WO2022059609A1 - Pressure-sensitive-adhesive polarizing film, and laminate for image display device - Google Patents

Abstract

Provided is a pressure-sensitive-adhesive polarizing film whereby an increase in the surface resistivity of a pressure-sensitive-adhesive layer in a high-temperature environment can be suppressed.　Through the present invention, there is provided a pressure-sensitive-adhesive polarizing film constituted by layering a pressure-sensitive-adhesive layer and a polarizing film, wherein the pressure-sensitive-adhesive layer is formed from a pressure-sensitive-adhesive composition containing a pressure-sensitive adhesive and an electroconductive polymer, and the storage modulus (G') at 80°C of the pressure-sensitive-adhesive layer is 20-1000 kPa.

Description

Adhesive polarizing film and laminate for image display device

The present invention relates to an adhesive polarizing film and a laminate for an image display device.

The image display member as disclosed in Patent Document 1 is composed of a plurality of members, and conventionally, an adhesive (adhesive layer) has been used for bonding each member.

International Publication No. 2014/042248

In the image display member, an image display abnormality due to the accumulation of static electricity in various members has become an issue, and in order to prevent the accumulation of static electricity, it is required that the adhesive for adhering the image display member has a low resistance value. There is. As a method of lowering the resistance value of the pressure-sensitive adhesive (pressure-sensitive adhesive layer), there is a method of blending a conductive material such as a conductive polymer with the pressure-sensitive adhesive.

The image display member may be exposed to a high temperature or high temperature / high humidity environment, and in the above environment, the members constituting the image display member shrink. When the pressure-sensitive adhesive layer used for bonding the members also shrinks with the shrinkage of the members, there is a problem that the arrangement of the conductive polymer in the pressure-sensitive adhesive layer is broken and the surface resistivity of the pressure-sensitive adhesive layer increases. ..

The present invention has been made in view of such circumstances, and provides an adhesive polarizing film capable of suppressing an increase in the surface resistivity of the adhesive layer in a high temperature environment.

According to the present invention, in an adhesive polarizing film composed of a pressure-sensitive adhesive layer and a polarizing film laminated, the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive and a conductive polymer. Provided is an adhesive polarizing film having a storage elasticity (G') of the pressure-sensitive adhesive layer at 80 ° C. of 20 to 1000 kPa.

In the adhesive polarizing film of the present invention, the adhesive layer has a relatively high storage elastic modulus even in a high temperature environment of 80 ° C. Therefore, even when the polarizing film tries to shrink due to heat, the adhesive layer Shrinkage is suppressed, and as a result, an increase in surface modulus due to shrinkage of the pressure-sensitive adhesive layer is suppressed.

It is a layer block diagram of the adhesive polarizing film 1 of one Embodiment of this invention. It is a layer block diagram of the laminated body 5 for an image display device of one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail.

1. 1. Adhesive polarizing film As shown in FIG. 1, the adhesive polarizing film 1 of the embodiment of the present invention is configured by laminating the pressure-sensitive adhesive layer 2 and the polarizing film 3. It is preferable that the adhesive surface 1a of the adhesive polarizing film 1 is provided with a release film 4 for protecting the adhesive surface 1a. The release film 4 can be made of PET or the like.
Hereinafter, each configuration will be described.

1-1. Adhesive layer 2
The pressure-sensitive adhesive layer 2 is formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive and a conductive polymer. Conductivity is imparted to the pressure-sensitive adhesive layer 2 by the conductive polymer, and the surface resistivity of the pressure-sensitive adhesive layer 2 is reduced.

The storage elastic modulus (G') of the pressure-sensitive adhesive layer 2 at 80 ° C. is 20 to 1000 kPa. Hereinafter, unless otherwise specified, the storage elastic modulus means the storage elastic modulus (G') at 80 ° C., and the measurement frequency of the storage elastic modulus is 1 Hz. When the storage elastic modulus is within such a range, an increase in surface resistivity due to shrinkage of the pressure-sensitive adhesive layer 2 in a high temperature environment is suppressed. The storage elastic modulus is, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 kPa. Yes, it may be within the range between any two of the numerical values exemplified here. The storage elastic modulus of the pressure-sensitive adhesive layer 2 can be adjusted by changing the composition of the pressure-sensitive adhesive.

The thickness of the pressure-sensitive adhesive layer 2 is usually 5 to 75 μm, preferably 10 to 50 μm in terms of dry film thickness.

