WO2011136173A1 - 偏光板用粘着剤組成物、並びにそれを用いた粘着剤付偏光板及び液晶表示装置 - Google Patents
偏光板用粘着剤組成物、並びにそれを用いた粘着剤付偏光板及び液晶表示装置 Download PDFInfo
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- WO2011136173A1 WO2011136173A1 PCT/JP2011/060058 JP2011060058W WO2011136173A1 WO 2011136173 A1 WO2011136173 A1 WO 2011136173A1 JP 2011060058 W JP2011060058 W JP 2011060058W WO 2011136173 A1 WO2011136173 A1 WO 2011136173A1
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
-
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
- C09K2323/053—Organic silicon compound, e.g. organosilicon
-
- 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
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
- C09K2323/057—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Definitions
- the present invention relates to a pressure-sensitive adhesive composition for a polarizing plate, a polarizing plate with a pressure-sensitive adhesive using the same, and a liquid crystal display device.
- the present invention relates to a pressure-sensitive adhesive composition for a polarizing plate comprising at least a (meth) acrylic copolymer containing a carboxyl group and a (meth) acrylic copolymer containing a carboxyl group and a hydroxyl group
- the present invention relates to a pressure-sensitive adhesive polarizing plate and a liquid crystal display device.
- a liquid crystal display device is usually composed of a liquid crystal cell in which a liquid crystal component oriented in a predetermined direction is sandwiched between two supporting substrates such as glass, and an optical film such as a polarizing plate, a retardation film, and a brightness enhancement film. ing.
- An adhesive is used when the optical films are laminated or when the optical film is attached to the liquid crystal cell.
- Liquid crystal display devices are widely used as display devices for personal computers, televisions, car navigation systems, and the like. Liquid crystal display devices are used in various environments including severe environments such as high temperature and high humidity. Accordingly, it is required to develop a pressure-sensitive adhesive having excellent durability that does not peel off or generate bubbles even after long-term use. In a severe environment such as high temperature and high humidity, stress is generated in the polarizing plate due to a dimensional change due to shrinkage or expansion.
- Patent Document 1 a pressure-sensitive adhesive composition for a polarizing plate comprising a high molecular weight acrylic copolymer, a low molecular weight acrylic copolymer having a weight average molecular weight of 30,000 or less, and a polyfunctional compound is disclosed (Patent Document). 1). Since the pressure-sensitive adhesive composition described in Patent Document 1 follows the dimensional change of the polarizing plate, generation of white spots can be suppressed.
- the pressure-sensitive adhesive composition described in Patent Document 1 has a large amount of low-molecular weight acrylic copolymer having a weight average molecular weight of 30,000 or less, the pressure-sensitive adhesive composition is foamed or peeled off under high temperature and high humidity. May occur.
- a pressure-sensitive adhesive composition having a gel fraction of less than 30% by weight, comprising a mixture of coalesces, a crosslinking agent capable of reacting with a functional group, and an isocyanate compound see Patent Document 2.
- the pressure-sensitive adhesive composition described in Patent Document 2 forms a crosslinked structure in the molecule of the high Tg acrylic copolymer, and the intermolecular molecule of the low Tg acrylic copolymer is isocyanate.
- the movement of the pressure-sensitive adhesive component in the pressure-sensitive adhesive layer can be controlled.
- the liquid crystal display device using this pressure-sensitive adhesive composition is less likely to cause white spots, but the crosslinking density is not sufficient and the cohesive force is insufficient at high temperatures. Therefore, in the durability evaluation, the pressure-sensitive adhesive is foamed or peeled off. It is difficult to suppress the occurrence of
- the required size of the polarizing plate is increasing with the increase in size of the liquid crystal display device. Since a dimensional change such as expansion and contraction of the polarizing plate increases with an increase in size, durability at a higher level and suppression of white spots are required.
- a pressure-sensitive adhesive that satisfies durability even when used in such a large-sized liquid crystal display device, a pressure-sensitive adhesive composition having a high cohesive force is disclosed.
- an acrylic copolymer (A) containing a carboxyl group or an amide group and not containing a hydroxyl group, and an acrylic copolymer (B) containing a carboxyl group or an amide group and a hydroxyl group are used as 20 / 80-
- a pressure-sensitive adhesive composition for polarizing plates is disclosed, in which an isocyanate compound is blended with a mixture obtained by mixing at a weight ratio of 50/50 (see Patent Document 3).
- Patent Document 3 Although the pressure-sensitive adhesive composition described in Patent Document 3 suppresses foaming and peeling under high temperature and high humidity, the cohesive force necessary to achieve a good level of white spots in a large liquid crystal display device. Therefore, a large-sized liquid crystal display device using this pressure-sensitive adhesive composition cannot completely suppress white spots.
- An object of the present invention is an adhesive composition for a polarizing plate that is used for sticking a polarizing plate, exhibits excellent durability even under high temperature and high humidity, and suppresses the occurrence of white spots, and an adhesive using the same It is providing a polarizing plate with an agent and a liquid crystal display device.
- the present invention At least (meth) acrylic copolymer (A) containing carboxyl group, (meth) acrylic copolymer (B) containing carboxyl group and hydroxyl group, tolylene diisocyanate isocyanate compound (C), and silane
- the weight average molecular weights of the (meth) acrylic copolymer (A) containing the carboxyl group and the (meth) acrylic copolymer (B) containing the carboxyl group and the hydroxyl group are 950,000 or more and 105, respectively.
