WO2014208699A1 - アクリル系粘着剤組成物、粘着剤層の製造方法、粘着剤層付偏光フィルム及びアクリル系粘着剤組成物の架橋促進方法 - Google Patents
アクリル系粘着剤組成物、粘着剤層の製造方法、粘着剤層付偏光フィルム及びアクリル系粘着剤組成物の架橋促進方法 Download PDFInfo
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- WO2014208699A1 WO2014208699A1 PCT/JP2014/067066 JP2014067066W WO2014208699A1 WO 2014208699 A1 WO2014208699 A1 WO 2014208699A1 JP 2014067066 W JP2014067066 W JP 2014067066W WO 2014208699 A1 WO2014208699 A1 WO 2014208699A1
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- sensitive adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
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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
- C09J7/30—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—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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- 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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- 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
Definitions
- the present invention relates to an acrylic pressure-sensitive adhesive composition, a method for producing an acrylic pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive layer produced by the production method, and a pressure-sensitive adhesive having the acrylic pressure-sensitive adhesive layer.
- TECHNICAL FIELD The present invention relates to a polarizing film with a layer, a laminate in which the polarizing film with an acrylic pressure-sensitive adhesive layer and a transparent conductive substrate are laminated, an image display device using the laminated body, and a method for promoting crosslinking of the acrylic pressure-sensitive adhesive composition. .
- the pressure-sensitive adhesive is a film with a pressure-sensitive adhesive layer previously provided as a pressure-sensitive adhesive layer on one side of the various films. Is generally used.
- a crosslinking agent is often blended together with a base polymer such as a (meth) acrylic polymer for the purpose of improving durability, for example, (meth) acrylic
- a base polymer such as a (meth) acrylic polymer for the purpose of improving durability
- (meth) acrylic A pressure-sensitive adhesive containing a peroxide and an isocyanate-based compound in addition to a polymer has been proposed (see, for example, Patent Document 1).
- a pressure-sensitive adhesive composition containing a peroxide and an isocyanate crosslinking agent has been proposed (see, for example, Patent Document 2). .
- a catalyst or the like that promotes the urethane reaction may be added.
- the pot life may be very short.
- amine-based and metal-based additives may be used as a catalyst, but this has been a cause of product defects and physical property degradation due to amine odor.
- the cross-linking is completed by providing an aging period.
- the aging period is usually required for about 1 day to 1 week, and the productivity is lowered by providing an aging process.
- an acrylic pressure-sensitive adhesive composition containing an acrylic polymer, an organic peroxide-based crosslinking agent and / or an isocyanate-based crosslinking agent, it is difficult to efficiently crosslink with the crosslinking agent.
- the present invention includes an acrylic pressure-sensitive adhesive composition that includes one or more cross-linking agents selected from the group consisting of acrylic polymers, organic peroxide cross-linking agents, and isocyanate cross-linking agents, and can be efficiently cross-linked.
- the purpose is to provide goods.
- a method for producing an acrylic pressure-sensitive adhesive layer using the acrylic pressure-sensitive adhesive composition an acrylic pressure-sensitive adhesive layer obtained by the production method, a polarizing film with a pressure-sensitive adhesive layer, a laminate, and an image display device. The purpose is to do. It is another object of the present invention to provide a method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition.
- the present inventors have found that the object can be achieved by using the following acrylic pressure-sensitive adhesive composition, and have completed the present invention.
- the present invention includes at least one crosslinking agent selected from the group consisting of (meth) acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents, and the following general formula (1): (Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom) Containing a compound represented by
- the acrylic pressure-sensitive adhesive composition is characterized in that the content of the compound represented by the general formula (1) is 0.005 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. .
- the compound represented by the general formula (1) is preferably a phosphate ester having an acid value of 80 to 900 mgKOH / g.
- organic peroxide crosslinking agent 0.05 to 2 parts by weight is contained with respect to 100 parts by weight of the (meth) acrylic polymer.
- the acrylic pressure-sensitive adhesive composition contains an organic peroxide crosslinking agent and an isocyanate crosslinking agent, and the content of the isocyanate crosslinking agent is 5 to 1000 with respect to 100 parts by weight of the organic peroxide crosslinking agent. It is preferable that it is a weight part.
- the weight average molecular weight of the (meth) acrylic polymer is preferably 1.2 million to 3 million.
- this invention includes the process of apply
- the manufacturing method of the acrylic adhesive layer characterized by these.
- the acrylic pressure-sensitive adhesive composition is crosslinked by heating at 70 to 170 ° C. for 30 to 240 seconds.
- the present invention also relates to an acrylic pressure-sensitive adhesive layer produced by the method for producing an acrylic pressure-sensitive adhesive layer.
- the gel fraction after 5 days after crosslinking is preferably 60 to 95% by weight, and the gel fraction after 2 hours after crosslinking is more preferably 55 to 85% by weight.
- the present invention also relates to a polarizing film with an adhesive layer, characterized in that the acrylic adhesive layer is provided on at least one surface of the polarizing film.
- the transparent conductive base material which has the said polarizing film with an adhesive layer and a transparent conductive film is laminated
- the present invention relates to a laminate in which a film is in contact.
- the transparent conductive film is made of indium tin oxide.
- the present invention also relates to an image display device using a laminate.
- the present invention provides a crosslink of an acrylic pressure-sensitive adhesive composition
- a (meth) acrylic polymer comprising a (meth) acrylic polymer, and one or more crosslinking agents selected from the group consisting of an organic peroxide crosslinking agent and an isocyanate crosslinking agent.
- a promotion method In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1): (Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom)
- the present invention relates to a method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition, which comprises adding 0.005 to 5 parts by weight of a compound represented by formula (100) by weight to 100 parts by weight of the (meth) acrylic polymer and crosslinking.
- the acrylic pressure-sensitive adhesive composition of the present invention is an acrylic pressure-sensitive adhesive composition comprising at least one crosslinking agent selected from the group consisting of acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents.
- the crosslinking reaction of the crosslinking agent is promoted, the three-dimensional crosslinking network of the pressure-sensitive adhesive layer is efficiently formed, and the crosslinking reaction can proceed efficiently.
- an organic peroxide-based crosslinking agent is used as the crosslinking agent, the addition of the compound represented by the general formula (1) suppresses radical crosslinking inhibition by oxygen and efficiently performs a crosslinking reaction.
- the compound represented by the general formula (1) serves as a catalyst for urethane reaction formation and can efficiently perform the crosslinking reaction. it can.
- the crosslinking reaction of the organic peroxide crosslinking agent and / or the isocyanate crosslinking agent is promoted. It is suppressed, processability can be improved, and productivity is excellent.
- the acrylic pressure-sensitive adhesive composition of the present invention has high crosslinking efficiency, and it is not necessary to perform an aging operation by heating or standing at room temperature after crosslinking.