1-2. Adhesive The adhesive is composed of any adhesive that can disperse the conductive polymer. Examples of the adhesive include an acrylic adhesive and a rubber adhesive.

1-2-1. Acrylic Adhesives Acrylic adhesives are adhesives containing (meth) acrylic polymers and cross-linking agents. The (meth) acrylic polymer is a polymer containing a repeating structure having a (meth) acrylic unit structure. Examples of the (meth) acrylic-based unit structure include a unit structure derived from the (meth) acrylic acid ester.

When the pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive, the storage elastic modulus of the pressure-sensitive adhesive layer 2 is preferably 20 to 200 kPa. This is because if the storage elastic modulus is too high, the adhesive strength may be too low. Specifically, the storage elastic modulus is, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200 kPa. Yes, it may be within the range between any two of the numerical values exemplified here.

When the pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive, the storage elastic modulus of the pressure-sensitive adhesive layer 2 can be changed by changing the storage elastic modulus of the (meth) acrylic polymer alone or changing the content of the cross-linking agent. Can be adjusted.

<(Meta) acrylic polymer>
The storage elastic modulus of the (meth) acrylic polymer alone is preferably 20 to 200 kPa, more preferably 30 to 100 kPa. Specifically, the storage elastic modulus is, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200 kPa. Yes, it may be within the range between any two of the numerical values exemplified here.

Even when the storage elastic modulus of the polymer alone is low, the storage elastic modulus of the pressure-sensitive adhesive layer 2 can be increased by increasing the amount of the cross-linking agent added, but in that case, the toughness of the polymer is lowered. In some cases, the storage elastic modulus of the polymer alone is preferably in the above range.

The weight average molecular weight Mw of the (meth) acrylic polymer is, for example, 400,000 to 3 million, preferably 600,000 to 2.5 million, and more preferably 1 million to 2 million. In this case, the storage elastic modulus of the (meth) acrylic polymer tends to be a preferable value. Specifically, this Mw is, for example, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, 1 million, 1.1 million, 1.2 million, 1.3 million, 1.4 million, 1.5 million, 1.6 million, 170. It is 10,000, 1.8 million, 1.9 million, 2 million, 2.5 million, and 3 million, and may be within the range between any two of the numerical values exemplified here. Mw is measured by gel permeation chromatography (GPC) method.

The molecular weight distribution (Mw / Mn; Mn is a number average molecular weight) of the (meth) acrylic polymer is, for example, 1 to 15, preferably 5 to 10. Specifically, this value is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, and is any of the numerical values exemplified here. It may be within the range between the two. Mn is measured by the GPC method in the same manner as Mw.

The (meth) acrylic polymer is preferably a polymer of a monomer mixture containing the first and second monomers. Assuming that the total amount of the monomer mixture is 100% by mass, the content of the first monomer is preferably 0.05 to 10% by mass, and the content of the second monomer is preferably 51 to 99.5% by mass. The monomer mixture may contain a third monomer. The content of the third monomer is the balance of 100% by mass minus the contents of the first and second monomers. When a (meth) acrylic polymer is formed by using a monomer mixture having such a composition, the storage elastic modulus of the (meth) acrylic polymer tends to be a preferable value.

The content of the first monomer is preferably 1 to 5% by mass. Specifically, this content is, for example, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10% by mass, and is exemplified here. It may be within the range between any two of the given numerical values.

The content of the second monomer is preferably 60 to 99.5% by mass. This content is specifically, for example, for example, 51, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.5% by mass. It may be within the range between any two of the numerical values exemplified here.

-First monomer The first monomer is a crosslinkable functional group-containing monomer.

The "crosslinkable functional group" is incorporated into a polymer chain as a polymerization component, and then, when the pressure-sensitive adhesive layer is formed, the functional group reacts with a functional group in another polymer chain, or the functional group. Refers to a functional group capable of forming a three-dimensional crosslink between polymer chains in the system of the pressure-sensitive adhesive layer by the reaction between the polymer chain and the cross-linking agent. Examples of such a crosslinkable functional group include a hydroxyl group, an amino group, and a carboxyl group.

Examples of the monomer having a hydroxyl group as a crosslinkable functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 2-Hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, ethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene Glycol (meth) acrylate and the like can be mentioned, and one of them can be used alone or in combination of two or more.

