、老化防止剤、吸湿剤、加水分解防止剤、増感剤、帯電防止剤、消泡剤、無機粒子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、必要に応じて適宜含有してもよい。
本粘着剤組成物の特に好ましい組成の一例として、(メタ)アクリル系共重合体(A)として、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を含有し、架橋剤(B)として、2官能、3官能などの多官能(メタ)アクリル酸エステル化合物を含有し、光重合開始剤(C)として、開裂型光重合開始剤を含有し、紫外線吸収剤(D)として、ベンゾトリアゾール構造又はベンゾフェノン構造を有する紫外線吸収剤を含有する組成例を挙げることができる。但し、このように組成に限定されるものではない。
本粘着シートは、単一層からなるシートであっても、2層以上が積層してなる多層シートであってもよい。
本粘着シートを多層の粘着シートとする場合には、すなわち、中間層と最外層とを備えた積層構成の粘着シートを形成する場合には、その最外層を、本粘着剤組成物から形成することが好ましい。
中間層の厚みが、上記範囲であれば、積層体における粘着材層の厚みの寄与が大きくなりすぎず、柔軟すぎて裁断や取回しに係る作業性が劣るようになることがなく好ましい。
また、最外層が上記範囲であれば、凹凸や屈曲した面への追随性に劣ることがなく、被着体への接着力や濡れ性を維持することができて、好ましい。
具体的な積層構成としては、β層/α層/β層、β層/α層/β層/α層/β層などを挙げることができる。中でもβ層/α層/β層である2種3層がより好ましい。α層とβ層との間に、アウトガスバリアー層をはじめとした他の層を必要に応じて介在させてもよい。
(メタ)アクリル系共重合体(A)及び架橋剤(B)を含有し、且つ紫外線吸収剤(D)を含有しない表層(β層)を設けることで、α層内の紫外線吸収剤(D)がブリードアウトするのを抑制することができる。
上記の観点から、β層は光硬化性を有さないことが好ましく、熱硬化性を有することがより好ましい。中でも、β層は光重合開始剤(C)および紫外線吸収剤(D)を含まない樹脂組成物であることがより好ましい。
α層の架橋剤(B)の含有量は、α層のアクリル系共重合体(A)100質量部に対して0.5~50質量部、中でも1質量部以上或いは40質量部以下、その中でも5質量部以上或いは30質量部以下の割合であるのが好ましい。架橋剤(B)を当該範囲で含有することで、硬化反応が短時間で十分に進行するため、硬化後の信頼性と耐湿熱白化性、柔軟性、シート状に成形する際の加工適性等をバランス化しやすくなる。
β層の架橋剤(B)の含有量は、β層のアクリル系共重合体(A)100質量部に対して0.1~20質量部、中でも0.2質量部以上或いは10質量部以下の割合であるのが好ましい。架橋剤(B)を当該範囲で含有することで、硬化反応が短時間で十分に進行するため、硬化後に粘着シートとして、タック性と信頼性、耐発泡性、段差吸収性(異物噛み込み性)、柔軟性、シート状に成形する際の加工適性等をバランス化しやすくなる。
また、β層に比べてα層により多くの架橋剤(B)が添加されることがより好ましい。硬化後のα層に高い弾性を付与して芯材としての機能を発揮させ、粘着シートに優れたハンドリング性を付与することが可能である。
方法I:未硬化のα層とβ層を積層したのちに、光照射や熱などによってα層とβ層を硬化させる方法。
方法II:未硬化のα層に、熱などによって硬化させたβ層を積層したのち、光照射によってα層を硬化させる方法。
方法III:光照射によって硬化したα層に、未硬化のβ層を積層したのち、熱などによってβ層を硬化させる方法。
方法IV:別々に成形して硬化させたα層およびβ層を重ね合わせる方法。
中でも、層間密着力が強く、耐湿熱発泡性、信頼性に優れ、かつ紫外線吸収剤のブリードアウトを抑制することが可能であることから、方法IIがより好ましい。
β層を硬化させるための加熱温度については特に限定されず、β層に含まれる架橋剤(B)の種類と量に応じて適宜調整することが可能である。硬化前の樹脂組成物のハンドリング性や樹脂の耐熱性等を考慮すると、具体的には40~200℃が好ましく、中でも50℃以上或いは180℃以下がより好ましく、中でも60℃以上或いは150℃以下がさらに好ましい。
α層を硬化させるための光照射量は、波長405nm基準で、100~8000mJ/cm2が好ましく、中でも500mJ/cm2以上或いは5000mJ/cm2以下がより好ましく、中でも1000mJ/cm2以上或いは4000mJ/cm2以下がさらに好ましい。
光を出射する光源としては、例えば高圧水銀ランプ、メタルハライドランプ、LEDランプなどを挙げることができる。
このとき、波長380nm以下の波長の光を実質含まない光線、好ましくは可視光線を本粘着シートに照射し、本粘着シートを光架橋させてもよい。「380nm未満の波長の光を実質含まない光線」とは、380nm未満の波長の光の光線透過率が10%未満の光であるという意味である。紫外線領域の波長の光を含まない可視光線を照射する方法としては、紫外線領域の波長の光を含まない可視光線のみを出射する光源を用いてもよいし、紫外線領域の波長の光を透過しないフィルターを介して照射するようにしてもよい。