- Acrylic pressure-sensitive adhesive composition is one or more cross-linking agents selected from the group consisting of (meth) acrylic polymers, organic peroxide-based cross-linking agents, and isocyanate-based cross-linking agents. And the following general formula (1): (Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom) And The content of the compound represented by the general formula (1) is 0.005 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
- phosphoric acid H 3 PO 4 in which R 1 and R 2 are hydrogen atoms in general formula (1)
- phosphoric acid salts sodium, potassium, and Metal salts such as magnesium, ammonium salts, etc.
- a phosphate ester in which at least one of R 1 and R 2 in the general formula (1) may contain an oxygen atom is a hydrocarbon residue having 1 to 18 carbon atoms is also suitable.
- the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, (CH 2 CH 2 O) n R 3 (R 3 is an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and n is an integer of 0 to 15).
- the alkyl group and alkenyl group may be linear or branched.
- examples of the compound represented by the general formula (1) include the following general formula (2): (Wherein R 1 is as defined above, R 3 is an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and n is an integer of 0 to 15). Esters are preferred.
- R 3 examples include an alkyl group having 1 to 18 carbon atoms or an alkenyl group, and an alkyl group having 1 to 18 carbon atoms is preferable.
- N is an integer of 0 to 15, and preferably an integer of 0 to 10.
- salts of the compound represented by the general formula (2) metal salts such as sodium, potassium and magnesium, ammonium salts, etc.
- metal salts such as sodium, potassium and magnesium, ammonium salts, etc.
- the acid value of the phosphate ester used in the present invention is preferably 80 to 900 mgKOH / g, more preferably 80 to 700 mgKOH / g, still more preferably 80 to 600 mgKOH / g, It is more preferably ⁇ 500 mg KOH / g, further preferably 100 to 400 g KOH / g, particularly preferably 150 to 300 mg KOH / g. If the acid value of the phosphate ester is too high, when an isocyanate crosslinking agent is used as the crosslinking agent, it may act as a crosslinking reaction catalyst for the isocyanate crosslinking agent, and the pressure-sensitive adhesive composition will gel. The pot life of the pressure-sensitive adhesive composition tends to be shortened.
- the pot life of the pressure-sensitive adhesive composition can be sufficiently ensured, and in the crosslinking step, the crosslinking agent can be promoted to be crosslinked, from the initial stage of production, The gel fraction of the pressure-sensitive adhesive layer can be increased, and as a result, a pressure-sensitive adhesive layer excellent in processability can be obtained.
- R 1 an oxygen atom
- diesters monoester Forma (2), 1 carbon atoms
- the mixing ratio of the monoester and the diester of the “mono / di mixture” can be calculated from the measurement result of 31 P-NMR.
- the measuring method is as described in the examples.
- the phosphate ester used in the present invention is a compound selected from the group consisting of a compound represented by the general formula (1) (or a compound represented by the general formula (2)), or a salt or multimer thereof. May be used alone or in admixture of two or more. However, phosphoric acid, phosphoric acid monoester, and phosphorus may be used from the viewpoint of reducing the addition amount and obtaining a better effect. It is preferably a mixture of two or more selected from the group consisting of acid diesters. Moreover, it can also be used as a mixture containing phosphoric acid and phosphoric acid monoester.
- the phosphoric acid monoester is a carbon atom having 1 to 18 carbon atoms in which one of R 1 and R 2 in the general formula (1) is a hydrogen atom and the other may contain an oxygen atom. It is a compound that is a hydrogen residue (in the case of the general formula (2), a compound in which R 1 is a hydrogen atom), and a phosphoric acid diester is a compound in which R 1 and R 2 in the general formula (1) are oxygen atoms
- a compound which is a hydrocarbon residue having 1 to 18 carbon atoms which may be contained in the case of the general formula (2), R 1 may contain an oxygen atom and a hydrocarbon residue having 1 to 18 carbon atoms may be contained. Compound which is a group).
- phosphoric acid can be further added to the phosphoric ester compound, and the amount of phosphoric acid added in that case is the phosphoric ester compound 100 from the viewpoint of the pot life of the pressure-sensitive adhesive composition.
- the amount is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less, and particularly preferably 20 parts by weight or less with respect to parts by weight.
- the lower limit of the addition amount of phosphoric acid is not particularly limited, and is added to the extent that it does not affect the pot life of the pressure-sensitive adhesive composition, and used to adjust the acid value of the phosphoric acid compound. Can do. *
- a compound represented by the general formula (1) or a multimer such as a dimer or trimer of a phosphate ester represented by (2) can also be used.
- the addition amount of the compound represented by the general formula (1) is preferably 0.005 to 5 parts by weight, and 0.01 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer described later. More preferred is 0.01 to 3 parts by weight, still more preferred is 0.01 to 2.5 parts by weight, and particularly preferred is 0.01 to 1 part by weight.
- the amount of the compound represented by the general formula (1) is less than 0.005 parts by weight, the effects of the present invention tend not to be obtained. Since the durability of the obtained pressure-sensitive adhesive layer tends to decrease, it is not preferable.
- two or more compounds represented by the general formula (1) can be used. In that case, the total amount can be added within the above range.
- the (meth) acrylic polymer used in the present invention is not particularly limited.
- the (meth) acrylic polymer is preferably obtained by polymerizing a monomer component containing an alkyl (meth) acrylate. It is preferably obtained by polymerizing a monomer component containing a (meth) acrylate and a hydroxyl group-containing monomer.
- 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 various linear or branched ones can be used.
- Specific examples of the alkyl (meth) acrylate include, for example, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n- Nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth)
- alkyl (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are preferable, (meth) acrylates having an alkyl group having 4 to 10 carbon atoms are more preferable, n-butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate is more preferred, and n-butyl acrylate is particularly preferred.
- the alkyl (meth) acrylate is preferably 50 parts by weight or more, preferably 60 parts by weight or more, and 70 parts by weight or more with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. Is more preferably 80 parts by weight or more, further preferably 90 parts by weight or more, and particularly preferably 95 parts by weight or more.
- hydroxyl 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 hydroxyl group can be used without particular limitation.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and the like. Can be used alone or in admixture of two or more.
- 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferable.
- an isocyanate-based crosslinking agent is used as the crosslinking agent described later, the use of 4-hydroxybutyl acrylate as the hydroxyl group-containing monomer can efficiently secure a crosslinking point with the isocyanate group of the isocyanate-based crosslinking agent. This is preferable because it is possible.
- the hydroxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 1 to 3 parts by weight is more preferable.
- the monomer component forming the (meth) acrylic polymer used in the present invention may contain the alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, and optionally the hydroxyl group-containing monomer. However, besides these monomers, a carboxyl group-containing monomer and other copolymerization monomers can be used as the monomer component.
- carboxyl 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 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.
- the carboxyl group-containing monomer is preferably 10 parts by weight or less, more preferably 6 parts by weight or less, still more preferably 2 parts by weight or less, based on 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 0.5 parts by weight or less is particularly preferable. Moreover, although a lower limit is not specifically limited, For example, it is preferable that it is 0.01 weight part or more.
- copolymerization monomers are not particularly limited as long as they have a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and examples thereof include alkyl having 1 to 3 carbon atoms.