Examples of the monomer having an amino group as a crosslinkable functional group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and the like. N, N'-dimethylaminoethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, acrylamide, etc. may be mentioned, and one of them may be used alone or in combination of two or more. can.

Examples of the monomer having a carboxyl group as a crosslinkable functional group include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride and the like, and one of them is used. It can be used alone or in combination of two or more.

Among the monomers having a crosslinkable functional group, a monomer having a hydroxyl group is preferable, and more specifically, 2-hydroxyethyl (meth) acrylate, because it is easy to form a three-dimensional crosslinked structure in the system of the pressure-sensitive adhesive layer. 4-Hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate are preferable.

-Second monomer The second monomer is not the first monomer, but a (meth) acrylic acid alkyl ester having a homopolymer glass transition temperature (Tg) of -60 to 20 ° C. and a homopolymer glass transition temperature of -60. At least one selected from (meth) acrylic acid alkoxyalkyl esters at ~ 20 ° C. For the glass transition temperature (Tg) of the homopolymer, the value described in Polymer Handbook Fourth Edition (Wiley-Interscience 1999) is adopted.

Examples of such (meth) acrylic acid alkyl esters include butyl acrylate (-50 ° C), methyl acrylate (8 ° C), octyl methacrylate (-20 ° C), isooctyl methacrylate (-45 ° C), and 2-ethylhexyl. Examples thereof include methacrylate (-10 ° C.), isodecyl methacrylate (−41 ° C.), and isostearyl methacrylate (-18 ° C.). Examples of such (meth) acrylic acid alkoxyalkyl ester include 2-methoxyethyl acrylate (-50 ° C) and methoxy-triethylene glucol acrylate (-50 ° C). The temperature in parentheses for the second to third monomers is the homopolymer Tg.

Specifically, the Tg of the second monomer is, for example, -60, -50, -40, -30, -20, -10, 0, 10, 20 ° C., and any two of the numerical values exemplified here. It may be within the range between.

-Third monomer The third monomer is a monomer that is neither the first nor the second monomer. Such monomers include (meth) acrylic acid alkyl esters or (meth) acrylic acid alkoxyalkyl esters, other (meth) acrylic acid esters, and other ethylenes in which Tg is outside the range specified by the second monomer. It is a monomer having a sex unsaturated double bond.

-Polymerization method A (meth) acrylic polymer can be obtained by polymerizing the above-mentioned monomer mixture by various known methods such as solution polymerization, emulsion polymerization and bulk polymerization. The solution polymerization method is preferable from the viewpoint of the balance of characteristics such as the adhesive force and the holding force of the pressure-sensitive adhesive and the cost. Ethyl acetate, toluene and the like are used as the solvent for solution polymerization. The solution concentration is usually about 20 to 80% by weight. As the polymerization initiator, various known agents such as azo type and peroxide type can be used. Chain transfer agents may be used to adjust the molecular weight. The reaction temperature is usually 50 to 80 ° C., and the reaction time is usually 1 to 8 hours.

<Crosslinking agent>
From the viewpoint of giving the pressure-sensitive adhesive an appropriate cohesive force, it is preferable to introduce a crosslinked structure into the (meth) acrylic polymer. For example, a cross-linking structure is introduced by adding a cross-linking agent to the solution after polymerizing the (meth) acrylic polymer and heating as necessary. Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, metal chelate-based cross-linking agents and the like. These cross-linking agents react with the cross-linking functional groups introduced into the (meth) acrylic polymer to form a cross-linked structure.

Since a crosslinked structure can be introduced into the (meth) acrylic polymer by heating, a polyisocyanate having two or more isocyanate groups in one molecule is preferable as the crosslinked agent. Examples of the polyisocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-triisocyanate. Aromatic isocyanates such as range isocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylol propane / tolylene diisocyanate trimer adduct (eg, "Coronate L" manufactured by Toso), trimethylol propane / hexa Methylene diisocyanate trimeric adduct (eg, "Coronate HL" manufactured by Tosoh), trimethylol propane adduct of xylylene diisocyanate (eg, "Takenate D110N" manufactured by Mitsui Chemicals, isocyanurate of hexamethylene diisocyanate (eg, manufactured by Tosoh). Examples thereof include isocyanate additives such as "Coronate HX" and "Y-75" manufactured by Soken Kagaku.

