WO2016158608A1 - 粘着剤組成物、透明導電層用粘着剤層、粘着剤層付偏光フィルム、及び画像表示装置 - Google Patents

粘着剤組成物、透明導電層用粘着剤層、粘着剤層付偏光フィルム、及び画像表示装置 Download PDF

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WO2016158608A1
WO2016158608A1 PCT/JP2016/059180 JP2016059180W WO2016158608A1 WO 2016158608 A1 WO2016158608 A1 WO 2016158608A1 JP 2016059180 W JP2016059180 W JP 2016059180W WO 2016158608 A1 WO2016158608 A1 WO 2016158608A1
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Prior art keywords
adhesive layer
sensitive adhesive
pressure
transparent conductive
meth
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PCT/JP2016/059180
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English (en)
French (fr)
Japanese (ja)
Inventor
昌邦 藤田
智之 木村
雄祐 外山
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日東電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention is formed from a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer to be used by being bonded to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and the pressure-sensitive adhesive composition It is related with the adhesive layer for transparent conductive layers. Moreover, this invention relates to the image display apparatus containing the polarizing film with an adhesive layer which has the said adhesive layer, and the said polarizing film with an adhesive layer.
  • a liquid crystal panel used for a liquid crystal display device or the like usually has a polarizing film laminated on both sides of a liquid crystal cell formed of a liquid crystal layer disposed between a pair of transparent substrates via an adhesive layer.
  • Such an adhesive layer is required to have high durability. For example, in an endurance test such as heating and humidification that is usually performed as an environmental promotion test, defects such as peeling or floating due to the adhesive layer may not occur. Desired.
  • a transparent conductive film such as an indium tin oxide (ITO) thin film is formed on one transparent substrate of the liquid crystal cell constituting the liquid crystal panel, and the pressure-sensitive adhesive layer in contact with the transparent conductive film is peeled off.
  • ITO indium tin oxide
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of Patent Document 1 has poor adhesion to an indium tin oxide (ITO) layer, and is not sufficient as a pressure-sensitive adhesive composition for a liquid crystal panel having a transparent conductive layer. .
  • the pressure-sensitive adhesive layer may be bonded to the transparent conductive film after long-term storage for 6 months or longer, and excellent durability is required even after such long-term storage.
  • the present invention has high durability even when bonded to a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and particularly excellent in durability in a humidified environment.
  • An object of the present invention is to provide a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer that can maintain high durability even after being left for a long time.
  • this invention provides the image display apparatus containing the adhesive layer for transparent conductive layers formed from the said adhesive composition, the polarizing film with an adhesive layer which has the said adhesive layer, and the said polarizing film with an adhesive layer. Also aimed.
  • the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer to be used by bonding to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate
  • the present invention relates to a pressure-sensitive adhesive composition comprising a (meth) acrylic polymer and an oligomer type epoxy group-containing silane coupling agent.
  • the oligomer type epoxy group-containing silane coupling agent has two or more alkoxysilyl groups in the molecule.
  • the blending amount of the oligomer type epoxy group-containing silane coupling agent is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
  • the epoxy equivalent of the oligomer type epoxy group-containing silane coupling agent is preferably 300 g / mol or less.
  • the present invention also relates to a pressure-sensitive adhesive layer for a transparent conductive layer, which is formed from the pressure-sensitive adhesive composition.
  • the present invention is a polarizing film with a pressure-sensitive adhesive layer used by bonding to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate, It has a polarizing film and the polarizing film with an adhesive layer characterized by having the said adhesive layer.
  • the present invention is an image display device comprising a liquid crystal cell comprising the polarizing film with an adhesive layer, and a transparent conductive substrate having a transparent conductive layer on the transparent substrate, The pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film is bonded to the transparent conductive layer of the liquid crystal cell.
  • the pressure-sensitive adhesive composition of the present invention includes an oligomer type epoxy group-containing silane coupling agent, even if the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is bonded to the transparent conductive layer, it is high. It has durability, particularly excellent durability in a humidified environment, and can maintain high durability even after being left for a long time.
  • the present invention also provides an adhesive layer formed from the adhesive composition having high durability, a polarizing film with an adhesive layer having the adhesive layer, and an image display device having the polarizing film with the adhesive layer. Can be provided.