- the weight ratio (A) / (B) of the (meth) acrylic copolymer (A) containing the carboxyl group and the (meth) acrylic copolymer (B) containing the carboxyl group and the hydroxyl group is: In the range of 70/30 to 90/10,
- the (meth) acrylic copolymer (A) containing a carboxyl group contains at least 1.5 wt% to 3 wt% of a (meth) acrylic monomer containing a carboxyl group, and a reactive functional group.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group contains at least 0.5 wt% to 3 wt% of a (meth) acrylic monomer containing a carboxyl group, and a hydroxyl group Containing (meth) acrylic monomer containing from 0.3% by weight to 1% by weight and (meth) acrylic monomer having no reactive functional group from 96% by weight to 99.2% by weight
- a copolymer using The pressure-sensitive adhesive composition contains 10 to 20 parts by weight of the tolylene diisocyanate isocyanate compound (C) with respect to 100 parts by weight of the total amount of (meth) acrylic copolymer.
- the present invention provides a pressure-sensitive adhesive polarizing plate in which a polarizing plate pressure-sensitive adhesive composition is laminated.
- the present invention provides a liquid crystal display device using a polarizing plate with an adhesive.
- the pressure-sensitive adhesive composition for a polarizing plate of the present invention and a polarizing plate with a pressure-sensitive adhesive and a liquid crystal display device using the same, it is used for sticking a polarizing plate and has excellent durability even in a high-temperature and high-humidity environment.
- a pressure-sensitive adhesive composition for polarizing plates that suppresses the occurrence of white spots, a polarizing plate with a pressure-sensitive adhesive using the same, and a liquid crystal display device can be provided.
- a pressure-sensitive adhesive composition for a polarizing plate, a polarizing plate with a pressure-sensitive adhesive using the same, and a liquid crystal display device that can be suitably used for a large-sized liquid crystal display device of 19 inches wide or larger can be provided.
- Embodiments of the present invention At least (meth) acrylic copolymer (A) containing carboxyl group, (meth) acrylic copolymer (B) containing carboxyl group and hydroxyl group, tolylene diisocyanate isocyanate compound (C), and silane
- the weight average molecular weights of the (meth) acrylic copolymer (A) containing the carboxyl group and the (meth) acrylic copolymer (B) containing the carboxyl group and the hydroxyl group are 950,000 or more and 105, respectively.
- the weight ratio (A) / (B) of the (meth) acrylic copolymer (A) containing the carboxyl group and the (meth) acrylic copolymer (B) containing the carboxyl group and the hydroxyl group is: In the range of 70/30 to 90/10,
- the (meth) acrylic copolymer (A) containing a carboxyl group contains at least 1.5 wt% to 3 wt% of a (meth) acrylic monomer containing a carboxyl group, and a reactive functional group.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group contains at least 0.5 wt% to 3 wt% of a (meth) acrylic monomer containing a carboxyl group, and a hydroxyl group.
- the (meth) acrylic monomer is contained in an amount of 0.3 wt% to 1 wt%, and the (meth) acrylic monomer having no reactive functional group is added in an amount of 96 wt% to 99.2 wt%.
- the pressure-sensitive adhesive composition contains 10 to 20 parts by weight of the tolylene diisocyanate isocyanate compound (C) with respect to 100 parts by weight of the total amount of (meth) acrylic copolymer. It is an adhesive composition for board.
- the pressure-sensitive adhesive composition for polarizing plate of the present invention is used for sticking a polarizing plate, exhibits excellent durability even under high temperature and high humidity, and is a liquid crystal display using the pressure-sensitive adhesive composition for polarizing plate of the present invention. Suppresses the occurrence of white spots on the device. In particular, it can be suitably used for a large liquid crystal display device of 19 inches wide or larger.
- the carboxyl group-containing (meth) acrylic copolymer (A) is mainly composed of a (meth) acrylic monomer having no reactive functional group and no reactive functional group. It is a copolymer using a (meth) acrylic monomer and a (meth) acrylic monomer containing a carboxyl group.
- the polymerization component of the (meth) acrylic copolymer (A) containing a carboxyl group does not contain a (meth) acrylic monomer containing a hydroxyl group.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is mainly composed of a (meth) acrylic monomer having no reactive functional group and having no reactive functional group. It is a copolymer using a (meth) acrylic monomer, a (meth) acrylic monomer containing a carboxyl group, and a (meth) acrylic monomer containing a hydroxyl group.
- the type of the mer may be different from each other in (A) and (B), or may be the same.
- (meth) acryl refers to both “acryl” and “methacryl”
- (meth) acrylate refers to both “acrylate” and “methacrylate”.
- the reactive functional group represents, for example, a carboxyl group or a hydroxyl group.
- a (meth) acrylic acid ester in particular, a linear or branched alkyl ester having an ester group having 1 to 18 carbon atoms can be used. . Moreover, 1 type, or 2 or more types (meth) acrylic acid ester of these various derivatives can be used.
- n-butyl (meth) acrylate and t-butyl (meth) acrylate can be preferably used because they easily adjust the cohesive force and adhesive force of the pressure-sensitive adhesive.
- the (meth) acrylic monomer containing a carboxyl group for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone mono (meth) acrylate and the like can be used. Especially, since the reactivity with another monomer is high at the time of a copolymerization reaction and an unreacted monomer can be reduced, acrylic acid can be used conveniently.
- Examples of the (meth) acrylic monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, 3-methyl-3-hydroxybutyl (meth) acrylate, 1,3-dimethyl-3-hydroxybutyl (meth) acrylate, 2,2,4-trimethyl-3-hydroxypentyl (meth) acrylate, 2- Ethyl-3-hydroxyhexyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc.
- the weight average molecular weight of each of the (meth) acrylic copolymer (A) containing a carboxyl group and the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is 950,000 to 1,050,000. preferable. If the weight average molecular weight of each (meth) acrylic copolymer is 950,000 or more, it does not become brittle while having an appropriate hardness even under high temperature and high humidity, and the entanglement of molecules contained in the copolymer The degree is appropriate, and the pressure-sensitive adhesive composition is preferable because it exhibits excellent durability.
