TWI741031B - Polarizing film with adhesive layer, image display panel and image display device - Google Patents

Abstract

The present invention is a polarizing film with an adhesive layer, which has an adhesive layer and a polarizing film, and the adhesive layer is attached to the transparent conductive layer of the transparent conductive substrate with a transparent conductive layer for use And the adhesive composition used to form the adhesive layer contains a (meth)acrylic polymer and a thiol group-containing silane coupling agent. The polarizing film with an adhesive layer of the present invention has high durability even when it is attached to a transparent conductive substrate with a transparent conductive layer on a transparent substrate, especially in a humidified environment. And the heavy workability is also excellent.

Description

Polarizing film with adhesive layer, image display panel and image display device

The present invention relates to a polarizing film with an adhesive layer and an adhesive layer attached to the polarizing film. The adhesive layer is attached to the transparent conductive layer of the transparent conductive substrate with a transparent conductive layer. . In addition, the present invention relates to an image display panel provided with a transparent conductive substrate using the above-mentioned polarizing film with an adhesive layer. Furthermore, the present invention relates to an image display device including the above-mentioned image display panel.

An image display panel, such as a liquid crystal panel used in a liquid crystal display device, etc., usually has a polarizing film laminated via an adhesive layer on both sides of a liquid crystal cell formed of a liquid crystal layer arranged between a pair of transparent substrates. For this type of adhesive layer, high durability is required. For example, in durability tests such as heating and humidification, which are usually performed as environmental promotion tests, it is required that no defects such as peeling or swelling of the adhesive layer occur.

The industry has conducted various researches on adhesive compositions for optical applications. For example, it has been proposed that there is an adhesive composition that does not peel or foam when the optical film is laminated and placed under high humidity and heat conditions ( For example, refer to Patent Document 1).

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2009-242767

If a transparent conductive film such as an indium tin oxide (ITO) film or an organic conductive film using a conductive polymer is formed on one of the transparent substrates of the liquid crystal cell constituting the liquid crystal panel, the adhesive layer in contact with the transparent conductive film is easy There is a tendency for peeling or swelling, etc., to decrease durability. In addition, especially in a humidified environment, the durability is significantly reduced. The adhesive layer formed from the adhesive composition of Patent Document 1 has poor adhesion to an indium tin oxide (ITO) layer, and is not sufficient as an adhesive composition for a liquid crystal panel having a transparent conductive layer.

In addition, since the adhesive layer designed to ensure heat resistance has high adhesion to the transparent conductive layer, there may be cases where the paste remains or the polarized film breaks during heavy work. The above-mentioned adhesive layer also requires heavy workability without such disadvantages.

Therefore, the object of the present invention is to provide a polarizing film provided with an adhesive layer of the following adhesive layer on the polarizing film. The adhesive layer has a transparent conductive substrate with a transparent conductive layer even when the adhesive layer is attached to a transparent substrate In this case, it also has high durability, especially in humidified environments, and it has excellent reworkability.

In addition, an object of the present invention is to provide an image display panel with a transparent conductive substrate using the above-mentioned polarizing film with an adhesive layer. Furthermore, the object of the present invention is also to provide an image display device including the above-mentioned image display panel.

In order to solve the above-mentioned problems, the inventors of the present invention have made great efforts, and as a result, discovered the following polarizing film with an adhesive layer, thereby completing the present invention.

That is, the present invention relates to a polarizing film with an adhesive layer, which is characterized by having an adhesive layer and a polarizing film, and the adhesive layer is attached to a transparent substrate with a transparent conductive layer of a transparent conductive substrate. The above-mentioned transparent conductive layer is used, and the adhesive composition used to form the above-mentioned adhesive layer contains (meth)acrylic polymer and Silane coupling agent containing thiol group.

The aforementioned thiol group-containing silane coupling agent is preferably an oligomer type thiol group-containing silane coupling agent.

The aforementioned thiol group-containing silane coupling agent preferably has two or more alkoxysilyl groups in the molecule.

The compounding amount of the thiol group-containing silane coupling agent is preferably 0.01 to 3 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer.

The thiol group equivalent of the thiol group-containing silane coupling agent is preferably 700 g/mol or less.

Furthermore, the present invention relates to an image display panel, which is characterized by comprising: the above-mentioned polarizing film with an adhesive layer, and a transparent conductive substrate with a transparent conductive layer on the transparent substrate, and The adhesive layer of the polarizing film with the adhesive layer is attached to the transparent conductive layer of the image display panel.

Furthermore, the present invention relates to an image display device characterized by having the above-mentioned image display panel.

Since the adhesive composition forming the adhesive layer in the polarizing film with the adhesive layer of the present invention contains a thiol group-containing silane coupling agent, even when the adhesive layer is attached to the transparent conductive layer, It also has high durability, especially in humidified environments. In addition, the above-mentioned adhesive layer has good reworkability, and can prevent paste residue or polarization film breakage during heavy work. In this way, the polarizing film with the adhesive layer of the present invention can balance the durability and reworkability of the transparent conductive layer. Furthermore, according to the present invention, it is possible to provide an image display panel having the polarizing film with the adhesive layer, and further provide an image display device having the image display panel.

1: LCD panel

2: Transparent protective film on the visual recognition side

3: Polarizing element

4: Transparent protective film on the liquid crystal cell side

5: Adhesive layer

6: Transparent conductive layer

7: Transparent substrate

8: Liquid crystal layer

9: Transparent substrate

10: Adhesive layer

11: Transparent protective film on the side of the liquid crystal cell

12: Polarizing element

13: Transparent protective film on the light source side

FIG. 1 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel as one of the image display panels that can be used in the present invention.

1. Adhesive composition

The adhesive composition of the present invention is characterized in that it is used to form an adhesive layer that is attached to the transparent conductive layer of a transparent conductive substrate having a transparent conductive layer on a transparent substrate. Used, and it contains (meth)acrylic polymer and thiol group-containing silane coupling agent. Hereinafter, the composition of the adhesive composition of the present invention will be described.

(1) (Meth) acrylic polymer

The adhesive composition of the present invention preferably contains a (meth)acrylic polymer and a thiol group-containing silane coupling agent, and contains a (meth)acrylic polymer as a main component. Here, the so-called main component refers to the component with the largest ratio among all solid components contained in the adhesive composition, for example, a component that accounts for more than 50% by weight of all solid components contained in the adhesive composition , Which in turn occupies more than 70% by weight of the ingredients.

The (meth)acrylic polymer usually contains an alkyl (meth)acrylate as a main component as a monomer unit. Furthermore, (meth)acrylate refers to acrylate and/or methacrylate, and (meth) has the same meaning in the present invention.

As the (meth)acrylic acid alkyl ester constituting the main skeleton of the (meth)acrylic polymer, a linear or branched alkyl group having 1 to 18 carbon atoms can be exemplified. For example, examples of the above-mentioned alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, Nonyl, decyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3-9.

As the monomers constituting the (meth)acrylic polymer, in addition to the above-mentioned (meth)acrylic acid alkyl esters, carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, (Meth) acrylates containing aromatic rings, etc.

The carboxyl group-containing single system contains a carboxyl group in its structure and contains a polymerizable unsaturated double bond such as a (meth)acryloyl group and a vinyl group. Specific examples of carboxyl group-containing monomers include, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, Butenoic acid and so on. Among the above-mentioned carboxyl group-containing monomers, acrylic acid is preferred from the viewpoints of copolymerization, price, and adhesive properties.

