WO2015145635A1 - 粘着剤層および飛散防止粘着シート - Google Patents
粘着剤層および飛散防止粘着シート Download PDFInfo
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- WO2015145635A1 WO2015145635A1 PCT/JP2014/058651 JP2014058651W WO2015145635A1 WO 2015145635 A1 WO2015145635 A1 WO 2015145635A1 JP 2014058651 W JP2014058651 W JP 2014058651W WO 2015145635 A1 WO2015145635 A1 WO 2015145635A1
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- sensitive adhesive
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- adhesive layer
- scattering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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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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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to an anti-scattering adhesive sheet that is affixed to at least one surface of a cover glass used in a capacitive touch panel, and an adhesive layer for the anti-scattering adhesive sheet.
- capacitive touch panels there are various configurations of capacitive touch panels, but as a typical example, a display module such as a liquid crystal module, a film sensor laminated thereon with an adhesive layer, and an adhesive on it The structure provided with the cover glass laminated
- a display module such as a liquid crystal module
- a film sensor laminated thereon with an adhesive layer and an adhesive on it
- stacked through the layer is mentioned.
- the mobile electronic device as described above has a problem that when a large impact is applied due to dropping or the like, the cover glass is broken and glass fragments are scattered. For this reason, it has been proposed to prevent scattering of the glass by attaching a scattering prevention film (scattering prevention adhesive sheet) with an adhesive layer to the surface of the cover glass (for example, Patent Document 1).
- a scattering prevention film scattering prevention adhesive sheet
- the film sensor is usually composed of a base film and a transparent conductive film made of patterned tin-doped indium oxide (ITO). Moreover, what is comprised from the transparent conductive film which consists of ITO patterned by the glass substrate as an example of the said cover glass is illustrated. In a touch panel having such a patterned transparent conductive film, there is a so-called bone appearance problem in which the circuit pattern of the transparent conductive film is visible and the appearance is impaired.
- ITO patterned tin-doped indium oxide
- Patent Document 2 discloses an insulating transparent base material, a high refractive index layer formed on the surface of the transparent base material, and a low refractive index formed on the surface of the high refractive index layer.
- a transparent conductive laminate having a refractive index layer and a transparent wiring layer patterned on the surface of a low refractive index layer, wherein irregularities are formed on the low refractive index layer or the high refractive index layer (silica-based particles, metal oxide).
- a transparent conductive laminate in which physical particles are arranged is proposed.
- the surfaces of the low refractive index layer and the transparent wiring layer constitute an uneven surface, whereby transmitted light that passes through the transparent conductive laminate and reflection that is reflected by the transparent conductive laminate. Light is scattered so that the transparent wiring layer is not noticeable.
- the above transparent conductive laminate is used in a touch panel equipped with a high-definition liquid crystal module, scattering of image light of the liquid crystal module occurs, and so-called “glare” occurs in which the portion glares, and the touch panel Display performance deteriorates.
- the present invention has been made in view of such a situation, and prevents scattering of a patterned transparent conductive film and can prevent glare on a touch panel, and the scattering prevention adhesive sheet.
- An object of the present invention is to provide a pressure-sensitive adhesive layer.
- the present invention is an adhesive layer for an anti-scattering adhesive sheet that is affixed to at least one surface of a cover glass used in a capacitive touch panel
- the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component and light diffusing fine particles, and the difference in refractive index between the pressure-sensitive adhesive component and the light diffusing fine particles is 0.005 to 0.2.
- a pressure-sensitive adhesive layer, wherein the light-diffusing fine particles have an average particle diameter measured by a centrifugal sedimentation light transmission method of 0.8 to 2.9 ⁇ m, and a haze value of the pressure-sensitive adhesive layer is 55% or less. (Invention 1).
- the anti-scattering adhesive sheet provided with the adhesive layer according to the above invention (Invention 1), it is possible to prevent the cover glass from scattering on the touch panel.
- the refractive index difference, the average particle diameter of the light diffusing fine particles, and the haze value are defined as described above, the patterned transparent conductive film becomes inconspicuous and glaring without providing a separate layer. In particular, even in a high-definition touch panel, an excellent glare-suppressing effect can be obtained.
- the adhesive component preferably contains a (meth) acrylic acid ester polymer (Invention 2).
- the said (meth) acrylic acid ester polymer is a monomer which has a carboxyl group as a monomer unit which comprises the said polymer. Is preferably not contained (Invention 3).
- the said adhesive component contains a crosslinking agent further,
- the said (meth) acrylic acid ester polymer is a functional unit which reacts with the said crosslinking agent as a monomer unit which comprises the said polymer. It is preferable to contain a monomer having a group (Invention 4).
- the adhesive component may further contain an active energy ray-curable compound (Invention 5).
- the active energy ray-curable compound is preferably a polyfunctional acrylate monomer having a molecular weight of 1000 or less (Invention 6).
- the present invention is a scattering-preventing pressure-sensitive adhesive sheet that is affixed to at least one surface of a cover glass used in a capacitive touch panel, comprising a base material and the pressure-sensitive adhesive layer (Inventions 1 to 6).
- a scattering prevention pressure-sensitive adhesive sheet is provided (Invention 7).
- the substrate may be a resin film having a hard coat layer (Invention 8).
- a transparent conductive film may be provided on one surface of the cover glass (Invention 8).
- the cover glass on the touch panel can be prevented from scattering, the patterned transparent conductive film is not noticeable, and glare can be suppressed.
- an excellent glare suppressing effect can be obtained.
- the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer for an anti-scattering pressure-sensitive adhesive sheet that is affixed to at least one surface of a cover glass used for a capacitive touch panel.
- This pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component and light diffusing fine particles (hereinafter referred to as “pressure-sensitive adhesive composition P”).
- the difference in refractive index between the adhesive component and the light diffusing fine particles is 0.005 to 0.2, and the average particle diameter of the light diffusing fine particles by the centrifugal sedimentation light transmission method is 0.8 to 2.9 ⁇ m.
- the haze value of the adhesive layer which concerns on this embodiment is 55% or less.
- Adhesive Component The adhesive component contained in the adhesive composition P preferably contains the (meth) acrylic acid ester polymer (A), and more preferably contains the crosslinking agent (B). Moreover, you may contain an active energy ray hardening compound (C) further if desired.
- (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms. Further, the “polymer” includes the concept of “copolymer”.
- (Meth) acrylic acid ester polymer (Meth) acrylic acid ester polymer (A) is a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group as a monomer constituting the polymer. It is preferable to contain. Thereby, the obtained adhesive can express preferable adhesiveness.
- the (meth) acrylic acid ester polymer (A) includes a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms and a monomer having a reactive functional group (reactive functional group-containing monomer). And a copolymer with other monomer used as desired.
- the (meth) acrylic acid ester polymer (A) contains a reactive functional group-containing monomer as a monomer constituting the polymer, it can react with the crosslinking agent (B) to form a crosslinked structure. .
- Examples of (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n- (meth) acrylate.
- examples thereof include n-dodecyl, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
- (meth) acrylic acid esters having an alkyl group having 1 to 8 carbon atoms are preferred, such as methyl (meth) acrylate, n-butyl (meth) acrylate and (meth) acrylic.
- the acid 2-ethylhexyl is particularly preferred.
- these may be used independently and may be used in combination of 2 or more type.
- the (meth) acrylic acid ester polymer (A) contains 10 to 98% by mass of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a monomer unit constituting the polymer.
- the content is preferably 30 to 90% by mass, more preferably 50 to 85% by mass.
- a monomer having a hydroxyl group in the molecule a monomer having a carboxyl group in the molecule (carboxyl group-containing monomer), a monomer having an amino group in the molecule (amino group-containing) Monomer) and the like, and a hydroxyl group-containing monomer is particularly preferable.
- hydroxyl group-containing monomer a monomer having a hydroxyl group in the molecule
- carboxyl group in the molecule carboxyl group in the molecule
- a monomer having an amino group in the molecule amino group-containing
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth And (meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate.
- 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of the reactivity of the hydroxyl group in the resulting (meth) acrylic acid ester polymer (A) with the crosslinking agent (B) and the copolymerizability with other monomers. Is preferred. These may be used alone or in combination of two or more.