The blending amount of the cross-linking agent is, for example, 0.005 to 2 parts by mass, preferably 0.01 to 1 part by mass, and further preferably 0.05 to 0.15 with respect to 100 parts by mass of the (meth) acrylic polymer. preferable. The storage elastic modulus of the pressure-sensitive adhesive layer 2 tends to be a preferable value. Specifically, the blending amount is, for example, 0.005, 0.01, 0.05, 0.10, 0.15, 0.20, 0.50, 1.0, 2.0 parts by mass. , It may be within the range between any two of the numerical values exemplified here.

1-2-2. Rubber-based adhesives Examples of the rubber-based adhesives include rubber-based adhesive compositions using natural rubber or synthetic rubber as a polymer, and preferably contain a hydrogenated block copolymer, a tackifier resin, and a softening agent. ..

<Hydrogenated block copolymer>
The block copolymer is thermoplastic having a segment composed of a polymer component of an aromatic vinyl monomer (hard segment) and a segment composed of a polymer component of a conjugated diene monomer (soft segment). It is an elastomer. Here, more specifically, the aromatic vinyl compound is preferably styrene or α-methylstyrene (more preferably styrene), and the conjugated diene compound is preferably butadiene or isoprene.

Specific examples of the hydrogenated block copolymer include, for example, a styrene- (ethylene-propylene) -styrene type block copolymer (SEPS) (a hydrogenated additive of a styrene-isoprene-styrene type block copolymer (SIS)). , Stylite- (butadiene-butylene) -styrene type block copolymer (SBBS) hydrogenated product, styrene- (ethylene-butylene) -styrene type block copolymer (SEBS) (styrene-butadiene-styrene type block copolymer weight Combined (SBS) hydrogen additive), styrene- (ethylene-propylene) type block copolymer (SEP) (styrene-isoprene type block copolymer (SI) hydrogen additive), styrene- (ethylene-butylene) Examples thereof include a type block copolymer (SEB) (a hydrogenated additive of a styrene-butadiene type block copolymer (SB)). Among them, the hydrogenated block copolymers are styrene- (ethylene-propylene) -styrene type block copolymer (SEPS) and styrene- (ethylene-butylene) from the viewpoint of excellent compatibility with the tackifier resin. -ABA type hydrogenated block copolymers such as styrene type block copolymers (SEBS) are particularly preferable. These may be used alone or in combination of two or more.

<Adhesive-imparting resin>
The tackifier resin has the property of being compatible with the hard segments constituting the hydrogenated block copolymer. The tackifier resin can be, for example, an aromatic tackifier resin. The aromatic tackifier resin used as the tackifier resin preferably has a molecular weight of 5,000 or less from the viewpoint of compatibility.

The tackifier resin preferably has a softening point of 80 ° C. or higher. The softening point is, for example, 80 to 200 ° C., specifically, for example, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200 ° C., and here. It may be within the range between any two of the numerical values exemplified in.

Examples of the aromatic pressure-sensitive adhesive resin that can be used as the pressure-sensitive adhesive resin include aromatic petroleum resins, styrene-based polymers, α-methylstyrene-based polymers, styrene- (α-methylstyrene) -based copolymers, and styrene. -Examples include aliphatic hydrocarbon-based copolymers, styrene- (α-methylstyrene) -aliphatic hydrocarbon-based copolymers, and styrene-aromatic hydrocarbon-based copolymers. More specifically, for example, FMR-0150 as a commercially available styrene-aromatic hydrocarbon-based polymer (softening point 145 ° C., manufactured by Mitsui Chemicals, Inc.), FTR-6100 as a styrene-aliphatic hydrocarbon-based copolymer. (Softening point 100 ° C, manufactured by Mitsui Chemicals), FTR-6110 (softening point 110 ° C, manufactured by Mitsui Chemicals) and FTR-6125 (softening point 125 ° C, manufactured by Mitsui Chemicals), styrene- (α-methylstyrene) -aliphatic FTR-7100 (softening point 100 ° C., manufactured by Mitsui Chemicals) as a hydrocarbon-based polymer, FTR-8120 (softening point 120 ° C., manufactured by Mitsui Chemicals) and SX-100 (softening point 100 ° C.) as styrene-based polymers. , Yasuhara Chemical Co., Ltd., FTR-0100 as an α-methylstyrene polymer (softening point 100 ° C, manufactured by Mitsui Chemicals), FTR-2120 as a styrene- (α-methylstyrene) polymer (softening point 120 ° C) , Mitsui Chemicals), FTR-2140 (softening point 145 ° C, manufactured by Mitsui Chemicals), Crystalx 3100 (softening point 100 ° C, manufactured by Eastman Chemical), Crystalex 3085 (softening point 85 ° C, manufactured by Eastman Chemical), Crystalx 5140 (softening point 140 ° C., manufactured by Eastman Chemical), Crystalx 1120 (softening point 120 ° C., manufactured by Eastman Chemical), Crystalx F85 (softening point 85 ° C., manufactured by Eastman Chemical), Crystalx F100 (softening point) A point of 100 ° C., manufactured by Eastman Chemical), Crystalx F115 (softening point of 115 ° C., manufactured by Eastman Chemical), and the like can also be used.