The hydroxyl-containing single system contains a hydroxyl group in its structure and contains a polymerizable unsaturated double bond such as a (meth)acryloyl group and a vinyl group. Specific examples of hydroxyl-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (methyl) )6-Hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylate Ester or methacrylic acid (4-hydroxymethylcyclohexyl) ester, etc. Among the above-mentioned hydroxyl-containing monomers, in terms of durability, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred, and (meth)acrylic acid 4 is particularly preferred. -Hydroxybutyl ester.

啉、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶等N-丙烯醯基雜環單體；N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺等含N-乙烯基之內醯胺系單體等。就滿足耐久性之方面而言，較佳為含醯胺基之單體，含醯胺基之單體中，就兼顧對透明導電層之耐久性及重工性方面而言，尤佳為含有N-乙烯基之內醯胺系單體。 A single system containing an amide group is a compound containing an amide group in its structure and a polymerizable unsaturated double bond such as a (meth)acrylic group and a vinyl group. Specific examples of monomers containing amide groups include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)propylene Amide, N-isopropylacrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-hydroxyl Methyl (meth)acrylamide, N-hydroxymethyl-N-propane (meth)acrylamide, aminomethyl (meth)acrylamide, aminoethyl (meth)acrylamide , Mercaptomethyl (meth)acrylamide, mercaptoethyl (meth)acrylamide and other acrylamide monomers; N-(meth)acrylamide

N-acryloyl heterocyclic monomers such as morpholine, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, etc.; N-vinylpyrrolidone, N-vinyl-ε -N-vinyl-containing lactam-based monomers such as caprolactam. In terms of satisfying durability, monomers containing amide groups are preferred. Among monomers containing amide groups, in terms of both durability and reworkability to the transparent conductive layer, it is particularly preferred to contain N -Vinyl internal amide monomers.

The above-mentioned aromatic ring-containing (meth)acrylate is a compound containing an aromatic ring structure and a (meth)acryloyl group in its structure. Examples of the aromatic ring include a benzene ring, a naphthalene ring, or a biphenyl ring. The aromatic ring-containing (meth)acrylate can satisfy the durability (especially the durability of the transparent conductive layer).

Specific examples of aromatic ring-containing (meth)acrylates include, for example, benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, (meth) Phenoxy acrylate, phenoxy ethyl (meth) acrylate, phenoxy propyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, modified with ethylene oxide Nonylphenol (meth)acrylate, cresol (meth)acrylate modified with ethylene oxide, (meth)acrylate modified with phenol ethylene oxide, (meth)acrylic acid 2- Hydroxy-3-phenoxypropyl ester, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, tolyl (meth)acrylate, polystyrene (meth)acrylate, etc. Those with a benzene ring; hydroxyethylated β-naphthol acrylate, 2-naphthylethyl (meth)acrylate, 2-naphthoxyethyl acrylate, 2-(4-methoxy) (meth)acrylate Those having a naphthalene ring such as -1-naphthyloxy) ethyl ester; those having a biphenyl ring such as biphenyl (meth)acrylate.

The above-mentioned carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, and aromatic ring-containing (meth)acrylates react with the crosslinking agent when the adhesive composition contains a crosslinking agent point. In particular, carboxyl group-containing monomers and hydroxyl group-containing monomers are highly reactive with intermolecular crosslinking agents, so they can be preferably used to improve the agglomeration or heat resistance of the obtained adhesive layer.

The (meth)acrylic polymer used in the present invention preferably contains the above-mentioned monomers as monomer units in the following amounts in the weight ratio of all constituent monomers (100% by weight).

The weight ratio of the above-mentioned alkyl (meth)acrylate may be the residue of monomers other than the alkyl (meth)acrylate, and specifically, it is preferably 70% by weight or more. In terms of ensuring adhesiveness, it is preferable to set the weight ratio of the alkyl (meth)acrylate to the above-mentioned range.

The weight ratio of the above-mentioned 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, still more preferably 0.05 to 1% by weight, and particularly preferably 0.05 ~0.5% by weight. If the weight ratio of the carboxyl group-containing monomer is less than 0.01% by weight, there is a tendency that durability and heavy workability cannot be balanced. On the other hand, when it exceeds 2% by weight, the transparent conductive layer may corrode, and there is a tendency that durability and heavy workability cannot be balanced.

The weight ratio of the hydroxyl-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, still more preferably 0.1 to 2% by weight, and particularly preferably 0.2 to 2% by weight. If the weight ratio of the hydroxyl-containing monomer is less than 0.01% by weight, the cross-linking of the adhesive layer is insufficient, and durability and reworkability cannot be balanced, or the adhesive characteristics tend not to be satisfied. On the other hand, when it exceeds 3% by weight, there is a tendency that durability and heavy workability cannot be balanced.

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, still more preferably 0.3 to 4% by weight, particularly preferably 0.7~2.5% by weight. If the weight ratio of the monomer containing an amide group is less than 0.1% by weight, there is a tendency that durability and reworkability of the transparent conductive layer cannot be balanced. On the other hand, if it exceeds 8% by weight, there is a tendency that durability and heavy workability cannot be satisfied.

The weight ratio of the aromatic ring-containing (meth)acrylate is preferably 25% by weight or less, more preferably 0-22% by weight, and still more preferably 0-18% by weight. If the weight ratio of the aromatic ring-containing (meth)acrylate exceeds 25% by weight, there is a tendency that durability and heavy workability cannot be satisfied at the same time.

In the above-mentioned (meth)acrylic polymer, in addition to the above-mentioned monomer units, there is no need to specifically contain other monomer units, but in order to improve the adhesion or to take into account heat resistance and heavy workability, it can also be introduced by copolymerization. One or more comonomers of polymerizable functional groups containing unsaturated double bonds, such as (meth)acrylic groups or vinyl groups.

Regarding the ratio of the above-mentioned comonomers in the (meth)acrylic polymer, in the weight ratio of all the constituent monomers (100% by weight) of the above-mentioned (meth)acrylic polymer, it is preferably 0-10% by weight % Is about, more preferably about 0 to 7% by weight, and still more preferably about 0 to 5% by weight.

The (meth)acrylic polymer of the present invention usually uses one having a weight average molecular weight of 1 million to 2.5 million. In consideration of durability, especially heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. If the weight average molecular weight is less than 1 million, it is not good in terms of heat resistance. In addition, if the weight average molecular weight is more than 2.5 million, the adhesive tends to become hard, and peeling becomes easy to occur. In addition, the weight average molecular weight (Mw)/number average molecular weight (Mn) representing the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8-7, and still more preferably 1.8-5. When the molecular weight distribution (Mw/Mn) exceeds 10, it is not good in terms of durability. In addition, the weight average molecular weight and the molecular weight distribution (Mw/Mn) are measured by GPC (Gel Permeation Chromatography), and are calculated from the values calculated in terms of polystyrene.

For the production of such a (meth)acrylic polymer, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. In addition, the obtained (meth)acrylic polymer may be any of random copolymers, block copolymers, graft copolymers, and the like.

In addition, in solution polymerization, as a polymerization solvent, for example, ethyl acetate, toluene, etc. are used. As a specific example of solution polymerization, the reaction is started by adding polymerization under a stream of inert gas such as nitrogen. The starting agent is usually carried out under the reaction conditions of about 5-30 hours at about 50-70°C.