- carboxyl group-containing monomer examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
- carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
- acrylic acid is preferable from the viewpoint of the reactivity of the resulting (meth) acrylic acid ester polymer (A) with the crosslinking agent (B) of the carboxyl group and the copolymerizability with other monomers. These may be used alone or in combination of two or more.
- amino group-containing monomer examples include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
- the (meth) acrylic acid ester polymer (A) is a reactive functional group-containing monomer (especially a hydroxyl group-containing monomer) as a monomer unit constituting the polymer from the viewpoint of achieving both heat and heat whitening resistance and adhesive strength.
- the content is preferably 2 to 30% by mass, more preferably 7 to 20% by mass, and even more preferably 10 to 20% by mass.
- a reactive functional group-containing monomer (particularly a hydroxyl group-containing monomer) is contained in an amount of 7% by mass or more, preferably 10% by mass or more, a predetermined amount of the reactive functional group remains in the pressure-sensitive adhesive layer.
- the reactive functional group (especially hydroxyl group) is usually a hydrophilic group, and when such a hydrophilic group is present in a predetermined amount in the pressure-sensitive adhesive layer, even when the pressure-sensitive adhesive layer is placed under high temperature and high humidity conditions, The compatibility with the moisture that has entered the pressure-sensitive adhesive layer under high-temperature and high-humidity conditions is good, and as a result, whitening of the pressure-sensitive adhesive layer is suppressed.
- the (meth) acrylic acid ester polymer (A) preferably does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Thereby, it can suppress that a transparent conductive film is corroded or changing the resistance value of a transparent conductive film.
- the (meth) acrylic acid ester polymer (A) contains a carboxyl group-containing monomer as a monomer unit in an amount of 0.1% by mass or less, preferably 0.01% by mass or less. It is acceptable.
- the (meth) acrylic acid ester polymer (A) may contain a monomer having an alicyclic structure having 7 or more carbon atoms (an alicyclic structure-containing monomer) as another monomer constituting the polymer. Good.
- the (meth) acrylic acid ester polymer (A) contains the alicyclic structure-containing monomer so that the (meth) acrylic acid ester polymer (A) is an acid component ( Even if it does not contain (carboxyl group), the obtained pressure-sensitive adhesive has high adhesion to the transparent conductive film and has excellent durability. This is probably because the affinity and interaction between the transparent conductive film and the alicyclic structure having 7 or more carbon atoms are relatively strong.
- the alicyclic carbocycle having 7 or more carbon atoms may have a saturated structure or may have an unsaturated bond.
- the alicyclic structure having 7 or more carbon atoms may be a monocyclic alicyclic structure or a polycyclic alicyclic structure such as a bicyclic ring or a tricyclic ring. From the viewpoint of durability when applied to a conductive film, a polycyclic alicyclic structure is preferable.
- the carbon number of the alicyclic structure is preferably 7 to 15, and particularly preferably 9 to 12.
- Examples of the alicyclic structure having 7 or more carbon atoms include dicyclopentadiene skeleton, adamantane skeleton, isobornyl skeleton, cycloalkane skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cycloundecane skeleton, cyclododecane skeleton, Skeleton), cycloalkene skeleton (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeleton, norbornadiene skeleton, polycyclic skeleton (cuban skeleton, basketn skeleton, howsan skeleton, etc.), spiro skeleton, etc. Those containing a dicyclopentadiene skeleton, an adamantane skeleton, or an isobornyl skeleton
- the alicyclic structure-containing monomer is preferably a (meth) acrylic acid ester monomer containing the above skeleton, specifically, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid adamantyl, (meth) Examples include isobornyl acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Among them, (meth) acrylic diester that exhibits better adhesion and durability improvement effects. Cyclopentanyl, adamantyl (meth) acrylate or isobornyl (meth) acrylate is preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the (meth) acrylic acid ester polymer (A) contains the alicyclic structure-containing monomer as a monomer unit constituting the polymer
- the alicyclic structure-containing monomer is contained in an amount of 1 to 50% by mass.
- the content is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass.
- Examples of other monomers that the (meth) acrylic acid ester polymer (A) can contain as a monomer constituting the polymer include (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl and the like ( Non-crosslinkable acrylamide such as (meth) acrylic acid alkoxyalkyl ester, acrylamide, methacrylamide, etc. Non-crosslinkable such as (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl (Meth) acrylic acid ester having a tertiary amino group, vinyl acetate, styrene and the like. These may be used alone or in combination of two or more.
- the polymerization mode of the (meth) acrylic acid ester polymer (A) may be a random copolymer or a block copolymer.
- the (meth) acrylic acid ester polymer (A) preferably has a weight average molecular weight of 100,000 to 2,000,000, particularly preferably 300,000 to 1,400,000, and more preferably 400,000 to 900,000. preferable.
- the weight average molecular weight is less than 100,000, there is a possibility that floating or the like may occur at the end of the pressure-sensitive adhesive layer when exposed to high temperature conditions or warm and humid conditions for a long time.
- a printed layer that is a step is often provided at the peripheral edge of the cover material.
- the said weight average molecular weight exceeds 2 million, there exists a possibility that the followable
- the weight average molecular weight in this specification is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the (meth) acrylic acid ester polymer (A) may be used alone or in combination of two or more.
- the adhesive composition P contains a crosslinking agent (B) as an adhesive component.
- the adhesive component of the adhesive composition P contains a (meth) acrylic acid ester polymer (A) containing a reactive functional group-containing monomer as a monomer unit constituting the polymer, and a crosslinking agent (B)
- the crosslinking agent (B) reacts with the reactive functional group of the reactive functional group-containing monomer constituting the (meth) acrylic acid ester polymer (A).
- crosslinked with the crosslinking agent (B) is formed, and the cohesion force of the adhesive obtained is improved.
- the crosslinking agent (B) may be any one that reacts with the reactive functional group of the (meth) acrylic acid ester polymer (A).
- an isocyanate crosslinking agent for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, and an amine crosslinking agent.
- Melamine crosslinking agent aziridine crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline crosslinking agent, metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, ammonium salt crosslinking agent, etc. Is mentioned.
- a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.
- the isocyanate-based crosslinking agent contains at least a polyisocyanate compound.
- the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, etc.
- biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
- low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
- trimethylolpropane-modified aromatic polyisocyanates particularly trimethylolpropane-modified xylylene diisocyanate and trimethylolpropane-modified tolylene diisocyanate are preferred from the viewpoint of reactivity with hydroxyl groups.
- the content of the crosslinking agent (B) is preferably 0.01 to 10 parts by weight, particularly 0.05 to 1 part by weight, with respect to 100 parts by weight of the (meth) acrylic acid ester polymer (A). It is preferable that the amount is 0.1 to 0.5 parts by mass.
- the adhesive composition P may contain an active energy ray-curable compound (C) as an adhesive component.
- the pressure-sensitive adhesive containing light diffusing fine particles generally tends to have low cohesive force, and when the release sheet is peeled from the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer may be taken on the release sheet side, but the active energy
- the pressure-sensitive adhesive composition P containing the linear curable compound (C) is less likely to cause the above-described problems when cured by irradiation with active energy rays, and the resulting pressure-sensitive adhesive layer has excellent handling properties. Become.
- the active energy ray-curable compound (C) may be any of a monomer, an oligomer or a polymer, or a mixture thereof. Among them, a polyfunctional acrylate monomer having a molecular weight of 1000 or less that is excellent in compatibility with the (meth) acrylic acid ester polymer (A) and the like can be preferably exemplified.
- polyfunctional acrylate monomers having a molecular weight of 1000 or less examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene.
- the content of the active energy ray-curable compound (C) is 100 parts by mass of the (meth) acrylic acid ester polymer (A).
- the amount is preferably 1 to 50 parts by mass, particularly preferably 5 to 30 parts by mass, and more preferably 7 to 20 parts by mass.
- the resulting pressure-sensitive adhesive layer has excellent handling properties, and also depends on the (meth) acrylic acid ester polymer (A). Adhesiveness is maintained well.
- the light diffusing fine particles contained in the pressure-sensitive adhesive composition P according to this embodiment have a refractive index difference of 0.005 to 0.2 with respect to the adhesive component, and have an average particle diameter determined by the centrifugal sedimentation light transmission method. 0.8 to 2.9 ⁇ m.