β層の厚さは1~60μmであることが好ましく、中でも3μm以上或いは40μm以下がより好ましく、中でも5μm以上或いは25μm以下であることがさらに好ましい。
α層の厚さとβ層の厚さとの比率は1:1~1:20であるのが好ましく、中でも1:2~1:15であることがより好ましい。
α層(中間層)の厚さが上記範囲であれば、紫外線吸収性能が得られやすく、かつα層の光硬化性能と両立しやすくなる。また、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。β層(表層)の厚さ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るため好ましい。
本粘着シートの厚みについては、シート厚を薄くすることで、薄肉化要求に応えることができる一方、シート厚を薄くし過ぎると、たとえば被着面に凹凸部あった場合に充分に凹凸に追従できなかったり、十分な接着力を発揮できなかったりする可能性がある。
かかる観点から、本粘着シートの厚みは20~500μmであるのが好ましく、中でも25μm以上或いは350μm以下、その中でも50μm以上或いは250μm以下であるのが特に好ましい。
本粘着シートの紫外線透過率(JIS K7361-1)は、波長380nmにおいて50%以下であるのが好ましく、中でも30%以下、その中でも10%以下であるのがさらに好ましい。
一方、可視光領域である波長420nmでの光線透過率が好ましくは70%以上、より好ましくは80%以上、さらに好ましくは85%以上である。
本粘着シートは、そのまま単独で使用することも可能である。また、他の部材と積層して使用することも可能である。
例えば、本粘着シートの一側又は両側に、フィルム例えば離型フィルムや保護フィルムやこれらを積層してなるフィルムを積層して粘着シート積層体(「本粘着シート積層体」と称する)を構成することが可能である。
かかる観点から、一方又は両方の離型フィルムが、波長410nm以下での光の光線透過率が40%以下であるのが好ましく、中でも30%以下、その中でも20%以下であるのがさらに好ましい。
離型フィルムの厚みは、厚すぎると裁断加工性に劣り、薄すぎるとハンドリング性に劣り、粘着シートに打痕がつき易くなる可能性がある。かかる観点から、離型フィルムの厚みは20μm以上300μm以下であるのが好ましく、中でも25μm以上或いは250μm以下、その中でも38μm以上或いは200μm以下であるのが好ましい。
両側に離型フィルムを積層した構成とする場合は、一方の離型フィルムと他方の離型フィルムの厚さや剥離力を異ならしめるのが好ましい。
かかる観点から、本粘着シート積層体における一側又は両側のフィルムは、波長380nm以上410nm以下での光の光線透過率が40%以下、中でも30%以下、その中でも20%以下、その中でも10%以下であるのがさらに好ましい。
本粘着シート積層体の少なくとも一方の面に、波長410nm以下での光の光線透過率が40%以下の表面保護フィルムを積層することで、本粘着シートが波長405nmでの吸光係数が10mL/(g・cm)以上である光重合開始剤(C)を含有していても、可視光の照射により光重合が進むのを効果的に防ぐことができるからである。
かかる観点から、本粘着シート積層体の一方又は両方面に積層する表面保護フィルムは、波長410nm以下での光の光線透過率が40%以下であるのが好ましく、中でも30%以下、その中でも20%以下であるのがさらに好ましい。
上記表面保護フィルムは、帯電防止層やハードコート層、アンカー層など、必要に応じて他の層を有していてもよい。
また、2つの画像表示装置用構成部材を、本粘着シートを介して積層して画像表示装置構成用積層体(「本画像表示装置構成用積層体」と称する)を構成することも可能である。
上記タッチパネルは、保護パネルにタッチパネル機能を内在させた構造体や、画像表示パネルにタッチパネル機能を内在させた構造体も含む。
本粘着シートは、紫外線によって硬化するものではなく、可視光によって硬化するため、画像表示装置構成部材が紫外線吸収性能を備えたものであっても、当該画像表示装置構成部材を通して可視光を照射することにより、本粘着シートを硬化させることができる。
上記のような本粘着シート又は本画像表示装置構成用積層体を用いて、画像表示装置(「本画像表示装置」と称する)を構成することができる。
本画像表示装置としては、例えば液晶ディスプレイ、有機ELディスプレイ、無機ELディスプレイ、電子ペーパー、プラズマディスプレイ及びマイクロエレクトロメカニカルシステム(MEMS)ディスプレイなどの画像表示装置を構成することができる。
本粘着シートは、紫外線によって硬化するものではなく、可視光によって硬化するため、画像表示装置構成部材が紫外線吸収性能を備えたものであっても、当該画像表示装置構成部材を通して可視光を照射することにより、本粘着シートを硬化させることができる。
