WO2014208550A1 - 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着剤層付き光学フィルム、液晶表示装置、及び、積層体 - Google Patents
光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着剤層付き光学フィルム、液晶表示装置、及び、積層体 Download PDFInfo
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- WO2014208550A1 WO2014208550A1 PCT/JP2014/066699 JP2014066699W WO2014208550A1 WO 2014208550 A1 WO2014208550 A1 WO 2014208550A1 JP 2014066699 W JP2014066699 W JP 2014066699W WO 2014208550 A1 WO2014208550 A1 WO 2014208550A1
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- optical film
- adhesive layer
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- film
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- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KVZJLSYJROEPSQ-UHFFFAOYSA-N CC1C(C)CCCC1 Chemical compound CC1C(C)CCCC1 KVZJLSYJROEPSQ-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N CC1CCCCC1 Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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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- 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
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- 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
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- 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/02—Homopolymers or copolymers of monomers containing phosphorus
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- C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/04—Homopolymers or copolymers of monomers containing silicon
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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]
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- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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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- 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
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/031—Polarizer or dye
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- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
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- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
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- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
- C09K2323/057—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
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- G—PHYSICS
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- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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- G—PHYSICS
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- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- the present invention relates to an optical film pressure-sensitive adhesive composition, an optical film pressure-sensitive adhesive layer, an optical film with a pressure-sensitive adhesive layer, a liquid crystal display device, and a laminate.
- a transparent conductive laminate in which a transparent conductive layer such as an indium tin oxide (ITO) thin film is formed on one surface of a transparent substrate made of a transparent resin film or a glass plate has been widely used in various applications. ing.
- ITO indium tin oxide
- the transparent conductive layer is formed on the opposite side of the liquid crystal display device using a liquid crystal cell using, for example, an in-plane switching (IPS) method, from the side in contact with the liquid crystal layer of the transparent substrate constituting the liquid crystal cell. It is known to be a layer. Moreover, it is also known that the transparent conductive film in which the transparent conductive layer is formed on a transparent resin film is used for an electrode substrate of a touch panel. A polarizing plate may be formed on such a transparent conductive layer via an adhesive layer.
- IPS in-plane switching
- pressure-sensitive adhesives for optical members include, for example, an acrylic copolymer having a hydroxyl group and an alkylene oxide chain in the side chain, an ionic compound, a curing agent, and a phosphate ester compound.
- An antistatic acrylic pressure-sensitive adhesive is known (for example, see Patent Document 1).
- Patent Document 1 describes that the pressure-sensitive adhesive is suitable as a pressure-sensitive adhesive for a surface protective pressure-sensitive adhesive film of an optical member such as a polarizing plate.
- a polarizing plate may be laminated on the transparent conductive layer via an adhesive layer.
- This polarizing plate was obtained by swelling an unoriented polyvinyl alcohol film in a swelling bath, adsorbing iodine, and further subjecting it to treatment such as crosslinking and stretching in an aqueous solution containing boric acid.
- An iodine polarizing plate in which a transparent protective film is bonded to at least one surface of a polarizer is widely used.
- an iodine-based polarizing plate is laminated on a transparent conductive layer such as an ITO thin film via an adhesive and stored under heating and humidification, the surface resistance value of the transparent conductive layer increases. was there.
- Patent Document 1 does not discuss the surface resistance value of such a transparent conductive layer, and the antistatic acrylic pressure-sensitive adhesive of Patent Document 1 is used as a pressure-sensitive adhesive for a surface protective pressure-sensitive adhesive film. For optical films, it was not sufficient in terms of adhesive strength, adhesive reliability, and the like.
- the present invention also provides a layered product including a configuration in which an optical film such as a polarizing plate is laminated on a transparent conductive layer via an adhesive layer, even when the transparent conductive layer is stored under heating and humidification. It aims at providing the adhesive layer for optical films which can suppress that a surface resistance value raises, and the adhesive composition for optical films which can form the said adhesive layer for optical films.
- the present invention uses an optical film with an adhesive layer, which has the adhesive layer for an optical film on one surface of the optical film, and a liquid crystal using the optical film with an adhesive layer.
- Another object of the present invention is to provide a laminate comprising a display device, the pressure-sensitive adhesive layer of the optical film with the pressure-sensitive adhesive layer, and the transparent conductive layer of the transparent conductive film.
- the present inventors have found that the object can be achieved by using a pressure-sensitive adhesive composition containing a phosphate ester compound, and have completed the present invention.
- the present invention provides a (meth) acrylic polymer obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having a C 4-18 alkyl group as a main component, and a phosphate ester compound. It is related with the adhesive composition for optical films characterized by including.
- the phosphate ester compound is preferably 0.005 to 2 parts by weight with respect to 100 parts by weight of all monomer components constituting the (meth) acrylic polymer.
- the monomer component further contains a phosphate group-containing monomer.
- the phosphoric acid group-containing monomer is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of all monomer components constituting the (meth) acrylic polymer.
- this invention has the said adhesive layer for optical films in the at least one surface of the adhesive layer for optical films characterized by being formed from the said adhesive composition for optical films, and an optical film.
- the present invention relates to an optical film with an adhesive layer.
- the optical film is a polarizing plate having protective films on both sides of a polarizer, and the thickness of the protective film on at least one side is 50 ⁇ m or less, and at least the pressure-sensitive adhesive layer for optical film is in contact with the protective film. It is preferable.
- the optical film may be a polarizing plate having a protective film on one side of a polarizer, and the optical film pressure-sensitive adhesive layer may be in contact with at least a surface of the polarizer that does not have a protective film.
- the present invention also relates to a liquid crystal display device using the optical film with the pressure-sensitive adhesive layer.
- the present invention relates to a laminate characterized in that the pressure-sensitive adhesive layer of the optical film with the pressure-sensitive adhesive layer and the transparent conductive layer of the transparent conductive film are bonded together.
- an increase in the surface resistance of the transparent conductive layer can be suppressed.
- the optical film pressure-sensitive adhesive composition of the present invention contains a phosphate ester compound, and thus the phosphate ester compound is selectively adsorbed on the surface of the transparent conductive layer to form a film. It is thought that corrosion of the transparent conductive layer by a substance that can corrode the transparent conductive layer is prevented, and an increase in the surface resistance value can be suppressed.
- optical film Adhesive Composition The optical film adhesive composition of the present invention is obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms as a main component (meta ) An acrylic polymer and a phosphate ester compound are included.
- phosphate ester compounds examples include phosphate ester compounds represented by the following general formula (1) and salts thereof.
- R 1 is an alkyl group having 2 to 18 carbon atoms or an alkenyl group
- R 2 is a hydrogen atom, or — (CH 2 CH 2 O) n
- R 3 is carbon N is an integer of 0 to 15).
- R 1 is an alkyl group having 2 to 18 carbon atoms or an alkenyl group, preferably an alkyl group having 2 to 18 carbon atoms, and more preferably an alkyl group having 4 to 15 carbon atoms.
- R 1 may be linear or branched, but is preferably linear.
- R 2 is a hydrogen atom or — (CH 2 CH 2 O) n R 3 , and examples of R 3 include the same as R 1 .
- R 2 is a hydrogen atom
- the compound of the general formula (1) is a monoester
- R 2 is — (CH 2 CH 2 O) n R 3
- the compound of the general formula (1) is a diester. is there.
- R 1 and R 3 may be the same or different.
- n is an integer of 0 to 15, and preferably an integer of 0 to 10.
- the phosphate ester compound represented by the general formula (1) two or more different R 1 compounds may be used as a mixture, or a monoester (R 2 : H) and Mixtures of diesters (R 2 : — (CH 2 CH 2 O) n R 3 ) may be used.
- the phosphate ester compound represented by the general formula (1) is obtained as a mixture of a monoester and a diester.
- salts of phosphoric acid ester compounds represented by the general formula (1) metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.
- metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.
- the present invention by laminating an optical film such as a polarizing plate and a transparent conductive layer through an optical film adhesive layer formed from the optical film adhesive composition containing the phosphate ester compound,
- the increase in surface resistance of the transparent conductive layer can be suppressed.
- the phosphoric acid ester compound contained in the pressure-sensitive adhesive layer is selectively adsorbed on the surface of the transparent conductive layer to form a film, so that the substance that corrodes the transparent conductive layer such as iodine is the surface of the transparent conductive layer. This is probably because corrosion of the transparent conductive layer is hindered.
- the optical film is an iodine polarizing plate, the above effect is remarkable.