- the light diffusing fine particles include inorganic fine particles such as silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc and titanium dioxide; organic fine particles such as acrylic resin, polystyrene resin, polyethylene resin and epoxy resin. Translucent fine particles; fine particles made of a silicon-containing compound having an intermediate structure between inorganic and organic (for example, Tospearl series manufactured by Momentive Performance Materials Japan, which is fine particles of silicone resin). Among these, acrylic resin fine particles and fine particles made of a silicon-containing compound having an intermediate structure between inorganic and organic are preferable from the viewpoint of the effect of suppressing glare.
- inorganic fine particles such as silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc and titanium dioxide
- organic fine particles such as acrylic resin, polystyrene resin, polyethylene resin and epoxy resin.
- Translucent fine particles fine particles made of a silicon-containing compound having an intermediate structure between inorganic and organic (for example, Tos
- fine particles made of a silicon-containing compound having an intermediate structure between inorganic and organic are particularly preferable because they exert their effect even when added in a small amount and the adhesiveness of the adhesive component is maintained well.
- the above light diffusing fine particles may be used alone or in combination of two or more.
- acrylic resin fine particles examples include those composed of a homopolymer of methyl methacrylate and a copolymer of monomers such as methyl methacrylate and vinyl acetate, styrene, methyl acrylate, and ethyl (meth) acrylate. Can be mentioned. *
- the shape of the light diffusing fine particles is preferably spherical fine particles with uniform light diffusion.
- the average particle diameter of the light diffusing fine particles by the centrifugal sedimentation light transmission method needs to be 0.8 to 2.9 ⁇ m, preferably 1 to 2.7 ⁇ m, particularly 1.2 to 2.5 ⁇ m. It is preferable. Since the average particle size of the light diffusing fine particles is relatively small in this manner, the patterned transparent conductive film is not noticeable and has high definition due to the interaction between the adhesive component and the refractive index difference of the light diffusing fine particles. Also on the touch panel, glare is suppressed. When the average particle diameter of the light diffusing fine particles exceeds 2.9 ⁇ m, glare occurs in the touch panel to which the obtained adhesive is applied. On the other hand, when the average particle diameter of the light diffusing fine particles is less than 0.8 ⁇ m, the patterned transparent conductive film is easily visually recognized.
- the average particle diameter by the centrifugal sedimentation light transmission method was obtained by sufficiently stirring 1.2 g of fine particles and 98.8 g of isopropyl alcohol as a measurement sample, and using a centrifugal automatic particle size distribution measuring apparatus (manufactured by Horiba, Ltd., Measured using CAPA-700).
- the content of the light diffusing fine particles in the adhesive composition P is preferably 0.5 to 30 parts by mass, particularly 0.8 to 15 parts by mass with respect to 100 parts by mass of the adhesive component. It is preferably 2 to 4 parts by mass.
- the content of the light diffusing fine particles is within the above range, the patterned transparent conductive film is not visually recognized, the glare is effectively suppressed, and the adhesiveness due to the adhesive component is not inhibited.
- the adhesive composition P is optionally added with various additives such as a photopolymerization initiator, a silane coupling agent, a refractive index adjusting agent, an antistatic agent, a tackifier, an antioxidant, an ultraviolet absorber, a light It may contain stabilizers, softeners, fillers and the like.
- the adhesive component of the adhesive composition P contains the active energy ray-curable compound (C)
- the adhesive composition P when ultraviolet rays are used as the active energy ray for curing the adhesive composition P, the adhesive composition P is light. It preferably contains a polymerization initiator. By containing the photopolymerization initiator, the adhesive component containing the active energy ray-curable compound (C) can be efficiently cured, and the polymerization curing time and the amount of active energy ray irradiation can be reduced. .
- photopolymerization initiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethyla Nobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthr
- the photopolymerization initiator is preferably used in an amount in the range of 0.1 to 30 parts by mass, particularly 1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (C).
- the adhesive composition P preferably contains a silane coupling agent from the viewpoint of improving the adhesive strength of the obtained adhesive.
- the silane coupling agent is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule, having good compatibility with the adhesive component and having light transmittance.
- silane coupling agents include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) silicon compounds having an epoxy structure such as ethyltrimethoxysilane, mercapto group-containing silicon compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane Amino group-containing compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.
- silicon compounds such as
- the content of the silane coupling agent in the adhesive composition P is preferably 0.01 to 2 parts by mass, particularly 0.05 to 1 part by mass with respect to 100 parts by mass of the adhesive component. More preferably, it is 0.1 to 0.5 parts by mass.
- the difference in refractive index between the adhesive component and the light diffusing fine particles needs to be 0.005 to 0.2, and 0.007 to 0.1 is preferable, and 0.008 to 0.08 is particularly preferable. Since the difference in refractive index between the adhesive component and the light diffusing fine particles is relatively small as described above, glare is suppressed even in a high-definition touch panel due to the interaction with the average particle diameter of the light diffusing fine particles described above. When the refractive index difference is less than 0.005, the haze expression is lowered, and the effect of making the patterned transparent conductive film inconspicuous cannot be obtained. Moreover, when said refractive index difference exceeds 0.2, it will become impossible to suppress glare.
- the refractive index of the adhesive component is preferably 1.40 to 1.55, particularly preferably 1.42 to 1.50, and more preferably 1.44 to 1.49. . Further, the refractive index of the light diffusing fine particles is preferably 1.40 to 1.55, particularly preferably 1.41 to 1.52, and further preferably 1.42 to 1.50. preferable.
- the refractive index of the adhesive component is a value measured according to JIS K0062-1992 using an Abbe refractometer.
- the refractive index of the adhesive component may be a value measured before curing or a value measured after curing.
- the refractive index of the light diffusing fine particles is a value measured using a refractive index standard solution, as shown in a test example described later.
- the adhesive composition P can be produced by mixing an adhesive component, light diffusing fine particles, and, if desired, an additive.
- the pressure-sensitive adhesive component contains the (meth) acrylic acid ester polymer (A)
- the (meth) acrylic acid ester polymer (A) is first prepared, and if desired, the crosslinking agent (B) and / or active energy.
- a linear curable compound (C) is mix
- the (meth) acrylic acid ester polymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by an ordinary radical polymerization method.
- the polymerization of the (meth) acrylic acid ester polymer (A) can be performed by a solution polymerization method or the like using a polymerization initiator as desired.
- the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like, and two or more kinds may be used in combination.
- Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more kinds may be used in combination.
- Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
- organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
- organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
- examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
- the weight average molecular weight of the resulting polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
- the solution of the (meth) acrylic acid ester polymer (A) is added to the light diffusing fine particles, and optionally, the crosslinking agent (B), active energy ray curable.
- a compound (C) and an additive are added and mixed well to obtain an adhesive composition P (coating solution) diluted with a solvent.
- Examples of the dilution solvent for diluting the adhesive composition P to form a coating solution include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, methylene chloride, ethylene chloride, and the like.
- Halogenated hydrocarbons alcohols such as methanol, ethanol, propanol, butanol and 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethyl
- a cellosolv solvent such as cellosolve is used.
- the concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, dilution is performed so that the concentration of the adhesive composition P is 10 to 40% by mass. In addition, when obtaining a coating solution, addition of a dilution solvent etc. is not a necessary condition, and if a viscosity etc. which can be coated with the adhesive composition P are not necessary, a dilution solvent does not need to be added.
- the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition P.
- the coating solution of the pressure-sensitive adhesive composition P is made of a desired material (a release sheet or a base material for an anti-scattering pressure-sensitive adhesive sheet). Etc.) and cured (crosslinked).
- the pressure-sensitive adhesive composition P does not contain the active energy ray-curable compound (C)
- the pressure-sensitive adhesive composition P can be dried after application, preferably heat-treated and cured to obtain a pressure-sensitive adhesive layer. it can. After the heat treatment, a curing period of about 1 to 2 weeks may be provided at room temperature (for example, 23 ° C., 50% RH) as necessary.
- the adhesive composition P contains an active energy ray-curable compound (C)
- the adhesive composition P is dried after application, preferably after heat treatment, and then cured by irradiation with active energy rays.
- a pressure-sensitive adhesive layer can be obtained.
- a method for applying the coating solution of the adhesive composition P for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
- drying of the adhesive composition P may be performed by air drying, it is usually performed by heat treatment (preferably hot air drying).