- (Meth) acrylic alicyclic hydrocarbon esters such as alkyl (meth) acrylate having a group, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate; for example, (meth) acrylic acid (Meth) acrylic acid aryl esters such as phenyl; vinyl esters such as vinyl acetate and vinyl propionate; styrenic monomers such as styrene; for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate Epoxy group-containing monomers such as methacrylic acid (meth) acrylate Alkoxy group-containing monomers such as ethyl and ethoxyethyl (meth) acrylate; for example, cyano group-containing monomers such as acrylonitrile and methacrylonitrile; for example, functional monomers such as 2-methacryloyl
- 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 other copolymerization monomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less with respect to 100 parts by weight of the monomer component forming the (meth) acrylic polymer. 10 parts by weight or less is particularly preferable.
- the ratio of the copolymerization monomer is too large, the adhesive properties such as reduced adhesion to various adherends such as glass and film of the adhesive layer formed from the acrylic adhesive composition, and transparent conductive film, etc. May decrease.
- the weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably in the range of 1,200,000 to 3,000,000, more preferably 1,200,000 to 2,700,000, and even more preferably 1,200,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it may not be preferable in terms of heat resistance. Moreover, when the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may impair transparency. Moreover, the pressure-sensitive adhesive layer obtained using a (meth) acrylic polymer having a weight average molecular weight of less than 1,200,000 may have poor solvent resistance and mechanical properties.
- the weight average molecular weight is larger than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Moreover, it is preferable from a viewpoint of corrosion resistance and durability because a weight average molecular weight exists in the said range.
- the weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).
- 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. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
- solution polymerization for example, ethyl acetate or toluene 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, 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 with respect to parts.
- 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
- 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
- the silane coupling agent may be used alone or in combination of two or more, but the total content is 100% of all monomer components constituting the (meth) acrylic polymer.
- the amount is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.8 part by weight, and more preferably 0.05 to 1 part by weight. Particularly preferred is 0.7 part by weight.
- 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 proportion is preferably 0.005 to 0.7 parts by weight with respect to 100 parts by weight of all monomer components constituting the (meth) acrylic polymer.
- the acrylic pressure-sensitive adhesive composition of the present invention contains one or more types of cross-linking agents selected from the group consisting of organic peroxide cross-linking agents and isocyanate cross-linking agents. Addition is preferable because cohesive force related to the durability of the pressure-sensitive adhesive layer can be imparted.
- Any organic peroxide crosslinking agent can be used as long as it generates radical active species by heating or light irradiation to promote crosslinking of the base polymer of the pressure-sensitive adhesive composition.
- a peroxide having a one-minute half-life temperature 80 ° C. to 160 ° C.
- peroxides examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl
- the peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half.
- the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic Peroxide Catalog No. 9 of Nippon Oil & Fats Co., Ltd.” Edition (May 2003) ".
- the content of the organic peroxide crosslinking agent is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight, with respect to 100 parts by weight of the (meth) acrylic polymer. If the amount is less than 0.05 parts by weight, the required properties of the crosslinked structure tend not to be obtained. On the other hand, if the amount exceeds 2 parts by weight, the pressure-sensitive adhesive layer may contain peroxides or decomposition products thereof. Since durability characteristics tend to decrease, it is not preferable.
- 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 cross-linking agent examples include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and trimethylolpropane. And the like, and isocyanate compounds added with isocyanurates, burette type compounds, and urethane prepolymer type isocyanates such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. .
- a polyisocyanate compound which is one or a polyisocyanate compound derived from one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
- hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified is selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate or a polyisocyanate compound derived therefrom.
- Examples include hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate.
- isocyanate crosslinking agents include trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct.
- the content of the isocyanate-based crosslinking agent is preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the (meth) acrylic polymer. If the amount is less than 0.02 parts by weight, the required properties of the crosslinked structure tend not to be obtained. On the other hand, if the amount is more than 2 parts by weight, the pressure-sensitive adhesive becomes hard because the crosslinked structure becomes dense, As a result, there is a tendency that physical properties such as durability and adhesive strength tend not to be satisfied.
- an organic peroxide crosslinking agent or an isocyanate crosslinking agent may be used, or may be used in combination, but an organic peroxide crosslinking agent or an isocyanate crosslinking agent is used in combination.
- the content of the isocyanate crosslinking agent is preferably 5 to 1000 parts by weight with respect to 100 parts by weight of the organic peroxide crosslinking agent. 20 to 300 parts by weight is more preferable.
- crosslinking agent other crosslinking agents can be used in addition to the peroxide crosslinking agent and the isocyanate crosslinking agent.
- crosslinking agents polyfunctional compounds are used, and organic crosslinking agents and polyfunctional metal chelates are exemplified.
- organic crosslinking agent include an epoxy crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, and an aziridine crosslinking agent.
- a polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound.
- polyvalent metal atoms examples 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.
- 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.
- These crosslinking agents can be used alone or in combination of two or more. Among these, a peroxide type crosslinking agent and an isocyanate type crosslinking agent are preferable, and it is more preferable to use these in combination.
- the addition amount of the other crosslinking agent is not particularly limited, and can be added within a range not impairing the effects of the present invention.
- the amount of the (meth) acrylic polymer (solid content) is 100 parts by weight.
- it can mix
- the acrylic pressure-sensitive adhesive composition used in the present invention includes, as necessary, a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and others.
- a viscosity modifier e.g., a Brookcosity modifier, a stackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and others.
- Various kinds of fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, etc. which do not depart from the object of the present invention.
- These additives can also be used as appropriate.
- These additives can also be blended as an emulsion.
- the method for producing the acrylic pressure-sensitive adhesive layer of the present invention comprises a step of applying the acrylic pressure-sensitive adhesive composition on a substrate, and It includes a step of forming a pressure-sensitive adhesive layer by crosslinking an acrylic pressure-sensitive adhesive composition applied on a substrate.
- acrylic pressure-sensitive adhesive composition those described above can be used.
- the substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.
- Various methods are used as a coating method on the substrate or polarizing film. Specifically, for example, fountain coater, 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, Daiko Examples of the method include an extrusion coating method using a catalyst.
- the crosslinking temperature can be appropriately set depending on the composition and concentration of the acrylic pressure-sensitive adhesive composition, but is preferably 70 to 170 ° C, more preferably 90 to 165 ° C, and further preferably 140 to 160 ° C.
- the crosslinking time can be appropriately set depending on the composition and concentration of the acrylic pressure-sensitive adhesive composition, but is preferably 30 to 240 seconds and more preferably 60 to 180 seconds. It is preferable that the crosslinking condition is within the above range because the crosslinking reaction is efficiently performed.
- the thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and further preferably 12 to 40 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is less than 5 ⁇ 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 acrylic pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer cannot be fully dried at the time of drying and air bubbles remain, or the pressure-sensitive adhesive layer There is a tendency that unevenness in thickness occurs on the surface of the surface, 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, and more preferably about 5 to 100 ⁇ m.