The polymerization initiator, chain transfer agent, emulsifier, etc. used in radical polymerization are not particularly limited, and can be appropriately selected and used. Furthermore, the weight average molecular weight of the (meth)acrylic polymer can be controlled according to the usage amount of the polymerization initiator and the chain transfer agent, and the reaction conditions, and the usage amount can be appropriately adjusted according to the types.

As the polymerization initiator, for example, 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'-dimethylisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine) hydrate (trade name : VA-057, manufactured by Wako Pure Chemical Industries Co., Ltd.) and other azo-based initiators, persulfates such as potassium persulfate and ammonium persulfate, bis(2-ethylhexyl) peroxydicarbonate, peroxide Di(4-tertiary butylcyclohexyl) dicarbonate, di-second butyl peroxydicarbonate, tertiary butyl peroxyneodecanoate, tertiary hexyl peroxypivalate, pivalic acid peroxide Tertiary butyl ester, dilaurel peroxide, di-n-octyl peroxide, 1,1,3,3-tetramethylbutyl peroxide, 2-ethylhexanoic acid, di(4-methylbenzene) peroxide Formyl), dibenzyl peroxide, t-butyl peroxyisobutyrate, 1,1-bis(tert-hexyl peroxide) cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, etc. Peroxide-based initiator, combination of persulfate and sodium bisulfite, combination of peroxide and sodium ascorbate, etc. Redox initiator of peroxide and reducing agent, but not limited to Such.

The above-mentioned polymerization initiator can be used alone, or two or more of them can also be used in combination. The total content is preferably about 0.005 to 1 part by weight, more preferably about 0.02 to 0.5, relative to 100 parts by weight of the total monomer components. About parts by weight.

Furthermore, in order to use, for example, 2,2'-azobisisobutyronitrile as a polymerization initiator, to produce the above-mentioned (meth)acrylic polymer with a weight average molecular weight, the total weight of the monomer components is 100%. The amount of the polymerization initiator is preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight.

In addition, a chain transfer agent, an emulsifier, etc. can be suitably used conventionally known ones. These addition amounts can also be appropriately determined within a range that does not impair the effects of the present invention.

(2) Silane coupling agent containing thiol group

The present invention is characterized in that the adhesive composition contains a thiol group-containing silane coupling agent. Since the adhesive composition contains a thiol group-containing silane coupling agent, the durability of the adhesive layer formed by the adhesive composition can be improved, especially in a humidified environment, and it can take care of heavy work. sex. Furthermore, among the thiol group-containing silane coupling agents, oligomer type thiol group-containing silane coupling agents are particularly preferred. Here, the so-called oligomer type refers to a polymer having a monomer dimer or more and less than about 100 polymer. The weight average molecular weight of the oligomer type silane coupling agent is preferably about 300 to 30,000.

The oligomer type thiol group-containing silane coupling agent is preferably an oligomer type thiol group-containing silane coupling agent having two or more alkoxysilyl groups in the molecule. Specifically, for example, X-41-1805, X-41-1810, X-41-1818 manufactured by Shin-Etsu Chemical Co., Ltd. can be cited. These coupling agents are not easy to volatilize and have a plurality of alkoxysilyl groups, so they are more effective in improving durability and heavy workability, so they are preferred.

Examples of thiol group-containing silane coupling agents other than the oligomer type include 3-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and the like. Specifically, for example, KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd. can be cited.

The number of alkoxysilyl groups in the thiol group-containing silane coupling agent is not particularly limited, but it is preferably two or more in the molecule. In addition, the amount of the alkoxy group of the thiol group-containing silane coupling agent in the silane coupling agent is preferably 10-60% by weight, more preferably 20-50% by weight, and more preferably It is 20-40% by weight.

The type of alkoxy group is not particularly limited, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy. Among them, methoxy and ethoxy are preferred, and methoxy is more preferred. Furthermore, it is also preferable to contain both a methoxy group and an ethoxy group in one molecule.

The thiol group equivalent (mercapto equivalent) of the thiol group-containing silane coupling agent is preferably 1000 g/mol or less, more preferably 800 g/mol or less, more preferably 700 g/mol or less, and more preferably 500 g/mol or less. In addition, the lower limit of the thiol group equivalent is not particularly limited, and when the above-mentioned thiol group-containing silane coupling agent is an oligomer type, it is preferably 200 g/mol or more, for example.

The above-mentioned thiol group-containing silane coupling agent (especially oligomer type thiol group-containing silane coupling agent) can be used alone, or two or more of them can also be used in combination. Compared with the above-mentioned (meth)acrylic polymer 100 parts by weight, the total content is preferably 0.01-6 parts by weight, more preferably 0.01-3 parts by weight, and still more preferably 0.05-1 parts by weight. By containing the thiol group-containing silane coupling agent in the above range, the durability of the adhesive layer can be improved, especially in a humidified environment, with excellent durability and compatibility with heavy workability.

Furthermore, in the adhesive composition of the present invention, a silane coupling agent other than the above-mentioned thiol group-containing silane coupling agent may be added. Examples of other coupling agents include: 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxy Silane-N-(1,3-dimethylbutylene)propylamine, N-phenyl-γ-aminopropyltrimethoxysilane and other amino-containing silane coupling agents, 3-propenyloxypropyl Trimethoxysilane, 3-methacryloxypropyltriethoxysilane and other (meth)acrylic acid group-containing silane coupling agents, 3-isocyanatopropyltriethoxysilane, etc. Silane coupling agent of cyanate group, etc.

Silane coupling agents other than the above-mentioned thiol group-containing silane coupling agents can be used without impairing the effect of the present invention. It is added within the range of the fruit, and the addition amount is not particularly limited.

(3) Crosslinking agent

The adhesive composition used in the present invention preferably contains a crosslinking agent. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include isocyanate-based crosslinking agents, peroxide-based crosslinking agents, epoxy-based crosslinking agents, and imine-based crosslinking agents. The polyfunctional metal chelate is one in which a multivalent metal and an organic compound are covalently bonded or coordinately bonded. Examples of polyvalent metal atoms include: Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti Wait. Examples of the atoms in the covalently bonded or coordinately bonded organic compounds include oxygen atoms and the like, and examples of the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.

As the crosslinking agent, an isocyanate-based crosslinking agent and/or a peroxide-based crosslinking agent is preferred, and it is more preferred to use an isocyanate-based crosslinking agent and a peroxide-based crosslinking agent in combination.

As the isocyanate-based crosslinking agent, a compound having at least two isocyanate groups can be used. For example, well-known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc. used in the urethane reaction are generally used.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3 -Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

As the alicyclic polyisocyanate, for example, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diisocyanate Phenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, etc.

Examples of aromatic diisocyanates include benzene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl Methane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate Wait.

In addition, examples of the isocyanate-based crosslinking agent include: the above-mentioned diisocyanate polymers (dimers, trimers, pentamers, etc.), and carbamates formed by reacting with polyols such as trimethylolpropane Ester modified body, urea modified body, biuret modified body, allophanate modified body, isocyanurate modified body, carbodiimide modified body, etc.

Examples of commercially available products of isocyanate-based crosslinking agents include: "Millionate MT", "Millionate MTL", "Millionate MR-200", "Millionate MR-400", and "Millionate MT" manufactured by Nippon Polyurethane Industry Co., Ltd. Coronate L", "Coronate HL", "Coronate HX", brand names "Takenate D-110N", "Takenate D-120N", "Takenate D-140N", "Takenate D-160N" manufactured by Mitsui Chemicals Co., Ltd. , "Takenate D-165N", "Takenate D-170HN", "Takenate D-178N", "Takenate 500", "Takenate 600", etc. These compounds may be used individually by 1 type, and may mix and use 2 or more types.