- the heating temperature is preferably 50 to 150 ° C., particularly preferably 70 to 120 ° C.
- the heating time is preferably 10 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes.
- active energy rays ultraviolet rays, electron beams and the like are usually used.
- the dose of the active energy ray varies depending on the type of the energy ray, for example, in the case of ultraviolet rays, preferably 50 ⁇ 1000mJ / cm 2 in quantity, especially 100 ⁇ 500mJ / cm 2 preferably.
- an electron beam about 10 to 1000 krad is preferable.
- the adhesive component of the adhesive composition P contains the (meth) acrylic acid ester polymer (A) and the crosslinking agent (B), the (meth) acrylic acid ester is obtained by drying (heat treatment) of the adhesive composition P.
- the polymer (A) is crosslinked by the crosslinking agent (B) to form a crosslinked structure.
- the adhesive component of the adhesive composition P further contains an active energy ray-curable compound (C)
- a plurality of active energy ray-curable compounds (C) are irradiated by irradiating the adhesive composition P with active energy rays.
- a structure entangled with the crosslinked structure of the (meth) acrylate polymer (A) is formed.
- the thickness of the pressure-sensitive adhesive layer according to this embodiment is preferably 5 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m, and further preferably 15 to 30 ⁇ m.
- the haze value (value measured according to JIS K7105) of the pressure-sensitive adhesive layer according to this embodiment is required to be 55% or less.
- the regulation of the haze value and the regulation of the refractive index difference and the average particle diameter of the light diffusing fine particles described above can make the patterned transparent conductive film inconspicuous and suppress glare. From the viewpoint of satisfactorily satisfying these two effects, the haze value of the pressure-sensitive adhesive layer is preferably 5 to 50%, particularly preferably 10 to 45%, and more preferably 20 to 35%. Is preferred.
- the anti-scattering adhesive sheet provided with the adhesive layer according to the present embodiment While sticking the anti-scattering adhesive sheet provided with the adhesive layer according to the present embodiment to at least one surface of the cover glass of the touch panel, it is possible to prevent the glass from scattering even when the cover glass is broken. Further, glare can be suppressed, and an excellent glare suppressing effect can be obtained even in a high-definition touch panel, and the touch panel has excellent display performance.
- the scattering prevention adhesive sheet 1 which concerns on this embodiment is laminated
- the release surface of the release sheet in this specification refers to a surface having peelability in the release sheet, and includes both a surface that has been subjected to a release treatment and a surface that exhibits peelability without being subjected to a release treatment. .
- the pressure-sensitive adhesive layer 12 is composed of the pressure-sensitive adhesive layer according to the above-described embodiment.
- the base material 11 may be made of a material having a strength that can prevent the glass from being scattered when the cover glass of the touch panel is broken. It may consist of only a film, or a plastic film with a desired functional layer formed thereon.
- plastic film examples include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyurethane films, polyethylene films, polypropylene films, cellulose films such as triacetyl cellulose, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl Alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, norbornene resin film, plastic film such as cycloolefin resin film; laminates of two or more of these .
- the plastic film may be uniaxially stretched or biaxially stretched.
- Examples of the functional layer include a hard coat layer, an antireflection layer, an antiglare layer, a slippery layer, an antistatic layer, and a color correction layer.
- the thickness of the substrate 11 is usually 10 to 500 ⁇ m, preferably 50 to 300 ⁇ m, and particularly preferably 80 to 150 ⁇ m.
- release sheet 13 examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polyethylene naphthalate film.
- the release surface of the release sheet 13 (particularly the surface in contact with the pressure-sensitive adhesive layer 12) is preferably subjected to a release treatment.
- the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
- the thickness of the release sheet 13 is not particularly limited, but is usually about 20 to 150 ⁇ m.
- the adhesive layer 12 consists of an adhesive which does not have active energy ray curability, as one manufacture example of the scattering prevention adhesive sheet 1, on the peeling surface of the peeling sheet 13, After apply
- a curing period is required, a curing period is set, and when the curing period is unnecessary, the coating layer becomes the pressure-sensitive adhesive layer 12 as it is. Thereby, the said scattering prevention adhesive sheet 1 is obtained.
- the conditions for the heat treatment and curing are as described above.
- the pressure-sensitive adhesive layer 12 is made of a pressure-sensitive adhesive having active energy ray curability, as one production example of the anti-scattering pressure-sensitive adhesive sheet 1, the coating liquid of the pressure-sensitive adhesive composition P is applied to the release surface of the release sheet 13. After apply
- the irradiation condition of the active energy ray is as described above.
- the adhesive layer 12 instead of forming the adhesive layer 12 by irradiating the active energy ray through the release sheet 13 as described above, a coating layer of the adhesive composition P is formed on the release sheet 13, and the coating is applied.
- the adhesive layer 12 may be formed by irradiating active energy rays while the film layer is exposed, and then the substrate 11 may be bonded to the adhesive layer 12.
- the adhesive layer 12 may be formed by directly forming the coating layer of the adhesive composition P on the substrate 11 instead of the release sheet 13.
- the capacitive touch panel 10A shown in FIG. 2 or the capacitive touch panel 10B shown in FIG. 3 is manufactured. Can do.
- the touch panel 10 ⁇ / b> A in the present embodiment in order from the bottom, is laminated with the display module 7, the film sensor 5 laminated thereon with an adhesive layer 6, and the adhesive layer 4 thereon.
- the cover glass 2 with the transparent conductive film 3 patterned and the anti-scattering pressure-sensitive adhesive sheet 1 (the release sheet 13 has been peeled off) pasted on the cover glass 2 via the pressure-sensitive adhesive layer 12 are configured.
- the scattering prevention adhesive sheet 1 is provided on the surface side of the cover glass 2 (the side opposite to the display body module 7).
- the touch panel 10B in this embodiment is laminated
- the anti-scattering adhesive sheet 1 (with the release sheet 13 already peeled) and the cover glass 2 with the patterned transparent conductive film 3 laminated via the adhesive layer 12 of the anti-scattering adhesive sheet 1 are provided. Composed. That is, in this touch panel 10 ⁇ / b> B, the scattering prevention adhesive sheet 1 is provided on the back side (the display module 7 side) of the cover glass 2.
- the transparent conductive film 3 is provided on the cover glass 2.
- the present invention is not limited to this, and the transparent conductive film 3 may be provided in another part.
- the adhesive layer 12 of the scattering prevention adhesive sheet 1 is adhere
- the (meth) acrylic acid ester polymer (A) of the pressure-sensitive adhesive composition P that constitutes does not contain a carboxyl group-containing monomer as a monomer unit that constitutes the polymer.
- Examples of the display module 7 include a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper. Even if the display module 7, particularly the liquid crystal (LCD) module, is a high-definition one, the touch panel 10 ⁇ / b> A, 10 ⁇ / b> B has excellent effects (especially glare) due to the adhesive layer 11 of the anti-scattering adhesive sheet 1. Display effect) and display performance is excellent. Such an excellent effect is naturally sufficiently exerted even when the display module 7 which is not high definition is used.
- LCD liquid crystal
- LED light emitting diode
- organic EL organic electroluminescence
- the pressure-sensitive adhesive layer 6 and the pressure-sensitive adhesive layer 4 may be formed of a desired pressure-sensitive adhesive or pressure-sensitive adhesive sheet, and may be formed of the same pressure-sensitive adhesive as the pressure-sensitive adhesive layer 11 of the anti-scattering pressure-sensitive adhesive sheet 1.
- the desired pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polyvinyl ether-based pressure-sensitive adhesives. preferable.
- the film sensor 5 is usually composed of a base film 51 and a patterned transparent conductive film 52.
- a base film 51 for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, a polymethylmethacrylate film, a triacetylcellulose film, a polypropylene film etc. are used.
- Examples of the transparent conductive film 52 include metals such as platinum, gold, silver and copper, oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
- oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
- Examples include composite oxides such as indium, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide, and non-oxidized compounds such as chalcogenide, lanthanum hexaboride, titanium nitride, and titanium carbide. Among these, those made of tin-doped indium oxide (ITO) are preferable.
- the transparent conductive film 52 of the film sensor 5 in the touch panels 10A and 10B is located above the film sensor 5 in FIGS. 2 and 3, but is not limited to this. It may be located on the lower side.