- the weight average molecular weight of each (meth) acrylic copolymer is 1050,000 or less, the viscosity suitable for coating of the pressure-sensitive adhesive composition can be maintained even if the solid content of the coating solution is increased. Is preferable.
- the weight ratio (A) / (B) of the (meth) acrylic copolymer (A) containing a carboxyl group and the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is 70 / A range of 30 to 90/10 is preferred.
- (B) is 30 or less in the weight ratio of (A) and (B)
- the pressure-sensitive adhesive can maintain an appropriate hardness, and the pressure-sensitive adhesive composition can be obtained after bonding the polarizing plate and the liquid crystal cell. It is preferable because peeling can be suppressed.
- (B) is 10 or more in the weight ratio of (A) and (B), foaming hardly occurs in the adhesive layer even when the liquid crystal display device is used under high temperature and high humidity.
- the carboxyl group-containing (meth) acrylic copolymer (A) has a carboxyl group-containing (meth) acrylic monomer in an amount of 1.5% by weight to 3% by weight and has a reactive functional group.
- a copolymer using 97 wt% or more and 98.5 wt% or less of the (meth) acrylic monomer is not preferable.
- an adhesive composition The product is preferable because it has a sufficient cohesive force and can prevent peeling of the polarizing plate and the liquid crystal cell even when the liquid crystal display device is used under high temperature and high humidity.
- the (meth) acrylic copolymer (A) containing a carboxyl group is a copolymer using 3% by weight or less of a (meth) acrylic monomer containing a carboxyl group
- the pressure-sensitive adhesive composition It is preferable because a pot life time at the time of coating can be sufficiently secured.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group contains 0.5 to 3% by weight of a (meth) acrylic monomer containing a carboxyl group and a hydroxyl group.
- a (meth) acrylic monomer is used in an amount of 0.3 wt% to 1 wt%, and a (meth) acrylic monomer having no reactive functional group is used in an amount of 96 wt% to 99.2 wt%.
- Preferred copolymer Preferred copolymer.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is a copolymer using 0.5% by weight or more of a (meth) acrylic monomer containing a carboxyl group, a liquid crystal Even when the display device is used at a high temperature, it is preferable because foaming hardly occurs in the pressure-sensitive adhesive layer.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is a copolymer using 3% by weight or less of a (meth) acrylic monomer containing a carboxyl group, (meth) This is preferable because the viscosity after the crosslinking reaction of the acrylic copolymer can be controlled, and the pot life time at the time of application of the pressure-sensitive adhesive composition can be sufficiently secured.
- the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is a copolymer using 0.3% by weight or more of a (meth) acrylic monomer containing a hydroxyl group, a liquid crystal display Even when the apparatus is used at a high temperature, it is preferable because foaming hardly occurs in the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive composition Is preferable because it has a sufficient cohesive force and can prevent peeling of the polarizing plate and the liquid crystal cell even when the liquid crystal display device is used under high temperature and high humidity.
- the pressure-sensitive adhesive composition for polarizing plates of the present invention contains 10 to 20 parts by weight of the tolylene diisocyanate isocyanate compound (C) with respect to 100 parts by weight of the total amount of the (meth) acrylic copolymer. Is preferred.
- the pressure-sensitive adhesive composition for polarizing plates contains 10 parts by weight or more of the tolylene diisocyanate isocyanate compound (C)
- sufficient cohesive force is exhibited to suppress the shrinkage stress of the polarizing plate after the pressure-sensitive adhesive is adhered. . Therefore, it is preferable because “white spots” in which light leaks from the peripheral portion of the liquid crystal display device combined with the adhesive-attached polarizing plate can be suppressed.
- the pressure-sensitive adhesive composition for polarizing plate contains 20 parts by weight or less of tolylene diisocyanate-based isocyanate compound (C), the polarizing plate has a sufficient cohesive force and can be used even when the liquid crystal display device is used under high temperature and high humidity. And is preferable because peeling of the liquid crystal cell can be suppressed.
- tolylene diisocyanate compound (C) a tolylene diisocyanate compound derived from various isocyanates such as dimer or trimer of isocyanate or an adduct of isocyanate and trimethylolpropane polyol can be used.
- tolylene diisocyanate compound (C) for example, those commercially available under the trade name “Coronate L” (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate is a registered trademark) can be suitably used.
- the pressure-sensitive adhesive composition for polarizing plate of the present invention preferably contains a silane coupling agent (D).
- D silane coupling agent
- the pressure-sensitive adhesive layer and the polarizing plate or the liquid crystal display device in which the polarizing plate is incorporated are placed in a high-temperature and high-humidity environment. It is preferable because peeling does not easily occur between the liquid crystal cell.
- the pressure-sensitive adhesive composition for polarizing plates of the present invention is preferable because it exhibits a sufficient adhesion to smooth glass.
- silane coupling agent (D) examples include polymerizable unsaturated group-containing silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Mercapto group-containing silane compounds such as 3-mercaptopropyltriethoxysilane and 3-mercaptopropyldimethoxymethylsilane, and 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Silane compounds having an epoxy structure such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane Amino group-containing silane compound,
- silane coupling agent (D) for example, those commercially available under the trade name “KBM-403” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be suitably used.
- the pressure-sensitive adhesive composition for polarizing plates of the present invention preferably contains an epoxy-based crosslinking agent.
- the polarizing plate pressure-sensitive adhesive composition contains an epoxy-based cross-linking agent, it is possible to easily adjust the cohesive force, and even if the liquid crystal display device is used under high temperature and high humidity, it is preferable because the appearance abnormality can be suppressed. .