The isocyanate-based crosslinking agent is preferably an aliphatic polyisocyanate and an aliphatic polyisocyanate-based compound of a modified product thereof. Compared with other isocyanate-based crosslinking agents, aliphatic polyisocyanate-based compounds are more flexible in their cross-linked structure, and are easy to relax the stress caused by the expansion/shrinkage of the optical film, and it is difficult to peel off in the durability test. As the aliphatic polyisocyanate compound, hexamethylene diisocyanate and its modified form are particularly preferred.

As a peroxide, as long as it is an active species that generates free radicals by heating or light irradiation, For cross-linking of the base polymer ((meth)acrylic polymer) of the adhesive composition, it can be used appropriately, but considering the workability or stability, it is preferable to use the one-minute half-life temperature of 80°C~ The peroxide at 160°C, it is more preferable to use the peroxide at 90°C~140°C.

Examples of peroxides that can be used include: bis(2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6°C), bis(4-tertiarybutylcyclohexyl) peroxydicarbonate Ester (1 minute half-life temperature: 92.1°C), di-second butyl peroxydicarbonate (1 minute half-life temperature: 92.4°C), tert-butyl peroxyneodecanoate (1 minute half-life temperature: 103.5°C), Tertiary hexyl pivalate oxide (1 minute half-life temperature: 109.1°C), tertiary pivalate peroxide (1 minute half-life temperature: 110.3°C), dilaurin peroxide (1 minute half-life temperature: 116.4°C) ), Di-n-octyl peroxide (1 minute half-life temperature: 117.4°C), Peroxy-2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl ester (1 minute half-life temperature: 124.3°C), Di(4-methylbenzyl peroxide) (1 minute half-life temperature: 128.2°C), dibenzoyl peroxide (1 minute half-life temperature: 130.0°C), tert-butyl peroxide isobutyrate (1 One-minute half-life temperature: 136.1°C), 1,1-bis(tertiary hexyl peroxide) cyclohexane (1-minute half-life temperature: 149.2°C), etc. Among them, since the crosslinking reaction efficiency is particularly excellent, it is preferable to use bis(4-tertiarybutylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1°C), dilaurin peroxide (1 minute half-life Temperature: 116.4°C), dibenzoyl peroxide (1 minute half-life temperature: 130.0°C), etc.

Furthermore, the half-life of peroxide is an indicator of the decomposition rate of peroxide, which is the time until the residual amount of peroxide becomes half. The decomposition temperature used to obtain the half-life in an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer’s catalog, for example, in the Nippon Oil & Fats Co., Ltd. "Organic Peroxide Catalog 9th Edition (May 2003) )"Wait.

The amount of crosslinking agent used relative to 100 parts by weight of the (meth)acrylic polymer is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, and still more preferably 0.03 to 1 parts by weight. Furthermore, if the crosslinking agent is less than 0.01 parts by weight, the crosslinking of the adhesive layer may become insufficient, and durability or adhesion characteristics may not be satisfied. On the other hand, if it is more than 3 parts by weight, adhesion may be seen The agent layer becomes too hard and the durability tends to decrease.

The above-mentioned isocyanate-based crosslinking agent may be used singly or in combination of two or more types. The total content is preferably 0.01 to 2 parts by weight relative to 100 parts by weight of the above-mentioned (meth)acrylic polymer. It is preferably 0.02 to 2 parts by weight, and more preferably 0.05 to 1.5 parts by weight. It can be appropriately contained in consideration of cohesive force, prevention of peeling in the durability test, etc.

The above-mentioned peroxide may be used alone or in combination of two or more. The total content is preferably 0.01 to 2 parts by weight, more preferably, relative to 100 parts by weight of the (meth)acrylic polymer 0.04 to 1.5 parts by weight, more preferably 0.05 to 1 part by weight. In order to adjust processability, crosslinking stability, etc., an appropriate selection is made within this range.

(4) Ionic compounds

The adhesive composition of the present invention may further contain an ionic compound. The ionic compound is not particularly limited, and users in the field can be preferably used. For example, the ionic compounds described in Japanese Patent Laid-Open No. 2015-4861 can be cited. Among them, (perfluoroalkylsulfonyl) iminium lithium salt is preferred, and bis(trifluoromethyl) is more preferred. Sulfonylimide) lithium. In addition, the ratio of the above-mentioned ionic compound is not particularly limited, and can be set in a range that does not impair the effect of the present invention. For example, relative to 100 parts by weight of the above-mentioned (meth)acrylic polymer, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 1 part by weight or less.

(5) Other

In the adhesive composition used in the present invention, a polyether compound having a reactive silyl group can be formulated. The polyether compound is preferable in terms of being able to improve heavy workability. Polyether compound For example, the one disclosed in Japanese Patent Laid-Open No. 2010-275522 can be used. Moreover, as the addition amount, it can determine suitably in the range which does not impair the effect of this invention.

Furthermore, the adhesive composition used in the present invention may also contain other well-known additives. For example, powders such as polyether compounds of polyalkylene glycols such as polypropylene glycol, colorants, pigments, etc. may be appropriately added according to the application. , Dyes, surfactants, plasticizers, adhesion imparting agents, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic Fillers, metal powders, particles, foils, etc. In addition, an oxidation-reduction system with a reducing agent can also be used within a controllable range. These additives are preferably used within a range of 5 parts by weight or less, further 3 parts by weight or less, and further 1 part by weight or less with respect to 100 parts by weight of the (meth)acrylic polymer.

2. Adhesive layer for transparent conductive layer

The adhesive layer for a transparent conductive layer of the present invention is formed of the above-mentioned adhesive composition. When forming the adhesive layer, it is preferable to adjust the total amount of crosslinking agent added, and to fully consider the effect of the crosslinking treatment temperature or the crosslinking treatment time.

The cross-linking treatment temperature and cross-linking treatment time can be adjusted according to the cross-linking agent used. The crosslinking treatment temperature is preferably 170°C or lower. In addition, the cross-linking treatment can be carried out at the temperature during the drying step of the adhesive layer, or it can be carried out by additionally providing a cross-linking treatment step after the drying step. In addition, the crosslinking treatment time can be set in consideration of productivity or workability, and is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.

The method for forming the adhesive layer is not particularly limited, and may be the following method: coating the adhesive composition on various substrates, drying by a dryer such as a hot oven to volatilize solvents, etc., and if necessary The above-mentioned cross-linking treatment forms an adhesive layer, and the adhesive layer is transferred to the following polarizing film or transparent conductive substrate; it can also be applied to the above-mentioned polarizing film or transparent conductive substrate The above-mentioned adhesive composition is directly coated on it to form an adhesive layer. In the present invention, the following method is preferred: prefabricating a polarizing film with an adhesive layer formed on the polarizing film, and attaching the polarizing film with the adhesive layer to the liquid crystal cell.

It does not specifically limit as said base material, For example, various base materials, such as a release film, a transparent resin film base material, and the following polarizing film, are mentioned.

As a method of applying the adhesive composition to the above-mentioned substrate or polarizing film, various methods can be used. Specifically, for example, spray coating, roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dipping roll coating, bar coating, knife coating, air knife coating, curtain coating Methods such as type coating, die lip coating, extrusion coating using die nozzle coater, etc.