- the glass material of the cover glass 2 is not particularly limited.
- chemically tempered glass, alkali-free glass, quartz glass, soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass examples thereof include barium borosilicate glass.
- a desired functional layer may be provided on the surface of the cover glass 2.
- the thickness of the cover glass 2 is not particularly limited, but is usually 0.5 to 2.0 mm, preferably 0.7 to 1.5 mm.
- the transparent conductive film 3 is patterned on the cover glass 2 and provided.
- the same material as the transparent conductive film 52 of the film sensor 5 can be used. Note that one of the transparent conductive film 3 and the transparent conductive film 52 of the film sensor 5 normally constitutes a circuit pattern in the X-axis direction, and the other constitutes a circuit pattern in the Y-axis direction.
- the touch panel 10A When manufacturing the touch panel 10A, the release sheet 13 of the anti-scattering adhesive sheet 1 is peeled off, and the exposed adhesive layer 12 is attached to the surface side of the cover glass 2 (the side where the transparent conductive film 3 does not exist), Using the cover glass 2 with the anti-scattering adhesive sheet 1, the touch panel 10A may be manufactured by a conventional method, or the touch panel (the touch panel 10A in a state where the anti-scattering adhesive sheet 1 is not attached) is manufactured by a conventional method. After that, the anti-scattering adhesive sheet 1 may be attached to the surface side of the cover glass 2 (the side opposite to the display body module 7).
- the release sheet 13 of the anti-scattering adhesive sheet 1 is peeled off, and the exposed adhesive layer 12 is applied to the transparent conductive film 3 provided on the back side of the cover glass 2. What is necessary is just to manufacture the touchscreen 10B by a conventional method using the cover glass 2 with the said scattering prevention adhesive sheet 1.
- the touch panels 10 ⁇ / b> A and 10 ⁇ / b> B even if the cover glass 2 is broken due to a large impact due to dropping or the like, glass fragments are scattered due to the presence of the anti-scattering adhesive sheet 1 affixed to the cover glass 2. It is prevented. Moreover, even if it is any form of the said touchscreens 10A and 10B, the pattern of the transparent conductive films 3 and 52 is not conspicuous (it is hard to be visually recognized) by the presence of the adhesive layer 11 of the scattering prevention adhesive sheet 1, and it is a glare. Suppression is suppressed and display performance is excellent.
- the release sheet 13 of the anti-scattering adhesive sheet 1 may be omitted.
- the transparent conductive film 3 in the touch panels 10A and 10B may not be in contact with the cover glass 2, and in that case, may be provided as a part of the second film sensor.
- Example 1 Preparation of (meth) acrylic acid ester polymer 65 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate were copolymerized to give a (meth) acrylic acid ester polymer ( A) was prepared. When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method described later, it was a weight average molecular weight (Mw) of 600,000.
- Table 1 shows the composition of the adhesive composition. Details of the abbreviations and the like described in Table 1 are as follows. [(Meth) acrylic acid ester polymer (A)] 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate IBXA: isobornyl acrylate BA: n-butyl acrylate MA: methyl acrylate AA: acrylic acid [crosslinking agent (B)] XDI: Trimethylolpropane-modified xylylene diisocyanate (Mitsui Takeda Chemicals, product name “Takenate D-110N”) TDI: Trimethylolpropane-modified tolylene diisocyanate (product name “Coronate L” manufactured by Nippon Polyurethane Co., Ltd.) [Light diffusion fine particles] Silicone fine particles (2 ⁇ m): Fine particles composed of silicon-containing compounds having an intermediate structure between inorganic and
- a release sheet obtained by peeling off the coating solution of the pressure-sensitive adhesive composition obtained in Step 2 above with a silicone release agent on one side of a polyethylene terephthalate film. , Thickness: 38 ⁇ m was applied with a knife coater to a release-treated surface, followed by heat treatment at 90 ° C. for 1 minute to form a coating layer of the adhesive composition.
- the hard coat layer coating agent obtained in the above step 3 is applied to one surface of a polyethylene terephthalate film (product name “Cosmo Shine A4300”, thickness 75 ⁇ m, manufactured by Toyobo Co., Ltd.), dried, and photocured.
- a substrate having a hard coat layer with a thickness of 3 ⁇ m was obtained.
- the obtained base material is bonded to the exposed surface side of the coating layer so that the surface having no hard coat layer is in contact with the coating layer, and is cured at 23 ° C. and 50% RH for 7 days.
- a pressure-sensitive adhesive layer was formed to obtain an anti-scattering pressure-sensitive adhesive sheet.
- the thickness of the formed adhesive layer was 25 micrometers.
- Examples 2 and 3 A scattering-preventing pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the type and ratio of each monomer constituting the (meth) acrylic acid ester polymer (A) were changed as shown in Table 1.
- Example 4 Preparation of (meth) acrylic acid ester polymer As in Example 1, except that the type and ratio of each monomer constituting the (meth) acrylic acid ester polymer (A) are changed as shown in Table 1, ) An acrylic ester polymer (A) was prepared. When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method described later, it was a weight average molecular weight (Mw) of 600,000.
- a release sheet (SP-PET3811, manufactured by Lintec Corporation, thickness: 38 ⁇ m) obtained by subjecting one side of a polyethylene terephthalate film to a release treatment using a silicone-based release agent was applied to the adhesive composition obtained in the above process.
- a release sheet (SP-PET3811, manufactured by Lintec Corporation, thickness: 38 ⁇ m) obtained by subjecting one side of a polyethylene terephthalate film to a release treatment using a silicone-based release agent was applied to the adhesive composition obtained in the above process. ) was applied with a knife coater and then heat-treated at 90 ° C. for 1 minute to form a coating layer of the adhesive composition.
- a substrate having a hard coat layer on one side of a polyethylene terephthalate film was produced in the same manner as in Example 1.
- the obtained base material was bonded to the exposed surface side of the coating film layer so that the surface on the side without the hard coat layer was in contact with the coating film layer.
- the scattering prevention adhesive sheet was obtained by irradiating an ultraviolet-ray on the following conditions through a peeling sheet, and making the said coating-film layer into an adhesive layer.
- the thickness of the formed adhesive layer was 25 micrometers.
- Examples 5 to 10 Comparative Examples 1 to 6
- Kind and ratio of each monomer constituting (meth) acrylic acid ester polymer (A), weight average molecular weight (Mw) of (meth) acrylic acid ester polymer (A), kind and blending amount of crosslinking agent (B) In the same manner as in Example 4, except that the blending amounts of the active energy ray-curable compound (C) and the photopolymerization initiator, and the type and blending amount of the light diffusing fine particles are changed as shown in Table 1, Manufactured.
- the above-mentioned weight average molecular weight (Mw) is a polystyrene-reduced weight average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
- GPC measurement device manufactured by Tosoh Corporation, HLC-8020 GPC column (passed in the following order): TSK guard column HXL-H manufactured by Tosoh Corporation TSK gel GMHXL ( ⁇ 2) TSK gel G2000HXL ⁇ Measurement solvent: Tetrahydrofuran ⁇ Measurement temperature: 40 ° C.
- the refractive index of the adhesive component used in Examples and Comparative Examples was measured by the following method.
- one side of the polyethylene terephthalate film was peeled off with a silicone-based release agent, instead of adding the light diffusing fine particles and replacing the base material used for the production of the anti-scattering pressure-sensitive adhesive sheet.
- Treated release sheet manufactured by Lintec, SP-PET3801, thickness: 38 ⁇ m
- release sheet SP-PET3801
- adhesive layer thickness: 25 ⁇ m
- a single pressure-sensitive adhesive layer obtained by peeling two release sheets from the pressure-sensitive adhesive sheet was used as a measurement sample.
- the refractive index was measured according to JIS K0062-1992 using an Abbe refractometer, and this was taken as the refractive index of the adhesive component.
- the glare caused by the scattering-preventing pressure-sensitive adhesive sheet is more likely to occur as the ppi in the lattice pattern increases, in other words, as the display becomes higher definition. Therefore, it means that generation
- a resist solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name “0FPR-800 LB”) is applied on the obtained ITO film to form a resist coating film, and the coating film is irradiated with a light irradiation portion having a width of 1 cm. And an unirradiated portion having a width of 1 cm were exposed so as to form a stripe pattern.