- release agent 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.
- Acrylic pressure-sensitive adhesive layer The acrylic pressure-sensitive adhesive layer of the present invention is produced by the method for producing an acrylic pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer obtained by the method for producing an acrylic pressure-sensitive adhesive layer of the present invention is obtained by crosslinking an acrylic pressure-sensitive adhesive composition containing a compound represented by the general formula (1). Since the compound represented by the general formula (1) has a cross-linking promoting effect of a cross-linking agent such as an isocyanate cross-linking agent or an organic peroxide cross-linking agent, the acrylic pressure-sensitive adhesive layer of the present invention is produced from the initial stage of production. The gel fraction of the pressure-sensitive adhesive layer can be increased. As a result, a pressure-sensitive adhesive layer excellent in processability can be obtained.
- a cross-linking agent such as an isocyanate cross-linking agent or an organic peroxide cross-linking agent
- the gel fraction of the acrylic pressure-sensitive adhesive layer of the present invention is preferably 60 to 95% by weight, more preferably 65 to 90% by weight, and 70 to 90% by weight 5 days after crosslinking. More preferably.
- the gel fraction after 2 hours after crosslinking is preferably 55 to 85% by weight, more preferably 60 to 85% by weight, and 65 to 85% by weight from the viewpoint of processability. Is more preferable.
- a gel fraction within the above range is preferable from the viewpoints of workability and productivity.
- the pressure-sensitive adhesive layer is too soft. If processing is performed in this state, problems such as sticking of the blade during processing occur. Tend to.
- the productivity tends to be inferior.
- the measurement of the gel fraction of an adhesive layer can be performed by the method as described in an Example.
- the rate of change in gel fraction is preferably 1.35 or less, more preferably 1-1.35. It is preferably 1 to 1.30, more preferably 1 to 1.25.
- the change rate of the gel fraction is within the above range, the cross-linking reaction proceeds quickly, and stable physical properties are obtained 2 hours after the cross-linking reaction, which is preferable from the viewpoint of aging and workability.
- the polarizing film with an adhesive layer has the said acrylic adhesive layer on the at least single side
- the method for laminating the pressure-sensitive adhesive layer on the polarizing film is not particularly limited. As described above, the acrylic pressure-sensitive adhesive layer is formed on various substrates, and the pressure-sensitive adhesive layer is transferred onto the polarizing film. Alternatively, the acrylic pressure-sensitive adhesive composition may be applied directly on the polarizing film to form a pressure-sensitive adhesive layer. In addition, the formation method of an adhesive layer is as above-mentioned.
- the polarizing film may be a single-sided protective polarizing film having a transparent protective film on one side of the polarizer or a double-sided protective polarizing film having transparent protective films on both sides of the polarizer.
- the pressure-sensitive adhesive layer can be directly provided on the surface of the polarizer 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.
- the polarizer and the transparent 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.
- 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.
- an anchor layer may be provided between the polarizing film and the pressure-sensitive adhesive layer.
- 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 polymers examples include polyaniline sulfonic acid (weight average molecular weight of 150,000 in terms of polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.).
- water-dispersible conductive polymers examples include polythiophene-based conductive polymers (Nagase Chemtech Co., Ltd.). ) And Denatron series).
- the blending amount of the antistatic agent is, for example, preferably 70 parts by weight or less, more 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 polarizing 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 polarizing film is as described above.
- the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer of the present invention when exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until practical use.
- a release film When a release film is used as a base material in the production of the above-mentioned pressure-sensitive adhesive layer, the release film is polarized with a pressure-sensitive adhesive layer by laminating the pressure-sensitive adhesive layer on the release film and the polarizing film. It can be used as a release film for the pressure-sensitive adhesive layer of the film, and the process can be simplified.
- the polarizing film with an adhesive layer of this invention can suppress corrosion of a transparent conductive film, when a transparent conductive film is laminated
- the surface of a transparent conductive film It is possible to suppress an increase in resistance. This is because the phosphoric acid compound contained in the pressure-sensitive adhesive layer selectively adsorbs on the surface of the transparent conductive film to form a film, so that a substance that corrodes the transparent conductive film such as acid migrates to the surface of the transparent conductive film. As a result, it is considered that corrosion of the transparent conductive film is hindered.
- the polarizing film with an acrylic adhesive layer and a transparent conductive film are laminated, and the adhesive layer of the polarizing film with an acrylic adhesive layer and the transparent conductive film are in contact with each other.
- the above-mentioned polarizing film with an adhesive layer can be used.
- the substrate having a transparent conductive film is not particularly limited, and a known material can be used, but generally, a substrate having a transparent conductive film 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 irradiation, electron beam irradiation, chemical conversion, oxidation, and undercoating treatment on the surface in advance, and the transparent conductive film provided thereon You may make it improve the adhesiveness with respect to a transparent base material. Moreover, before providing a transparent conductive film, you may remove and clean by solvent washing
- the constituent material of the transparent conductive film is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten.
- a metal oxide of at least one metal is used.
- the metal oxide may further contain a metal atom shown in the above group, if necessary.
- indium oxide (ITO) containing tin oxide and tin oxide containing antimony are preferably used, and ITO is particularly preferably used.
- ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
- examples of the ITO include crystalline ITO and non-crystalline (amorphous) ITO, both of which can be suitably used.
- the thickness of the transparent conductive film is not particularly limited, but is preferably 10 nm or more, more preferably 15 to 40 nm, and further preferably 20 to 30 nm.
- the method for forming the transparent conductive film 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.
- the thickness of the substrate having the transparent conductive film can be 15 to 200 ⁇ m. Further, from the viewpoint of thinning, the thickness is preferably 15 to 150 ⁇ m, and more preferably 15 to 50 ⁇ m.
- a thickness of 100 to 200 ⁇ m can be mentioned.
- a thickness of 15 to 100 ⁇ m is preferable, and in particular, a thickness of 15 to 50 ⁇ m is more preferable due to a recent demand for further thinning, and a thickness of 20 to 50 ⁇ m is more preferable. .
- an undercoat layer, an oligomer prevention layer, and the like can be provided between the transparent conductive film and the transparent substrate as necessary.
- Image display device The laminate of the present invention includes an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) provided with an input device (touch panel, etc.), input device
- image display device liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.
- input device touch panel, etc.
- the base material member
- it is especially suitable in manufacture of the optical base material for touch panels.
- it can be used suitably in manufacture of the base material (member) which comprises apparatuses, such as (a touch panel etc.), or the base material (member) used for these apparatuses
- it is especially suitable in manufacture of the optical base material for touch panels.
- it can be used.
- it can be used irrespective of systems, such as a touch panel, such as a resistive film system and a capacitive system.
- the laminated body of the present invention is subjected to treatments such as cutting, resist printing, etching, silver ink printing and the like, and the resulting transparent conductive film can be used as a substrate for optical devices (optical member).
- the substrate for an optical device is not particularly limited as long as it is a substrate having optical characteristics.