- epoxy-based crosslinking agent for example, those commercially available under the trade names of “TETRAD-X” and “TETRAD-C” (both manufactured by Mitsubishi Gas Chemical Co., Ltd., and TETRAD is a registered trademark) can be suitably used. .
- the glass transition temperature (Tg) of each of the (meth) acrylic copolymer (A) containing a carboxyl group and the (meth) acrylic copolymer (B) containing a carboxyl group and a hydroxyl group is ⁇ 60 ° C. or higher. It is preferably ⁇ 40 ° C. or lower.
- Tg of each (meth) acrylic copolymer is ⁇ 60 ° C. or higher, the pressure-sensitive adhesive composition has sufficient cohesive strength, and even if the liquid crystal display device is used under high temperature and high humidity, the polarizing plate and the liquid crystal This is preferable because cell peeling can be suppressed.
- the Tg of each (meth) acrylic copolymer is ⁇ 40 ° C. or lower, it is preferable because peeling does not easily occur between the pressure-sensitive adhesive layer and the polarizing plate or the liquid crystal cell.
- the glass transition temperature (Tg) of the (meth) acrylic copolymer is a value obtained by converting the temperature (K) obtained by the calculation of the following formula 1 into (° C.).
- Formula 1 1 / Tg M1 / Tg1 + M2 / Tg2 + M3 / Tg3 + ... + Mn / Tgn
- Tg1, Tg2, Tg3,..., And Tgn represent the glass transition temperatures (K) of the homopolymers of Component 1, Component 2, Component 3,.
- M1, M2, M3 ... and Mn show the mole fraction of various components.
- the polymerization method of the (meth) acrylic copolymer used in the present invention is not particularly limited, and methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used.
- Solution polymerization is preferable because the treatment process is relatively simple and can be performed in a short time.
- a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as needed are generally charged in a polymerization tank, and stirred in a nitrogen stream or under reflux of the organic solvent. Heat the reaction for several hours.
- the initiator used for the polymerization of the (meth) acrylic copolymer used in the present invention is not particularly limited, and for example, an azo compound can be used.
- the weight average molecular weight (Mw) of the (meth) acrylic copolymer used in the present invention can be adjusted to a desired molecular weight by adjusting the reaction temperature, time, solvent amount, catalyst type and amount.
- the weight average molecular weight (Mw) of the (meth) acrylic copolymer is a value measured by the following method. (Measurement method of weight average molecular weight (Mw)) Measure according to the following (1) to (3).
- a (meth) acrylic copolymer solution is coated on release paper and dried at 100 ° C. for 2 minutes to obtain a film-like (meth) acrylic copolymer.
- the film-like (meth) acrylic copolymer obtained in (1) is dissolved in tetrahydrofuran so that the solid content is 0.2%.
- the weight average molecular weight (Mw) of the (meth) acrylic copolymer is measured using gel permeation chromatography (GPC) under the following conditions.
- GPC HLC-8220 GPC [manufactured by Tosoh Corporation] Column: 4 TSK-GEL GMHXL used Mobile phase solvent: Tetrahydrofuran Standard sample: Standard polystyrene Flow rate: 0.6 ml / min Column temperature: 40 ° C
- the pressure-sensitive adhesive composition for polarizing plates of the present invention can be appropriately mixed with various additives and solvents.
- One adherend of the pressure-sensitive adhesive composition of the present invention is a polarizing plate, more specifically, cellulose triacetate (TAC). Since the tolylene diisocyanate-based isocyanate compound is in an appropriate amount, the pressure-sensitive adhesive composition of the present invention sufficiently adheres to cellulose triacetate (TAC).
- TAC cellulose triacetate
- the other adherend of the pressure-sensitive adhesive composition of the present invention is a liquid crystal cell, more specifically, an alkali-free glass. Since the silane coupling agent is included, the pressure-sensitive adhesive composition of the present invention sufficiently adheres even to smooth glass used in a liquid crystal display device.
- another embodiment of the present invention is a pressure-sensitive adhesive polarizing plate in which the pressure-sensitive adhesive composition of the present invention is laminated.
- the pressure-sensitive adhesive composition of the present invention After coating on a release sheet and drying, forming a pressure-sensitive adhesive layer on the release sheet, transferring the pressure-sensitive adhesive layer to a polarizing plate and curing it, the pressure-sensitive adhesive of the present invention A polarizing plate with an agent can be produced.
- a synthetic resin sheet such as polyester subjected to release treatment with a release agent such as fluorine resin, paraffin wax, or silicone can be used.
- a suitable thickness of the pressure-sensitive adhesive layer formed on the release sheet is 1 ⁇ m or more and 100 ⁇ m or less, preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 15 ⁇ m or more and 30 ⁇ m or less in terms of the thickness after drying.
- the pressure-sensitive adhesive composition coated on the release sheet is dried with a hot air dryer at a temperature of about 70 to 120 ° C. for about 1 to 3 minutes.
- the constitution of the polarizing plate used in the present invention is such that cellulose triacetate (TAC) is laminated on the front and back surfaces of a film made of a polarizer mainly composed of polyvinyl alcohol.
- the thickness of the polarizing plate used for this invention is about 190 micrometers.
- the polarizing plate with an adhesive of the present invention is applicable even when the size of the liquid crystal cell to be laminated is 19 inches wide (260 mm ⁇ 415 mm) or more.
- the size of the liquid crystal cell is 19 inches wide (260 mm ⁇ 415 mm) or more, expansion and contraction due to the influence of heat and humidity of the polarizing plate are increased. Therefore, the conventional pressure-sensitive adhesive polarizing plate cannot suppress the stress even under high temperature and high humidity, and cannot suppress “white spots” generated around the becel when the light source of the large liquid crystal display device is turned on.