- the resist film was washed with a basic solution (tetramethylammonium hydroxide solution), and the resist film in the unirradiated part was washed away. Subsequently, the ITO film in a portion where the resist coating film was not provided was removed by immersing in a mixed aqueous solution of hydrochloric acid and nitric acid (etching process).
- a basic solution tetramethylammonium hydroxide solution
- the resist coating film of the light irradiation part was washed away by washing with a strongly basic solution, and the ITO film was crystallized by heating at 200 ° C. for 90 minutes.
- a cover glass having a transparent conductive film patterned in a stripe shape so that an ITO film portion having a width of 1 cm and an ITO film non-existing portion having a width of 1 cm were alternately repeated was obtained.
- evaluation sample The release sheet of the anti-scattering adhesive sheet obtained in Examples and Comparative Examples was peeled off, and the exposed adhesive layer was attached to the transparent conductive film forming surface side of the cover glass.
- evaluation sample which consists of a structure (a laminated body of a cover glass and a scattering prevention adhesive sheet) of a glass plate / patterned transparent conductive film / adhesive layer / base material.
- FIG. 4 shows a cross-sectional view of the resistance value measurement sample S.
- a polyethylene terephthalate (PET) film 81 having an ITO film 82 provided on one surface 81a is prepared by sputtering, and the surface 81b of the PET film 81 on which the ITO film 82 is not provided and one surface 83a of the glass plate 83.
- Were joined via a joining tape 84 (trade name “Tack Liner TL-70”, manufactured by Lintec Corporation).
- a conductive resin material containing silver (trade name, manufactured by Fujikura Kasei Co., Ltd.) is provided on a surface 82a of the ITO film 82 opposite to the surface in contact with the PET film 81 (hereinafter referred to as "one surface”).
- the electrode 85 is heated to a temperature of 80 ° C. for 20 minutes and dried to be a resistance measurement point. Two points were formed. At that time, the positions of the two electrodes 85 were adjusted so that the distance between them was slightly larger than 20 mm.
- the anti-scattering adhesive sheet 1 obtained in the example or the comparative example was cut into a size of 20 mm ⁇ 250 mm, and the release sheet was peeled off (at this time, the anti-scattering adhesive sheet 1 is composed of the base material 11 and the adhesive). It is a laminate composed of the layer 12).
- the anti-scattering pressure-sensitive adhesive sheet 1 is applied to one surface 82a of the ITO film 82 so that the pressure-sensitive adhesive layer 12 of the anti-scattering pressure-sensitive adhesive sheet 1 is aligned with the two electrodes 85 and 85 (so as not to come into close contact).
- the sample S for resistance value measurement shown in FIG. 4 was prepared.
- Test Example 7 Evaluation of scattering prevention effect
- Two stainless steel plates were placed on a smooth table so as to be parallel to each other at an interval of 50 mm.
- the evaluation sample (laminated body of a cover glass and an anti-scattering adhesive sheet) obtained in Test Example 5 is an evaluation sample at both end portions 20 mm in the vertical direction of the evaluation sample so that the cover glass side is on the upper side.
- the base material of the scattering prevention pressure-sensitive adhesive sheet and the stainless steel plate were placed in contact with each other.
- the refractive index difference between the adhesive component and the light diffusing fine particles is in the range of 0.005 to 0.2, and the average particle size of the light diffusing fine particles is in the range of 0.8 to 2.9 ⁇ m.
- the anti-scattering adhesive sheets of Examples 1 to 10 having a haze value of the adhesive layer of 55% or less are excellent in anti-scattering effect, and it is difficult to visually recognize the pattern of the transparent conductive film. In use, the glare-suppressing effect was excellent.
- the anti-scattering adhesive sheets of Examples 1 to 9 using the (meth) acrylic acid ester polymer (A) that does not contain a carboxyl group-containing monomer as a constituent monomer component are the resistance values of the transparent conductive film as an adherend. It was difficult to change.
- the scattering prevention pressure-sensitive adhesive sheet and the pressure-sensitive adhesive according to the present invention are suitable as a scattering prevention pressure-sensitive adhesive sheet and a pressure-sensitive adhesive layer to be attached to a cover glass of a high-definition touch panel.
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Abstract
Description
〔粘着剤層〕
本発明の一実施形態に係る粘着剤層は、静電容量方式のタッチパネルに使用されるカバーガラスの少なくとも一方の面に貼付される飛散防止粘着シート用の粘着剤層である。この粘着剤層は、粘着成分と光拡散微粒子とを含有する粘着性組成物(以下「粘着性組成物P」という。)から形成される。