The drying conditions (temperature, time) are not particularly limited, and can be appropriately set according to the composition, concentration, etc. of the adhesive composition, for example, about 80 to 200°C, preferably 90 to 170°C, and 1 to 60 minutes, Preferably it is 2 to 30 minutes.

In addition, after drying, cross-linking treatment may be performed as necessary, and the conditions are as described above.

The thickness of the adhesive layer (after drying) is, for example, preferably 5-100 μm, more preferably 7-70 μm, and still more preferably 10-50 μm. If the thickness of the adhesive layer is less than 5μm, the adhesion to the adherend is insufficient, and the durability under humidified conditions tends to be insufficient. On the other hand, when the thickness of the adhesive layer exceeds 100 μm, there is a tendency that when the adhesive composition is applied and dried when the adhesive layer is formed, it cannot be dried sufficiently and air bubbles remain, or the adhesive Uneven thickness occurs on the surface of the layer, and the appearance of the problem is easy to become obvious.

Examples of the constituent materials of the above-mentioned release film include: resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabrics, nets, and hair A resin film can be preferably used for suitable sheet objects, such as foam sheets, metal foils, and laminates thereof, in terms of excellent surface smoothness.

Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, and polyterephthalic acid. Ethylene glycol film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the above-mentioned release film is usually 5 to 200 μm, preferably about 5 to 100 μm. For the above-mentioned mold release film, if necessary, mold release and antifouling treatment, or coating using silicone, fluorine, long-chain alkyl, or fatty acid amide-based mold release agents, silicon dioxide powder, etc., can also be carried out. Antistatic treatment for cloth type, kneading type, vapor deposition type, etc. In particular, by appropriately performing peeling treatments such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., on the surface of the release film, the releasability from the adhesive layer can be further improved.

The transparent resin film base material is not particularly limited, and various resin films having transparency can be used. The resin film is formed of a single-layer film. For example, the materials include: polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether turpentine resins, polycarbonate resins, and polyamides. Amine resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, Polyarylate resin, polyphenylene sulfide resin, etc. Among them, polyester-based resins, polyimide-based resins, and polyether-based resins are particularly preferred.

The thickness of the film substrate is preferably 15 to 200 μm.

3. Polarizing film with adhesive layer

The polarizing film with an adhesive layer of the present invention has the above-mentioned adhesive layer on at least one side of the polarizing film. The polarizing film with an adhesive layer of the present invention is used by bonding the adhesive layer of the polarizing film in contact with the transparent conductive layer of the transparent conductive substrate having a transparent conductive layer on the transparent substrate.

The method of forming the adhesive layer is as described above.

The polarizing film is not particularly limited, and it is usually used for a polarizing element having a transparent protective film on one or both sides.

The polarizing element is not particularly limited, and various polarizing elements can be used. As the polarizing element, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymer-based partially saponified film, and the like can adsorb iodine or a dichroic dye. Dichroic material and uniaxially stretched; polyene-based alignment films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among these, a polarizing element containing a dichroic substance such as a polyvinyl alcohol-based film and iodine is preferable, and an iodine-based polarizing element containing iodine and/or iodine ions is more preferable. In addition, the thickness of these polarizing elements is not particularly limited, and is usually about 5 to 80 μm.

A polarizing element formed by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretched can be fabricated, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine for dyeing, and extending to 3~ of the original length. 7 times. It can also be immersed in an aqueous solution of boric acid, potassium iodide, etc., which may contain zinc sulfate, zinc chloride, etc., if necessary. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the contamination on the surface of the polyvinyl alcohol-based film or the anti-blocking agent can be washed away. In addition, by swelling the polyvinyl alcohol-based film, it can also prevent uneven dyeing. Effect. Stretching can be carried out after dyeing with iodine, or it can be stretched while dyeing, and it can be stretched even in aqueous solutions or water baths such as boric acid or potassium iodide.

Furthermore, in the present invention, a thin polarizing element having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin-type polarizing element is preferable in that the thickness unevenness is small, the visibility is excellent, and the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

Representative examples of the thin polarizing element include: Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, or Japanese Patent No. 4751481, A thin polarizing film described in Japanese Patent Laid-Open No. 2012-073563. These thin polarizing films can be obtained by the following manufacturing method, which includes stretching the polyvinyl alcohol-based resin (hereinafter, also referred to as PVA-based resin) layer and the resin substrate for stretching in the state of a laminate The steps and the steps for dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be stretched without defects such as breakage due to stretching by being supported by the resin base material for stretching.

As the above-mentioned thin polarizing film, in the manufacturing method including the step of stretching in the state of a laminate and the step of dyeing, it can also be stretched at a high magnification to improve the polarization performance, preferably as International Publication No. 2010 /100917, or Japanese Patent No. 4751481, Japanese Patent Laid-Open No. 2012-073563, which is obtained by the method of preparation including a step of extending in an aqueous solution of boric acid, and Japanese Patent No. 4751481 is particularly preferred. Or, it is obtained by a manufacturing method described in Japanese Patent Laid-Open No. 2012-073563 by including a step of auxiliaryly performing aerial stretching before stretching in a boric acid aqueous solution.

烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂、及該等之混合物。再者，於偏光元件之單側，藉由接著劑層而貼合透明保護膜， 於另一單側，作為透明保護膜，能夠使用(甲基)丙烯酸系、胺基甲酸酯系、丙烯酸胺基甲酸酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂。於透明保護膜中亦可含有1種以上之任意適當之添加劑。作為添加劑，例如可列舉：紫外線吸收劑、防氧化劑、潤滑劑、塑化劑、脫模劑、防著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護膜中之上述熱塑性樹脂之含量較佳為50~100重量%，更佳為50~99重量%，進而較佳為60~98重量%，尤佳為70~97重量%。於透明保護膜中之上述熱塑性樹脂之含量為50重量%以下之情形時，有無法充分表現熱塑性樹脂原本所具有之高透明性等之虞。 As a material for forming a transparent protective film provided on one side or both sides of the above-mentioned polarizing element, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. can be used. Specific examples of such thermoplastic resins include cellulosic resins such as triacetyl cellulose, polyester resins, polyether resins, polycarbonate resins, polycarbonate resins, polyamide resins, and polyimide resins. , Polyolefin resin, (meth)acrylic resin, cyclic polyolefin resin

Olefin resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. Furthermore, on one side of the polarizing element, a transparent protective film is attached via an adhesive layer, and on the other side, as the transparent protective film, (meth)acrylic, urethane, or acrylic can be used. Thermosetting resins such as urethane-based, epoxy-based, and silicone-based resins or UV-curing resins. The transparent protective film may also contain one or more arbitrary appropriate additives. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the above-mentioned thermoplastic resin in the transparent protective film is preferably 50-100% by weight, more preferably 50-99% by weight, still more preferably 60-98% by weight, and particularly preferably 70-97% by weight. When the content of the above-mentioned thermoplastic resin in the transparent protective film is 50% by weight or less, there is a possibility that the high transparency originally possessed by the thermoplastic resin cannot be sufficiently expressed.

The thickness of the transparent protective film can be appropriately determined, but in terms of workability such as strength and handling properties, and film properties, it is usually about 1 to 500 μm.