- the addition amount of the phosphoric acid ester compound is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1.5 parts by weight, based on 100 parts by weight of the monomer component. More preferably, the content is 01 to 1.2 parts by weight. It is preferable that the addition amount of the phosphoric ester compound is in the above range since the increase in the surface resistance value of the transparent conductive layer can be further suppressed.
- the (meth) acrylic polymer used in the present invention is obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having a C 4-18 alkyl group as a main component.
- the “main component” means 50 parts by weight or more, preferably 60 parts by weight or more, and 70 parts by weight with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. More preferably, it is more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.
- Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
- alkyl group related to the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms various linear or branched ones can be used.
- Specific examples of the alkyl (meth) acrylate include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, and n-pentyl (meth).
- n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl (meth) acrylate is more preferable.
- the monomer component used by this invention contains a phosphate group containing monomer.
- a phosphate group-containing monomer a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a phosphate group can be used without particular limitation.
- the phosphate group-containing monomer include the following general formula (2): (Wherein R 4 represents a hydrogen atom or a methyl group, R 5 represents an alkylene group having 1 to 4 carbon atoms, m represents an integer of 2 or more, and M 1 and M 2 each independently represent a hydrogen atom. Or a phosphate group-containing monomer represented by the formula:
- m is an integer of 2 or more, preferably an integer of 4 or more, and usually preferably an integer of 40 or less.
- the m represents the degree of polymerization of the oxyalkylene group.
- the polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group, and these polyoxyalkylene groups may be random, block or graft units.
- the cation according to the salt of the phosphate group is not particularly limited, for example, an alkali metal such as sodium or potassium, for example, an inorganic cation such as an alkaline earth metal such as calcium or magnesium, for example, a quaternary amine And organic cations.
- the addition amount of the phosphate group-containing monomer is preferably 10 parts by weight or less, and preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. More preferably, it is 0.1 to 8 parts by weight, still more preferably 0.2 to 5 parts by weight. It is preferable that the addition amount of the phosphoric acid group-containing monomer be in the above range since the increase in the surface resistance value of the transparent conductive layer can be further suppressed.
- the present invention by using a phosphoric ester compound, an increase in the surface resistance value of the transparent conductive layer can be suppressed, but the monomer component contains a phosphate group-containing monomer.
- the monomer component contains a phosphate group-containing monomer.
- a further suppression effect can be obtained.
- the phosphoric acid group-containing monomer that does not contribute to the polymerization and the oligomer or polymer formed from the monomer component containing the phosphoric acid group-containing monomer are also adsorbed on the surface of the transparent conductive layer in the same manner as the phosphoric ester compound. It is thought to form.
- the present invention when only the phosphate group-containing monomer is included, a sufficient suppression effect cannot be obtained.
- the monomer component used in the present invention can contain a carboxyl group-containing monomer.
- carboxyl group-containing monomer those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation.
- the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These may be used alone or in combination. Can be used. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable.
- the carboxyl group-containing monomer is preferably 0 to 10 parts by weight, more preferably 0 to 8 parts by weight, further 0 to 6 parts by weight based on 100 parts by weight of the monomer component forming the (meth) acrylic polymer. preferable.
- the carboxyl group-containing monomer can be one of the corrosion factors, it is more preferable not to add the carboxyl group-containing monomer in the present invention.
- the (meth) acrylic polymer used in the present invention contains the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms as a main component, and optionally contains the phosphate group-containing monomer and the carboxyl group-containing monomer.
- the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms and the phosphate group-containing monomer a carboxyl group-containing monomer, the monomer, and the like.
- a copolymerizable monomer that can be copolymerized with the monomer component can be used as a monomer component.
- the copolymerization monomer is not particularly limited as long as it has a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- it has 1 to 3 carbon atoms or 19 or more carbon atoms.
- Alkyl (meth) acrylate having an alkyl group (meth) acrylic acid alicyclic hydrocarbon ester such as cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate; for example, (meth) acrylic (Meth) acrylic acid aryl esters such as phenyl acid; vinyl esters such as vinyl acetate and vinyl propionate; styrene monomers such as styrene; for example, glycidyl (meth) acrylate, methyl (meth) acrylate Epoxy group-containing monomers such as glycidyl; for example, 2-hydroxy acrylate Hydroxyl group-containing monomers such as ethyl and 2-hydroxypropyl acrylate; for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl
- copolymerizable monomers include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; for example, N-methylitaconimide, N-ethylitaconimide, N Itaconimide monomers such as butyl itaconimide, N-octyl itaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl itaconimide, N-lauryl itaconimide; N- (meth) acryloyloxymethylene succinimide, N- Succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide; for example, styrene sulfonic acid Examples include sulfonic acid group
- glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate
- examples include, for example, tetrahydrofurfuryl (meth) acrylate, a heterocyclic ring such as fluorine (meth) acrylate, and an acrylate monomer containing a halogen atom.
- a polyfunctional monomer can be used as the copolymerizable monomer.
- the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group.
- alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Esterified product of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compound such as divinylbenzene; allyl (meth) acrylate, (meth) Examples thereof include compounds having a reactive unsaturated double bond such as vinyl acrylate.
- polyester (meta) having two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as functional groups similar to the monomer component is added to a skeleton such as polyester, epoxy, and urethane.
- a skeleton such as polyester, epoxy, and urethane.
- Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can also be used.
- the proportion of the copolymerization monomer other than the carboxyl group-containing monomer and the phosphate group-containing monomer is preferably 40 parts by weight or less, and 30 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. Is more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less.
- the proportion of the copolymerization monomer is too large, the adhesive layer formed from the pressure-sensitive adhesive composition for optical films of the present invention, such as reduced adhesion to various adherends such as glass and film, transparent conductive layer, etc. There exists a possibility that an adhesive characteristic may fall.
- the (meth) acrylic polymer used in the present invention usually has a weight average molecular weight in the range of 500,000 to 3,000,000.
- the weight average molecular weight is preferably 700,000 to 2,700,000, more preferably 800,000 to 2,500,000. If the weight average molecular weight is less than 500,000, it may not be preferable in terms of heat resistance, and if the weight average molecular weight is more than 3 million, a large amount of diluent solvent is used to adjust the viscosity for coating. Is necessary from the viewpoint of cost.
- the weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography). However, since the pressure-sensitive adhesive obtained by emulsion polymerization generally has a large gel content and cannot be measured by GPC, it is often difficult to support the actual measurement related to molecular weight.
- the production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations, and is not particularly limited.
- an aqueous dispersion in which a (meth) acrylic polymer is dispersed and contained in water can be used.
- an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is contained.
- a polymer emulsion obtained by emulsion polymerization of the monomer component in the presence of an emulsifier, a radical polymerization initiator and the like described later can be used.
- a (meth) acrylic polymer obtained by solution polymerization of a monomer component containing (meth) acrylate can also be used.
- the obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out under an inert gas stream such as nitrogen and a polymerization initiator is added, usually at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, and the usage-amount is suitably adjusted according to these kinds.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, -Sec-butylperoxydicarbon
- the polymerization initiator may be used alone, or may be used in combination of two or more, but the total content is 100 weight of monomer component forming the (meth) acrylic polymer.
- the amount is preferably about 0.005 to 1 part by weight, more preferably about 0.005 to 0.5 part by weight.
- the amount of the polymerization initiator used is The amount is preferably about 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer.
- chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
- the radical polymerization initiator, and a chain transfer agent as necessary are appropriately blended in water together with the above-described monomer components.
- known emulsion polymerization methods such as a batch charging method (batch polymerization method), a monomer dropping method, and a monomer emulsion dropping method can be employed.
- the monomer dropping method continuous dropping or divided dropping is appropriately selected. These methods can be appropriately combined.
- the reaction conditions and the like are selected as appropriate, but the polymerization temperature is, for example, about 20 to 90 ° C.
- the emulsifier examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl.
- anionic emulsifiers such as phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer are listed. These emulsifiers may be used alone or in combination of two or more.
- a reactive emulsifier having one or more unsaturated double bonds capable of radical polymerization in the molecule can also be used.
- a reactive emulsifier having one or more unsaturated double bonds capable of radical polymerization in the molecule can also be used.
- Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Adekaria Soap SE10N Adekaria Soap SE10N (Asahi Denka Kogyo Co., Ltd.), and the like.
- R 6 is a divalent organic group that may or may not contain an oxygen atom, and may or may not contain 3 or less oxyalkylene repeating units, and M 3 is Na, K, or NH 4
- R 7 is an alkylene group having 1 to 20 carbon atoms
- the reactive emulsifier does not contain the oxyalkylene repeating unit, or the number of the oxyalkylene repeating unit is 3 or less (preferably 2 or less).
- the divalent organic group is not particularly limited, and examples thereof include a divalent hydrocarbon group that may include an ether bond or an ester bond.