粘着性組成物Pが含有する粘着成分は、(メタ)アクリル酸エステル重合体(A)を含有することが好ましく、さらに架橋剤(B)を含有することが好ましい。また、所望により、さらに活性エネルギー線硬化性化合物(C)を含有してもよい。なお、本明細書において、(メタ)アクリル酸エステルとは、アクリル酸エステル及びメタクリル酸エステルの両方を意味する。他の類似用語も同様である。また、「重合体」には「共重合体」の概念も含まれるものとする。
(メタ)アクリル酸エステル重合体(A)は、当該重合体を構成するモノマーとして、アルキル基の炭素数が1~20の(メタ)アクリル酸アルキルエステルを含有することが好ましい。これにより、得られる粘着剤は、好ましい粘着性を発現することができる。また、(メタ)アクリル酸エステル重合体(A)は、アルキル基の炭素数が1~20の(メタ)アクリル酸アルキルエステルと、反応性の官能基を有するモノマー(反応性官能基含有モノマー)と、所望により用いられる他のモノマーとの共重合体であることが特に好ましい。(メタ)アクリル酸エステル重合体(A)が、当該重合体を構成するモノマーとして反応性官能基含有モノマーを含有することにより、架橋剤(B)と反応して架橋構造を形成することができる。
粘着性組成物Pは、粘着成分として、架橋剤(B)を含有することが好ましい。粘着性組成物Pの粘着成分が、重合体を構成するモノマー単位として反応性官能基含有モノマーを含む(メタ)アクリル酸エステル重合体(A)と、架橋剤(B)とを含有する場合、当該粘着性組成物Pを加熱等すると、架橋剤(B)は、(メタ)アクリル酸エステル重合体(A)を構成する反応性官能基含有モノマーの反応性官能基と反応する。これにより、架橋剤(B)によって(メタ)アクリル酸エステル重合体(A)が架橋された構造が形成され、得られる粘着剤の凝集力が向上する。
粘着性組成物Pは、粘着成分として、活性エネルギー線硬化性化合物(C)を含有してもよい。光拡散微粒子を含有する粘着剤は、一般的に凝集力が低下し易く、粘着剤層から剥離シートを剥離する時に、粘着剤層が剥離シート側に取られてしまうことがあるが、活性エネルギー線硬化性化合物(C)を含有する粘着性組成物Pは、活性エネルギー線の照射によって硬化させることにより上記のような問題が発生し難く、得られる粘着剤層がハンドリング性に優れたものとなる。
本実施形態に係る粘着性組成物Pが含有する光拡散微粒子は、上記粘着成分との屈折率差が0.005~0.2であり、遠心沈降光透過法による平均粒径が0.8~2.9μmであるものである。
粘着性組成物Pは、所望により、各種添加剤、例えば光重合開始剤、シランカップリング剤、屈折率調整剤、帯電防止剤、粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、軟化剤、充填剤等を含有してもよい。
本実施形態に係る粘着性組成物Pにおいて、粘着成分の屈折率と光拡散微粒子との屈折率の差は、0.005~0.2であることを要し、0.007~0.1であることが好ましく、特に0.008~0.08であることが好ましい。このように粘着成分および光拡散微粒子の屈折率差が比較的小さいことにより、前述した光拡散微粒子の平均粒径との相互作用により、高精細なタッチパネルにおいても、ぎらつきが抑制される。上記の屈折率差が0.005未満であると、ヘイズ発現性が低下し、パターニングされた透明導電膜を目立たなくする効果が得られなくなる。また、上記の屈折率差が0.2を超えると、ぎらつきを抑制できなくなる。
粘着性組成物Pは、粘着成分と、光拡散微粒子と、所望により添加剤とを混合することにより製造することができる。粘着成分が(メタ)アクリル酸エステル重合体(A)を含有する場合には、先に(メタ)アクリル酸エステル重合体(A)を調製し、所望により架橋剤(B)および/または活性エネルギー線硬化性化合物(C)を配合する。
本実施形態に係る粘着剤層は、粘着性組成物Pから形成され、具体的には、粘着性組成物Pの塗布溶液を所望の材料(剥離シートや飛散防止粘着シートの基材等)に塗布し、硬化(架橋)することにより形成される。粘着性組成物Pが活性エネルギー線硬化性化合物(C)を含有しない場合、当該粘着性組成物Pを、塗布後に乾燥、好ましくは加熱処理して硬化させることにより、粘着剤層を得ることができる。なお、加熱処理後、必要に応じて、常温(例えば、23℃、50%RH)で1~2週間程度の養生期間を設けてもよい。
図1に示すように、本実施形態に係る飛散防止粘着シート1は、下から順に、剥離シート13と、剥離シート13の剥離面に積層された粘着剤層12と、粘着剤層12に積層された基材11とから構成される。なお、本明細書における剥離シートの剥離面とは、剥離シートにおいて剥離性を有する面をいい、剥離処理を施した面および剥離処理を施さなくても剥離性を示す面のいずれをも含むものである。
上記飛散防止粘着シート1において、粘着剤層12は、前述した実施形態に係る粘着剤層からなる。
基材11としては、タッチパネルのカバーガラスが割れたときに、ガラスの飛散を防止できる程度の強度を有する材料からなるものであればよく、通常はプラスチックフィルムを主体とし、プラスチックフィルムのみからなってもよいし、プラスチックフィルムに所望の機能性層が形成されたものであってもよい。
剥離シート13としては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニルフィルム、アイオノマー樹脂フィルム、エチレン・(メタ)アクリル酸共重合体フィルム、エチレン・(メタ)アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルム等が用いられる。また、これらの架橋フィルムも用いられる。さらに、これらの積層フィルムであってもよい。
粘着剤層12が活性エネルギー線硬化性を有さない粘着剤からなる場合、飛散防止粘着シート1の一製造例としては、剥離シート13の剥離面に、上記粘着性組成物Pの塗布液を塗布し、加熱処理を行って粘着性組成物Pを硬化し、塗布層を形成した後、その塗布層に基材11を貼合する。養生期間が必要な場合は養生期間をおくことにより、養生期間が不要な場合はそのまま、上記塗布層が粘着剤層12となる。これにより、上記飛散防止粘着シート1が得られる。加熱処理および養生の条件については、前述した通りである。
上記飛散防止粘着シート1を使用することにより、例えば、図2に示す静電容量方式のタッチパネル10Aまたは図3に示す静電容量方式のタッチパネル10Bを製造することができる。
1.(メタ)アクリル酸エステル重合体の調製
アクリル酸2-エチルヘキシル65質量部、メタクリル酸メチル20質量部およびアクリル酸2-ヒドロキシエチル15質量部を共重合させて、(メタ)アクリル酸エステル重合体(A)を調製した。この(メタ)アクリル酸エステル重合体(A)の分子量を後述する方法で測定したところ、重量平均分子量(Mw)60万であった。
上記工程1で得られた(メタ)アクリル酸エステル重合体(A)100質量部(固形分換算値;以下同じ)と、架橋剤(B)としてのトリメチロールプロパン変性キシリレンジイソシアネート(三井武田ケミカル社製,製品名「タケネートD-110N」)0.2質量部と、シランカップリング剤としての3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製,製品名「KBM-403」)0.2質量部、および光拡散微粒子としての、無機と有機の中間的な構造を有するケイ素含有化合物からなる微粒子(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製,製品名「トスパール120」,平均粒径:2.0μm,屈折率:1.43)5質量部を添加し、十分に撹拌し、酢酸エチルで希釈することにより、粘着性組成物の塗布溶液を得た。
[(メタ)アクリル酸エステル重合体(A)]
2EHA:アクリル酸2-エチルヘキシル
MMA:メタクリル酸メチル
HEA:アクリル酸2-ヒドロキシエチル
IBXA:アクリル酸イソボルニル
BA:アクリル酸n-ブチル
MA:アクリル酸メチル
AA:アクリル酸
[架橋剤(B)]
XDI:トリメチロールプロパン変性キシリレンジイソシアネート(三井武田ケミカル社製,製品名「タケネートD-110N」)
TDI:トリメチロールプロパン変性トリレンジイソシアネート(日本ポリウレタン社製,製品名「コロネートL」)
[光拡散微粒子]
シリコーン微粒子(2μm):無機と有機の中間的な構造を有するケイ素含有化合物からなる微粒子(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製,製品名「トスパール120」,平均粒径:2.0μm,屈折率:1.43)
シリコーン微粒子(4.5μm):無機と有機の中間的な構造を有するケイ素含有化合物からなる微粒子(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製,製品名「トスパール145」,平均粒径:4.5μm,屈折率:1.43)
PMMA微粒子(2.5μm):架橋したメタクリル酸重合体からなる樹脂ビーズ(積水化成品工業社製,製品名「SSX102」,平均粒径:2.5μm,屈折率:1.49)
PMMA微粒子(4μm):架橋したメタクリル酸重合体からなる樹脂ビーズ(積水化成品工業社製,製品名「SSX104」,平均粒径:4.0μm,屈折率:1.49)
紫外線硬化型化合物含有組成物(荒川化学工業社製,製品名「ビームセット575CB」,濃度:100質量%,光重合開始剤入り)100質量部に、レベリング剤(ビックケミージャパン社製,製品名「BYK-300」,濃度:52質量%)0.1質量部を加え、プロピレングリコールモノメチルエーテルで希釈して、40質量%濃度のハードコート層用コート剤を調製した。
上記工程2で得られた粘着性組成物の塗布溶液を、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した剥離シート(リンテック社製,製品名「SP-PET3811」,厚さ:38μm)の剥離処理面にナイフコーターで塗布したのち、90℃で1分間加熱処理して粘着性組成物の塗膜層を形成した。
(メタ)アクリル酸エステル重合体(A)を構成する各モノマーの種類および割合を表1に示すように変更する以外、実施例1と同様にして飛散防止粘着シートを製造した。
1.(メタ)アクリル酸エステル重合体の調製
(メタ)アクリル酸エステル重合体(A)を構成する各モノマーの種類および割合を表1に示すように変更する以外、実施例1と同様にして(メタ)アクリル酸エステル重合体(A)を調製した。この(メタ)アクリル酸エステル重合体(A)の分子量を後述する方法で測定したところ、重量平均分子量(Mw)60万であった。