本粘着シートは、紫外線吸収機能と、紫外領域以外の波長の光線、特に可視光線の照射で硬化する硬化性を備えている。このような本粘着シートの特性を利用して、例えば次のようにして、画像表示装置構成用積層体を作製することができる。
可視光領域の波長の光線を含む光は、紫外領域、すなわち波長380nm以下の波長の光を含んでいてもよいが、積層した画像表示装置構成部材が紫外線劣化しやすい部材である場合は、波長380nm以下の波長の光を実質含まない光線、すなわち可視光線を照射して、本粘着シートを光架橋させて硬化させる(二次貼着工程)ことが好ましい。
本粘着剤組成物をシート状に成形して本粘着シートを作製することができる。
本粘着剤樹脂組成物をシート状に成形する方法としては、現在公知の方法を任意に採用することができる。
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シート状に製膜して、当該画像表示装置構成部材上に本粘着シートを積層するようにしてもよい。
本粘着シートが、自己粘着性(タック性)を備えていれば、本粘着シートを介して2つの画像表示装置構成部材を重ねるだけで一次貼着することができる。
さらに形状保持性に優れているから、事前に任意の形状に加工しておくことが可能であることから、離型フィルム上に成形した本粘着シートを、積層する画像表示装置構成部材の寸法に合わせて予めカットしておくこともできる。
この際のカット方法は、トムソン刃による打ち抜き、スーパーカッターやレーザーでのカットが一般的であり、離型フィルムを剥がし易いように表裏どちらか一方の離型フィルムを額縁状に残してハーフカットするのがより好ましい。
本粘着シートの加熱手段としては、例えば各種の恒温槽や、ホットプレート、電磁加熱装置、加熱ロールなどを用いることができる。より効率的に貼合と加熱を行うためには、例えば電熱プレス機や、ダイアフラム方式のラミネータ、ロールラミネータなどが好ましく用いられる。
この際、画像表示装置構成部材の一方又は両方を加熱することにより、本粘着シートを加熱することもできる。
よって、本粘着シートの軟化温度は、50~100℃であるのが好ましく、中でも55℃以上或いは95℃以下、その中でも60℃以上或いは90℃以下であるのがさらに好ましい。
減圧環境下で積層体を加熱することのより、貼合後に本粘着シート内に気泡が混入したり、異物が混入したりするのを防ぐことができる。
二次貼着工程では、本粘着シートを介して2つの画像表示装置構成部材が積層してなる積層体に対して、少なくとも一方の画像表示装置構成用部材の外側から当該画像表示装置構成用部材を通して、少なくとも波長405nmの光、例えば可視光領域の波長の光線を含む光、すなわち可視光線を本粘着シートに照射し、本粘着シートを光架橋させて硬化させる。
可視光線を照射する際は、紫外線領域の波長の光、例えば365nm未満の波長の光を実質含まない可視光線を照射するのが好ましい。
ここで、「365nm未満の波長の光を実質含まない」とは、365nm未満の波長の光の発光強度が1mW/cm2未満であるという意味である。
ここで、「380nm以下の波長の光を実質含まない」とは、380nm以下の波長の光の発光強度が5mW/cm2以下、好ましくは1mW/cm2以下であるという意味である。
また、紫外領域の波長の光を透過しないフィルターを介して照射するようにしてもよい。例えば、紫外領域の波長の光も出射する高圧水銀ランプやメタルハライドランプ、キセノンアークランプ、カーボンアークランプ等の発光灯や太陽光を光源に用いて、波長380nmでの光線透過率が10%未満であって、且つ、波長405nmでの光線透過率が60%以上であるフィルターを介して、可視光線を接着剤組成物に照射する方法を挙げることができる。
前記フィルターは、本粘着シート積層体を構成する離型フィルムや、本粘着シート積層体の表面に積層して用いる表面保護フィルムであってもよい。
なお、一般的に「シート」とは、JISにおける定義上、薄く、その厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう(日本工業規格JIS K6900)。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シートおよびフィルムを包含するものである。
また、「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。
(メタ)アクリル系共重合体(A)として、数平均分子量3000のポリメタクリル酸メチルマクロモノマー(Tg80℃)15質量部、ブチルアクリレート81質量部、及び、アクリル酸4質量部からなる共重合体(A-1、質量平均分子量30万)1kgに対し、架橋剤(B)としてグリセリンジメタクリレート(日油社製、ブレンマーGMR)(B-1)100g、光重合開始剤(C)としてエザキュアKTO46(C-1)(Lanberti社製)を15g、紫外線吸収剤(D)として2,6-ジフェニル-4-(2-ヒドロキシ-4-ヘキシルオキシフェニル)-1,3,5-トリアジン(BASF社製、チヌビン1577)(D-1)を5g添加し、均一混合して、粘着剤組成物1を得た。
光重合開始剤(C-1)の405nmにおける吸光係数は7.4×101(mL/(g・cm))であった。