- the polarizing plate with the pressure-sensitive adhesive of the present invention is appropriate for the resin design of the copolymer and the type and amount of the crosslinking agent, and can suppress stress even under high temperature and high humidity, so that it is 19 inches wide (260 mm ⁇ 415 mm) or more. It is also suitable for a liquid crystal cell of the size.
- the reaction mixture was diluted with ethyl acetate and adjusted to a solid content of 23.0% to obtain a (meth) acrylic copolymer solution containing a carboxyl group.
- Mw weight average molecular weight of the (meth) acrylic copolymer was measured using gel permeation chromatography (GPC).
- the (meth) acrylic copolymer prepared in Production Example 1a contains 85 parts by weight in terms of solid content, and contains a carboxyl group and a hydroxyl group
- the (meth) acrylic copolymer (B) 15 parts by weight of the (meth) acrylic copolymer prepared in Production Example 1b was added in terms of solid content and stirred, and a mixture of the (meth) acrylic copolymer was added. Obtained.
- tolylene diisocyanate-based isocyanate compound (C) 14.0 parts by weight of coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd .; 75% active ingredient) in terms of solid content and a silane coupling agent (D KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 0.1 part by weight in terms of active ingredient, and the mixture was stirred in a reactor at 23 ° C. to obtain a pressure-sensitive adhesive composition for polarizing plate .
- coronate L manufactured by Nippon Polyurethane Industry Co., Ltd .
- D KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 2 to 12 and Comparative Examples 1 to 20 Each Example and each Comparative Example were changed to the composition of the (meth) acrylic monomer described in Table 3 and Table 4, the copolymer weight ratio, the crosslinking agent, and the composition of the silane coupling agent. In the same manner as in Example 1, a pressure-sensitive adhesive composition for polarizing plates was obtained.
- the adhesive composition for polarizing plates produced in the examples and comparative examples was evaluated.
- a method for preparing the test piece and various evaluation methods are as follows.
- polarizing plate with pressure-sensitive adhesive A pressure-sensitive adhesive composition was coated on a release sheet surface-treated with a silicone-based release agent. The coating amount of the pressure-sensitive adhesive composition at this time was adjusted so that the thickness of the pressure-sensitive adhesive composition was 25 ⁇ m after the solvent was dried. The solid content of the pressure-sensitive adhesive composition was 20.0% by weight. Next, using a hot-air circulating drier kept at 100 ° C., the release sheet coated with the adhesive was dried for 90 seconds to produce an adhesive layer. Subsequently, the pressure-sensitive adhesive layer was pressure-bonded to one surface of the polarizing plate through a pressure nip roll. After pressure bonding, it was cured for 10 days in an environment of 23 ° C. and 50% RH to obtain a polarizing plate with an adhesive.
- the polarizing plate with adhesive prepared in “(1) Preparation of polarizing plate with adhesive” was 260 mm so that the polarization axis of light and the long side of the polarizing plate were at an angle of 45 °. Cut to a rectangular size of 415 mm. Using a laminator, a cut adhesive-attached polarizing plate was attached to one side of a 0.7 mm-thick alkali-free glass plate (Corning, product number # 1737) to obtain a test piece for durability evaluation. Next, this test piece was held for 24 hours in an environment of 23 ° C. and 50% RH after autoclaving. The conditions of the autoclave were 20 minutes at a temperature of 50 ° C.
- the polarizing plate with the adhesive prepared in “(1) Preparation of polarizing plate with adhesive” has an angle of 45 ° and 135 ° with the polarization axis of light and the long side of the polarizing plate.
- one piece cut into a rectangular size of 260 mm ⁇ 415 mm was prepared.
- an alkali-free glass plate having a thickness of 0.7 mm product number # 1737, manufactured by Corning
- the cut adhesive-attached polarizing plate is attached using a laminator so that the polarization axes thereof are orthogonal to each other, It was set as the test piece of white blank evaluation. Next, this test piece was kept in an environment of 23 ° C.
- the conditions of the autoclave were 20 minutes at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 . Thereafter, the test piece was held in an environment of 80 ° C. for 500 hours. After standing, place a test piece on a uniform light source (manufactured by I-System Co., Ltd.) in an environment of 23 ° C. and 50% RH, and use a non-uniformity measuring system EyeScale-3W (manufactured by I-System Co., Ltd.) to Leakage was visually confirmed and measured. The CCD camera of the unevenness measurement system EyeScale-3W was installed at a position 200 cm away from the test piece, and white spots were evaluated.
- a uniform light source manufactured by I-System Co., Ltd.
- EyeScale-3W manufactured by I-System Co., Ltd.
- Adhesive composition coating suitability A pressure-sensitive adhesive composition was coated on a release sheet surface-treated with a silicone release agent. Adjust the solid content of the coating liquid of the pressure-sensitive adhesive composition to 20% using a solvent, and apply it at a speed of 10 m / min using an automatic coating machine (manufactured by Dazai Equipment Co., Ltd.). The presence or absence was evaluated. d) Coating suitability ⁇ Coating is possible without unevenness and appearance abnormality, and can be applied to liquid crystal cells. ⁇ Since there is coating unevenness or appearance abnormality, it cannot be applied to liquid crystal cells.
- Pressure-sensitive adhesive composition pot life
- the pressure-sensitive adhesive composition used in (4) was applied for 48 hours at 23 ° C. and 50% RH, and then coated, and the transparency and appearance of the pressure-sensitive adhesive composition and the coated surface were applied. Was visually evaluated.
- X The pressure-sensitive adhesive composition or the coated surface becomes cloudy and cannot be applied to a liquid crystal cell.