  • the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer to be used by being bonded to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate. Because It includes a (meth) acrylic polymer and an oligomer type epoxy group-containing silane coupling agent.
  • a (meth) acrylic polymer and an oligomer type epoxy group-containing silane coupling agent included in a (meth) acrylic polymer and an oligomer type epoxy group-containing silane coupling agent.
  • the pressure-sensitive adhesive composition of the present invention comprises a (meth) acrylic polymer and an oligomer type epoxy group-containing silane coupling agent, and is mainly composed of a (meth) acrylic polymer. It is preferable to include as.
  • the main component refers to a component having the highest content ratio among the total solids contained in the pressure-sensitive adhesive composition, and occupies more than 50% by weight of the total solids contained in the pressure-sensitive adhesive composition, for example. It is a component, and further refers to a component occupying more than 70% by weight.
  • (Meth) acrylic polymer usually contains alkyl (meth) acrylate as a main component as a monomer unit.
  • (meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.
  • alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer examples include linear or branched alkyl groups having 1 to 18 carbon atoms.
  • the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group.
  • the average carbon number of these alkyl groups is preferably 3 to 9.
  • Examples of the monomer constituting the (meth) acrylic polymer include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, and an aromatic ring-containing (meth) acrylate, in addition to the alkyl (meth) acrylate. it can.
  • the carboxyl group-containing monomer is a compound containing a carboxyl group in its structure and a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • Specific examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • acrylic acid is preferable from the viewpoints of copolymerizability, cost, and adhesive properties.
  • the hydroxyl group-containing monomer is a compound containing a hydroxyl group in its structure and a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8- Examples thereof include hydroxyalkyl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate, such as hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate.
  • hydroxyl group-containing monomers 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of durability, and 4-hydroxybutyl (meth) acrylate is particularly preferable.
  • the amide group-containing monomer is a compound containing an amide group in its structure and a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • Specific examples of the amide group-containing monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-methyl (meth) acrylamide, N- Butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl Acrylamide monomers such as (meth) acrylamide and mercaptoethyl (meth) acrylamide; N-actyl such as N-
  • the aromatic ring-containing (meth) acrylate is a compound containing an aromatic ring structure in its structure and a (meth) acryloyl group.
  • the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring.
  • the aromatic ring-containing (meth) acrylate can satisfy durability (particularly durability against the transparent conductive layer).
  • aromatic ring-containing (meth) acrylate examples include, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (Meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, ethylene oxide modified cresol (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, cresyl (meth) acrylate, polystyryl Having a benzene ring such as (meth) acrylate; hydroxyethylated ⁇ -napht
  • the carboxyl group-containing monomer, hydroxyl group-containing monomer, amide group-containing monomer, and aromatic ring-containing (meth) acrylate serve as a reaction point with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent.
  • the carboxyl group-containing monomer and the hydroxyl group-containing monomer are preferably used for improving the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer because they are highly reactive with the intermolecular crosslinking agent.
  • the (meth) acrylic polymer used in the present invention preferably contains the above monomers as monomer units in the following amounts in the weight ratio of all constituent monomers (100% by weight).
  • the weight ratio of the alkyl (meth) acrylate can be set as the remainder of the monomer other than the alkyl (meth) acrylate, and specifically, it is preferably 70% by weight or more. Setting the weight ratio of the alkyl (meth) acrylate within the above range is preferable for securing adhesiveness.
  • the weight ratio of the carboxyl group-containing monomer is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, still more preferably 0.05 to 1.5% by weight, Is more preferably from 1 to 1% by weight, particularly preferably from 0.05 to 0.5% by weight.
  • the weight ratio of the carboxyl group-containing monomer is less than 0.01% by weight, the durability tends not to be satisfied.
  • the transparent conductive layer may be corroded, and the durability tends not to be satisfied.
  • the weight ratio of the hydroxyl group-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, further preferably 0.1 to 2% by weight, and 0.2 to 2% by weight. % Is particularly preferred.