上記工程1で得られた(メタ)アクリル酸エステル重合体(A)92.5質量部と、架橋剤(B)としてのトリメチロールプロパン変性キシリレンジイソシアネート(三井武田ケミカル社製,製品名「タケネートD-110N」)0.2質量部と、活性エネルギー線硬化性化合物(C)としてのトリス(アクリロキシエチル)イソシアヌレート(東亜合成社製,製品名「アロニックスM-315」)7.5質量部とを混合した後、光重合開始剤としてのベンゾフェノンおよび1-ヒドロキシシクロヘキシルフェニルケトンを1:1の質量比で混合したもの(チバ・スペシャリティケミカルズ社製,製品名「イルガキュア500」)0.75質量部、シランカップリング剤としての3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製,製品名「KBM-403」)0.2質量部、および光拡散微粒子としての、無機と有機の中間的な構造を有するケイ素含有化合物からなる微粒子(モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製,製品名「トスパール120」,平均粒径:2.0μm,屈折率:1.43)5質量部を添加し、十分に撹拌し、酢酸エチルで希釈することにより、粘着性組成物の塗布溶液を得た。
上記工程で得られた粘着性組成物の塗布溶液を、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した剥離シート(リンテック社製,SP-PET3811,厚さ:38μm)の剥離処理面にナイフコーターで塗布したのち、90℃で1分間加熱処理して粘着性組成物の塗膜層を形成した。
<紫外線照射条件>
・フュージョン社製無電極ランプ Hバルブ使用
・照度600mW/cm2,光量150mJ/cm2
・UV照度・光量計はアイグラフィックス社製「UVPF-36」を使用
(メタ)アクリル酸エステル重合体(A)を構成する各モノマーの種類および割合、(メタ)アクリル酸エステル重合体(A)の重量平均分子量(Mw)、架橋剤(B)の種類および配合量、活性エネルギー線硬化性化合物(C)および光重合開始剤の配合量、ならびに光拡散微粒子の種類および配合量を表1に示すように変更する以外、実施例4と同様にして飛散防止粘着シートを製造した。
<測定条件>
・GPC測定装置:東ソー社製,HLC-8020
・GPCカラム(以下の順に通過):東ソー社製
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
・測定溶媒:テトラヒドロフラン
・測定温度:40℃
実施例および比較例で使用した光拡散微粒子の屈折率は、以下の方法により測定した。スライドガラス上に微粒子を載せ、屈折率標準液を微粒子上に滴下し、カバーガラスを被せ、試料を作製した。当該試料を顕微鏡で観察し、微粒子の輪郭が最も見づらくなった屈折率標準液の屈折率を微粒子の屈折率とした。
実施例および比較例にて飛散防止粘着シートの作製に使用した基材に替えて、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した剥離シート(リンテック社製,SP-PET3801,厚さ:38μm)を使用し、剥離シート(SP-PET3801)/粘着剤層(厚さ:25μm)/剥離シート(SP-PET3811)の構成からなる粘着シートを作製した。
実施例および比較例で得られた飛散防止粘着シートの剥離シートを剥がし、露出した粘着剤層をタブレット端末(アップル社製,iPad)の表示面に貼付した。そして、タブレット端末の表示面を緑一色の発光となるように調整し、飛散防止粘着シートによるぎらつき抑制効果を、目視にて以下の基準で評価した。結果を表2に示す。
◎:ぎらつきが全く見えない。
○:◎の物と比較したときに、僅かにぎらつきが感じられる程度のぎらつきが存在する。
△:他の物と比較せずにそれ単独で見ても、ぎらつきの存在が若干認められる程度にぎらつきが存在する。
×:表示面全体がぎらついている。
ガラス板上に金属蒸着層を設け、レジスト処理およびエッチング処理を行うことにより、60ppi(ピクセル/インチ)の大きさの光透過部を有する格子状パターンを形成した。この格子状パターンが設けられたガラス板を、バックライト(キング社製,ブライトボックス5000)上に載置した。
(1)パターニングされた透明導電膜を有するカバーガラスの作製
ガラス板(NSGプレシジョン社製,製品名「コーニングガラス イーグルXG」,縦90mm×横50mm×厚み0.5mm)の一方の面に、スパッタリングにより、透明導電膜として厚さ30nmのITO膜を形成した。次に、得られたITO膜上にレジスト液(東京応化工業社製,製品名「0FPR-800 LB」)を塗布してレジスト塗膜を形成し、当該塗膜を、幅1cmの光照射部と幅1cmの未照射部とを交互に繰り返すストライプ状のパターンとなるように露光した。
実施例および比較例で得られた飛散防止粘着シートの剥離シートを剥がし、露出した粘着剤層を上記カバーガラスの透明導電膜形成面側に貼付した。これにより、ガラス板/パターニングされた透明導電膜/粘着剤層/基材の構成(カバーガラスと飛散防止粘着シートとの積層体)からなる評価サンプルを得た。
得られた評価サンプルのカバーガラス面側から、パターニングされた透明導電膜を目視することにより、以下の基準で飛散防止粘着シートのパターン視認性(透明導電膜のパターンの目立ちにくさ)を評価した。結果を表2に示す。
◎:パターンが見えない。
○:パターンがうっすら見える。
×:パターンが見える。
実施例および比較例で得られた飛散防止粘着シートについて、以下の試験方法により、ITO膜の電気抵抗値を測定し、抵抗値増加率を計算した。
抵抗値増加率(%)={(R-R0)/R0}×100
平滑な台の上に、2枚のステンレススチール板(厚さ2cm)を50mmの間隔にて互いに平行になるように配置した。そして、試験例5で得られた評価サンプル(カバーガラスと飛散防止粘着シートとの積層体)を、カバーガラス側が上となるように、かつ、評価サンプルの縦方向の両端部20mmにて評価サンプルの飛散防止粘着シートの基材と上記ステンレススチール板とが接するように配置した。
11…基材
12…粘着剤層
13…剥離シート
2…カバーガラス
3…透明導電膜
4…粘着剤層
5…フィルムセンサー
51…基材フィルム
52…透明導電膜
6…粘着剤層
7…表示体モジュール
10A,10B…タッチパネル
80…デジタルハイテスタ
81…PETフィルム
81a,81b…面
82…ITO膜
82a…面
83…ガラス板
83a…面
84…接合テープ
85…電極
S…抵抗値測定用サンプル
Claims (9)
- 静電容量方式のタッチパネルに使用されるカバーガラスの少なくとも一方の面に貼付される飛散防止粘着シート用の粘着剤層であって、
前記粘着剤層が、粘着成分と光拡散微粒子とを含有する粘着性組成物から形成され、
前記粘着成分の屈折率と前記光拡散微粒子との屈折率の差が、0.005~0.2であり、
前記光拡散微粒子の遠心沈降光透過法による平均粒径が、0.8~2.9μmであり、
前記粘着剤層のヘイズ値が、55%以下である
ことを特徴とする粘着剤層。 - 前記粘着成分は、(メタ)アクリル酸エステル重合体を含有することを特徴とする請求項1に記載の粘着剤層。
- 前記(メタ)アクリル酸エステル重合体は、当該重合体を構成するモノマー単位として、カルボキシル基を有するモノマーを含有しないことを特徴とする請求項2に記載の粘着剤層。
- 前記粘着成分は、さらに架橋剤を含有し、
前記(メタ)アクリル酸エステル重合体は、当該重合体を構成するモノマー単位として、前記架橋剤と反応する官能基を有するモノマーを含有する
ことを特徴とする請求項2または3に記載の粘着剤層。 - 前記粘着成分は、さらに活性エネルギー線硬化性化合物を含有することを特徴とする請求項2~4のいずれか一項に記載の粘着剤層。
- 前記活性エネルギー線硬化性化合物は、分子量1000以下の多官能アクリレート系モノマーであることを特徴とする請求項5に記載の粘着剤層。
- 静電容量方式のタッチパネルに使用されるカバーガラスの少なくとも一方の面に貼付される飛散防止粘着シートであって、
基材と、
請求項1~6のいずれか一項に記載の粘着剤層と
を備えたことを特徴とする飛散防止粘着シート。 - 前記基材は、ハードコート層を有する樹脂フィルムであることを特徴とする請求項7に記載の飛散防止粘着シート。
- 前記カバーガラスの一方の面には、透明導電膜が設けられていることを特徴とする請求項7または8に記載の飛散防止粘着シート。
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JP2017061627A (ja) * | 2015-09-25 | 2017-03-30 | 王子ホールディングス株式会社 | 両面粘着シート及び光学部材 |
JP2017061628A (ja) * | 2015-09-25 | 2017-03-30 | 王子ホールディングス株式会社 | 両面粘着シート及び光学部材 |
JPWO2015146664A1 (ja) * | 2014-03-28 | 2017-04-13 | 王子ホールディングス株式会社 | 両面粘着シートおよび光学部材 |
JP2018090727A (ja) * | 2016-12-06 | 2018-06-14 | Dic株式会社 | 光学フィルム及びそれを用いた情報表示装置 |
WO2022034885A1 (ja) * | 2020-08-11 | 2022-02-17 | 王子ホールディングス株式会社 | 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法 |
JP2022032292A (ja) * | 2020-08-11 | 2022-02-25 | 王子ホールディングス株式会社 | 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法 |
JP2022032291A (ja) * | 2020-08-11 | 2022-02-25 | 王子ホールディングス株式会社 | 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法 |
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JP7485515B2 (ja) * | 2019-02-15 | 2024-05-16 | 日東電工株式会社 | 粘着剤層および粘着シート |
JP7406908B2 (ja) * | 2019-09-06 | 2023-12-28 | 株式会社きもと | ガラス飛散防止シート |
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JP2022032292A (ja) * | 2020-08-11 | 2022-02-25 | 王子ホールディングス株式会社 | 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法 |
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KR102245858B1 (ko) | 2021-04-28 |
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