<Softener>
The softener has the property of being compatible with the soft segments constituting the hydrogenated block copolymer. The softener is a liquid at 23 ° C.

Examples of the softening agent include polybutene-based compounds, polyisobutylene-based compounds, aliphatic hydrocarbons such as polyisobutylene-based compounds, and more specifically, commercially available softeners, for example, Nisseki polybutene LV-7 as a polybutene-based compound. , LV-50, LV-100, HV-15, HV-35, HV-50, HV-100, HV-300, HV-1900 and SV-7000 (all manufactured by JXTG Energy), as polyisobutylene compounds. Examples thereof include Trax 3T, 4T, 5T and 6T, Himor 4H, 5H, 5.5H and 6H (all manufactured by JXTG Energy), and as a polyisobutylene compound, Claprene LIR-290 (manufactured by Claret).

1-3. Conductive Polymer The conductive polymer of the present invention imparts conductivity to the pressure-sensitive adhesive composition and contributes to the antistatic property of the pressure-sensitive adhesive composition.

The conductive polymer is not particularly limited as long as it has the effect of the present invention as long as it is an organic polymer whose main chain is composed of a π-conjugated system. , Polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophenine-based conductive polymer, and their co-weights Coalescence and the like can be mentioned. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

The conductive polymer preferably has at least one of the structural units represented by the chemical formula (1) or (2). Since the π-conjugated polymer contained in this conductive polymer has R ¹ , the skeleton is easily distorted and the flexibility is improved. Therefore, the dispersibility in a solvent or a pressure-sensitive adhesive is good, and the conductivity of the pressure-sensitive adhesive composition can be most improved as compared with other π-conjugated polymer species.

The blending amount of the conductive polymer in the pressure-sensitive adhesive composition is preferably 0.01 to 35 parts by mass, more preferably 0.05 to 30 parts by mass, and 0.5 to 0.5 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. 20 parts by mass is more preferable. Specifically, the blending amount is, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 13, 14, 15, 20, 25, 30, 35 parts by mass, and may be within the range between any two of the numerical values exemplified here.

When R ¹ contains a silicone group, the blending amount of the conductive polymer is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. By adjusting the ratio of the silicone base portion in R ¹ , it is possible to achieve both dispersibility and conductivity even when the blending amount is small.

When R ¹ contains an alkyl group, the blending amount of the conductive polymer is preferably 0.01 to 35 parts by mass, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive.

R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms and having 1 to 12 carbon atoms, and a phenyl group which may have a substituent. Represents a heterocyclic group which may have a substituent or a fused ring group which may have a substituent, R ² is an oxygen atom or a sulfur atom, respectively, and R ³ is a hydrogen atom or an organic, respectively. It is a group. A ⁻ is a monoanion derived from a dopant. n is 2 or more and 300 or less.

The alkyl group having 1 or more and 12 or less carbon atoms may be linear, branched, cyclic or the like, and may be, for example, 1 or more and 8 or less carbon atoms, 1 or more and 6 or less carbon atoms, 1 or more and 4 or less carbon atoms, or the like. May be present, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl. Examples include a group and an adamantyl group.

The alkoxy group having 1 or more and 12 or less carbon atoms may be linear, branched, cyclic or the like, and may be, for example, 1 or more and 8 or less carbon atoms, 1 or more and 6 or less carbon atoms, 1 or more and 4 or less carbon atoms, or the like. Is.

Examples of the alkylene oxide group having 1 or more and 12 or less carbon atoms include 1 or more and 8 or less carbon atoms, 1 or more and 6 or less carbon atoms, and 1 or more and 4 or less carbon atoms.