(メタ)アクリル系共重合体(A)として、数平均分子量1400のポリメタクリル酸メチルマクロモノマー(Tg55℃)10質量部、及び2-エチルヘキシルアクリレート(Tg:-70℃)90質量部がランダム共重合してなるアクリル系グラフト共重合体(A-2)(重量平均分子量:23万)1kgと、架橋剤(B)としてトリシクロデカンジメタクリレート(新中村化学社製、製品名:DCP)(B-2)50gと、光重合開始剤(C)としてイルガキュア369(C-2)(BASF社製)15g、紫外線吸収剤(D)として2-(2H-ベンゾトリアゾール-2-イル)-4,6--ジ-tert-ペンチルフェノール(城北化学社製、JF-80)(D-2)20gを均一混合し、粘着樹脂組成物2を作製した。
光重合開始剤(C-2)の405nmにおける吸光係数は1.6×102(mL/(g・cm))であった。
(メタ)アクリル系共重合体(A)として、2-エチルヘキシルアクリレート76質量部、酢酸ビニル20質量部、及び、アクリル酸4質量部からなる共重合体(A-3、質量平均分子量40万)1kgに対して、架橋剤(B)としてプロポキシ化ペンタエリスリトールテトラアクリレート(新中村化学社製、ATM-4P)(B-3)200g、光重合開始剤(C)としてイルガキュア819(C-3)(BASF社製)7g、紫外線吸収剤(D)として2,2‘-ジヒドロキシ-4-メトキシベンゾフェノン(ケミプロ化成社製、Kemisorb111)(D-3)10g添加して均一混合し、粘着剤組成物3を得た。
光重合開始剤(C-3)の405nmにおける吸光係数は9.0×102(mL/(g・cm))であった。
剥離処理した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、厚さ100μm)上に、乾燥後の膜厚が20~30μmとなるように上記粘接着層用塗工液を塗工した後、80℃で5分乾燥させた。これを23℃で7日間養生して架橋剤を反応させ、粘着層用シート(β)を作成した。
さらに、剥離処理した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MRQ、厚さ75μm)上にも同様に、粘着剤組成物4を乾燥後の膜厚が20~30μmとなるように上記粘接着層用塗工液を塗工した後、80℃で5分乾燥させた。これを23℃で7日間養生して架橋剤を反応させ、粘着層用シート(β’)を作成した。
剥離処理したポリエチレンテレフタレートフィルム(ダイアホイルMRV、厚さ100μm)の代わりに、紫外線吸収剤入りのPETフィルム(厚さ100μm)にシリコーン離型剤を塗布した離型フィルムを用いた以外は実施例1-1と同様にして、粘着シート積層体4を作成した。
実施例1-1で作成した粘着シート積層体のポリエチレンテレフタレートフィルム(ダイアホイルMRV、厚さ100μm)の表面に、微粘着層(5μm)/ポリエチレンテレフタレートフィルム(25μm)/紫外線吸収層(3μm)からなる表面保護フィルムの微粘着層面を積層し、離型フィルム/粘着シート/離型フィルム/表面保護フィルムの構成からなる粘着シート積層体5を作成した。
光重合開始剤として、エザキュアKTO46(C-1)の代わりに、エザキュアTZT(C-5)を15g添加した以外は、実施例1-1と同様にして、粘着シート積層体6を作成した。
光重合開始剤(C-5)の405nmにおける吸光係数は10(mL/(g・cm))未満であり、低すぎて測定不能であった。
紫外線吸収剤(D-2)を加えない以外は、実施例1-2と同様にして、粘着シート積層体7を作成した。
市販のアクリル系共重合体(A-4、質量平均分子量130万)からなる粘着剤溶液(綜研化学社製、SKダイン1882、固形分濃度約17%)1kgに対し、イソシアネート系架橋剤としてL-45(B-5)(綜研化学社製)を1.85g及びエポキシ系架橋剤としてE-5XM(B-6)(綜研化学社製)を0.5g、紫外線吸収剤(D)として紫外線吸収剤(D)として2,2‘-ジヒドロキシ-4-メトキシベンゾフェノン(ケミプロ化成社製、Kemisorb111)(D-3)10g添加して均一混合し、粘着剤組成物7を作成した。
剥離処理した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MRQ、厚さ75μm)上にも同様に、乾燥後の厚みが50μmとなるように塗布した後、80℃で5分乾燥し、厚さ50μmのシート状の粘着剤組成物7を得た。これらを積層して厚さ100μmとした後、剥離処理した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MRQ、厚さ75μm)を被覆した。これを室温(23℃)で7日間養生して架橋剤を反応させ、粘着シート積層体8を作成した。
[光学特性]
実施例1-1~1-5及び比較例1-1~1-3で作製した粘着シート積層体の両側のPETフィルムを順次剥離し、粘着シートを2枚のソーダライムガラス(厚み0.5mm)で挟み込むように貼着し、オートクレーブ処理(70℃、ゲージ圧0.2MPa、20分)を施して仕上貼着した。粘着シート積層体1、2、4、5,6、7については、UVカットフィルターを介した高圧水銀ランプを用いて、波長405nmの積算光量が3000mJ/cm2となるよう光照射し、光学特性評価用サンプルを作成した。