The above-mentioned polarizing element and the transparent protective film are usually in close contact with each other via a water-based adhesive or the like. Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, ethylene-based latex-based adhesives, water-based polyurethanes, water-based polyesters, and the like. In addition to the above, examples of the adhesive between the polarizing element and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for electron beam hardening type polarizing film shows good adhesiveness to the above-mentioned various transparent protective films. In addition, the adhesive used in the present invention may contain a metal compound filler.

Moreover, in the present invention, a transparent protective film, such as a retardation film, instead of the polarizing film may be formed on the polarizing element. In addition, another transparent protective film or a retardation film may be further provided on the transparent protective film.

It is also possible to apply a hard coating or anti-reflection treatment, anti-sticking treatment, treatment for the purpose of diffusion or anti-glare on the surface of the transparent protective film that is not attached to the polarizing element.

In addition, there may be an adhesion promoting layer between the polarizing film and the adhesive layer. The material for forming the adhesion-promoting layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Among these, it is particularly preferable to use polymers. The use form of the above-mentioned polymers may be any form of a solvent-soluble type, a water-dispersed type, and a water-soluble type.

Examples of the above-mentioned polymers include: polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, and polyvinylpyrrolidone , Polystyrene resin, etc. In addition, among the above-mentioned polymers, conductive polymers such as polythiophene, which can be used as a material for forming the organic conductive layer described below, can be used.

In addition, when the adhesive layer of the polarizing film with the adhesive layer is exposed, a release film (isolation film) can also be used to protect the adhesive layer before being used. Examples of the release film include those described above. In the case of using a release film as a substrate when making the above-mentioned adhesive layer, by bonding the adhesive layer on the release film with the polarizing film, the release film can be used as the adhesion of the polarizing film with the adhesive layer The release film of the agent layer can be used to simplify the steps.

The polarizing film with the adhesive layer of the present invention is used by bonding the transparent conductive layer of the transparent conductive substrate with the transparent conductive layer on the transparent substrate.

The constituent material of the transparent conductive layer as a transparent conductive substrate is not particularly limited. It can be selected from indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, and palladium. , A metal oxide of at least one metal in the group consisting of tungsten. The metal oxide may further contain metal atoms shown in the above group as necessary. For example, it is preferable to use indium oxide (ITO) containing tin oxide, tin oxide containing antimony, etc., and ITO is particularly preferable. As ITO, it is preferable to contain 80-99 weight% of indium oxide and 1-20 weight% of tin oxide.

In addition, as the above-mentioned ITO, crystalline ITO and amorphous (amorphous) ITO can be cited, and both are suitably used.

Examples of the transparent conductive layer of the transparent conductive substrate include a metal mesh formed by forming thin metal wires into a grid pattern, or one formed by coating metal fine particles. As the constituent metal material, any appropriate metal (including alloy substances) can be used as long as it is a metal with high conductivity. Specifically, for example, one or more metals selected from the group consisting of gold, platinum, silver, aluminum, and copper are preferable, and from the viewpoint of conductivity, aluminum, silver, copper, or gold is preferable. .

The transparent conductive layer of the transparent conductive substrate can be formed of an organic conductive film. The material for forming the organic conductive film is not particularly limited. Examples include conductive polymers, ion conductive compositions containing electrolyte salts and organopolysiloxanes, ionic compounds, and various surfactants (cationic, anionic, etc.). And amphoteric surfactants) and so on. Among them, in terms of optical properties, appearance, antistatic effect, and stability of the antistatic effect when heated and humidified, it is preferable to use a conductive polymer. It is particularly preferable to use conductive polymers such as polyaniline and polythiophene. These conductive polymers can be water-soluble, water-dispersible, organic solvent-soluble, or organic solvent-dispersible. For water-soluble conductive polymers or water-dispersible conductive polymers, they can form an antistatic layer. The coating liquid of the time is prepared as an aqueous solution or a water dispersion liquid. The coating liquid does not need to use a non-aqueous organic solvent, and can prevent the deterioration of the transparent substrate caused by the organic solvent. In addition, the aqueous solution or aqueous dispersion may contain an aqueous solvent in addition to water. Examples include: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, tertiary butanol, n-pentanol, isoamyl alcohol, second pentanol, third pentanol Alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols.

In addition, it is preferable that the water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline and polythiophene has a hydrophilic functional group in the molecule. As the hydrophilic functional group, for example, a sulfo group, an amino group, an amide group, an imino group, a quaternary ammonium salt group, a hydroxyl group, a mercapto group, a hydrazine group, a carboxyl group, a sulfate group, a phosphate group, or the like The salt and so on. Due to the hydrophilic function in the molecule The water-soluble conductive polymer or the water-dispersible conductive polymer can be easily prepared by easily dissolving in water and dispersing in the form of fine particles in water.

As an example of a commercially available product of the water-soluble conductive polymer, polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight calculated by polystyrene conversion is 150,000) and the like can be cited. As an example of a commercially available product of a water-dispersible conductive polymer, a polythiophene-based conductive polymer (manufactured by Nagase Chemtex, trade name Denatron series) and the like can be cited.

唑啉基之聚合物、聚胺基甲酸酯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚醚系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、環氧樹脂、聚乙烯吡咯啶酮、聚苯乙烯系樹脂、聚乙二醇、季戊四醇等。尤佳為聚胺基甲酸酯系樹脂、聚酯系樹脂、丙烯酸系樹脂。該等黏合劑可根據其用途適當地使用1種或2種以上。 In addition, in order to improve the film forming properties of the conductive polymer, the adhesion to the transparent substrate, and the like, the conductive polymer may be added with a binder component. When the conductive polymer is a water-based material of a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. As an example of the adhesive, include:

Oxazoline-based polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone , Polystyrene resin, polyethylene glycol, pentaerythritol, etc. Particularly preferred are polyurethane resins, polyester resins, and acrylic resins. These binders can be used in one type or two or more types as appropriate according to the use.

Although the amount of conductive polymer and adhesive used depends on the type, it is preferable to make the surface resistance of the transparent conductive film 1×10 ⁸ ~1×10 ¹² Ω/□ Take control.

Furthermore, the organic conductive layer used in the present invention may also contain other well-known additives. For example, powders such as colorants and pigments, dyes, surfactants, plasticizers, and adhesion imparting agents can be appropriately added according to the application. , Surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, granules, foils, etc.

In addition, the organic conductive film can also be formed on a transparent substrate by forming a monomer of conductive polymer It is formed by electrolytic polymerization.

The thickness of the transparent conductive layer is not particularly limited, but is preferably 10 nm to 1000 nm, more preferably 50 to 400 nm.

The method for forming the above-mentioned transparent conductive layer is not particularly limited, and a conventionally known method can be used. Specifically, for example, a vacuum vapor deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, in the case of applying the coating liquid, for example, a microgravure coating method, a roll coating method, a dip coating method, a flow coating method, a spin coating method, a die coating method, a casting transfer method, and a spray coating method can be cited. Wait. In the case of a metal mesh, it can be obtained, for example, by applying a photosensitive composition containing silver salt (composition for forming a transparent conductive layer) on an adherend such as a release film, and then exposing it. Processing and development processing, forming thin metal wires into specific patterns. In addition, the transparent conductive layer can also be obtained by printing a paste containing metal fine particles (composition for forming a transparent conductive layer) in a specific pattern. In addition, an appropriate method can also be adopted according to the required film thickness.