  • the weight ratio of the hydroxyl group-containing monomer is less than 0.01% by weight, the pressure-sensitive adhesive layer is insufficiently crosslinked, and there is a tendency that durability and pressure-sensitive adhesive properties cannot be satisfied. On the other hand, if it exceeds 3% by weight, the durability tends not to be satisfied.
  • the weight ratio of the amide group-containing monomer is preferably 8% by weight or less, more preferably 0.1 to 8% by weight, further preferably 0.3 to 5% by weight, and 0.3 to 4% by weight. % Is more preferable, and 0.7 to 2.5% by weight is particularly preferable.
  • the weight ratio of the amide group-containing monomer is less than 0.1% by weight, the durability particularly with respect to the transparent conductive layer tends not to be satisfied. On the other hand, if it exceeds 8% by weight, the durability tends to decrease, which is not preferable.
  • the weight ratio of the aromatic ring-containing (meth) acrylate is preferably 25% by weight or less, more preferably 0 to 22% by weight, and further preferably 0 to 18% by weight. When the weight ratio of the aromatic ring-containing (meth) acrylate exceeds 25% by weight, durability tends to decrease.
  • (meth) acrylic polymer in addition to the monomer unit, it is not particularly necessary to contain other monomer units, but for the purpose of improving adhesiveness and heat resistance, (meth) acryloyl groups
  • one or more copolymerization monomers having a polymerizable functional group having an unsaturated double bond such as a vinyl group can be introduced by copolymerization.
  • the ratio of the copolymerization monomer in the (meth) acrylic polymer is preferably about 0 to 10% by weight in the weight ratio of all the constituent monomers (100% by weight) of the (meth) acrylic polymer, It is more preferably about 7% by weight, and further preferably about 0 to 5% by weight.
  • the (meth) acrylic polymer of the present invention usually has a weight average molecular weight of 1 million to 2.5 million. Considering durability, particularly heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. When the weight average molecular weight is less than 1,000,000, it is not preferable from the viewpoint of heat resistance. On the other hand, when the weight average molecular weight is larger than 2.5 million, the pressure-sensitive adhesive tends to be hard and peeling is likely to occur. Further, the weight average molecular weight (Mw) / number average molecular weight (Mn) indicating the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, more preferably 1.8 to More preferably, it is 5.
  • the weight average molecular weight and molecular weight distribution (Mw / Mn) are determined by GPC (gel permeation chromatography) and calculated from polystyrene.
  • 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. 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, toluene or the like is used as a polymerization solvent.
  • the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed 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, di- ec-butyl peroxydicarbon
  • the polymerization initiator may be used alone or in combination of two or more, but the total content is 0.005 with respect to 100 parts by weight of the total amount of monomer components. It is preferably about 1 to 1 part by weight, more preferably about 0.02 to 0.5 part by weight.
  • the amount of the polymerization initiator used is: The amount is preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight, based on 100 parts by weight of the total amount of monomer components.
  • the pressure-sensitive adhesive composition contains an oligomer-type epoxy group-containing silane coupling agent.
  • an oligomer type epoxy group-containing silane coupling agent in the pressure-sensitive adhesive composition, the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be improved, particularly in a humidified environment. It has excellent properties and can maintain high durability even after being left for a long time.
  • the oligomer type refers to a polymer of monomer dimer or more and less than about 100 mer, and the weight average molecular weight of the oligomer type silane coupling agent is preferably about 300 to 30,000.
  • the oligomer type epoxy group-containing silane coupling agent is preferably an oligomer type epoxy group-containing silane coupling agent having two or more alkoxysilyl groups in the molecule.
  • Specific examples include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. These coupling agents are preferable because they are difficult to volatilize and are effective in improving durability because they have a plurality of alkoxysilyl groups.
  • the number of alkoxysilyl groups in the oligomer type epoxy group-containing silane coupling agent is not particularly limited, but is preferably 2 or more in the molecule.
  • the amount of the alkoxy group in the oligomer type epoxy group-containing silane coupling agent is preferably 10 to 60% by weight, more preferably 20 to 50% by weight in the silane coupling agent, More preferably, it is ⁇ 40% by weight.
  • alkoxy group is not limited, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and the like. Among these, methoxy and ethoxy are preferable, and methoxy is more preferable. It is also preferred that both methoxy and ethoxy are contained in one molecule.