- an image display device liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel)
- Examples include base materials (members) constituting devices such as electronic paper) and input devices (touch panels, etc.) or base materials (members) used in these devices.
- the polarizing film with an adhesive layer of this invention can suppress corrosion of a transparent conductive film also when a transparent conductive film is laminated
- Method for promoting crosslinking of acrylic pressure-sensitive adhesive composition comprises a (meth) acrylic polymer, and a group consisting of an organic peroxide-based crosslinking agent and an isocyanate-based crosslinking agent.
- a method for promoting crosslinking of an acrylic pressure-sensitive adhesive composition comprising one or more selected crosslinking agents, In addition to the acrylic pressure-sensitive adhesive composition, the following general formula (1): Wherein R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom, 0.005 to 5 parts by weight is added to 100 parts by weight of the (meth) acrylic polymer to crosslink.
- crosslinking agents selected from the group consisting of (meth) acrylic polymers, organic peroxides, and isocyanate crosslinking agents, the aforementioned ones should be used.
- the blending ratio is also as described above.
- the crosslinking conditions are as described above.
- the acrylic pressure-sensitive adhesive composition of the present invention one or more crosslinking agents selected from the group consisting of (meth) acrylic polymers, organic peroxide crosslinking agents, and isocyanate crosslinking agents.
- the acrylic pressure-sensitive adhesive composition containing can further promote crosslinking of the acrylic pressure-sensitive adhesive composition by containing the compound represented by the general formula (1). This is because when an organic peroxide-based crosslinking agent is used as a crosslinking agent, the addition of the compound represented by the general formula (1) suppresses radical crosslinking inhibition by oxygen and efficiently performs a crosslinking reaction.
- the compound represented by the general formula (1) serves as a catalyst for urethane reaction formation and can efficiently perform a crosslinking reaction.
- the crosslinking reaction of the organic peroxide crosslinking agent and / or the isocyanate crosslinking agent is promoted. It is suppressed, processability can be improved, and productivity is excellent.
- a stretched laminate was produced by subjecting a laminate in which a polyvinyl alcohol (PVA) layer having a thickness of 9 ⁇ m to a non-crystalline polyethylene terephthalate (PET) substrate to a stretching temperature of 130 ° C. by air auxiliary stretching.
- PVA polyvinyl alcohol
- PET non-crystalline polyethylene terephthalate
- a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched in boric acid in water at a stretching temperature of 65 ° C. so that the total stretch ratio is 5.94 times.
- an optical film laminate including a 4 ⁇ m thick PVA layer stretched together.
- the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 ⁇ m that constitutes a highly functional polarizer. Furthermore, a 40 ⁇ m-thick acrylic resin film (transparent protective film (1)) subjected to saponification treatment was applied to one side of the polarizer of the optical film laminate while applying a polyvinyl alcohol-based adhesive, and then amorphous. The PET substrate was peeled off to produce a polarizing film using a single-side protected thin polarizer. Hereinafter, this is referred to as a polarizing film (1).
- Production Example 2 (Production of Polarizing Film (2)) A PVA film having a thickness of 80 ⁇ m was stretched up to 3 times while being dyed in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the film was stretched so that the total stretch ratio was 6 times while immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 ⁇ m.
- a polarizing film (2) After applying a saponified 40 ⁇ m thick acrylic resin film (transparent protective film (1)) while applying a polyvinyl alcohol-based adhesive on the surface of the polarizer of the optical film laminate, amorphous PET After peeling off the base material, a norbornene-based film (transparent protective film (2)) having a thickness of 40 ⁇ m was bonded to the other surface with a polyvinyl alcohol-based adhesive to prepare a double-sided protective polarizing film.
- a polarizing film (2) this is referred to as a polarizing film (2).
- Production Example 3 (Preparation of solution containing acrylic polymer (A-1))
- a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 2,2′-azobisisobutyroyl as an initiator 1 part of nitrile (AIBN) is added to 100 parts of monomer (solid content) together with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Then, ethyl acetate is added to the reaction solution to obtain a weight average.
- a solution containing an acrylic polymer (A-1) having a molecular weight of 150,000 was obtained (solid content concentration 30% by weight).
- Production Examples 4 to 6 Preparation of solutions containing acrylic polymers (A-2) to (A-4)
- a solution containing the acrylic polymers (A-2) to (A-4) was obtained in the same manner as in Production Example 3 except that the monomer composition was changed to the composition shown in Table 2 (for each solution, Solid content concentration 30% by weight).
- the weight average molecular weight of the acrylic polymers obtained in Production Examples 3 to 6 was measured by the following measuring method. ⁇ Measurement of weight average molecular weight (Mw) of acrylic polymer> The weight average molecular weight of the prepared acrylic polymer was measured by GPC (gel permeation chromatography).
- HLC-8220GPC column Sample column: TSK guard column Super HZ-H (1) + TSK gel Super HZM-H (2) manufactured by Tosoh Corporation Reference column: TSKgel Super H-RC (1 piece), manufactured by Tosoh Corporation Flow rate: 0.6mL / min Injection volume: 10 ⁇ L Column temperature: 40 ° C Eluent: THF Injection sample concentration: 0.2% by weight Detector: differential refractometer The weight average molecular weight was calculated in terms of polystyrene.
- Example 1 Adjustment of acrylic adhesive composition
- ⁇ -glycidoxypropylmethoxysilane trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
- the acrylic pressure-sensitive adhesive composition is uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes.
- a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m was formed on the surface of the substrate.
- the separator which formed the adhesive layer was transferred to the surface which does not have a protective film of a polarizing film (1), and the polarizing film with an adhesive layer was produced.
- Example 1 Adjustment of acrylic pressure-sensitive adhesive composition
- the adhesive amount was changed in the same manner as in Example 1 except that the amount of phosphate ester was changed from 0.05 parts to the number of parts shown in Table 3.
- a polarizing film with an agent layer was produced.
- Example 1 Preparation of polarizing film with pressure-sensitive adhesive layer
- the drying conditions were changed from 155 ° C. and 120 seconds to the conditions described in Table 3, the same as in Example 1 was followed.
- a polarizing film was produced.
- Example 7 In Example 1 (adjustment of acrylic pressure-sensitive adhesive composition), 0.05 part of phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was added to phosphanol RS-410 (trade name, A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the acid value was changed to 0.05 part (acid value: 105 mg KOH / g, manufactured by Toho Chemical Industry Co., Ltd.).
- Example 8 In Example 1 (preparation of acrylic pressure-sensitive adhesive composition), 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was added to phosphoric acid (special reagent grade) (Wako Pure Chemical Industries, Ltd.). A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1, except that the amount was changed to 0.05 part (produced by Kogyo Co., Ltd.).
- Example 1 Preparation of acrylic pressure-sensitive adhesive composition
- the solutions containing the acrylic polymer (A-1) obtained in Production Example 3 were used as the acrylic polymers obtained in Production Examples 4 to 6, respectively. Except for changing to a solution containing polymers (A-2) to (A-4) and changing the amount of phosphate ester from 0.05 part to 0.1 part, the same as in Example 1. Thus, a polarizing film with an adhesive layer was produced.