In addition, an overcoat (OC) layer (not shown) may also be provided on the above-mentioned transparent conductive layer. As the overcoat layer, the overcoat layer generally used in this field can be used without particular limitation. For example, it can be made of alkyd resin, acrylic resin, epoxy resin, polyurethane resin, isocyanate resin, etc. Floor. The thickness of the overcoat layer is not particularly limited, but for example, it is preferably 0.1 to 10 μm.

The transparent substrate may be a transparent substrate, and the material is not particularly limited, and examples thereof include glass and transparent resin film substrates. Examples of the transparent resin film substrate include those described above.

In addition, a primer layer, an oligomer prevention layer, etc. may be provided between the transparent conductive layer and the transparent substrate as needed.

4. Image display panel, image display device

The image display panel of the present invention is characterized by having the polarizing film with the adhesive layer, And a transparent conductive substrate with a transparent conductive layer on the transparent substrate, and The adhesive layer of the polarizing film with the adhesive layer is attached to the transparent conductive layer of the image display panel.

Furthermore, the image display device of the present invention is characterized by having the above-mentioned image display panel.

The polarizing film with the adhesive layer and the transparent conductive substrate are as described above. The image display panel has the above-mentioned transparent conductive substrate and forms a part of the image display device together with the above-mentioned polarizing film with adhesive.

The liquid crystal panel as a representative embodiment of the image display panel to which the polarizing film with the adhesive layer of the present invention is applied will be described. The liquid crystal cell used in the liquid crystal panel has a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and the transparent conductive substrate is usually provided on the surface of the visible side of the liquid crystal cell. Using FIG. 1, a liquid crystal panel including a liquid crystal cell that can be used in the present invention will be described. However, the present invention is not limited by FIG. 1.

As an embodiment of the liquid crystal panel 1 that can be included in the image display panel of the present invention, a transparent protective film on the visible side 2/polarizing element 3/transparent protective film on the liquid crystal cell side 4/adhesive layer is included from the visible side. 5/Transparent conductive 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/Polarizing element 12/Light source side transparent protective film 13. In FIG. 1, the polarizing film with the adhesive layer of the present invention corresponds to the visible side transparent protective film 2 / polarizing element 3 / liquid crystal cell side transparent protective film 4 / adhesive layer 5. In addition, in FIG. 1, the transparent conductive substrate used in the present invention is composed of a transparent conductive layer 6/transparent substrate 7. In addition, in FIG. 1, the liquid crystal cell equipped with the transparent conductive substrate used in the present invention is composed of a transparent conductive layer 6/transparent substrate 7/liquid crystal layer 8/transparent substrate 9.

Furthermore, in addition to the above-mentioned structure, optical films, such as a retardation film, a viewing angle compensation film, and a brightness improvement film, can also be suitably provided in the liquid crystal panel 1.

The liquid crystal layer 8 is not particularly limited. For example, any type such as TN type, STN type, π type, VA type, and IPS type can be used. The transparent substrate 9 (light source side) may be a transparent substrate, and its material is not particularly limited, and examples thereof include glass and transparent resin film substrates. Examples of the transparent resin film substrate include those described above.

In addition, the adhesive layer 10 on the light source side, the transparent protective film 11 on the liquid crystal cell side, the polarizing element 12, and the transparent protective film 13 on the light source side can be used by users in the field. By.

The above-mentioned liquid crystal panel 1 is characterized in that the transparent conductive layer 6 of the liquid crystal cell is in contact with the adhesive layer 5 of the polarizing film with the adhesive layer, and the polarizing film with the adhesive layer of the present invention is laminated on the liquid crystal cell. On the outermost transparent conductive layer 6 on the visible side.

The image display device of the present invention may be an image display panel including a polarizing film provided with the adhesive layer of the present invention and a transparent conductive substrate with a transparent conductive layer on the transparent substrate, and preferably includes The above-mentioned liquid crystal panel. Hereinafter, as an example, a liquid crystal display device will be described, but the present invention is not limited thereto.

Specific examples of image display devices to which the above-mentioned image display panel can be applied include: liquid crystal display devices, electroluminescence (EL) displays, plasma displays (PD), field emission displays (FED: Field Emission Display), etc. .

The image display device of the present invention only needs to be an image display panel including a polarizing film provided with the adhesive layer of the present invention and a transparent conductive substrate with a transparent conductive layer on the transparent substrate. Other configurations are the same as those in the previous The image display device is the same.

[Example]

Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited by these examples. Furthermore, all room temperature storage conditions without special regulations are 23°C and 65% R.H.

<Measurement of the weight average molecular weight of (meth)acrylic polymers>

The weight average molecular weight (Mw) of the (meth)acrylic polymer is measured by GPC (Gel Permeation Chromatography). Mw/Mn is also measured in the same way.

‧Analysis device: HLC-8120GPC, manufactured by Tosoh Co., Ltd.

‧Tube column: G7000HXL+GMHXL+GMHXL, manufactured by Tosoh Co., Ltd.

×30cm共計90cm ‧Pipe size: 7.8mm each

×30cm 90cm in total

‧Column temperature: 40℃

‧Flow rate: 0.8mL/min

‧Injection volume: 100μL

‧Lluent: Tetrahydrofuran

‧Detector: Differential Refractometer (RI)

‧Standard sample: Polystyrene

Production Example 1 (Production of Polarizing Film)

A polyvinyl alcohol film with a thickness of 80μm was dyed in an iodine solution with a concentration of 0.3% by weight at 30°C for 1 minute, and then stretched to 3 times between rollers with different speed ratios. Then, in an aqueous solution containing boric acid at a concentration of 4% by weight and potassium iodide at a concentration of 10% by weight at 60° C., the surface was immersed for 0.5 minutes while extending to a total extension ratio of 6 times. Next, after washing by immersing in an aqueous solution containing 1.5% by weight of potassium iodide at 30°C for 10 seconds, drying was performed at 50°C for 4 minutes to obtain a polarizing element with a thickness of 30 μm. A polyvinyl alcohol-based adhesive is used to bond a saponified triacetic cellulose film with a thickness of 80 μm on both sides of the polarizing element to produce a polarizing film.

Production Example 2 (Adjustment 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 added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. Enter And, with respect to 100 parts by weight of the above-mentioned monomer mixture (solid content), 0.1 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator is added together with 100 parts by weight of ethyl acetate. While stirring while introducing nitrogen and performing nitrogen replacement, the temperature of the liquid in the flask was maintained at around 55°C, and the polymerization reaction was performed for 8 hours to prepare acrylic polymer (a) with a weight average molecular weight (Mw) of 1.56 million and Mw/Mn 3.2 -1) The solution.

Manufacturing example 3~5

In Production Example 2, as shown in Table 1, the types of monomers used to prepare the acrylic polymer and their usage ratios were changed. Except for this, the acrylic polymer (a- 2) The solution of (a-4).

The abbreviations in Table 1 are as follows.

BA: Butyl acrylate

NVP: N-vinyl-2-pyrrolidone

AA: Acrylic

HBA: 4-hydroxybutyl acrylate

Example 1

(Preparation of acrylic adhesive composition)

With respect to 100 parts by weight of the solid content of the acrylic polymer (a-1) solution obtained in Production Example 2, an isocyanate crosslinking agent (trade name: Takenate D160N, trimethylol Propane hexamethylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd., 0.1 part, benzoyl peroxide (Nyper BMT 40SV, manufactured by Nippon Oil & Fat Co., Ltd.) 0.3 part, and 3-mercaptopropyl trimethoxysilane (commodity Name: KBM-803, amount of alkoxy group: 47% by weight, equivalent of thiol group: 196 g/mol, 0.3 part of Shin-Etsu Chemical Industry Co., Ltd.), to prepare a solution of acrylic adhesive composition.