- reactive emulsifiers include, for example, the following general formula (4): (Wherein M 3 is the same as above, and R 8 is an alkyl group having 1 to 20 carbon atoms), or the following general formula (5): (Wherein M 3 is the same as above, and R 9 is an alkyl group having 1 to 20 carbon atoms).
- M 3 is preferably Na, K, or NH 4 .
- R 8 and R 9 are each an alkyl group having 1 to 20 carbon atoms, and among them, an alkyl group having 10 to 20 carbon atoms is preferable.
- Specific examples of the reactive emulsifier represented by the general formula (3) include, for example, Eleminol JS-20 (manufactured by Sanyo Chemical Industries, Ltd.), Latemul S-180A (manufactured by Kao Corporation), and the like. Can do.
- the blending ratio of the emulsifier is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight based on 100 parts by weight of all monomer components constituting the (meth) acrylic polymer. Part by weight is more preferred.
- a water-dispersed (meth) acrylic polymer can be prepared as an aqueous dispersion (emulsion).
- the average particle diameter of such a water-dispersed (meth) acrylic polymer is preferably adjusted to, for example, 0.05 to 3 ⁇ m, and more preferably 0.05 to 1 ⁇ m.
- the water-dispersed optical film pressure-sensitive adhesive composition of the present invention can contain a water-soluble basic component in addition to the water-dispersed (meth) acrylic polymer.
- the water-soluble basic component is a compound that can form a salt by neutralization reaction between the carboxyl group and acid / base of the water-dispersed (meth) acrylic polymer, and is generally soluble in water. It is a compound that shows alkalinity in the state of the aqueous solution.
- water-soluble basic components include alkanolamines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, and aminomethylpropanol; alkylamines such as trimethylamine, triethylamine, and butylamine; ethylenediamine, diethylenetriamine, triethylenetetramine, Polyalkylene polymines such as tetraethylenepentamine; and other organic amine compounds such as ethyleneimine, polyethyleneimine, imidazole, 2-methylimidazole, pyridine, aniline, and morpholine.
- alkanolamines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, and aminomethylpropanol
- alkylamines such as trimethylamine, triethylamine, and butylamine
- ethylenediamine, diethylenetriamine, triethylenetetramine Polyalkylene polymines such as tetraethylenepentamine
- other organic amine compounds such as ethyleneimine, polyethylenei
- water-soluble basic component examples include inorganic base compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as barium hydroxide, calcium hydroxide and aluminum hydroxide. And ammonia.
- inorganic base compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as barium hydroxide, calcium hydroxide and aluminum hydroxide.
- ammonia is preferred from the standpoint of ease of handling and the balance of corrosion resistance and durability of the pressure-sensitive adhesive layer after coating and drying.
- ammonia is used as aqueous ammonia, and the amount of the aqueous ammonia is usually adjusted to 100 parts by weight of the solid content contained in the water of the aqueous dispersion containing the (meth) acrylic polymer. It is preferable that the amount of ammonia contained is about 0.1 to 20 parts by weight, and more preferably 0.2 to 5 parts by weight.
- Sodium hydroxide is used as an aqueous solution of sodium hydroxide, and the amount of the aqueous solution of sodium hydroxide is usually 100 parts by weight of the solid content contained in the water dispersion containing the (meth) acrylic polymer.
- it is preferable to blend so that the sodium hydroxide contained in the aqueous sodium hydroxide solution is about 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.
- silane coupling agents can be added in order to improve adhesion under high temperature and high humidity conditions.
- the silane coupling agent one having any appropriate functional group can be used. Examples of the functional group include vinyl group, epoxy group, amino group, mercapto group, (meth) acryloxy group, acetoacetyl group, isocyanate group, styryl group, polysulfide group and the like.
- vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycol Epoxy group-containing silane coupling agents such as sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine, N
- silane coupling agents those that can be copolymerized by radical polymerization with the monomer components such as vinyl group, (meth) acryloxy group, styryl group, etc. are preferable, and in particular, (meth) acryloxy group from the viewpoint of reactivity. Those having the following are preferred.
- the silane coupling agent may be used alone or as a mixture of two or more, but the total content is 1 weight with respect to 100 parts by weight of the (meth) acrylic polymer. Is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.8 part by weight, and more preferably 0.05 to 0.7 part by weight. Is particularly preferred. When the amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the viewpoint of durability.
- the silane coupling agent when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component.
- the ratio is preferably 0.005 to 0.7 parts by weight with respect to 100 parts by weight of the alkyl (meth) acrylate.
- the pressure-sensitive adhesive composition for an optical film of the present invention includes, as necessary, a viscosity modifier, a crosslinking agent, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, and metal powder.
- a viscosity modifier for an optical film of the present invention
- a crosslinking agent for polystyrene
- a release modifier for polystyrenethacrylate
- a tackifier e.g., poly(ethylene glycol)
- plasticizer e.g., poly(ethylene glycol)
- softener glass fiber, glass beads, and metal powder.
- Various additives can be used as appropriate. These additives can also be blended as an emulsion.
- a crosslinking agent is preferable because it can impart cohesive force related to the durability of the pressure-sensitive adhesive.
- a polyfunctional compound is used, and an organic cross-linking agent and a polyfunctional metal chelate are exemplified.
- the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, and an aziridine crosslinking agent.
- an isocyanate crosslinking agent is preferable.
- a polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound.
- Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned.
- Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
- the isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by blocking agents or quantification) in one molecule.
- isocyanate-based crosslinking agent examples include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexa Isocyanurate
- the blending ratio of the crosslinking agent in the optical film pressure-sensitive adhesive composition is not particularly limited.
- the crosslinking agent (solid content) is about 10 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer (solid content). It is blended at a ratio of The blending ratio of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight.
- optical film pressure-sensitive adhesive layer The optical film pressure-sensitive adhesive layer of the present invention is formed from the optical film pressure-sensitive adhesive composition.
- the production method of the optical film pressure-sensitive adhesive layer of the present invention is not particularly limited, but the optical film pressure-sensitive adhesive composition is applied on various substrates, dried by a dryer such as a heat oven, solvent, moisture, An adhesive layer can be formed by evaporating excess aqueous basic components and the like.
- the substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate, and an optical film described later is also preferably used as the substrate. Can do.
- Various methods are used as a method of applying the pressure-sensitive adhesive composition for optical films to a substrate. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
- the drying conditions are not particularly limited, and can be appropriately set depending on the composition, concentration, etc. of the pressure-sensitive adhesive composition for optical films. For example, about 80 to 170 ° C., preferably 90 to It is 1 to 60 minutes at 150 ° C., preferably 2 to 30 minutes.
- the thickness (after drying) of the pressure-sensitive adhesive layer is preferably, for example, 10 to 100 ⁇ m, more preferably 15 to 80 ⁇ m, and further preferably 20 to 60 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is less than 10 ⁇ m, the adhesion to the adherend becomes poor, and the durability under high temperature and high temperature and humidity tends to be insufficient.
- the thickness of the pressure-sensitive adhesive layer exceeds 100 ⁇ m, the pressure-sensitive adhesive composition for an optical film when forming the pressure-sensitive adhesive layer cannot be sufficiently dried at the time of drying and air bubbles remain, There is a tendency that unevenness in thickness occurs on the surface of the layer, and problems in appearance tend to become obvious.
- constituent material of the release film examples include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
- porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- An appropriate thin leaf body can be used, but a resin film is preferably used from the viewpoint of excellent surface smoothness.
- the resin film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
- -Vinyl acetate copolymer film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
- -Vinyl acetate copolymer film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybuty
- the thickness of the release film is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed.
- the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.
- the transparent resin film substrate is not particularly limited, and various resin films having transparency are used.
- the resin film is formed of a single layer film.
- the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
- polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
- the thickness of the film substrate is preferably 15 to 200 ⁇ m, and more preferably 25 to 188 ⁇ m.
- the resin film with an adhesive layer which formed the adhesive layer of this invention in the said resin film base material forms a transparent conductive layer further in the side which is not in contact with the adhesive layer of a resin film base material. It can be used as a touch panel electrode application.
- optical film with pressure-sensitive adhesive layer is obtained by forming the pressure-sensitive adhesive layer for an optical film on at least one surface of the optical film. Since the said optical film with an adhesive layer has the adhesive layer of this invention, even if it bonds together to the transparent conductive layer formed with the metal oxide, it can suppress corrosion of a transparent conductive layer.
- FIG. 1 shows an example of the optical film with an adhesive layer of this invention, and is not limited to this. Absent.