- Table 3 and Table 4 show the results of evaluation by the above evaluation methods together with the adhesive composition.
- the pressure-sensitive adhesive composition of the present invention exhibits excellent performance even when applied to a large-sized pressure-sensitive adhesive polarizing plate.
- the pressure-sensitive adhesive composition of Example 1 has a cohesive force within an appropriate range, foaming does not occur even at high temperatures, and the pressure-sensitive adhesive layer does not peel off even at high temperatures and high humidity.
- the crosslinking density of the copolymer is in an appropriate range, and thus the adhesive composition of Example 1 is free from white spots.
- it contains a silane coupling agent the pressure-sensitive adhesive composition of Example 1 exhibits a smooth glass surface and sufficient adhesive strength, and appearance abnormality does not occur in the durability test.
- the coating solution using the pressure-sensitive adhesive composition of Example 1 is excellent in coating suitability even if the solid content is high. Furthermore, since it was produced by a controlled crosslinking reaction, the coating liquid of the pressure-sensitive adhesive composition of Example 1 maintains a sufficient pot life.
- the pressure-sensitive adhesive composition of Comparative Example 2 has an inappropriate pot life because the crosslinking density is not in an appropriate range.
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Abstract
Description
少なくとも、カルボキシル基を含有する(メタ)アクリル系共重合体(A)、カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)、トリレンジイソシアネート系イソシアネート化合物(C)、及びシランカップリング剤(D)を含む粘着剤組成物において、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)、及び前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)の各々の重量平均分子量は、95万以上105万以下であり、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)と前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)との重量比(A)/(B)が、70/30から90/10の範囲であり、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)は、少なくとも、カルボキシル基を含有する(メタ)アクリル系単量体を1.5重量%以上3重量%以下と、反応性官能基を有しない(メタ)アクリル系単量体を97重量%以上98.5重量%以下とを用いた共重合体であり、
前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)は、少なくとも、カルボキシル基を含有する(メタ)アクリル系単量体を0.5重量%以上3重量%以下と、水酸基を含有する(メタ)アクリル系単量体を0.3重量%以上1重量%以下と、反応性官能基を有しない(メタ)アクリル系単量体を96重量%以上99.2重量%以下とを用いた共重合体であり、
前記粘着剤組成物は、(メタ)アクリル系共重合体の合計量100重量部に対し、前記トリレンジイソシアネート系イソシアネート化合物(C)を10重量部以上20重量部以下含むことを特徴とする偏光板用粘着剤組成物が提供される。
本発明の実施形態は、
少なくとも、カルボキシル基を含有する(メタ)アクリル系共重合体(A)、カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)、トリレンジイソシアネート系イソシアネート化合物(C)、及びシランカップリング剤(D)を含む粘着剤組成物において、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)、及び前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)の各々の重量平均分子量は、95万以上105万以下であり、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)と前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)との重量比(A)/(B)が、70/30から90/10の範囲であり、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)は、少なくとも、カルボキシル基を含有する(メタ)アクリル系単量体を1.5重量%以上3重量%以下と、反応性官能基を有しない(メタ)アクリル系単量体を97重量%以上98.5重量%以下とを用いた共重合体であり、
前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)は、少なくとも、カルボキシル基を含有する(メタ)アクリル系単量体を0.5重量%以上3重量%以下、水酸基を含有する(メタ)アクリル系単量体を0.3重量%以上1重量%以下、及び反応性官能基を有しない(メタ)アクリル系単量体を96重量%以上99.2重量%以下を用いた共重合体であり、
前記粘着剤組成物は、(メタ)アクリル系共重合体の合計量100重量部に対し、前記トリレンジイソシアネート系イソシアネート化合物(C)を10重量部以上20重量部以下含むことを特徴とする偏光板用粘着剤組成物である。