- Example 12 In Example 1 (Preparation of polarizing film with pressure-sensitive adhesive layer), the polarizing film (1) was changed to the polarizing film (2) obtained in Production Example 2, and the same procedure as in Example 1 was followed. A polarizing film with an agent layer was produced.
- Example 13 In Example 1 (production of polarizing film with pressure-sensitive adhesive layer), the addition amount of adduct body (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.) of hexamethylene diisocyanate with trimethylolpropane is from 0.1 part.
- a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the content was changed to 0.12 parts and dibenzoyl peroxide was not added.
- Example 14 In Example 1 (production of polarizing film with pressure-sensitive adhesive layer), the amount of dibenzoyl peroxide added was changed from 0.3 part to 0.4 part, and hexamethylene diisocyanate was adducted with trimethylolpropane.
- a polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that (trade name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.) was not added.
- Example 15 In Example 1 (adjustment of acrylic pressure-sensitive adhesive composition), 0.05 part of Phosphanol SM-172 (trade name, manufactured by Toho Chemical Co., Ltd.) was added to MP-4 (trade name, acid value: A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the content was changed to 0.05 part (670 mg KOH / g, mono / di mixture, manufactured by Daihachi Chemical Industry Co., Ltd.).
- Example 1 Adjustment of acrylic pressure-sensitive adhesive composition
- a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the phosphate ester was not added.
- Comparative Example 2 A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that phosphate ester and dibenzoyl peroxide were not added in (Adjustment of acrylic pressure-sensitive adhesive composition) in Example 1.
- Example 1 Adjustment of acrylic pressure-sensitive adhesive composition
- the phosphoric acid ester was not added
- the drying conditions were changed from 155 ° C. for 120 seconds to Table 3.
- a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the conditions were changed to those described in 1. above.
- the phosphoric acid compounds used in Examples and Comparative Examples were analyzed as follows. The results are shown in Table 3. (Analysis method) The composition of the phosphoric acid compound used in Examples and Comparative Examples was calculated based on the measurement result of 31 P-NMR (Acetone-d6, room temperature). After calculating mol% from the integrated value of the peak obtained by measurement, the content ratio (% by weight) was calculated from the alkyl chain of the alcohol component of the ester.
- the phosphoric acid monoester has 1 to 18 carbon atoms in which either one of R 1 and R 2 in the general formula (1) is a hydrogen atom, and the other may contain an oxygen atom. It is a compound that is a hydrocarbon residue (in the case of general formula (2), a compound in which R 1 is a hydrogen atom), and a phosphoric acid diester is a compound in which R 1 and R 2 in general formula (1) are oxygen atoms A compound that is a hydrocarbon residue having 1 to 18 carbon atoms (in the case of the general formula (2), R 1 may contain an oxygen atom and a hydrocarbon having 1 to 18 carbon atoms) Compound that is a residue).
- the acrylic adhesive composition obtained by the Example and the comparative example it processed on the same dry conditions (temperature, time) as each Example and the comparative example, forms an adhesive layer, and also temperature 23 degreeC and humidity 65 Fluorine resin film (TEMISH NTF-1122, manufactured by Nitto Denko Corporation) in which 0.2 g of the pressure-sensitive adhesive layer was taken and weighed in advance after being left for 2 hours under the condition of% RH and for 5 days. Wrapped in (weight: Wa) and tied so that the acrylic pressure-sensitive adhesive composition did not leak. This is a measurement sample. The measurement sample was weighed (weight: Wb) and placed in a sample bottle.
- TEMISH NTF-1122 manufactured by Nitto Denko Corporation
- B-1 Phosphanol SM-172, acid value: 219 mg KOH / g (manufactured by Toho Chemical Industry Co., Ltd.)
- B-2 Phosphanol RS-410, acid value: 105 mg KOH / g (manufactured by Toho Chemical Industry Co., Ltd.)
- B-3 Phosphoric acid (special grade reagent) (manufactured by Wako Pure Chemical Industries, Ltd.)