Examples of the heterocyclic group include a silol ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an oxadiazole ring, a triazole ring, an imidazole ring, and a pyrazole. Ring, thiazole ring, indole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, quinoxalin ring, quinazoline ring, phthalazine ring, thienothiophene ring, carbazole ring, azacarbazole ring (any of the carbon atoms constituting the carbazole ring) (Representing one or more replaced with a nitrogen atom), a ring in which any one or more of the carbon atoms constituting the dibenzosilol ring, dibenzofuran ring, dibenzothiophene ring, benzothiophene ring or dibenzofuran ring is replaced with a nitrogen atom, Benzodifuran ring, benzodithiophene ring, aclysine ring, benzoquinoline ring, phenazine ring, phenanthridine ring, phenanthroline ring, cyclazine ring, kindrin ring, tepenidine ring, quinindrin ring, triphenodithiadin ring, triphenodioxazine ring, fe. Nantradine ring, anthrazine ring, perimidine ring, naphthofuran ring, naphthothiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthone ring, phenoxatiin ring. , Dibenzocarbazole ring, indolocarbazole ring, dithienobenzene ring, epoxy ring, aziridine ring, thiirane ring, oxetane ring, azetidine ring, thietan ring, tetrahydrofuran ring, dioxolan ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine Ring, tetrahydrothiophene ring, sulforane ring, thiazolidine ring, ε-caprolactone ring, ε-caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazin ring, morpholin ring, tetrahydropyran ring, 1,3-dioxane Ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholin ring, thiomorpholin-1,1-dioxide ring, pyranose ring, diazabicyclo [2,2,2] -octane ring, phenoxazine ring, Examples thereof include a monovalent group derived from a phenothiazine ring, an oxanthrene ring, a thioxanthene ring, and a phenoxatiin ring.

As the fused ring group, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthane ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluorene ring, pentacene ring, perylene ring, etc. Examples thereof include a pentaphene ring, a picene ring, and a pyrenethrene ring.

Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, the alkyl ether group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 12 carbon atoms, and an aromatic group. Examples thereof include a group group, a hydroxy group, a carboxyl group, a halogen such as fluorine, chlorine, bromine and iodine, an aldehyde group, an amino group, a cycloalkyl group having 3 or more carbon atoms and 8 or less carbon atoms, and a hydroxy group and a carboxyl group are preferable.

R ¹ preferably contains at least one of an alkyl group which may have a substituent and a silicone group, and preferably contains a silicone group. Since the silicone group has a low free energy, when R ¹ contains a silicone group, the conductive polymer tends to gather near the surface in the pressure-sensitive adhesive composition, and the surface resistance tends to be reduced.

Examples of the alkyl group include an alkyl group having 1 or more carbon atoms and 12 or less carbon atoms. Examples of this alkyl group include those described above.

A silicone group is a group in which an organic group is bonded to a siloxane bond in which silicon and oxygen are alternately bonded as the main skeleton of the bond. The organic group is preferably an aromatic group or an alkyl group having 1 or more and 12 or less carbon atoms, and a methyl group is preferable.

R ¹ preferably has an ester bond. Examples of the ester bond of R ¹ include a carboxylic acid ester bond, a phosphoric acid ester bond, a sulfonic acid ester bond, and the like, and a carboxylic acid ester bond is preferable. When R ¹ has an acid group (carboxyl group or the like) that has not been esterified, the polarity of the conductive polymer becomes too high, and the cohesiveness of the conductive polymer in the pressure-sensitive adhesive composition becomes low. Esterification of the acid group lowers the polarity and improves dispersibility in the pressure-sensitive adhesive composition.

R ¹ preferably has a structure represented by the chemical formula (3).

(In the chemical formula (3), * is a bond, R ⁴ is a direct bond or an organic group, and R ⁵ contains at least one of an organic group and a silicone group.)

As the organic group of R ³ , R ⁴ or R ⁵ , it may have a substituent, an alkyl group having 1 or more and 12 or less carbon atoms, an alkyl ether group having 1 or more and 12 or less carbon atoms, and 1 or more and 12 carbon atoms or less. Examples thereof include an alkoxy group of the above, an alkylene oxide group having 1 or more and 12 or less carbon atoms, an aromatic group, a heterocyclic group and the like. R ⁵ preferably has a hydroxyl group at the β-position.

The description of the alkyl group, alkoxy group, alkylene oxide group and heterocyclic group here is the same as described above.

The alkyl ether group having 1 or more and 12 or less carbon atoms may be linear, branched, cyclic or the like, and may be, for example, 1 or more and 8 or less carbon atoms, 1 or more and 6 or less carbon atoms, 1 or more and 4 or less carbon atoms, or the like. Is.