- the optical film with an adhesive layer of the present invention has an optical film adhesive layer 2 (hereinafter sometimes referred to as an adhesive layer 2) on one surface of the optical film 1 (FIG. 1).
- the optical film 1 used for the optical film with an adhesive layer of the present invention those used for forming an image display device such as a liquid crystal display device are used, and the kind thereof is not particularly limited.
- the optical film 1 includes a polarizing plate.
- the polarizing plate one having a transparent protective film on one side or both sides of a polarizer is generally used.
- it is a single-sided protective polarizing plate having a transparent protective film only on one side of the polarizer, and the surface not having the protective film of the polarizer and the pressure-sensitive adhesive layer for an optical film are in contact with each other.
- the effect of this invention is remarkable when it is a polarizing plate which has a protective film on both surfaces of a child, Comprising:
- the thickness of the protective film of the side which contacts the adhesive layer for optical films of the said polarizer is 50 micrometers or less.
- the pressure-sensitive adhesive layer can be directly provided on the polarizer surface on the side not having the transparent protective film.
- the polarizer is not particularly limited, and various types can be used.
- polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
- a thin polarizer having a thickness of 10 ⁇ m or less can also be used.
- the thickness is preferably 1 to 7 ⁇ m.
- Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing plate can be reduced.
- the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, WO2010 / 100917, or a patent.
- the thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned.
- These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
- PVA-based resin polyvinyl alcohol-based resin
- International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing.
- those obtained by a production method including a step of stretching in a boric acid aqueous solution as described in International Publication No. 2010/100917 pamphlet, or Japanese Patent No. 47514881 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
- Those obtained by a production method including a step of stretching in the air before stretching in a boric acid aqueous solution described in the specification of 4751481 and Japanese Patent Application Laid-Open No. 2012-0753563 are preferable.
- polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic polymers such as polymethyl methacrylate
- styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
- AS resin acrylonitrile / styrene copolymer
- polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include blends of the polymer.
- the transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
- the thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin film properties. Moreover, in this invention, even if it is a case where the thickness of the protective film of the side which contacts the adhesive layer for optical films is as thin as 50 micrometers or less, the increase inhibitory effect of the surface resistance value of a transparent conductive layer can fully be acquired. it can.
- the polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like.
- the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
- examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
- the electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films.
- the adhesive used in the present invention can contain a metal compound filler.
- the surface of the transparent protective film to which the polarizer is not bonded may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
- optical film other than the polarizing plate examples include liquid crystal display devices such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation of etc. is mentioned. These can be used alone as an optical film, or can be laminated on the polarizing plate for practical use and used in one layer or in two or more layers.
- the optical film can be activated.
- Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.
- the method for forming the pressure-sensitive adhesive layer on the optical film is as described above.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until it is put to practical use.
- a release film Separatator
- the above-mentioned thing can be mentioned as a release film.
- the release film is an optical film with a pressure-sensitive adhesive layer by laminating the pressure-sensitive adhesive layer on the release film and the optical film. It can be used as a release film for the pressure-sensitive adhesive layer of the film, and the process can be simplified.
- an anchor layer (not shown) may be provided between the optical film 1 and the optical film pressure-sensitive adhesive layer 2.
- the material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Among these, polymers are particularly preferably used.
- the polymer may be used in any of a solvent-soluble type, a water-dispersed type, and a water-soluble type.
- polymers examples include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, polystyrene resins, and the like.
- polyurethane resins, polyester resins, and acrylic resins are particularly preferable. These resins can be appropriately mixed with a crosslinking agent.
- These other binder components can be used singly or in combination of two or more as appropriate.
- a water dispersion polymer When the anchor layer is formed of a water dispersion material, a water dispersion polymer is used.
- the water-dispersible polymer include those obtained by emulsifying various resins such as polyurethane and polyester using an emulsifier, and introducing a water-dispersible anionic group, cationic group, or nonionic group into the resin. Examples include self-emulsified ones.
- the anchor agent can contain an antistatic agent.
- the antistatic agent is not particularly limited as long as it is a material that can impart conductivity, and examples thereof include ionic surfactants, conductive polymers, metal oxides, carbon black, and carbon nanomaterials. Among these, a conductive polymer is preferable, and a water-dispersible conductive polymer is more preferable.
- water-soluble conductive polymer examples include polyaniline sulfonic acid (weight average molecular weight of 150,000 in terms of polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.). TRON series).
- the blending amount of the antistatic agent is, for example, 70 parts by weight or less, preferably 50 parts by weight or less with respect to 100 parts by weight of the polymers used for the anchor agent. From the viewpoint of the antistatic effect, it is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more.
- the thickness of the anchor layer is not particularly limited, but is preferably 5 to 300 nm.
- the method for forming the anchor layer is not particularly limited and can be performed by a generally known method.
- the optical film can be activated.
- Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.
- the method for forming the pressure-sensitive adhesive layer on the anchor layer on the optical film is as described above.
- the use of the optical film with the pressure-sensitive adhesive layer of the present invention is not limited to the use for the liquid crystal display device, for example, the transparent conductive layer of the transparent conductive film used for the electrode substrate of the touch panel, and the optical film with the pressure-sensitive adhesive layer. It can also be used as a touch panel application to which an adhesive layer is attached.
- Liquid crystal display device The optical film with an adhesive layer of this invention can be used suitably in various liquid crystal display devices.
- a transparent conductive layer is formed as an antistatic layer on the side opposite to the side in contact with the liquid crystal layer of the transparent substrate constituting the liquid crystal cell. It is preferable to apply the adhesive layer of the optical film with the adhesive layer of the present invention on the transparent conductive layer because corrosion of the transparent conductive layer as the antistatic layer can be suppressed. .
- FIG. 2 An example of a liquid crystal display device using the optical film with an adhesive layer of the present invention is shown in FIG.
- the liquid crystal display device of FIG. 2 includes an optical film 1, an optical film adhesive layer 2, a transparent conductive layer 3, a liquid crystal cell 4, an adhesive layer 5, and an optical film 6.
- the liquid crystal display device of the present invention is not limited to this, and various layers used for the liquid crystal display device can be included in the configuration.
- the optical film 1 and the transparent conductive adhesive layer 2 correspond to the optical film with the adhesive layer. Moreover, the optical film 6 can mention the same thing as the said optical film 1.
- FIG. 1 The optical film 1 and the transparent conductive adhesive layer 2 correspond to the optical film with the adhesive layer. Moreover, the optical film 6 can mention the same thing as the said optical film 1.
- the liquid crystal cell is not particularly limited, and for example, any type such as TN type, STN type, ⁇ type, VA type, IPS type, etc. can be applied. In particular, an excellent effect is obtained when an IPS liquid crystal cell is used.
- the pressure-sensitive adhesive layer 5 may be the pressure-sensitive adhesive layer of the present invention, but is not particularly limited as long as it is a pressure-sensitive adhesive layer usually used in a liquid crystal image display device.
- an adhesive layer made of an adhesive based on an acrylic polymer, silicone polymer, polyester, polyurethane, polyether, fluorine-based or synthetic rubber-based polymer can be used.
- acrylic pressure-sensitive adhesives that are excellent in optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like are preferably used.
- the constituent material of the transparent conductive layer 3 provided on the liquid crystal cell is not particularly limited, and examples thereof include metal oxides.
- the metal oxide indium oxide containing tin oxide is suitable.
- the metal oxide preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
- the thickness of the transparent conductive layer 3 is not particularly limited, but is preferably 10 nm or more.
- the film thickness is preferably 15 to 35 nm, more preferably in the range of 20 to 30 nm, since transparency is lowered when the film thickness becomes too thick.
- the thickness is less than 15 nm, the surface electrical resistance increases and it becomes difficult to form a continuous film. Moreover, when it exceeds 35 nm, transparency will fall.
- the method for forming the transparent conductive layer 3 is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.
- an undercoat layer can be formed with an inorganic substance, an organic substance, or a mixture of an inorganic substance and an organic substance.
- an inorganic substance such as NaF (1.3), Na 3 AlF 6 (1.35), LiF (1.36), MgF 2 (1.38), CaF 2 (1.4), BaF 2 (1. 3), inorganic materials such as SiO 2 (1.46), LaF 3 (1.55), CeF 3 (1.63), Al 2 O 3 (1.63)
- SiO 2 , MgF 2 , A1 2 O 3 and the like are preferably used.
- SiO 2 is suitable.
- a composite oxide containing about 10 to 40 parts by weight of cerium oxide and about 0 to 20 parts by weight of tin oxide with respect to indium oxide can be used.
- the undercoat layer formed of an inorganic material can be formed as a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method, or by a wet method (coating method).