  • the epoxy equivalent of the oligomer type epoxy group-containing silane coupling agent is preferably 1000 g / mol or less, more preferably 500 g / mol or less, and more preferably 300 g / mol or less.
  • the lower limit of an epoxy equivalent is not specifically limited, For example, it is preferable that it is 200 g / mol or more.
  • the oligomer type epoxy group-containing silane coupling agent may be used alone or in combination of two or more, but the total content is the (meth) acrylic polymer 100 0.01 to 6 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.05 to 1 part by weight with respect to parts by weight.
  • the durability of the pressure-sensitive adhesive layer can be improved. However, high durability can be maintained.
  • a silane coupling agent other than the oligomer type epoxy group-containing silane coupling agent can be added to the pressure-sensitive adhesive composition of the present invention.
  • Other coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene)
  • Amino group-containing silane coupling agents such as propylamine and N-phenyl- ⁇ -aminopropyltrimethoxysilane, (meth) acryl group-containing silanes such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane
  • Examples thereof include coupling agents and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.
  • a silane coupling agent other than the oligomer type epoxy group-containing silane coupling agent can be added within a range not impairing the effects of the present invention, and the amount of addition is not particularly limited.
  • the pressure-sensitive adhesive composition used in the present invention preferably contains a crosslinking agent.
  • a crosslinking agent an organic crosslinking agent or a polyfunctional metal chelate can be used.
  • the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent.
  • a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to an organic compound.
  • polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like.
  • Examples of the atom in the organic compound to be covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.
  • an isocyanate crosslinking agent and / or a peroxide crosslinking agent are preferable, and it is more preferable to use an isocyanate crosslinking agent and a peroxide crosslinking agent in combination.
  • isocyanate crosslinking agent a compound having at least two isocyanate groups can be used.
  • known aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate and the like generally used for urethanization reaction are used.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl. And hexamethylene diisocyanate.
  • Examples of the alicyclic isocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tolylene diisocyanate hydrogen. Examples include added tetramethylxylylene diisocyanate.
  • aromatic diisocyanate for example, phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4 Examples include '-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate.
  • isocyanate-based crosslinking agent examples include the above-mentioned diisocyanate multimers (dimers, trimers, pentamers, etc.), urethane-modified products reacted with polyhydric alcohols such as trimethylolpropane, urea-modified products, and biurets.
  • examples include modified products, alphanate modified products, isocyanurate modified products, and carbodiimide modified products.
  • isocyanate-based crosslinking agents include, for example, trade names “Millionate MT”, “Millionate MTL”, “Millionate MR-200”, “Millionate MR-400”, “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd. ”,“ Coronate HL ”,“ Coronate HX ”, trade names“ Takenate D-110N ”,“ Takenate D-120N ”,“ Takenate D-140N ”,“ Takenate D-160N ”, manufactured by Mitsui Chemicals, Inc. “Takenate D-165N”, “Takenate D-170HN”, “Takenate D-178N”, “Takenate 500”, “Takenate 600” and the like. These compounds may be used alone or in combination of two or more.
  • an aliphatic polyisocyanate and an aliphatic polyisocyanate-based compound which is a modified product thereof are preferable.
  • Aliphatic polyisocyanate compounds are more flexible in cross-linking structures than other isocyanate cross-linking agents, tend to relieve stress associated with the expansion / contraction of optical films, and do not easily peel off in durability tests.
  • the aliphatic polyisocyanate compound hexamethylene diisocyanate and modified products thereof are particularly preferable.
  • Any peroxide can be used as long as it generates radical active species by heating or light irradiation to promote crosslinking of the base polymer ((meth) acrylic polymer) of the pressure-sensitive adhesive composition.
  • a peroxide having a half-life temperature of 80 ° C. to 160 ° C. for 1 minute it is preferable to use a peroxide having a temperature of 90 ° C. to 140 ° C.
  • peroxides examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-tert-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-tetramethylbuty
  • di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.)
  • dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C.
  • dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C.) and the like are preferably used.