380nmにおける光線透過率が50%未満のものを、UV吸収性「○(good)」、50%以上のものをUV吸収性「×(poor)」と判定した。結果は表1に示す。
実施例1-1~1-5及び比較例1-1~1-3で作製した粘着シートについて、一方の離型フィルムを剥がし、裏打ちフィルムとしてポリエチレンテレフタレートフィルム(東洋紡績社製;商品名「コスモシャインA4300」、厚み100μm)をハンドローラーにてロール圧着した。これを10mm巾×100mm長の短冊状に裁断し、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ハンドローラーを用いてロール貼着した。オートクレーブ処理(70℃、ゲージ圧0.2MPa、20分)を施して仕上貼着した後、粘着シート積層体1、2、4、5,6、7については、UVカットフィルターを介した高圧水銀ランプを用いて、波長405nmの積算光量が3000mJ/cm2、波長365nmの積算光量が5mJ/cm2以下となるよう可視光を照射し、粘着力測定サンプルを作成した。
58mm×110mm×厚さ0.8mmのガラスの周縁部(長辺側3mm、短辺側15mm)に、厚さ20μmの印刷を施し、開口部が52mm×80mmの印刷段差付きガラス板1を準備した。
また、58mm×110mm×厚さ0.8mmのガラスの周縁部(長辺側3mm、短辺側15mm)に、厚さ10μmの印刷を施し、開口部が52mm×80mmの印刷段差付きガラス板2を準備した。
粘着シート積層体の一方の離型フィルムを剥がし、54mm×82mm厚さ0.5mmのソーダライムガラスにロール貼合した。
次いで、残る離型フィルムを剥がし、印刷段差付きガラス板1及び2の印刷面に、粘着面の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後(絶対圧5kPa、温度70℃、プレス圧0.04MPa)、オートクレーブ処理(70℃、ゲージ圧0.2MPa、20分)を施して仕上げ貼着した。粘着シート積層体1、2、4、5,6、7については、印刷を施したガラス側から、UVカットフィルターを介した高圧水銀ランプを用いて、波長405nmの積算光量が3000mJ/cm2となるよう光照射し、評価用サンプルを作成した。
実施例1-1~1-5及び比較例1-1~1-3で作成した粘着シートの片面の離型フィルムを剥がし、その露出面にCOPフィルム(日本ゼオン社製100μm)をハンドローラーにて貼着した。次に、前記粘着シートを50mm×80mmに切り出した後、残る離型フィルムを剥がして、厚さ0.5mmのソーダライムガラスにハンドローラーにて貼着し、オートクレーブ処理(温度80℃、気圧0.4MPa、30分)を施した。粘着シート積層体1、2、4、5、6、7については、COP面から、UVカットフィルターを介した高圧水銀ランプを用いて、波長405nmの積算光量が3000mJ/cm2となるよう光照射し、評価用サンプルを作成した。
粘着シート積層体の一方の離型フィルムを剥がし、150mm×200mm厚さ2mmのソーダライムガラスにロール貼合した。次いで、残る離型フィルムを剥がし、露出した粘着面に、150mm×200mm厚さ2mmのソーダライムガラスにロール貼合し、オートクレーブ処理(温度80℃、気圧0.4MPa、30分)を施した。
粘着シート積層体1、2、4、5、6、7については、高圧水銀ランプを用いて、波長405nmの積算光量が3000mJ/cm2となるよう光照射し、評価用サンプルを作成した。
2)上記SUSメッシュを100mLの酢酸エチルに24時間浸漬する。
3)SUSメッシュを取り出し、75℃で4時間半乾燥する。
4)乾燥後の重量(W2)を求め、下記式より粘着剤組成物のゲル分率を測定する。
ゲル分率(%)=100×(W2-W0)/W1
これに対し、比較例1-1は波長405nmでの吸光係数が10mL/(g・cm)未満の光重合開始剤を用いたため、すなわち波長405nmでの吸光係数が10mL/(g・cm)以上の光重合開始剤を用いていないため、光照射しても粘着材が硬化せず、2次貼着後の粘着力や貼合後の信頼性が得られなかった。
比較例1-2は、紫外線吸収剤(D)を含まず、紫外線吸収性能が得られなかった。このため、耐光性試験にて粘着シートの発泡がみられ、貼合信頼性に劣るものであった。
比較例1-3は、熱架橋により粘着材組成物を架橋した粘着シートである。光硬化性層を有さないため、貼合時の凹凸吸収性に劣るものであった。
但し、本発明はこれらに限定されるものではない。なお、後述の実施例および比較例で用いる各層の粘着樹脂組成物の組成は表3に示す。
(メタ)アクリル系共重合体(2-A)として、2-エチルヘキシルアクリレート76質量部、酢酸ビニル20質量部、アクリル酸4質量部からなる共重合体(2-A-1、質量平均分子量40万)1kgに対して、架橋剤(2-B)として、プロポキシ化ペンタエリスリトールテトラアクリレート(新中村化学社製、ATM-4P)(2-B-1)200g、光重合開始剤(2-C)としてイルガキュア369(2-C-1)(BASF社製)を8g、紫外線吸収剤(2-D)として2,2’-ジヒドロキシ-4-メトキシベンゾフェノン(ケミプロ化成社製、Kemisorb111)(2-D-1)10g添加して均一混合し、粘着樹脂組成物2-1を得た。