Examples of the aromatic group include various condensed ring groups in addition to the phenyl group and the benzyl group. As the fused ring group, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthane ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluorene ring, pentacene ring, perylene ring, etc. Examples thereof include a pentaphene ring, a picene ring, and a pyrenethrene ring.

Examples of the dopant include any compound that can impart conductivity to the π-conjugated polymer and become a monoanion. Dopants include vinyl sulfonic acid, methane sulfonic acid, p-toluene sulfonic acid, dodecyl sulfonic acid, dodecylbenzene sulfonic acid, sulfonic acid such as di (2-ethylhexyl) sulfosuccinic acid, tetrafluoroboric acid, trifluoroacetic acid, hexa. Examples thereof include monovalent acids such as fluorophosphate, trifluoromethanesulfonic acid and naphthalenesulfonic acid, and alkali metal salts thereof. When a dopant that becomes a monoanion is used, the conductivity of the conductive polymer is likely to be improved. The structure of the dopant affects the dispersibility in the pressure-sensitive adhesive composition, and among these, dodecylbenzene sulfonic acid is preferable from the viewpoint of the balance between conductivity and dispersibility.

The number of the structural units (1) and (2) contained in the conductive polymer is not particularly limited, but is preferably 2 or more and 300 or less. Specifically, for example, it is 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200 or 300, and is within the range between any two of the numerical values exemplified here. May be.

The content ratios of the structural units (1) and (2) contained in the conductive polymer can be adjusted by the ratio of the addition amount of the thiophene derivative represented by the chemical formula (4) to the aldehyde. The molar ratio of the amount of the thiophene derivative to the aldehyde added (thiophene derivative / aldehyde) is, for example, 1/1, 2/1, 3/1, 4/1, 5/1, etc., and any two of these values are used. Although it may be within the range between them, the ratio of 1/1 to 4/1 is preferable, and the ratio of 1/1 to 2/1 is more preferable from the viewpoint of the balance between solubility and conductivity.

In the chemical formula (4), R ² and R ³ are defined in the same manner as R ² and R ³ in the chemical formulas (1) and (2), respectively.

The method for synthesizing the conductive polymer is not particularly limited, but for example, it can be obtained by adding a dopant and an oxidizing agent to a thiophene derivative and an aldehyde, heating and stirring in a solvent under an inert gas atmosphere, and polymerizing the polymer. Can be done. Further, a decomposition accelerator for an oxidizing agent may be added.

As the aldehyde, an aldehyde having an acid group may be used, or an aldehyde having an ester bond may be used. Examples of the aldehyde having an acid group include phthalaldehyde acid. Examples of the aldehyde having an ester bond include those obtained by esterifying the acid group of an aldehyde having an acid group. Esterification can be carried out, for example, by reacting an acid group with an epoxy group of an epoxy group-containing compound (eg, epoxyalkyl, one-ended epoxy silicone). When an aldehyde having an acid group is used, the interaction between molecules becomes strong, so that the conductivity tends to be high.

The molar ratio of the dopant to the thiophene derivative (dopant / thiophene derivative) is, for example, 0.01 to 0.5, preferably 0.1 to 0.5. Specifically, the molar ratio is, for example, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, and any two of the numerical values exemplified here are used. It may be within the range between. If this molar ratio is too small, the conductivity of the conductive polymer may be too low.

The oxidizing agent is not particularly limited as long as it is an oxidizing agent in which the polymerization reaction proceeds, and it may be ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, iron (III) chloride, iron (III) sulfate, or hydroxide. Iron (III), Iron Tetrafluoroborate (III), Iron Hexafluorophosphate (III), Copper Sulfate (II), Copper Chloride (II), Copper Tetrafluoroborate (II), Copper Hexafluorophosphate (II) II) and organic peroxides such as ammonium oxodisulfate, benzoyl peroxide and lauroyl peroxide can be mentioned.

The solvent is not particularly limited as long as it is a solvent in which the reaction between the heterocyclic compound and the aldehyde derivative proceeds, and it may be γ-butyrolactone, propylene carbonate, ethylene carbonate, acetonitrile, tert-butylmethyl ether, ethyl acetate, benzene, anisole. , Heptane, water, methanol, ethanol, isopropyl alcohol, butanol and other alcohol solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and other ketone solvents, methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, propylene glycol ethyl Examples thereof include glycol-based solvents such as ether, and lactic acid-based solvents such as methyl lactate and ethyl lactate. An aprotic solvent is preferable because of the efficiency of the oxidizing agent.