  • 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 amount of the crosslinking agent used is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, and more preferably 0.03 to 1 part by weight with respect to 100 parts by weight of the (meth) acrylic polymer. preferable. If the cross-linking agent is less than 0.01 parts by weight, the pressure-sensitive adhesive layer may be insufficiently cross-linked and the durability and adhesive properties may not be satisfied. On the other hand, if it exceeds 3 parts by weight, the pressure-sensitive adhesive layer becomes too hard. The durability tends to decrease.
  • the isocyanate-based crosslinking agent may be used alone or in combination of two or more, but the total content is 100 parts by weight of the (meth) acrylic polymer. On the other hand, it is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and even more preferably 0.05 to 1.5 parts by weight. It can be appropriately contained in consideration of cohesive force, prevention of peeling in a durability test, and the like.
  • the peroxide may be used alone or as a mixture of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer.
  • the content is preferably 0.01 to 2 parts by weight, more preferably 0.04 to 1.5 parts by weight, and still more preferably 0.05 to 1 part by weight. In order to adjust processability, cross-linking stability, etc., it is appropriately selected within this range.
  • the pressure-sensitive adhesive composition of the present invention can further contain an ionic compound.
  • the ionic compound is not particularly limited, and those used in this field can be suitably used. Examples thereof include those described in JP-A-2015-4861, among which (perfluoroalkylsulfonyl) imide lithium salt is preferable, and bis (trifluoromethanesulfonylimide) lithium is more preferable.
  • the ratio of the ionic compound is not particularly limited, and can be within a range not impairing the effects of the present invention.
  • the ratio of the ionic compound is 10 with respect to 100 parts by weight of the (meth) acrylic polymer. Parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 1 part by weight or less.
  • a polyether compound having a reactive silyl group can be blended.
  • Polyether compounds are preferred because they can improve reworkability.
  • the polyether compound for example, those disclosed in JP 2010-275522 A can be used.
  • the addition amount can be appropriately determined within a range not impairing the effects of the present invention.
  • the pressure-sensitive adhesive composition used in the present invention may contain other known additives, such as polyether compounds of polyalkylene glycols such as polypropylene glycol, powders of colorants and pigments, dyes, and the like. , Surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, It can be added as appropriate depending on the application in which metal powder, particles, foil, etc. are used. Moreover, you may employ
  • These additives are preferably used in an amount of 5 parts by weight or less, further 3 parts by weight or less, and further 1 part by weight or less based on 100 parts by weight of the (meth) acrylic polymer.
  • Pressure-sensitive adhesive layer for transparent conductive layer is formed from the pressure-sensitive adhesive composition. In forming the pressure-sensitive adhesive layer, it is preferable to fully consider the influence of the crosslinking treatment temperature and the crosslinking treatment time as well as adjusting the addition amount of the entire crosslinking agent.
  • the crosslinking treatment temperature and crosslinking treatment time can be adjusted depending on the crosslinking agent used.
  • the crosslinking treatment temperature is preferably 170 ° C. or lower.
  • this crosslinking process may be performed at the temperature at the time of the drying process of an adhesive layer, and you may carry out by providing a crosslinking process process separately after a drying process.
  • the crosslinking treatment time can be set in consideration of productivity and workability, but is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.
  • the method for forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive composition is applied on various substrates, dried with a dryer such as a heat oven to volatilize the solvent, etc.
  • a method of transferring the pressure-sensitive adhesive layer onto a polarizing film or a transparent conductive substrate, which will be described later, by forming a pressure-sensitive adhesive layer by crosslinking treatment, may be used.
  • the pressure-sensitive adhesive composition may be directly applied to form a pressure-sensitive adhesive layer.
  • the method of producing the polarizing film with an adhesive layer which formed the adhesive layer on the polarizing film previously, and sticking the said polarizing film with an adhesive layer to a liquid crystal cell is preferable.
  • the substrate is not particularly limited, and examples thereof include various substrates such as a release film, a transparent resin film substrate, and a polarizing film described later.
  • Various methods are used as a method of applying the pressure-sensitive adhesive composition to 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 A method such as an extrusion coating method using a tar or the like.
  • the drying conditions are not particularly limited and can be appropriately set depending on the composition, concentration, etc. of the pressure-sensitive adhesive composition, and are, for example, about 80 to 170 ° C., preferably 90 to 200 ° C. 1 to 60 minutes, preferably 2 to 30 minutes.