光重合開始剤(2-C-1)の405nmにおける吸光係数は1.6×102mL/(g・cm)であった。
粘着樹脂組成物2-1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MRF、厚さ75μm/三菱樹脂社製、ダイアホイルMRT、厚さ38μm)で挟み、厚さ110μmとなるようシート状に賦形し、中間層用シート(α-1)を作成した。
さらに、剥離処理した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MRQ、厚さ75μm)上にも同様に、粘着樹脂組成物2を乾燥後の厚さが20μmとなるように塗工した後、80℃で5分乾燥してβ層を熱硬化させ、表層用シート(β’-1)を作成した。
中間層用シート(α-1)の両側のPETフィルムを順次剥離除去すると共に、表層用シート(β-1)及び(β’-1)の粘着面を両表面に順次貼合し、(β-1)/(α-1)/(β’-1)からなる積層体を作製した。
(β-1)及び(β’-1)の表面に残るPETフィルムを介して、波長405nmの積算光量が1500mJ/cm2となるよう高圧水銀ランプを用いて照射し、α層を硬化させて、透明両面粘着シート積層体2-1(厚さ150μm)を作製した。
(メタ)アクリル系共重合体(2-A-1)1kgに対して、架橋剤(2-B-1)を200g、光重合開始剤(2-C)としてエザキュアKTO46(2-C-2)(Lanberti社製)を20g、紫外線吸収剤(2-D-1)を20g添加して均一混合し、粘着樹脂組成物2-3を得た。
光重合開始剤(2-C-2)の405nmにおける吸光係数は、7.4×101mL/(g・cm)であった。
粘着樹脂組成物2-3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MRF、厚さ75μm/三菱樹脂社製、ダイアホイルMRT、厚さ38μm)で挟み、厚さ60μmとなるようシート状に賦形し、中間層用シート(α-2)を作成した。
実施例2-1同様に、中間層用シート(α-2)の両側のPETフィルムを順次剥離除去すると共に、表層用シート(β-1)及び(β’-1)の粘着面を両表面に順次貼合し、(β-1)/(α-2)/(β’-1)からなる積層体を作製した。
(β-1)及び(β’-1)の表面に残るPETフィルムを介して、波長405nmの積算光量が3000mJ/cm2となるよう高圧水銀ランプを用いて照射し、α層を硬化させて、透明両面粘着シート積層体2-2(厚さ100μm)を作製した。
(メタ)アクリル系共重合体(2-A-1)1kgに対して、架橋剤(2-B-1)を200g、光重合開始剤(2-C-2)を8g、紫外線吸収剤(2-D-1)を20g添加して均一混合し、粘着樹脂組成物2-4を得た。
粘着樹脂組成物2-4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MRF、厚さ75μm/三菱樹脂社製、ダイアホイルMRT、厚さ38μm)で挟み、厚さ60μmとなるようシート状に賦形し、中間層用シート(α-3)を作成した。
実施例2-1同様に、中間層用シート(α-3)の両側のPETフィルムを順次剥離除去すると共に、表層用シート(β-1)及び(β’-1)の粘着面を両面に順次貼合し、(β-1)/(α-3)/(β’-1)からなる積層体を作製した。
(β-1)及び(β’-1)の表面に残るPETフィルムを介して、波長405nmの積算光量が3000mJ/cm2となるよう高圧水銀ランプを用いて照射し、α層を硬化させて、透明両面粘着シート積層体2-3(厚さ100μm)を作製した。
(メタ)アクリル系共重合体(2-A-1)1kgに対して、架橋剤(2-B-1)200g、光重合開始剤(2-C)としてエサキュアTZT(2-C-3)(Lanberti社製)を10g、紫外線吸収剤(2-D)として2,2’-ジヒドロキシ-4-メトキシベンゾフェノン(ケミプロ化成社製、Kemisorb111)(2-D-1)20g添加して均一混合し、粘着樹脂組成物2-5を得た。
光重合開始剤(2-C-3)の405nmにおける吸光係数は、10mL/(g・cm)未満であり、低すぎて測定不能であった。
粘着樹脂組成物2-5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MRF、厚さ75μm/三菱樹脂社製、ダイアホイルMRT、厚さ38μm)で挟み、厚さ110μmとなるようシート状に賦形し、中間層用シート(α-4)を作成した。
実施例2-1同様に、中間層用シート(α-4)の両側のPETフィルムを順次剥離除去すると共に、表層用シート(β-1)及び(β’-1)の粘着面を両表面に順次貼合し、(β-1)/(α-4)/(β’-1)からなる積層体を作製した。