(Making of polarizing film with adhesive layer)

Apply a solution of the acrylic adhesive composition to a polyethylene terephthalate film treated with a silicone release agent (separation film, trade name: One side of MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., was dried at 155°C for 1 minute to form an adhesive layer on the surface of the isolation film. Next, the adhesive layer formed on the isolation film was transferred to the polarizing film produced in Production Example 1 to produce an adhesive layer-attached polarizing film.

Examples 2~13, Comparative Examples 1~5

In Example 1, as shown in Table 2, the type of acrylic polymer, the type of silane coupling agent, and the amount of addition thereof were changed as shown in Table 2. Except for this, an acrylic adhesive combination was prepared by the same method as in Example 1.物的Solution. Furthermore, in Example 12, the ionic compound was blended at the ratio shown in Table 2. Using the obtained acrylic adhesive composition solution, the adhesive layer-attached polarizing film was produced by the same method as in Example 1.

The following evaluations were performed on the polarizing films with adhesive layers obtained in the above-mentioned Examples and Comparative Examples. The evaluation results are shown in Table 2.

<Preparation of Evaluation Samples>

The polarizing film with the adhesive layer obtained in the Examples and Comparative Examples was cut into 15 inches, and the obtained was used as a sample. The sample was attached to glass with a transparent conductive layer. As attached transparency Conductive layer of glass, used on alkali-free glass (trade name: EG-XG, manufactured by Corning) with a thickness of 0.7mm, glass with ITO layer with amorphous ITO layer, and on the same alkali-free glass as above Glass with organic conductive film with organic conductive film. Use a laminator to stick the above samples on the ITO layer of the glass with ITO layer and the organic conductive film of the glass with organic conductive film. Next, autoclave treatment was carried out at 50°C and 0.5 MPa for 15 minutes, so that the above samples were completely adhered to the glass with ITO layer and the glass with organic conductive film, respectively.

Furthermore, the ITO layer is formed by sputtering. In the composition of ITO, the Sn ratio is 3% by weight, and a heating step of 140°C×60 minutes is performed before bonding the samples. Furthermore, the Sn ratio of ITO is calculated from the weight of Sn atoms/(the weight of Sn atoms + the weight of In atoms). The organic conductive film uses polyethylenedioxythiophene. The coating liquid of polyvinyl sulfonate is formed by spin coating.

<Durability test immediately after coating>

After performing the treatment for 500 hours in each atmosphere of 60°C/95%RH (humidification test) on the samples that have undergone this treatment, visually evaluate the polarization between the polarizing film and the glass with ITO layer and the polarization according to the following criteria The appearance between the film and the glass with organic conductive film.

(Evaluation criteria)

◎: There is no change in appearance such as peeling.

○: The edges are slightly peeled, but there is no practical problem.

△: There is peeling at the end, but there is no practical problem as long as it is not used for special purposes.

×: There is significant peeling at the end, and there is a practical problem.

<Adhesive force>

The polarizing film with the adhesive layer obtained in the Examples and Comparative Examples was cut into a width of 25 mm, and the obtained was used as an evaluation sample. Except for this, the same operation as in the above <Preparation of Evaluation Sample> was used to paste Suitable for glass with transparent conductive layer (both of glass with ITO layer and organic conductive film Glass), perform the same treatment to make the polarizing film with the adhesive layer completely adhere to the glass with the transparent conductive layer (initial stage).

Then, heat treatment (after heating) was performed under drying conditions of 60°C for 48 hours. Measure the adhesive force of the above sample. The adhesive force was determined by measuring the adhesive force (N/25mm) when the sample was peeled off using a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. In the measurement, samples were taken at intervals of 1 time/0.5 second, and the average value was used as the measurement value.

<Heavy workability>

The polarizing film with the adhesive layer obtained in the Examples and Comparative Examples was cut into a length of 350 mm × a width of 250 mm, and the obtained was used as an evaluation sample. Other than that, the same treatment as the measurement target of the adhesive force was performed. The sample was peeled from the glass with a transparent conductive layer by hand, and the reworkability was evaluated based on the following criteria. The evaluation of heavy workability was carried out 3 times in accordance with the above procedure.

⊚: There is no paste residue or film breakage in all 3 sheets, and it can be peeled off well.

○: Film breakage occurred in one part of 3 sheets, but peeled off by peeling again.

△: Film breakage occurred in all 3 sheets, but peeled off by peeling again.

×: The paste remained in all 3 sheets, or the peeling film was broken several times and it could not be peeled off.

The abbreviations in Table 2 are as follows.

Isocyanate series: Trade name: Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd.; Peroxide series: Trade name: Nyper BMT 40SV, Benzyl peroxide, Nippon Oil & Fat Co., Ltd. Manufactured by the company; KBM-803: 3-mercaptopropyltrimethoxysilane, alkoxy content: 47% by weight, thiol equivalent: 196g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.; X-41-1805: low Polymer type thiol group-containing silane coupling agent, alkoxy content: 50% by weight, thiol group equivalent: 800g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.; X-41-1818: oligomer type sulfur-containing Alcohol-based silane coupling agent, alkoxy content: 60% by weight, thiol equivalent: 850g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.; X-41-1810: oligomer type thiol-containing silane coupling Mixture, alkoxy content: 30% by weight, thiol equivalent: 450g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-403: γ-glycidoxypropylmethoxysilane, alkoxy content: 39% by weight, manufactured by Shin-Etsu Chemical Co., Ltd.; X-41-1056: oligomer type epoxy-containing silane coupling agent, alkoxy content: 17% by weight, epoxy equivalent: 280g/mol, Shin-Etsu Chemical Manufactured by Industrial Co., Ltd.; Ionic compound: Lithium bis(trifluoromethanesulfonylimide), manufactured by Mitsubishi Materials Co., Ltd.

Claims (6)

A polarizing film with an adhesive layer, characterized in that: it has an adhesive layer and a polarizing film, and the adhesive layer is attached to the transparent conductive substrate of the transparent conductive substrate with a transparent conductive layer. The adhesive composition used to form the above-mentioned adhesive layer contains a (meth)acrylic polymer and a thiol group-containing silane coupling agent, and the above-mentioned thiol group-containing silane coupling agent is an oligomer type A thiol group-containing silane coupling agent, and the thiol group equivalent of the above-mentioned thiol group-containing silane coupling agent is 700g/mol or less, as a comonomer of acrylic polymer, containing monomers containing amide groups and/ Or carboxyl-containing monomers, and then use hydroxyl-containing monomers. According to claim 1, the polarizing film with an adhesive layer, wherein the above-mentioned thiol group-containing silane coupling agent has two or more alkoxysilyl groups in the molecule. The polarizing film with an adhesive layer of claim 1, wherein the blending amount of the thiol group-containing silane coupling agent is 0.01 to 3 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. The polarizing film with an adhesive layer according to any one of claims 1 to 3, wherein the transparent conductive layer is an organic conductive film. An image display panel, which is characterized by: The polarizing film of the adhesive layer and the transparent conductive substrate with a transparent conductive layer on the transparent substrate, and the adhesive layer of the polarizing film with the adhesive layer is attached to the transparent conductive layer of the image display panel. An image display device characterized by having an image display panel as claimed in claim 5.

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