  • a crosslinking treatment can be performed as necessary, and the conditions are as described above.
  • the thickness of the pressure-sensitive adhesive layer (after drying) is, for example, preferably 5 to 100 ⁇ m, more preferably 7 to 70 ⁇ m, and even more preferably 10 to 50 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is less than 5 ⁇ m, the adhesion to the adherend tends to be poor, and the durability under humidified conditions tends to be insufficient.
  • the thickness of the pressure-sensitive adhesive layer exceeds 100 ⁇ m, the pressure-sensitive adhesive composition is not sufficiently dried during the application and drying of the pressure-sensitive adhesive layer, and bubbles remain or the surface of the pressure-sensitive adhesive layer. There is a tendency that unevenness in thickness occurs and problems in appearance tend to become apparent.
  • 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. Suitable thin leaf bodies and the like can be mentioned, but a resin film is suitably 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, ethylene- A vinyl acetate copolymer film etc. are mentioned.
  • the thickness of the release film is usually 5 to 200 ⁇ m, 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.
  • the polarizing film with an adhesive layer of this invention has the said adhesive layer in the at least one surface of a polarizing film, It is characterized by the above-mentioned.
  • the polarizing film with the pressure-sensitive adhesive layer of the present invention is used by bonding so that the pressure-sensitive adhesive layer of the polarizing film is in contact with the transparent conductive layer of the transparent conductive substrate having a transparent conductive layer on the transparent substrate. It is.
  • the method for forming the pressure-sensitive adhesive layer is as described above.
  • the polarizing film is not particularly limited, but a polarizing film having a transparent protective film on one side or both sides is generally used.
  • 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.
  • 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 substance such as iodine is preferable, and an iodine polarizer containing iodine and / or iodine ions is more 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 of potassium iodide or the like 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.
  • the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. 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 of 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 film can be reduced.
  • the thin polarizer typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, 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 and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this production 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 an aqueous boric acid 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.
  • thermoplastic resins excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like are used.
  • thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • a transparent protective film is bonded to one side of the polarizer by an adhesive layer.
  • a transparent protective film (meth) acrylic, urethane-based, acrylurethane-based, epoxy-based, silicone
  • a thermosetting resin such as a system or an ultraviolet curable resin can be used.
  • One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
  • the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
  • content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
  • the thickness of the protective film can be appropriately determined, 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 protective film are usually in close contact with each other through an aqueous adhesive or the like.
  • the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
  • examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
  • the electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films.
  • the adhesive used in the present invention can contain a metal compound filler.
  • a retardation film or the like can be formed on the polarizer instead of the transparent protective film of the polarizing film. Further, another transparent protective film or a retardation film can be provided on the transparent protective film.
  • the surface of the transparent protective film to which the polarizer is not adhered can be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, antisticking, 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.
  • the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer may be protected with a release film (separator) until it is practically used.
  • a release film separator
  • the above-mentioned thing can be mentioned as a release film.
  • 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 the present invention is used by being bonded to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate.
  • the constituent material of the transparent conductive layer of the transparent conductive substrate is not particularly limited and is composed of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten.
  • a metal oxide of at least one metal selected from the group is used.
  • the metal oxide may further contain a metal atom shown in the above group, if necessary.
  • ITO indium oxide
  • ITO indium oxide
  • ITO indium oxide
  • ITO indium oxide
  • ITO indium oxide
  • 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 layer 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 layer 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 transparent substrate may be a transparent substrate, and the material is not particularly limited. Examples thereof include glass and a transparent resin film substrate. Examples of the transparent resin film substrate include those described above.
  • an undercoat layer, an oligomer prevention layer, etc. can be provided between the transparent conductive layer and the transparent substrate, if necessary.
  • Image display device The image display device of the present invention is an image display device comprising a liquid crystal cell comprising the polarizing film with an adhesive layer, and a transparent conductive substrate having a transparent conductive layer on the transparent substrate, The pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer is bonded to the transparent conductive layer of the liquid crystal cell.
  • the polarizing film with the adhesive layer and the transparent conductive substrate are as described above.