(β-1)及び(β’-1)の表面に残るPETフィルムを介して、波長405nmの積算光量が1500mJ/cm2となるよう高圧水銀ランプを用いて照射し、α層を硬化させて、透明両面粘着シート積層体2-4(厚さ100μm)を作製した。
(メタ)アクリル系共重合体(2-A-1)1kgに対して、架橋剤(2-B-1)を200g、光重合開始剤(2-C-2)を8g加えて均一混合し、粘着樹脂組成物2-6を得た。この時、紫外線吸収剤(2-D)は添加しなかった。
粘着樹脂組成物2-6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MRF、厚さ75μm/三菱樹脂社製、ダイアホイルMRT、厚さ38μm)で挟み、厚さ110μmとなるようシート状に賦形し、中間層用シート(α-5)を作成した。
実施例2-1と同様に、中間層用シート(α-5)の両側のPETフィルムを順次剥離除去すると共に、表層用シート(β-1)及び(β’-1)の粘着面を両表面に順次貼合し、(β-1)/(α-5)/(β’-1)からなる積層体を作製した。
(β-1)及び(β’-1)の表面に残るPETフィルムを介して、波長405nmの積算光量が1500mJ/cm2となるよう高圧水銀ランプを用いて照射し、α層を硬化させて、透明両面粘着シート積層体2-5(厚さ150μm)を作製した。
[紫外線吸収性能]
実施例2-1~2-3及び比較例2-1~2-2で作製した透明両面粘着シート積層体の両側のPETフィルムを順次剥離し、粘着シートを2枚のソーダライムガラス(54×82mm、厚さ0.5mm)で挟み込むように貼着したのち、オートクレーブ処理(70℃、ゲージ圧0.2MPa、20分)を施して仕上貼着し、紫外線吸収性能評価用サンプルとした。
作成した試験片の波長域360~430nmにおける光線透過率を分光光度計(島津製作所株式会社製;機器名「UV2450」)にて測定した。380nmにおける光線透過率が50%未満のものを「○(good)」、50%以上のものを「×(poor)」と判定した。結果は表4に示す。
実施例2-1~2-3及び比較例2-1~2-2で作製した透明両面粘着シートについて、一方の剥離フィルムを剥がし、裏打ちフィルムとしてポリエチレンテレフタレートフィルム(東洋紡績社製;商品名「コスモシャインA4300」、厚さ100μm)をハンドローラーにてロール圧着した。これを10mm巾×100mm長の短冊状に裁断し、残る剥離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ハンドローラーを用いてロール貼着した。これをオートクレーブ処理(70℃、ゲージ圧0.2MPa、20分)を施して仕上貼着し、粘着力測定サンプルを作成した。裏打ちフィルムを180°をなす角度に剥離速度60mm/分にて引っ張りながらガラスから粘着シートを剥離し、ロードセルで引張強度を測定して、粘着シートのガラスに対する180°剥離強度を測定し、結果は表4に示す。
実施例2-1~2-3及び比較例2-1~2-2で作製した粘着シートを50mm×100mmに裁断した後、片面の剥離フィルムを剥がし、該粘着シートの片面が、裏打用のポリエチレンテレフタレートフィルム(厚さ38μm)に重なるようにハンドローラーで貼着し、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、残る剥離フィルムを剥がして、垂直に立設したSUS板(厚さ120mm、5mm×1.5mm)に対して、試験片が20mmの長さだけ重なるようにしてハンドローラーで貼着した。この時、透明両面粘着シートとSUS板の貼着面積は25mm×20mmとなる。
その後、試験片を40℃の雰囲気下で15分養生させた後、試験片に荷重500g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長さ(mm)を測定した。
ズレ長さが1mm未満のものを「◎(Excellent)」、ズレ長さが1mm以上2mm未満のものを「〇(Good)」、ズレ長さが2mm以上のものを「×(poor)」と判定した。結果を表4に示す。
耐発泡信頼性評価用サンプルとして、紫外線吸収性能評価用サンプルと同じものを2枚使用した。これを85℃で100時間養生し、発泡等なく外観に変化がみられなかったものを「○(good)」、発泡や剥離がみられたものを「×(poor)」と判定した。結果を表4に示す。
実施例2-1~2-3の粘着シート積層体は、粘着力や保持力、耐湿熱信頼性といった特性を維持しながら、優れた紫外線吸収性能を付与したものであった。
比較例2-1は波長405nmの吸光係数が10mL/(g・cm)未満の光重合開始剤を用いた為、光照射しても粘着剤が硬化せず、粘着力や貼合後の信頼性に劣るものであった。
比較例2-2はα層に紫外線吸収剤(D)を含まないため、紫外線吸収性能に劣るものであった。
Claims (22)
- (メタ)アクリル系共重合体(A)、架橋剤(B)、波長405nmでの吸光係数が10mL/(g・cm)以上である光重合開始剤(C)及び紫外線吸収剤(D)を含有する粘着剤樹脂組成物からなる透明両面粘着シート。