- B-4 MP-4, acid value: 670 mg KOH / g, mono-di mixture, manufactured by Daihachi Chemical Industry Co., Ltd .: dibenzoyl peroxide isocyanate system: adduct form of hexamethylene diisocyanate with trimethylolpropane (Product name: Takenate D160N, manufactured by Mitsui Chemicals, Inc.)
- Silane coupling agent ⁇ -glycidoxypropylmethoxysilane (trade
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Abstract
Description
(式中、R1及びR2は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基である)
で表される化合物を含有し、
前記一般式(1)で表される化合物の含有量が、前記(メタ)アクリル系ポリマー100重量部に対して0.005~5重量部であることを特徴とするアクリル系粘着剤組成物に関する。
基材上に塗布されたアクリル系粘着剤組成物を架橋させて粘着剤層を形成する工程を含むことを特徴とするアクリル系粘着剤層の製造方法に関する。
本発明のアクリル系粘着剤組成物は、(メタ)アクリル系ポリマー、有機過酸化物系架橋剤、及びイソシアネート系架橋剤からなる群から選択される1種以上の架橋剤、並びに、下記一般式(1):
(式中、R1及びR2は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基である)で表される化合物を含有し、
前記一般式(1)で表される化合物の含有量が、前記(メタ)アクリル系ポリマー100重量部に対して0.005~5重量部であることを特徴とする。
(式中、R1は、前記同様であり、R3は、炭素数1~18のアルキル基、又は、アルケニル基であり、nは0~15の整数である。)で表されるリン酸エステルが好ましい。
本発明で用いるリン酸エステルとしては、一般式(1)で表される化合物(又は、一般式(2)で表される化合物)、又はこれらの塩や多量体からなる群から選択される化合物を1種単独で使用しても2種以上を混合して使用してもよいが、添加量を減らし、より良い効果を得ることができる観点から、リン酸、リン酸モノエステル、及び、リン酸ジエステルからなる群から選択される2つ以上の混合物であることが好ましい。また、リン酸とリン酸モノエステルを含む混合物として使用することもできる。ここで、リン酸モノエステルとは、一般式(1)のR1及びR2のいずれか一方が水素原子であり、他方が、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基である化合物(一般式(2)の場合は、R1が水素原子である化合物)であり、リン酸ジエステルとは、一般式(1)のR1及びR2が、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基である化合物(一般式(2)の場合は、R1が酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基である化合物)である。
本発明のアクリル系粘着剤層の製造方法は、前記アクリル系粘着剤組成物を基材上の塗布する工程、及び、
基材上に塗布されたアクリル系粘着剤組成物を架橋させて粘着剤層を形成する工程を含むことを特徴とする。
本発明のアクリル系粘着剤層は、前記アクリル系粘着剤層の製造方法により製造されたことを特徴とする。
本発明の粘着剤層付偏光フィルムは、偏光フィルムの少なくとも片面に、前記アクリル系粘着剤層を有することを特徴とする。
本発明の積層体は、前記アクリル系粘着剤層付偏光フィルムと、透明導電膜が積層されており、前記アクリル系粘着剤層付偏光フィルムの粘着剤層と透明導電膜が接することを特徴とする。
本発明の積層体は、入力装置(タッチパネル等)を備えた画像表示装置(液晶表示装置、有機EL(エレクトロルミネッセンス)表示装置、PDP(プラズマディスプレイパネル)、電子ペーパーなど)、入力装置(タッチパネル等)等の機器を構成する基材(部材)又はこれらの機器に用いられる基材(部材)の製造において好適に用いることができるが、特に、タッチパネル用の光学基材の製造において好適に用いることができる。また、抵抗膜方式や静電容量方式といったタッチパネル等の方式に関係なく使用することができる。
本発明のアクリル系粘着剤組成物の架橋促進方法は、(メタ)アクリル系ポリマー、並びに、有機過酸化物系架橋剤及びイソシアネート系架橋剤からなる群から選択される1種以上の架橋剤を含むアクリル系粘着剤組成物の架橋促進方法であって、
前記アクリル系粘着剤組成物に、さらに、下記一般式(1):
(式中、R1及びR2は、それぞれ独立して、水素原子、又は、酸素原子を含んでいてもよい、炭素数1~18の炭化水素残基である)で表される化合物を、前記(メタ)アクリル系ポリマー100重量部に対して0.005~5重量部添加して、架橋することを特徴とする。
非晶性ポリエチレンテレフタレート(PET)基材に、厚さ9μmのポリビニルアルコール(PVA)層が製膜された積層体を、延伸温度130℃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倍になるように非晶性PET基材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段延伸によって非晶性PET基材に製膜された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ポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光子を構成する、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。さらに、当該光学フィルム積層体の偏光子の片面に、ポリビニルアルコール系接着剤を塗布しながら、けん化処理した40μm厚のアクリル樹脂フィルム(透明保護フィルム(1))を貼合せたのち、非晶性PET基材を剥離し、片面保護の薄型偏光子を用いた偏光フィルムを作製した。以下、これを偏光フィルム(1)という。
厚さ80μmのPVAフィルムを、速度比の異なるロール間において、30℃、0.3%濃度のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。その後、60℃、4%濃度のホウ酸、10%濃度のヨウ化カリウムを含む水溶液中に0.5分間浸漬しながら総合延伸倍率が6倍になるように延伸した。次いで、30℃、1.5%濃度のヨウ化カリウムを含む水溶液中に10秒間浸漬することで洗浄した後、50℃で4分間乾燥を行い、厚さ20μmの偏光子を得た。さらに、当該光学フィルム積層体の偏光子の表面にポリビニルアルコール系接着剤を塗布しながら、けん化処理した40μm厚のアクリル樹脂フィルム(透明保護フィルム(1))を貼合せたのち、非晶性PET基材を剥離した後、他の片面に厚さ40μmのノルボルネン系フィルム(透明保護フィルム(2))を、ポリビニルアルコール系接着剤により貼り合せて、両面保護偏光フィルムを作製した。以下、これを偏光フィルム(2)という。
冷却管、窒素導入管、温度計、及び撹拌装置を備えた反応容器に、アクリル酸ブチル99部、アクリル酸4-ヒドロキシブチル1部、及び開始剤として、2,2’-アゾビスイソブチロニトリル(AIBN)をモノマー(固形分)100部に対して1部を酢酸エチルと共に加えて窒素ガス気流下、60℃で7時間反応させた後、その反応液に酢酸エチルを加えて、重量平均分子量155万のアクリル系ポリマー(A-1)を含有する溶液を得た(固形分濃度30重量%)。
モノマーの組成を表2に示す組成に変更した以外は、製造例3と同様にして、アクリル系ポリマー(A-2)~(A-4)を含有する溶液を得た(それぞれの溶液について、固形分濃度30重量%)。
BA:ブチルアクリレート
AA:アクリル酸
HEA:2-ヒドロキシエチルアクリレート
HBA:4-ヒドロキシブチルアクリレート
<アクリル系ポリマーの重量平均分子量(Mw)の測定>
作製したアクリル系ポリマーの重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィー)により測定した。
カラム:
サンプルカラム;東ソー社製、TSKguardcolumn Super HZ-H(1本)+TSKgel Super HZM-H(2本)
リファレンスカラム;東ソー社製、TSKgel Super H-RC(1本)
流量:0.6mL/min
注入量:10μL
カラム温度:40℃
溶離液:THF
注入試料濃度:0.2重量%
検出器:示差屈折計
なお、重量平均分子量はポリスチレン換算により算出した。
(アクリル系粘着剤組成物の調整)
製造例3で得られたアクリル系ポリマー(A-1)、架橋剤として、前記アクリル系ポリマー溶液の固形分100部あたり、ヘキサメチレンジイソシアネートのトリメチロールプロパンとのアダクト体(商品名:タケネートD160N、三井化学(株)製)0.1部と、ジベンゾイルパーオキサイド0.3部と、リン酸エステル(商品名:フォスファノールSM-172、東邦化学工業(株)製)0.05部と、γ-グリシドキシプロピルメトキシシラン(商品名:KBM-403、信越化学工業(株)製)0.075部を混合して、アクリル系粘着剤組成物を得た。