本発明の偏光板用粘着剤組成物は、偏光板の貼着に使用され、高温高湿下においても優れた耐久性を示すと共に、本発明の偏光板用粘着剤組成物を用いた液晶表示装置の白ヌケの発生を抑制する。特に、19インチワイド以上の大型液晶表示装置に好適に用いることができる。
式1 1/Tg=M1/Tg1+M2/Tg2+M3/Tg3+・・・・+Mn/Tgn
式中、Tg1、Tg2、Tg3・・・及びTgnは、成分1、成分2、成分3・・・及び成分nそれぞれのホモポリマーのガラス転移温度(K)を示す。また、式中、M1、M2、M3・・・及びMnは各種成分のモル分率を示す。
(重量平均分子量(Mw)の測定方法)
下記(1)~(3)に従って測定する。
(1)(メタ)アクリル系共重合体溶液を剥離紙に塗工し、100℃で2分間乾燥し、フィルム状の(メタ)アクリル系共重合体を得る。
(2)前記(1)で得られたフィルム状の(メタ)アクリル系共重合体をテトラヒドロフランにて固形分0.2%になるように溶解させる。
(3)下記条件にて、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、(メタ)アクリル系共重合体の重量平均分子量(Mw)を測定する。
(条件)
GPC:HLC-8220 GPC〔東ソー(株)製〕
カラム:TSK-GEL GMHXL4本使用
移動相溶媒:テトラヒドロフラン
標準試料:標準ポリスチレン
流速:0.6ml/min
カラム温度:40℃
(製造例1a)
温度計、撹拌機、窒素導入管、及び還流冷却管を備えた反応器内に、n-ブチルアクリレート(BA)98.0重量部、アクリル酸(AA)2.0重量部、酢酸エチル(EAc)90.0重量部、及びアゾビスジメチルバレロニトリル(ABVN)0.3重量部を入れた後、反応器内を窒素置換した。その後、前記混合物を撹拌し、反応器内の混合物を65℃に昇温し、8時間保持し、重合反応を行なった。重合反応終了後、反応混合物を酢酸エチルで希釈、固形分23.0%に調整し、カルボキシル基を含有する(メタ)アクリル系共重合体溶液を得た。前記条件で、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、(メタ)アクリル系共重合体の重量平均分子量(Mw)を測定した。
表1に記載した各製造例の(メタ)アクリル系単量体の部数に変更し、適宜ABVNとEAcの添加量を調整した以外は、製造例1aと同様にして、カルボキシル基を含有する(メタ)アクリル系共重合体溶液を得た。
(製造例1b)
温度計、撹拌機、窒素導入管、及び還流冷却管を備えた反応器内に、n-ブチルアクリレート(BA)84.5重量部、t-ブチルアクリレート(tBA)14.0重量部、アクリル酸(AA)1.0重量部、2-ヒドロキシエチルアクリレート(2EHA)0.5重量部、酢酸エチル(EAc)90重量部、及びアゾビスジメチルバレロニトリル(ABVN)0.3重量部を入れた後、反応器内を窒素置換した。その後、前記混合物を撹拌し、反応器内の混合物を65℃に昇温し、8時間保持し、重合反応を行なった。重合反応終了後、反応混合物を酢酸エチルで希釈、固形分23.0%に調整し、カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体溶液を得た。前記条件で、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、(メタ)アクリル系共重合体の重量平均分子量(Mw)を測定した。
表2に記載した各製造例の(メタ)アクリル系単量体の重量部数に変更し、適宜ABVNとEAcの添加量を調整した以外は、製造例1bと同様にして、カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体溶液を得た。
(実施例1)
カルボキシル基を含有する(メタ)アクリル系共重合体(A)として、製造例1aで作製した(メタ)アクリル系共重合体を固形分換算で85重量部、並びにカルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)として、製造例1bで作製した(メタ)アクリル系共重合体を固形分換算で15重量部加えて撹拌し、(メタ)アクリル系共重合体の混合物を得た。共重合体混合物に、トリレンジイソシアネート系イソシアネート化合物(C)として、コロネートL(日本ポリウレタン工業株式会社製;有効成分75%)を固形分換算で14.0重量部、及びシランカップリング剤(D)として、KBM-403(信越化学工業株式会社製)を有効成分換算で0.1重量部加え、23℃の環境下、反応器内にて撹拌し、偏光板用粘着剤組成物を得た。
各実施例及び各比較例は、表3、及び表4に記載した(メタ)アクリル系単量体の組成、共重合体重量比、架橋剤、及びシランカップリング剤の組成に変更した以外は実施例1と同様にして、偏光板用粘着剤組成物を得た。
シリコーン系離型剤で表面処理した剥離シート上に、粘着剤組成物を塗工した。このときの粘着剤組成物の塗工量は、溶剤乾燥後に、粘着剤組成物の厚みが25μmとなるように調製した。粘着剤組成物の固形分は20.0重量%とした。次に、100℃に保持した熱風循環式乾燥機を用いて、粘着剤を塗工した剥離シートを、90秒間乾燥させて粘着剤層を作製した。続いて、偏光板の一方の面に、粘着剤層を加圧ニップロールに通して圧着した。圧着後、23℃、50%RH環境下で10日間養生させて、粘着剤付偏光板を得た。
「(1)粘着剤付偏光板の作製」において作製した粘着剤付偏光板を、光の偏光軸と偏光板の長辺が45°の角度になるように、260mm×415mmの長方形状の大きさにカットした。厚さ0.7mmの無アルカリガラス板(コーニング社製、品番#1737)の片面に、ラミネーターを用いて、カットした粘着剤付偏光板を貼り付け、耐久性評価の試験片とした。次に、この試験片を、オートクレーブ処理後、23℃、50%RHの環境下で24時間保持した。オートクレーブの条件は、温度50℃、圧力5kg/cm2で20分間とした。試験片を2つ用意した。試験片を、1)80℃条件、及び2)60℃90%RH条件の各環境下でそれぞれ1つずつ500時間保持し、耐久性試験終了後、粘着剤層の発泡の有無、並びに粘着剤層と偏光板またはガラス板との剥がれの有無の目視確認を行い、耐久性の評価とした。
耐久性評価基準は以下の通りである。
a) 発泡
○ 発泡が全く見られず、液晶セルに適用可能である。
△ 発泡がわずかに認められるが、液晶セルに適用可能である。
× 発泡が顕著に認められ、液晶セルに適用不可である。
b) 剥がれ
○ 剥がれがなく、液晶セルに適用可能である。
× 剥がれがあり、液晶セルに適用不可である。
「(1)粘着剤付偏光板の作製」において作製した粘着剤付偏光板を、光の偏光軸と偏光板の長辺が、45°及び135°の角度となるように、260mm×415mmの長方形状の大きさにカットしたものを各々1枚ずつ用意した。厚さ0.7mmの無アルカリガラス板(コーニング社製、品番#1737)の表面及び裏面に、カットした粘着剤付偏光板を、互いの偏光軸が直交するようにラミネーターを用いて貼り付け、白ヌケ評価の試験片とした。次に、この試験片を、オートクレーブ処理後、23℃、50%RH環境下で24時間保持した。オートクレーブの条件は、温度50℃、圧力5kg/cm2で20分間とした。その後、試験片を、80℃の環境下で500時間保持した。放置後、23℃、50%RH環境下で、均一光源(株式会社 アイ・システム製)上に試験片を設置し、ムラ測定システムEyeScale-3W(株式会社 アイ・システム製)を用いて、白ヌケを目視確認測した。ムラ測定システムEyeScale-3WのCCDカメラは、試験片から200cm離れた位置に設置し、白ヌケを評価した。
c) 白ヌケ評価
◎ 白ヌケが全く見られず、液晶セルに適用可能である。
○ 白ヌケが見られるものの、液晶セルに適用可能である。