- 紫外線吸収剤(D)がベンゾトリアゾール構造、トリアジン構造およびベンゾフェノン構造からなる群より選択される1つ又は2つ以上の構造を有することを特徴とする請求項1に記載の透明両面粘着シート。
- 光重合開始剤(C)100質量部に対して紫外線吸収剤(D)を25~400質量部の割合で含有することを特徴とする請求項1又は2に記載の透明両面粘着シート。
- (メタ)アクリル系共重合体(A)が、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ことを特徴とする請求項1~3の何れかに記載の透明両面粘着シート。
- 架橋剤(B)として、多官能(メタ)アクリル酸エステル化合物を含有し、
光重合開始剤(C)として、開裂型光重合開始剤を含有することを特徴とする請求項1~4の何れかに記載の透明両面粘着シート。 - 前記粘着剤樹脂組成物が室温(20℃)において粘着性を示し、且つ、100℃で軟化乃至流動化する性質を備えた、請求項1~5の何れかに記載の透明両面粘着シート。
- (メタ)アクリル系共重合体(A)、架橋剤(B)、波長405nmでの吸光係数が10mL/(g・cm)以上である光重合開始剤(C)及び紫外線吸収剤(D)を含有する粘着剤樹脂組成物からなる中間層(α層)と、
(メタ)アクリル系共重合体(A)及び架橋剤(B)を含有し、且つ紫外線吸収剤(D)を含有しない表層(β層)と、を有する請求項1~3の何れかに記載の透明両面粘着シート。 - 上記表層(β層)は、熱硬化することができる層、又は、熱硬化された層であることを特徴とする請求項7に記載の透明両面粘着シート。
- 上記中間層(α層)の表裏両側にそれぞれ上記表層(β層)を有する積層構成を備えた請求項7又は8に記載の透明両面粘着シート。
- 請求項1~9の何れかに記載の透明両面粘着シートと、離型フィルムとを積層してなる構成を備えた粘着シート積層体。
- 上記離型フィルムは、波長410nm以下での光の光線透過率が40%以下であることを特徴とする、請求項10に記載の粘着シート積層体。
- 上記離型フィルムの表面に、波長410nm以下での光の光線透過率が40%以下である表面保護フィルムを積層してなる構成を備えた、請求項10又は11に記載の粘着シート積層体。
- (メタ)アクリル系共重合体(A)、架橋剤(B)、波長405nmでの吸光係数が10mL/(g・cm)以上である光重合開始剤(C)及び紫外線吸収剤(D)を含有する粘着剤樹脂組成物からなる透明両面粘着シートと、
波長380nm以上410nm以下での光の光線透過率が40%以下であるフィルムと、を積層してなる構成を備えた粘着シート積層体。 - 2つの画像表示装置構成部材間を、請求項1~9の何れかに記載の透明両面粘着シートを介して積層してなる構成を備えた画像表示装置構成用積層体。
- 上記2つの画像表示装置構成部材のうちの少なくとも一つが紫外線吸収性能を備えたものである請求項14に記載の画像表示装置構成用積層体。
- 前記画像表示装置構成部材が、タッチセンサー、画像表示パネル、表面保護パネル及び偏光フィルムからなる群のうちの何れか或いは2種類以上の組み合わせからなる積層体であることを特徴とする請求項14又は15に記載の画像表示装置構成用積層体。
- 請求項14~16の何れかに記載の画像表示装置構成用積層体を用いて構成された画像表示装置。
- 画像表示装置を構成する画像表示装置構成部材のうちの少なくとも一つが紫外線吸収性能を備えたものである請求項17に記載の画像表示装置。
- 請求項1~9の何れかに記載の透明両面粘着シートを介して画像表示装置構成部材が積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、少なくとも次の(1)及び(2)の工程を有することを特徴とする画像表示装置構成用積層体の製造方法。
(1) (メタ)アクリル系共重合体(A)、架橋剤(B)、及び、波長405nmでの吸光係数が10mL/(g・cm)以上である光重合開始剤(C)を含有する粘着剤組成物からなる、光硬化前の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する工程。
(2)透明両面粘着シートを介して2つの画像表示装置構成用部材を積層した後、少なくとも一方の画像表示装置構成用部材の外側から当該画像表示装置構成用部材を通して、少なくとも波長405nmの光を前記透明両面粘着シートに照射して該両面粘着シートを架橋させて硬化させる工程。 - 少なくとも波長405nmの光は、太陽、蛍光灯、LED、有機EL、無機ELおよび画像表示装置用発光モジュールから選択される少なくとも1種又は2種以上の組合せからなる光源から照射される光であることを特徴とする、請求項19に記載の画像表示装置構成用積層体の製造方法。
- 前記工程(1)において、透明両面粘着シートを加熱して2つの画像表示装置構成部材を積層することを特徴とする請求項19又は20に記載の画像表示装置構成用積層体の製造方法。
- 画像表示装置構成部材の一方又は両方を加熱して、透明両面粘着シートを加熱することを特徴とする請求項21に記載の画像表示装置構成用積層体の製造方法。
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