- a wet method coating method
- SiO 2 is preferable as described above.
- a SiO 2 film can be formed by applying silica sol or the like.
- an optional optical compensation layer, an adhesive layer, etc. on each layer and / or outside shown in FIG. can also be included.
- Laminate The laminate of the present invention is characterized in that the pressure-sensitive adhesive layer of the optical film with the pressure-sensitive adhesive layer and the transparent conductive layer of the transparent conductive film are bonded together.
- optical film with an adhesive layer can be used.
- the transparent conductive film is not particularly limited, and a known film can be used. Generally, a film having a transparent conductive layer on a transparent substrate is used.
- the transparent substrate may be any material as long as it has transparency, and examples thereof include a resin film and a substrate made of glass (for example, a sheet-like, film-like, or plate-like substrate). A film is particularly preferred.
- the thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 ⁇ m, more preferably about 15 to 150 ⁇ m.
- the material of the resin film is not particularly limited, and various plastic materials having transparency can be mentioned.
- the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins.
- polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.
- the transparent base material is subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation and undercoating treatment on the surface in advance, and the transparent conductive layer provided thereon You may make it improve the adhesiveness with respect to the said transparent base material.
- etching treatment such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation and undercoating treatment on the surface in advance, and the transparent conductive layer provided thereon You may make it improve the adhesiveness with respect to the said transparent base material.
- dust may be removed and cleaned by solvent cleaning or ultrasonic cleaning as necessary.
- Examples of the transparent conductive layer include those similar to the transparent conductive layer described in “4. Liquid Crystal Display Device”.
- Example 1 (Preparation of monomer emulsion) In a container, 785 parts of butyl acrylate, 160 parts of methyl methacrylate, 5 parts of a phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.), phosphate group-containing ester (trade name: Phosphanol SM) -172, manufactured by Toho Chemical Co., Ltd.) 1 part, acrylic acid 50 parts, 3-methacryloyloxypropyl-triethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part, Eleminol Add 20 parts of JS-20 (manufactured by Sanyo Chemical Industries Co., Ltd.) and 1381 parts of water, use a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and stir at 6000 rpm for 5 minutes. Prepared.
- a stretched laminate is produced by air-assisted stretching at a stretch ratio of 2 times, then a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched by boric acid in water at a stretching temperature of 65 ° C.
- PVA molecules in the PVA layer formed on the A-PET film by such two-stage stretching are oriented in a higher order, and the iodine adsorbed by the dye forms a complex with PVA, and is high in one direction as a PVA-iodine complex.
- an optical film laminate including a PVA layer having a thickness of 4 ⁇ m constituting the oriented high-functional polarizing layer could be produced.
- an acrylic film having a thickness of 40 ⁇ m is bonded to the surface of the polarizing layer of the optical film laminate through a polyvinyl alcohol adhesive, and then the A-PET film is peeled off to produce a polarizing plate using a thin polarizing layer. did. It is called single-sided protective polarizing plate (1).
- the pressure-sensitive adhesive layer for optical film obtained in the above (formation of pressure-sensitive adhesive layer for optical film) is bonded to the polarizer (the surface on which the protective film is not laminated) of the single-sided protective polarizing plate (1), A polarizing plate with an agent layer was produced.
- Example 2 In Example 1 (production of polarizing plate with pressure-sensitive adhesive layer), the following double-sided protective polarizing plate (1) was used, and on the protective film side of the double-sided protective polarizing plate having a thickness of 40 ⁇ m, A polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer for optical film obtained in (Formation of pressure-sensitive adhesive layer for optical film) was bonded.
- a stretched laminate was produced by air-assisted stretching with a stretch ratio of 2 times.
- a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further integrated with the A-PET film so that the total draw ratio becomes 5.94 times by stretching in boric acid water at a stretching temperature of 65 ° C.
- An optical film laminate including a PVA layer having a thickness of 5 ⁇ m that was stretched into a film was produced.
- PVA molecules in the PVA layer formed on the A-PET film by such two-stage stretching are oriented in a higher order, and the iodine adsorbed by the dye forms a complex with PVA, and is high in one direction as a PVA-iodine complex.
- an optical film laminate including a PVA layer having a thickness of 5 ⁇ m constituting the oriented high-functional polarizing layer could be produced.
- A-PET film is peeled off, and a single-side protective polarizing plate using a thin polarizer (2) was produced.
- a 25 ⁇ m-thick norbornene film (trade name: ARTON, manufactured by JSR Corporation) is bonded to the polarizer surface of the produced single-side protective polarizing plate (2) via a UV curable adhesive. ) was produced.
- Example 3 In Example 1 (preparation of monomer emulsion), except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 10 parts. A polarizing plate with an adhesive layer was produced in the same manner as in Example 1.
- the phosphate group-containing ester trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.
- Example 4 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 790 parts, and phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts. Polarized light with adhesive layer in the same manner as in Example 1 except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 2 parts. A plate was made.
- Example 5 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 790 parts, and phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts. Polarized light with adhesive layer in the same manner as in Example 1 except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 10 parts. A plate was made.
- phosphate group-containing monomer trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.
- Polarized light with adhesive layer in the same manner as in Example 1 except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 10 parts. A plate was made.
- Example 6 In Example 1 (Preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 770 parts, and phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 20 parts. With adhesive layer as in Example 1, except that phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 0.3 part. A polarizing plate was produced.
- phosphate group-containing monomer trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.
- Phosphanol SM-172 manufactured by Toho Chemical Industry Co., Ltd.
- Example 7 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 770 parts, and phosphoric acid group-containing monomer (trade name: SimperPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 20 parts. In the same manner as in Example 1 except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 10 parts. A polarizing plate was produced.
- phosphoric acid group-containing monomer trade name: SimperPAM200, manufactured by Rhodia Nikka Co., Ltd.
- Phosphanol SM-172 manufactured by Toho Chemical Industry Co., Ltd.
- Example 8 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 740 parts, and phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 50 parts.
- a polarizing plate with an adhesive layer was produced in the same manner as in Example 1 except that.
- Example 9 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 780 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 10 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to MP-4 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.).
- Phosphanol SM-172 trade name, manufactured by Toho Chemical Industry Co., Ltd.
- MP-4 trade name, manufactured by Daihachi Chemical Industry Co., Ltd.
- Example 10 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 770 parts, and phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 20 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to MP-4 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.).
- a polarizing plate with an adhesive layer was produced.
- Example 11 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 790 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to Phosphanol GF-185 (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
- a polarizing plate with an adhesive layer was produced in the same manner as Example 1 except for the above.
- Example 12 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 780 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 10 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to Phosphanol GF-185 (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
- a polarizing plate with an adhesive layer was produced in the same manner as Example 1 except for the above.
- Example 13 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 790 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to Phosphanol BH-650 (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
- a polarizing plate with an adhesive layer was produced in the same manner as Example 1 except for the above.
- Example 14 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 780 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 10 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to Phosphanol BH-650 (trade name, manufactured by Toho Chemical Industry Co., Ltd.).
- a polarizing plate with an adhesive layer was produced in the same manner as in Example 1 except that.
- Example 15 In Example 1 (preparation of monomer emulsion), butyl acrylate was changed from 785 parts to 780 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 10 parts.
- the phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to Phosphanol RS-710 (trade name, manufactured by Toho Chemical Industry Co., Ltd.)
- a polarizing plate with an adhesive layer was produced in the same manner as Example 1 except for the above.
- Example 16 (Monomer emulsion (1) adjustment) In a container, 180 parts of butyl acrylate, 800 parts of methyl methacrylate, 20 parts of acrylic acid, 0.5 part of 3-methacryloyloxypropyl-triethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), Add 75 parts of Eleminol JS-20 (Sanyo Kasei Kogyo Co., Ltd.) and 4150 parts of water and stir at 6000 rpm for 5 minutes using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Monomer emulsion (1) was prepared.
- an aqueous dispersion (emulsion) having a solid content concentration of 40% was obtained.
- a water-dispersed acrylic pressure-sensitive adhesive was prepared by adding 3 parts of 10% ammonia water to 100 parts by weight of the aqueous dispersion (emulsion).
- a polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the optical film pressure-sensitive adhesive layer obtained above was used in (Preparation of polarizing plate with a pressure-sensitive adhesive layer) in Example 1.
- Example 17 In Example 16 (preparation of monomer emulsion (2)), butyl acrylate was changed from 917.5 parts to 942.5 parts, and a phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) A polarizing plate with an adhesive layer was produced in the same manner as in Example 16 except that the amount was changed from 25 parts to 0 parts.