  • the liquid crystal cell used in the image display device of the present invention is provided with a transparent conductive substrate having a transparent conductive layer on a transparent substrate, but the transparent conductive substrate is usually on the viewing side of the liquid crystal cell. Provided on the surface.
  • a liquid crystal panel including a liquid crystal cell that can be used in the present invention will be described with reference to FIG. However, the present invention is not limited to FIG.
  • the viewing side transparent protective film 2 / polarizer 3 / liquid crystal cell side transparent protective film 4 / adhesive layer 5 / transparent conductive material from the viewing side, the viewing side transparent protective film 2 / polarizer 3 / liquid crystal cell side transparent protective film 4 / adhesive layer 5 / transparent conductive material.
  • the structure which consists of layer 6 / transparent base material 7 / liquid crystal layer 8 / transparent base material 9 / adhesive layer 10 / liquid crystal cell side transparent protective film 11 / polarizer 12 / light source side transparent protective film 13 can be mentioned.
  • the polarizing film with an adhesive layer of this invention corresponds to the visual recognition side transparent protective film 2 / polarizer 2 / liquid crystal cell side transparent protective film 3 / adhesive layer 5.
  • FIG. 1 the viewing side transparent protective film 2 / polarizer 3 / liquid crystal cell side transparent protective film 4 / adhesive layer 5 / transparent conductive material.
  • the transparent conductive base material used by this invention is comprised by the transparent conductive layer 6 / transparent base material 7.
  • FIG. 1 the liquid crystal cell including the transparent conductive substrate used in the present invention is composed of transparent conductive layer 6 / transparent substrate 7 / liquid crystal layer 8 / transparent substrate 9.
  • the liquid crystal panel 1 can be appropriately provided with an optical film such as a retardation film, a viewing angle compensation film, and a brightness enhancement film.
  • an optical film such as a retardation film, a viewing angle compensation film, and a brightness enhancement film.
  • the liquid crystal layer 8 is not particularly limited, and for example, an arbitrary type such as an arbitrary type such as a TN type, an STN type, a ⁇ type, a VA type, and an IPS type can be used.
  • the transparent substrate 9 (light source side) may be a transparent substrate, and the material thereof is not particularly limited, and examples thereof include glass and a transparent resin film substrate. Examples of the transparent resin film substrate include those described above.
  • the pressure-sensitive adhesive layer 10 on the light source side the liquid crystal cell-side transparent protective film 11, the polarizer 12, and the light source-side transparent protective film 13, those conventionally used in this field can be used. Those described in the book can also be suitably used.
  • the liquid crystal panel 1 includes the polarizing film with the adhesive layer of the present invention on the transparent conductive layer 6 formed on the outermost layer on the viewing side of the liquid crystal cell, and the transparent conductive layer 6 of the liquid crystal cell and the polarizing film with the adhesive layer.
  • the adhesive layer 5 is laminated so as to be in contact with it.
  • the image display apparatus of this invention should just contain the liquid crystal cell provided with the polarizing film with an adhesive layer of this invention, and the transparent conductive base material which has a transparent conductive layer on a transparent base material. It is preferable to include.
  • a liquid crystal display device will be described as an example, but the present invention is not limited thereto.
  • the image display device to which the liquid crystal panel can be applied include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED: Field Emission Display) and the like.
  • EL electroluminescence
  • PD plasma display
  • FED Field Emission Display
  • the image display apparatus of this invention should just contain the liquid crystal cell provided with the polarizing film with an adhesive layer of this invention, and the transparent conductive base material which has a transparent conductive layer on a transparent base material, Other structures are This is the same as the conventional image display device.
  • room temperature standing conditions not particularly specified are all 23 ° C. and 65% R.S. H. It is.
  • Production Example 1 (Preparation of polarizing film) A 80 ⁇ m-thick polyvinyl alcohol film was stretched up to 3 times while being dyed in an iodine solution of 0.3 wt% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched up to 6 times while being immersed in an aqueous solution containing boric acid at 4% by weight at 60 ° C. and 10% by weight potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5 wt% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 30 ⁇ m. A saponified 80 ⁇ m thick triacetyl cellulose film was bonded to both sides of the polarizer with a polyvinyl alcohol adhesive to produce a polarizing film.