× 白ヌケが見られ、かつ白ヌケ部位の輝度が高く、液晶セルに適用不可である。
シリコーン系離型剤で表面処理した剥離シート上に、粘着剤組成物を塗工した。粘着剤組成物の塗工液の固形分を20%に溶剤を用いて調整し、自動塗工機(太佑機材株式会社製)を用い、速度10m/分で塗工し、ムラ、外観異常の有無を評価した。
d) 塗工適性
○ ムラ、外観異常なく塗工可能であり、液晶セルに適用可能である。
× 塗工ムラ、または外観異常があるため、液晶セルに適用不可である。
(4)で用いた粘着剤組成物を、23℃、50%RH条件で48時間保持後塗工し、粘着剤組成物及び塗工面の、透明性及び外観を目視で評価した。
e) ポットライフ
○ 粘着剤組成物及び塗工面の透明性が維持され、液晶セルに適用可能である。
× 粘着剤組成物または塗工面が白濁し、液晶セルに適用不可である。
Claims (3)
- 少なくとも、カルボキシル基を含有する(メタ)アクリル系共重合体(A)、カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)、トリレンジイソシアネート系イソシアネート化合物(C)、及びシランカップリング剤(D)を含む粘着剤組成物において、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)、並びに前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)の各々の重量平均分子量は、95万以上105万以下であり、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)と前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)との重量比(A)/(B)が、70/30から90/10の範囲であり、
前記カルボキシル基を含有する(メタ)アクリル系共重合体(A)は、少なくとも、カルボキシル基を含有する(メタ)アクリル系単量体を1.5重量%以上3重量%以下と、反応性官能基を有しない(メタ)アクリル系単量体を97重量%以上98.5重量%以下とを用いた共重合体であり、
前記カルボキシル基及び水酸基を含有する(メタ)アクリル系共重合体(B)は、少なくとも、カルボキシル基を含有する(メタ)アクリル系単量体を0.5重量%以上3重量%以下、水酸基を含有する(メタ)アクリル系単量体を0.3重量%以上1重量%以下、及び反応性官能基を有しない(メタ)アクリル系単量体を96重量%以上99.2重量%以下用いた共重合体であり、
前記粘着剤組成物は、(メタ)アクリル系共重合体の合計量100重量部に対し、前記トリレンジイソシアネート系イソシアネート化合物(C)を10重量部以上20重量部以下含む
ことを特徴とする偏光板用粘着剤組成物。 - 請求項1に記載の粘着剤組成物が積層された粘着剤付偏光板。
- 請求項2に記載の粘着剤付偏光板を用いた液晶表示装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP11774954.9A EP2565247A4 (en) | 2010-04-26 | 2011-04-25 | Adhesive composition for polarizing plates, polarizing plate with adhesive using same, and liquid crystal display device using same |
KR1020127030707A KR101819768B1 (ko) | 2010-04-26 | 2011-04-25 | 편광판용 점착제 조성물, 및 그것을 이용한 점착제 부착 편광판 및 액정 표시 장치 |
US13/643,220 US8673412B2 (en) | 2010-04-26 | 2011-04-25 | Adhesive composition for polarizing plates, polarizing plate with adhesive using same, and liquid crystal display device using same |
CN201180021335.6A CN102892854B (zh) | 2010-04-26 | 2011-04-25 | 偏振板用粘着剂组合物、以及使用了该组合物的带粘着剂的偏振板和液晶显示装置 |
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JP2010101524A JP5555043B2 (ja) | 2010-04-26 | 2010-04-26 | 偏光板用粘着剤組成物、並びにそれを用いた粘着剤付偏光板及び液晶表示装置 |
JP2010-101524 | 2010-04-26 |
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EP (1) | EP2565247A4 (ja) |
JP (1) | JP5555043B2 (ja) |
KR (1) | KR101819768B1 (ja) |
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WO2013183563A1 (ja) * | 2012-06-05 | 2013-12-12 | 日本カーバイド工業株式会社 | 偏光板用粘着剤組成物、粘着剤付偏光板、及び表示装置 |
CN104109843A (zh) * | 2014-08-01 | 2014-10-22 | 苏州普京真空技术有限公司 | 一种蒸发镀膜白点消除方法 |
JP6484484B2 (ja) * | 2015-03-30 | 2019-03-13 | 日本カーバイド工業株式会社 | 粘着剤組成物及び粘着シート |
JP6730348B2 (ja) * | 2017-03-29 | 2020-07-29 | 日東電工株式会社 | 粘着剤層付片保護偏光フィルム、画像表示装置およびその連続製造方法 |
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- 2011-04-25 WO PCT/JP2011/060058 patent/WO2011136173A1/ja active Application Filing
- 2011-04-25 KR KR1020127030707A patent/KR101819768B1/ko active IP Right Grant
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TWI470051B (zh) | 2015-01-21 |
TW201141983A (en) | 2011-12-01 |
US20130040075A1 (en) | 2013-02-14 |
JP2011231190A (ja) | 2011-11-17 |
EP2565247A4 (en) | 2017-08-09 |
KR20130058009A (ko) | 2013-06-03 |
JP5555043B2 (ja) | 2014-07-23 |
CN102892854A (zh) | 2013-01-23 |
EP2565247A1 (en) | 2013-03-06 |
US8673412B2 (en) | 2014-03-18 |
KR101819768B1 (ko) | 2018-01-17 |
CN102892854B (zh) | 2014-09-03 |
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