- a phosphate group-containing monomer trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.
- Example 18 In Example 16 (preparation of monomer emulsion (2)), butyl acrylate was changed from 917.5 parts to 930 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was 25 parts.
- the type of phosphoric acid group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to MP-4 (trade name, Daihachi Chemical Industry Co., Ltd.).
- a polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 16 except that the product was changed to).
- Example 19 In Example 16 (preparation of monomer emulsion (2)), the type of phosphate group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to MP-4 (trade name, large size). A polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 16 except that the product was changed to Hachi Chemical Industry Co., Ltd.).
- Example 20 (Preparation of adhesive solution) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 944 parts of butyl acrylate, 50 parts of acrylic acid, and a phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) ) A monomer mixture containing 5 parts and 1 part of 2-hydroxyethyl acrylate was charged.
- SimmerPAM200 manufactured by Rhodia Nikka Co., Ltd.
- an isocyanate group-containing compound (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) is 0.6 parts with respect to 100 parts of polymer solids, and a silane coupling agent (trade name: KBM-403).
- a silane coupling agent (trade name: KBM-403).
- Shin-Etsu Chemical Co., Ltd.) with a polymer solid content of 0.075 parts per 100 parts of polymer solids, and phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.)
- a solvent for adjusting viscosity (ethyl acetate) was added to 0.1 part per 100 parts to prepare an adhesive solution (solid content 11%).
- a polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 1 except that the optical film pressure-sensitive adhesive layer obtained above was used in (Preparation of polarizing plate with a pressure-sensitive adhesive layer) in Example 1.
- Example 21 In Example 20 (production of polarizing plate with pressure-sensitive adhesive layer), the double-sided protective polarizing plate (1) obtained in Example 2 was used, and the polarizer of the double-sided protective polarizing plate had a thickness of 40 ⁇ m.
- Example 22 In Example 20, the type of phosphate group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to Phosphanol GF-185 (trade name, manufactured by Toho Chemical Industry Co., Ltd.). A polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 20 except for changing to.
- Example 23 In Example 20, the type of phosphate group-containing ester was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) to Phosphanol BH-650 (trade name, manufactured by Toho Chemical Industries, Ltd.) A polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 20 except for changing to.
- Example 24 In Example 20, the butyl acrylate was changed from 944 parts to 949 parts, the phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts, and the phosphate group-containing ester ( A polarizing plate with a pressure-sensitive adhesive layer was obtained in the same manner as in Example 20, except that the product name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd. was changed from 0.1 part to 0.03 part. Produced.
- the phosphate group-containing monomer trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.
- the phosphate group-containing ester A polarizing plate with a pressure-sensitive adhesive layer was obtained in the same manner as in Example 20, except that the product name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd. was changed from 0.1 part to 0.03 part. Produced.
- Example 25 In Example 20, the butyl acrylate was changed from 944 parts to 949 parts, the phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts, and the phosphate group-containing ester ( A polarizing plate with an adhesive layer was produced in the same manner as in Example 20, except that the trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd. was changed from 0.1 part to 1 part.
- the trade name: Phosphanol SM-172 manufactured by Toho Chemical Industry Co., Ltd. was changed from 0.1 part to 1 part.
- Example 26 In Example 20, the butyl acrylate was changed from 944 parts to 949 parts, the phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts, and the phosphate group-containing ester was changed. Except that the type was changed from Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) to MP-4 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.), the same as in Example 20. Thus, a polarizing plate with an adhesive layer was produced.
- the phosphate group-containing monomer trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.
- MP-4 trade name, manufactured by Daihachi Chemical Industry Co., Ltd.
- Example 1 Comparative Example 1
- butyl acrylate was changed from 785 parts to 790 parts, and phosphoric acid group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts.
- Polarized light with an adhesive layer in the same manner as in Example 1 except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 0 part.
- a plate was made.
- Comparative Example 2 An adhesive layer for an optical film was formed with the same composition as in Comparative Example 1.
- the pressure-sensitive adhesive layer of the obtained pressure-sensitive adhesive layer for an optical film was bonded to the 40 ⁇ m-thick protective film side of the double-sided protective polarizing plate (1) obtained in Example 2 to produce a polarizing plate with a pressure-sensitive adhesive layer. did.
- Example 1 preparation of monomer emulsion
- butyl acrylate was changed from 785 parts to 770 parts
- phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 20 parts.
- Polarized light with an adhesive layer in the same manner as in Example 1 except that the phosphate group-containing ester (trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd.) was changed from 1 part to 0 part.
- a plate was made.
- Example 1 preparation of monomer emulsion
- butyl acrylate was changed from 785 parts to 740 parts
- phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 50 parts.
- a plate was made.
- Example 20 Comparative Example 5
- the butyl acrylate was changed from 944 parts to 949 parts
- the phosphate group-containing monomer (trade name: SimmerPAM200, manufactured by Rhodia Nikka Co., Ltd.) was changed from 5 parts to 0 parts
- the phosphate group-containing ester ( A polarizing plate with an adhesive layer was produced in the same manner as in Example 20, except that the trade name: Phosphanol SM-172, manufactured by Toho Chemical Industry Co., Ltd. was changed from 0.1 part to 0 part.
- thermosetting resin having a weight ratio of 2: 2: 1 of melamine resin: alkyd resin: organosilane condensate on one surface of a polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 25 ⁇ m
- PET film polyethylene terephthalate film
- a first undercoat layer having a thickness of 180 nm was formed.
- SiO 2 was vacuum-deposited on the first undercoat layer by an electron beam heating method at a vacuum degree of 1.33 ⁇ 10 ⁇ 2 to 2.67 ⁇ 10 ⁇ 2 Pa to obtain a thickness of 40 nm.
- a second undercoat layer (SiO 2 film) was formed.
- a film having an ITO thin film was obtained by forming an ITO film having a thickness of 22 nm by a reactive sputtering method using a thin film.
- the obtained ITO film was amorphous.
- the film having the ITO thin film was crystallized by heating at 140 ° C. for 90 minutes to obtain a crystallized ITO thin film.
- the polarizing plate with an adhesive layer obtained in Examples and Comparative Examples was cut into 8 mm ⁇ 8 mm. Moreover, the sample which laminated
- the resistance value of the crystallized ITO film of the film having the crystallized ITO thin film (this is referred to as the resistance value after loading) was measured in the same manner as described above.
- the rate of increase in resistance value before and after the sample was put in the atmosphere was calculated according to the following equation.
- Increase rate of resistance value (%) (resistance value after input / resistance value before input) ⁇ 100 The lower the increase rate of the resistance value, the better.
- the resistance increase rate of 120% or less was judged to satisfy the corrosion resistance, and the evaluation was performed according to the following criteria. ⁇ : Increase rate of resistance value is 120% or less ⁇ : Increase rate of resistance value exceeds 120%
- ⁇ Corrosion resistance to amorphous ITO thin film> As a film having an amorphous ITO thin film having a thickness of 22 nm, ELECTRYSTAR P400L-TNME manufactured by Nitto Denko Corporation was used. The film having the amorphous ITO thin film was heat-treated at 140 ° C. for 90 minutes before the evaluation test. The ITO thin film of the film after the treatment was amorphous.
- the polarizing plate with an adhesive layer obtained in Examples 1, 9, 16, 18, 20 and Comparative Examples 1 and 5 was cut into 8 mm ⁇ 8 mm. Moreover, the sample which laminated
- the resistance value of the amorphous ITO film of the film having the amorphous ITO thin film (hereinafter referred to as resistance value before loading) was measured by a Hall effect measuring device (product name: HL5500PC, manufactured by nano metrics). The sample was left in an atmosphere of 60 ° C. and 95% RH for 500 hours.
- the resistance value of the ITO film of the film having the amorphous ITO thin film (this is referred to as the resistance value after throwing) was measured for the sample after being left standing.
- the rate of increase in resistance value before and after the sample was put in the atmosphere was calculated according to the following equation.
- Increase rate of resistance value (%) (resistance value after input / resistance value before input) ⁇ 100 It is preferable that the resistance value increase rate is as low as possible. If the resistance value increase rate is 130% or less, it can be determined that the corrosion resistance is satisfied.
- ⁇ Increase rate of resistance value is 130% or less, it can be determined that the corrosion resistance is satisfied.
- Increase rate of resistance value is 130% or less, it can be determined that the corrosion resistance is satisfied.
- Increase rate of resistance value is 130% or less
- SM-172 Phosphanol SM-172 (manufactured by Toho Chemical Industry Co., Ltd.)
- GF-185 Phosphanol GF-185 (manufactured by Toho Chemical Industry Co., Ltd.)