  • Production Example 2 (Preparation of acrylic polymer (a-1) solution) A monomer mixture containing 99 parts by weight of butyl acrylate and 1 part by weight of 4-hydroxybutyl acrylate was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Furthermore, with respect to 100 parts by weight of the monomer mixture (solid content), 0.1 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged together with 100 parts by weight of ethyl acetate, while gently stirring. After introducing nitrogen gas and substituting with nitrogen, the temperature of the liquid in the flask was kept at around 55 ° C. for 8 hours to conduct a polymerization reaction, and an acrylic polymer having a weight average molecular weight (Mw) of 1560,000 and Mw / Mn3.2 ( A solution of a-1) was prepared.
  • Mw weight average molecular weight
  • Production Examples 3-5 In Production Example 2, as shown in Table 1, the acrylic polymer (a-2) was prepared in the same manner as in Production Example 2, except that the type of monomer used for the preparation of the acrylic polymer and the use ratio thereof were changed. A solution of (a-4) was prepared.
  • Example 1 Adjustment of acrylic adhesive composition
  • an isocyanate crosslinking agent (trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) ) 0.1 part, 0.3 part of benzoyl peroxide (Niper BMT 40SV, manufactured by NOF Corporation), and oligomer type epoxy group-containing silane coupling agent (trade name: X-41-1053, amount of alkoxy group) : 50 wt%, epoxy equivalent: 830 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 part was prepared to prepare an acrylic pressure-sensitive adhesive composition solution.
  • an isocyanate crosslinking agent trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc.
  • benzoyl peroxide (Niper BMT 40SV, manufactured by NOF Corporation)
  • Example 2 Comparative Examples 1 to 4
  • the acrylic pressure-sensitive adhesive composition was changed in the same manner as in Example 1 except that the type of acrylic polymer, the type of silane coupling agent, and the amount added were changed.
  • a solution was prepared.
  • ionic compounds were blended in the proportions shown in Table 2.
  • a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1.
  • Samples obtained by cutting the polarizing film with pressure-sensitive adhesive layer obtained in Examples and Comparative Examples into 15-inch sizes were used as samples.
  • the sample was attached to an ITO layer of a glass with an ITO layer having an amorphous ITO layer on a non-alkali glass (trade name: EG-XG, manufactured by Corning) having a thickness of 0.7 mm using a laminator.
  • the sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to completely adhere the sample to the glass with an ITO layer.
  • the ITO layer was formed by sputtering.
  • the composition of ITO was 3 wt% Sn ratio, and a heating step of 140 ° C. ⁇ 60 minutes was performed before the samples were bonded.
  • the Sn ratio of ITO was calculated from the weight of Sn atoms / (weight of Sn atoms + weight of In atoms). (Evaluation criteria) A: No change in appearance such as peeling.
  • ⁇ Slightly peeled off at the end, but no problem in practical use. ⁇ : Although there is peeling at the end, there is no practical problem unless it is a special use. X: Remarkably peeled off at the end, causing practical problems.
  • Isocyanate type Trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Ltd.
  • Peroxide type Product name: Niper BMT 40SV, benzoyl peroxide, manufactured by Nippon Oil & Fats Co., Ltd.
  • X-41-1056 Oligomer type epoxy group-containing silane coupling agent, alkoxy group amount: 17% by weight, epoxy equivalent: 280 g / mol, Shin-Etsu Chemical Co., Ltd.
  • X-41-1053 oligomer type epoxy group-containing silane coupling agent, Alkoxy group amount: 50% by weight, epoxy equivalent: 830 g / mol, Shin-Etsu Chemical Co., Ltd.
  • X-41-1059A oligomer type epoxy group-containing silane coupling agent, alkoxy group amount: 43% by weight, epoxy equivalent: 350 g / mol, Shin-Etsu Chemical Co., Ltd.
  • ionicity Compounds bis (trifluoromethanesulfonyl imide) lithium, Mitsubishi Materials Corp. KBM-403: .gamma.-glycidoxypropyl silane, manufactured by Shin-Etsu Chemical Co.,

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