前記アクリル系粘着剤組成物を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(基材)の表面に、ファウンテンコーターで均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、基材の表面に厚さ20μmの粘着剤層を形成した。次いで、偏光フィルム(1)の保護フィルムを有さない面に、粘着剤層を形成したセパレータを移着させ、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、リン酸エステルの添加量を、0.05部から表3に記載の部数に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(粘着剤層付偏光フィルムの作製)において、乾燥条件を155℃、120秒間から、表3に記載した条件に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.05部を、フォスファノールRS-410(商品名、酸価:105mgKOH/g、東邦化学工業(株)製)0.05部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.05部を、リン酸(試薬特級)(和光純薬工業(株)製)0.05部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、製造例3で得られたアクリル系ポリマー(A-1)を含有する溶液を、それぞれ、製造例4~6で得られたアクリル系ポリマー(A-2)~(A-4)を含有する溶液に変更し、かつ、リン酸エステルの配合量を0.05部から0.1部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(粘着剤層付偏光フィルムの作製)において、偏光フィルム(1)を、製造例2で得られた偏光フィルム(2)に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(粘着剤層付偏光フィルムの作製)において、ヘキサメチレンジイソシアネートのトリメチロールプロパンとのアダクト体(商品名:タケネートD160N、三井化学(株)製)の添加量を0.1部から0.12部に変更し、かつ、ジベンゾイルパーオキサイドを添加しなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(粘着剤層付偏光フィルムの作製)において、ジベンゾイルパーオキサイドの添加量を0.3部から0.4部に変更し、かつ、ヘキサメチレンジイソシアネートのトリメチロールプロパンとのアダクト体(商品名:タケネートD160N、三井化学(株)製)を添加しなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、フォスファノールSM-172(商品名、東邦化学工業(株)製)0.05部を、MP-4(商品名、酸価:670mgKOH/g、モノ・ジ混合物、大八化学工業(株)製)0.05部に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、リン酸エステルを添加しなかった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、リン酸エステル、ジベンゾイルパーオキサイドを添加しなった以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
実施例1の(アクリル系粘着剤組成物の調整)において、リン酸エステルを添加せず、かつ、(粘着剤層付偏光フィルムの作製)において、乾燥条件を155℃、120秒間から、表3に記載した条件に変更した以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。
(分析方法)
実施例及び比較例で使用したリン酸系化合物の組成を、31P-NMR(Acetone-d6、室温)の測定結果に基づき算出した。測定により得られたピークの積分値より、mol%を算出した後、エステルのアルコール成分のアルキル鎖から含有量比(重量%)を算出した。
(31P-NMR測定条件)
測定装置:Bruker Biospin、AVANCEIII-400
観測周波数:160MHz(31P)
フリップ角:30°
測定溶媒:Acetone-d6(重アセトン)
測定温度:室温
化学シフト標準:P=(OCH3)3 in Acetone-d6(31P;140ppm 外部標準)
実施例及び比較例で得られたアクリル系粘着剤組成物について、各実施例、比較例と同じ乾燥条件(温度、時間)で処理して粘着剤層を形成し、さらに温度23℃、湿度65%RHの条件に2時間放置した後、及び、5日間放置した後、当該粘着剤層を0.2gとり、あらかじめ重量を測定したフッ素樹脂フィルム(TEMISH NTF-1122、日東電工(株)製)(重量:Wa)に包み、アクリル系粘着剤組成物が漏れないように縛った。これを、測定サンプルとする。測定サンプルの重量を測定し(重量:Wb)、サンプル瓶にいれた。サンプル瓶に酢酸エチルを40cc加えて、7日間放置した。その後、測定サンプル(フッ素樹脂フィルム+アクリル系粘着剤組成物)を取り出し、当該測定サンプルをアルミカップ上で、130℃、2時間乾燥させた。測定サンプルの重量(Wc)を測定し、次式によりゲル分率を求めた。
実施例及び比較例で得られた粘着剤層付偏光フィルムについて、作製後24時間以内に1辺の長さが270mmの正方形に打ち抜いたものについて、目視、手触りで観察して、偏光フィルム側面の粘着感の有無があるか否か、また、偏光フィルムの表面が粘着剤によって汚れているか否かを判断した。
◎:粘着剤による汚れが見られない。
○:粘着剤による汚れが問題ない程度ではあるが見られる。
△:粘着感があり、汚れが一部確認される。
×:粘着感があり、汚れが端部の大部分に確認される。
実施例、比較例において架橋剤添加後12時間放置し、その後、塗工したものについて以下の基準で判断した。
◎:塗工したものの外観に問題がなかった。
○:塗工したものの外観に少しブツが確認される。
×:外観に大きなゲルの塊が確認される、若しくは配合溶液がゲル化している。
実施例、比較例で得られた粘着型偏光フィルムサンプルのセパレータフィルムを剥がし、無アルカリガラスに貼り合わせ、50℃、5atm、15分間のオートクレーブ処理を行った後、85℃の加熱オーブンおよび60℃/90%RHの恒温恒湿機に投入した。500h後の偏光板の剥がれおよび発泡を目視で観察し、以下の基準で判断した。
◎:全く剥がれまたは発泡が認められなかった。
○:目視では確認できない程度の剥がれまたは発泡が発生した。
△:目視で確認できる小さな剥がれまたは発泡が発生した。
×:明らかな剥がれまたは発泡が認められた。
B-1:フォスファノールSM-172、酸価:219mgKOH/g(東邦化学工業(株)製)
B-2:フォスファノールRS-410、酸価:105mgKOH/g(東邦化学工業(株)製)
B-3:リン酸(試薬特級)(和光純薬工業(株)製)
B-4:MP-4、酸価:670mgKOH/g、モノ・ジ混合物、大八化学工業(株)製
過酸化物:ジベンゾイルパーオキサイド
イソシアネート系:ヘキサメチレンジイソシアネートのトリメチロールプロパンとのアダクト体(商品名:タケネートD160N、三井化学(株)製)
シランカップリング剤:γ-グリシドキシプロピルメトキシシラン(商品名:KBM-403、信越化学工業(株)製)
Claims (15)
- 前記一般式(1)で表される化合物が、酸価が80~900mgKOH/gであるリン酸エステルであることを特徴とする請求項1に記載の粘着剤組成物。
- 前記(メタ)アクリル系ポリマー100重量部に対し、前記有機過酸化物系架橋剤を0.05~2重量部含有することを特徴とする請求項1又は2に記載のアクリル系粘着剤組成物。
- 前記アクリル系粘着剤組成物が、有機過酸化物系架橋剤及びイソシアネート系架橋剤を含み、イソシアネート系架橋剤の含有量が、有機過酸化物系架橋剤100重量部に対して、5~1000重量部であることを特徴とする請求項1~3のいずれかに記載のアクリル系粘着剤組成物。
- 前記(メタ)アクリル系ポリマーの重量平均分子量が、120万~300万であることを特徴とする請求項1~4のいずれかに記載のアクリル系粘着剤組成物。
- 請求項1~5のいずれかに記載のアクリル系粘着剤組成物を基材上の塗布する工程、及び基材上に塗布されたアクリル系粘着剤組成物を架橋させて粘着剤層を形成する工程を含むことを特徴とするアクリル系粘着剤層の製造方法。
- 前記架橋が、70~170℃で30~240秒間加熱することにより行われることを特徴とする請求項6に記載のアクリル系粘着剤層の製造方法。
- 請求項6又は7に記載のアクリル系粘着剤層の製造方法により製造されたことを特徴とするアクリル系粘着剤層。
- 架橋後、5日後のゲル分率が60~95重量%であることを特徴とする請求項8に記載のアクリル系粘着剤層。
- 架橋後、2時間後のゲル分率が55~85重量%であることを特徴とする請求項8又は9のいずれかに記載のアクリル系粘着剤層。
- 偏光フィルムの少なくとも片面に、請求項8~10のいずれかに記載のアクリル系粘着剤層を有することを特徴とする粘着剤層付偏光フィルム。
- 請求項11に記載の粘着剤層付偏光フィルムと透明導電膜を有する透明導電性基材が積層されており、前記粘着剤層付偏光フィルムの粘着剤層と透明導電性基材の透明導電膜が接することを特徴とする積層体。
- 前記透明導電膜が、酸化インジウムスズから形成されることを特徴とする請求項12に記載の積層体。
- 請求項12又は13記載の積層体を用いることを特徴とする画像表示装置。
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| WO2011068102A1 (ja) * | 2009-12-03 | 2011-06-09 | 日東電工株式会社 | 粘着シート |
| WO2012091283A2 (ko) * | 2010-12-31 | 2012-07-05 | 제일모직 주식회사 | 편광판용 점착제 조성물 및 이를 포함하는 편광판 |
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