- BH-650 Phosphanol BH-650 (manufactured by Toho Chemical Industry Co., Ltd.)
- RS-710 Phosphanol RS-710 (manufactured by Toho Chemical Industry Co., Ltd.) MP-4: Product name, manufactured by Daihachi Chemical Industry Co., Ltd.
- addition amount (parts by weight) in Tables 1 and 2 is based on 100 parts by weight of the monomer component.
- the addition amount (parts by weight) of Examples 20 to 26 in Tables 1 and 2 is based on 100 parts by weight of (meth) acrylic polymer solid content.
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Abstract
Description
本発明の光学フィルム用粘着剤組成物は、炭素数4~18のアルキル基を有するアルキル(メタ)アクリレートを主成分として含有するモノマー成分を重合して得られる(メタ)アクリル系ポリマー、及び、リン酸エステル系化合物を含むことを特徴とする。
本発明の光学フィルム用粘着剤層は、前記光学フィルム用粘着剤組成物から形成されることを特徴とする。
本発明の粘着剤層付き光学フィルムは、光学フィルムの少なくとも一方の面に、前記光学フィルム用粘着剤層を形成したものである。当該粘着剤層付き光学フィルムは、本発明の粘着剤層を有するため、金属酸化物により形成された透明導電層に貼り合せても、透明導電層の腐食を抑制することができるものである。
本発明の粘着剤層付き光学フィルムは、各種液晶表示装置において好適に用いることができる。
本発明の積層体は、前記粘着剤層付き光学フィルムの粘着剤層と、透明導電性フィルムの透明導電層とを貼り合せたことを特徴とする。
(モノマーエマルションの調製)
容器に、原料としてブチルアクリレート785部、メチルメタクリレート160部、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)5部、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)1部、アクリル酸50部、3-メタクリロイルオキシプロピル-トリエトキシシラン(商品名:KBM-503、信越化学工業(株)製)0.5部、エレミノールJS-20(三洋化成工業(株)製)20部、及び、水1381部を加えて、ホモミキサー(特殊機化工業(株)製)を用い、5分間、6000rpmで攪拌し、モノマーエマルションを調製した。
次に、冷却管、窒素導入管、温度計、滴下ロート、及び、攪拌羽根を備えた反応容器に、上記で調製したモノマーエマルションを仕込み、次いで、反応容器を十分窒素置換した後、内浴温度を65℃に調整し、アンモニウムペルオキソ硫酸ナトリウム(APS)を0.1部添加して、5時間重合して、固形分濃度40%の水分散液(エマルション)を得た。当該水分散液(エマルション)100重量部に、濃度10%のアンモニア水3部を添加して、水分散型アクリル系粘着剤を調製した。
上記水分散型アクリル系粘着剤を、乾燥後の厚みが25μmとなるように、離型フィルム(商品名:ダイアホイルMRF-38、ポリエチレンテレフタラート基材、三菱化学ポリエステル(株)製)上にアプリケーターにより塗布した後、熱風循環式オーブンにより135℃で2分間乾燥して、光学フィルム用粘着剤層を形成した。
A-PET(アモルファス-ポリエチレンテレフタレート)フィルム(商品名:ノバクリア SH046、厚さ:200μm、三菱樹脂(株)製)に、9μm厚のPVA層が製膜された積層体を、延伸温度130℃及び延伸倍率2倍の空中補助延伸によって延伸積層体を生成し、次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度65℃のホウ酸水中延伸によって総延伸倍率が5.94倍になるようにA-PETフィルムと一体に延伸された4μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によってA-PETフィルムに製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がPVAと錯体を形成しPVA-ヨウ素錯体として一方向に高次に配向された高機能偏光層を構成する、厚さ4μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の偏光層の表面にポリビニルアルコール系接着剤を介し40μm厚のアクリルフィルムを貼合せたのち、A-PETフィルムを剥離して、薄型偏光層を用いた偏光板を作製した。片面保護偏光板(1)という。
実施例1の(粘着剤層付き偏光板の作製)において、以下の両面保護偏光板(1)を使用し、かつ、前記両面保護偏光板の偏光子の厚さ40μmの保護フィルム側に、前記(光学フィルム用粘着剤層の形成)で得られた光学フィルム用粘着剤層の粘着剤層を貼り合わせたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
A-PET(アモルファス-ポリエチレンテレフタレート)フィルム(商品名:ノバクリア SH046、厚さ:200μm、三菱樹脂(株)製)に、12μm厚のPVA層が製膜された積層体を、延伸温度130℃及び延伸倍率2倍の空中補助延伸によって延伸積層体を生成した。次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度65℃のホウ酸水中延伸によって、総延伸倍率が5.94倍になるようにA-PETフィルムと一体に延伸された5μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によってA-PETフィルムに製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がPVAと錯体を形成しPVA-ヨウ素錯体として一方向に高次に配向された高機能偏光層を構成する、厚さ5μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の偏光層の表面にポリビニルアルコール系接着剤を介し40μm厚のアクリルフィルムを貼合せたのち、A-PETフィルムを剥離して、薄型偏光子を用いた片面保護偏光板(2)を作製した。作製された片面保護偏光板(2)の偏光子面に、UV硬化型接着剤を介し25μm厚のノルボルネン系フィルム(商品名:ARTON、JSR(株)製)を貼合せ両面保護偏光板(1)を作製した。
実施例1の(モノマーエマルションの調製)において、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から10部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調製)において、ブチルアクリレートを785部から790部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から2部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調製)において、ブチルアクリレートを785部から790部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から10部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)においてブチルアクリレートを785部から770部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から20部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から0.3部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から770部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製))を5部から20部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から10部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から740部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から50部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から780部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から10部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からMP-4(商品名、大八化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から770部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から20部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からMP-4(商品名、大八化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から790部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からフォスファノールGF-185(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から780部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から10部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からフォスファノールGF-185(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から790部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からフォスファノールBH-650(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から780部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から10部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製))からフォスファノールBH-650(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から780部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から10部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からフォスファノールRS-710(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
(モノマーエマルション(1)調整)
容器に、原料としてブチルアクリレート180部、メチルメタクリレート800部、アクリル酸20部、3-メタクリロイルオキシプロピル-トリエトキシシラン(商品名:KBM-503、信越化学工業(株)製)0.5部、エレミノールJS-20(三洋化成工業(株)製)75部、及び、水4150部を加えて、ホモミキサー(特殊機化工業(株)製)を用い、5分間、6000rpmで攪拌し、モノマーエマルション(1)を調製した。
容器に、原料としてブチルアクリレート917.5部、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)25部、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)1.25部、アクリル酸57.5部、3-メタクリロイルオキシプロピル-トリエトキシシラン(商品名:KBM-503、信越化学工業(株)製)0.5部、エレミノールJS-20(三洋化成工業(株)製)6.25部、及び、水1080部を加えて、ホモミキサー(特殊機化工業(株)製)を用い、5分間、6000rpmで攪拌し、モノマーエマルション(2)を調製した。
次に、冷却管、窒素導入管、温度計、滴下ロート、及び、攪拌羽根を備えた反応容器に、上記で調製したモノマーエマルション(1)のうち860部を仕込み、次いで、反応容器を十分窒素置換した後、内浴温度を65℃に調整し、アンモニウムペルオキソ硫酸ナトリウム(APS)を0.1部添加して、2時間重合した。次いで、アンモニウムペルオキソ硫酸ナトリウム(APS)を0.5部添加した後、内浴温度を65℃に保ちながらモノマーエマルション(2)のうち1643部を3時間かけて滴下した後、さらに3時間重合して、固形分濃度40%の水分散液(エマルション)を得た。当該水分散液(エマルション)100重量部に、濃度10%のアンモニア水3部を添加して、水分散型アクリル系粘着剤を調製した。
上記水分散型アクリル系粘着剤を、乾燥後の厚みが25μmとなるように、離型フィルム(商品名:ダイアホイルMRF-38、ポリエチレンテレフタラート基材、三菱化学ポリエステル(株)製)上にアプリケーターにより塗布した後、熱風循環式オーブンにより150℃10分間乾燥して、光学フィルム用粘着剤層を形成した。
実施例1の(粘着剤層付き偏光板の作製)において、上記で得られた光学フィルム用粘着剤層を用いた以外は、実施例と同様にして粘着剤層付き偏光板を作製した。
実施例16の(モノマーエマルション(2)の調整)において、ブチルアクリレートを917.5部から942.5部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を25部から0部に変えたこと以外は、実施例16と同様にして粘着剤層付き偏光板を作製した。
実施例16の(モノマーエマルション(2)の調整)において、ブチルアクリレートを917.5部から930部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を25部から12.5部に変えたこと、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からMP-4(商品名、大八化学工業(株)製)に変えたこと以外は、実施例16と同様にして粘着剤層付き偏光板を作製した。
実施例16の(モノマーエマルション(2)の調整)において、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からMP-4(商品名、大八化学工業(株)製)に変えたこと以外は、実施例16と同様にして粘着剤層付き偏光板を作製した。
(粘着剤溶液の調製)
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート944部、アクリル酸50部、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)5部、2-ヒドロキシエチルアクリレート1部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物(固形分)100部に対して、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2重量部、及び重合溶媒として酢酸エチル133重量部を投入し、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を60℃付近に保って7時間重合反応を行い、固形分濃度30%のアクリル系ポリマー溶液を調製した。上記アクリル系ポリマー溶液にイソシアネート基含有化合物(商品名:コロネートL、日本ポリウレタン工業(株)製)をポリマー固形分100部に対して0.6部、シランカップリング剤(商品名:KBM-403、信越化学工業(株)製)をポリマー固形分100部に対して0.075部、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)をポリマー固形分100部に対して0.1部、粘度調整のための溶剤(酢酸エチル)を加え、粘着剤溶液(固形分11%)を調製した。
当該粘着剤溶液を、乾燥後の厚みが25μmとなるように、離型フィルム(商品名:ダイアホイルMRF-38、ポリエチレンテレフタラート基材、三菱化学ポリエステル(株)製)上にリバースロールコート法により塗布した後、熱風循環式オーブンで、130℃で、3分間乾燥し、光学フィルム用粘着剤層を形成した。
実施例1の(粘着剤層付き偏光板の作製)において、上記で得られた光学フィルム用粘着剤層を用いた以外は、実施例と同様にして粘着剤層付き偏光板を作製した。
実施例20の(粘着剤層付き偏光板の作製)において、実施例2で得られた両面保護偏光板(1)を使用し、かつ、前記両面保護偏光板の偏光子の厚さ40μmの保護フィルム側に、前記(光学フィルム用粘着剤層の形成)で得られた光学フィルム用粘着剤層の粘着剤層を貼り合わせたこと以外は、実施例20と同様にして粘着剤層付き偏光板を作製した。
実施例20において、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からフォスファノールGF-185(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例20と同様にして粘着剤層付き偏光板を作製した。
実施例20において、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からフォスファノールBH-650(商品名、東邦化学工業(株)製)に変えたこと以外は、実施例20と同様にして粘着剤層付き偏光板を作製した。
実施例20において、ブチルアクリレートを944部から949部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を0.1部から0.03部に変えたこと以外は、実施例20と同様にして粘粘着剤層付き偏光板を作製した。
実施例20において、ブチルアクリレートを944部から949部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を0.1部から1部に変えたこと以外は、実施例20と同様にして粘着剤層付き偏光板を作製した。
実施例20において、ブチルアクリレートを944部から949部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステルの種類をフォスファノールSM-172(商品名、東邦化学工業(株)製)からMP-4(商品名、大八化学工業(株)製)に変えたこと以外は、実施例20と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から790部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から0部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
比較例1と同様の組成にて、光学フィルム用粘着剤層を形成した。得られた光学フィルム用粘着剤層の粘着剤層を、実施例2で得られた両面保護偏光板(1)の厚さ40μmの保護フィルム側に貼り合わせて、粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から770部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から20部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から0部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例1の(モノマーエマルションの調整)において、ブチルアクリレートを785部から740部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から50部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を1部から0部に変えたこと以外は、実施例1と同様にして粘着剤層付き偏光板を作製した。
実施例20において、ブチルアクリレートを944部から949部に変え、リン酸基含有モノマー(商品名:SimpomerPAM200、ローディア日華(株)製)を5部から0部に変え、リン酸基含有エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)を0.1部から0部に変えたこと以外は、実施例20と同様にして粘着剤層付き偏光板を作製した。
フィルム基材として、厚さ25μmのポリエチレンテレフタレートフィルム(以下、PETフィルムという)の一方の面に、メラミン樹脂:アルキド樹脂:有機シラン縮合物の重量比2:2:1の熱硬化型樹脂により、厚さが180nmの第一層目のアンダーコート層を形成した。次いで、第1層目のアンダーコート層上に、SiO2を、電子ビーム加熱法により1.33×10-2~2.67×10-2Paの真空度で真空蒸着して、厚さ40nmの第二層目のアンダーコート層(SiO2膜)を形成した。
抵抗値の上昇率(%)=(投入後抵抗値/投入前抵抗値)×100
前記抵抗値の上昇率は低いほど好ましく、前記抵抗値の上昇率が120%以下であれば、耐腐食性を満足すると判断し、下記基準により評価を行った。
○:抵抗値の上昇率が120%以下
×:抵抗値の上昇率が120%を超える
厚さ22nmの非晶性ITO薄膜を有するフィルムとして、日東電工(株)製のエレクリスタP400L-TNMEを用いた。当該非晶性ITO薄膜を有するフィルムは、評価試験前に140℃で90分間加熱処理を行った。処理後のフィルムのITO薄膜はアモルファスであった。
抵抗値の上昇率(%)=(投入後抵抗値/投入前抵抗値)×100
前記抵抗値の上昇率は低いほど好ましく、前記抵抗値の上昇率が130%以下であれば、耐腐食性を満足すると判断できる。
○:抵抗値の上昇率が130%以下
×:抵抗値の上昇率が130%を超える
SM-172:フォスファノールSM-172(東邦化学工業(株)製)
GF-185:フォスファノールGF-185(東邦化学工業(株)製)
BH-650:フォスファノールBH-650(東邦化学工業(株)製)
RS-710:フォスファノールRS-710(東邦化学工業(株)製)
MP-4:商品名、大八化学工業(株)製
2 光学フィルム用粘着剤層
3 透明導電層
4 液晶セル
5 粘着剤層
6 光学フィルム
Claims (10)
- 炭素数4~18のアルキル基を有するアルキル(メタ)アクリレートを主成分として含有するモノマー成分を重合して得られる(メタ)アクリル系ポリマー、及び、リン酸エステル系化合物を含むことを特徴とする、光学フィルム用粘着剤組成物。
- 前記リン酸エステル系化合物が、前記(メタ)アクリル系ポリマーを構成する全モノマー成分100重量部に対して0.005~2重量部であることを特徴とする、請求項1に記載の光学フィルム用粘着剤組成物。
- 前記モノマー成分が、さらに、リン酸基含有モノマーを含むことを特徴とする、請求項1又は2に記載の光学フィルム用粘着剤組成物。
- 前記リン酸基含有モノマーが、前記(メタ)アクリル系ポリマーを構成する全モノマー成分100重量部に対して0.1~10重量部であることを特徴とする、請求項3に記載の光学フィルム用粘着剤組成物。
- 請求項1~4のいずれかに記載の光学フィルム用粘着剤組成物から形成されることを特徴とする、光学フィルム用粘着剤層。
- 光学フィルムの少なくとも一方の面に、請求項5に記載の光学フィルム用粘着剤層を有することを特徴とする、粘着剤層付き光学フィルム。
- 前記光学フィルムが、偏光子の両面に保護フィルムを有する偏光板であって、少なくとも片側の保護フィルムの厚みが50μm以下であり、少なくとも当該保護フィルムに前記光学フィルム用粘着剤層が接触していることを特徴とする、請求項6に記載の粘着剤層付き光学フィルム。
- 前記光学フィルムが、偏光子の片面に保護フィルムを有する偏光板であって、少なくとも前記偏光子の保護フィルムを有さない面に前記光学フィルム用粘着剤層が接触していることを特徴とする、請求項6に記載の粘着剤層付き光学フィルム。
- 請求項6~8のいずれかに記載の粘着剤層付き光学フィルムを用いることを特徴とする液晶表示装置。
- 請求項6~8のいずれかに記載の粘着剤層付き光学フィルムの粘着剤層と、透明導電性フィルムの透明導電層とを貼り合せたことを特徴とする積層体。
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Also Published As
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TWI666281B (zh) | 2019-07-21 |
JP2015028138A (ja) | 2015-02-12 |
KR20160025494A (ko) | 2016-03-08 |
KR102281964B1 (ko) | 2021-07-26 |
TW201510134A (zh) | 2015-03-16 |
US10883022B2 (en) | 2021-01-05 |
CN105339455B (zh) | 2018-09-14 |
CN105339455A (zh) | 2016-02-17 |
US20160130478A1 (en) | 2016-05-12 |
JP6472172B2 (ja) | 2019-02-20 |
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