1-4. Solvent The pressure-sensitive adhesive composition of the present invention may contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the conductive polymer, and preferably contains an organic solvent. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether and propylene. Glycol-based solvents such as glycol ethyl ether, lactic acid-based solvents such as methyl lactate and ethyl lactate, toluene, anisol, ethyl acetate, propylene carbonate, γ-butyrolactone, toluene, isopropyl alcohol, ethylene glycol, dimethyl sulfoxide, methanol, benzyl alcohol and the like. However, propylene carbonate, γ-butyrolactone, methyl ethyl ketone, toluene, anisole, isopropyl alcohol, ethylene glycol, dimethyl sulfoxide, methanol, benzyl alcohol and the like are particularly preferable. The organic solvent may be used in combination of a plurality of solvents, and may be the same as or different from the solvent used for synthesizing the conductive polymer.

In order to disperse and stabilize the conductive polymer in water, excess sulfonic acid that does not contribute to doping is required. However, when the conductive polymer composition contains an organic solvent, the conductivity is high even if the amount of excess sulfonic acid is small. It is possible to stably dissolve or disperse the molecule in an organic solvent.

The non-volatile content of the conductive polymer composition excluding the organic solvent is not particularly limited, but is, for example, 0.1% by mass or more and 20.0% by mass or less. Specifically, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 5.0, 10.0, 15.0, 20.0 mass%. It may be within the range between any two of the numerical values exemplified here.

The solvent of the conductive polymer composition may contain water in addition to the above organic solvent, but the water content is preferably 50% or less with respect to the solvent, more preferably 10% or less, from the viewpoint of substrate adhesion. preferable.

1-5. Other Ingredients The pressure-sensitive adhesive composition of the present invention may contain components such as a silane coupling agent, a silicone resin, a platinum catalyst, and a photopolymerization initiator. Further, the pressure-sensitive adhesive composition of the present invention comprises a solvent, a tackifier resin, a sensitizer, a filler, a flame retardant, a filler, an organopolysiloxane compound, an ionic compound, a plasticizer, a curing auxiliary catalyst, a dispersant, and a pigment /. A dye, a viscosity modifier, a lubricant, a settling inhibitor, a rheology control agent, an ultraviolet absorber, a light resistance imparting agent, an antioxidant, a water repellent agent, an antifoaming agent and the like may be appropriately blended.

〔Silane coupling agent〕
The silane coupling agent forms a bond such as a chemical bond with various adherends, and enhances the adhesiveness between the substrate and the adherend. It is especially effective for adhesion to glass substrates.

Examples of the silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane and metharoxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane and 3-glycidoxy. Silicon compounds having an epoxy structure such as propylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxy Examples thereof include amino group-containing silicon compounds such as silane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents.

The blending amount of the silane coupling agent is usually 0.01 to 0.3 parts by mass, preferably 0.05 to 0.25 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. Further, the silane coupling agent may be used alone or in combination of two or more.

1-6. Polarizing film 3
The polarizing film 3 may include a polarizing element 3a and may include a polarizing element protective film 3b. The polarizing element 3a is arranged between the pressure-sensitive adhesive layer 2 and the polarizing element protective film 3b.

Examples of the polarizing element 3a include a stretched film obtained by incorporating a polarizing component into a film made of a polyvinyl alcohol-based resin and stretching the film. Examples of the polyvinyl alcohol-based resin include saponified products of polyvinyl alcohol, polyvinylformal, polyvinyl acetal, and ethylene-vinyl acetate copolymer. Examples of the polarizing component include iodine and dichroic dyes.

Examples of the polarizing element protective film 3b include a film made of a thermoplastic resin. Examples of the thermoplastic resin include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, and cyclic polyolefin resins (norbornen). (Based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and a mixture of two or more selected from these resins can be mentioned.

The thickness of the polarizing film 3 is usually 10 to 200 μm, preferably 30 to 100 μm. In the present invention, the polarizing element protective film 3b formed on the polarizing element 3a can be omitted, so that the polarizing film 3 can be made thinner.

By the way, the polarizing film 3 may have a property of easily shrinking in a high temperature environment. In this case, the pressure-sensitive adhesive layer 2 tends to shrink as the polarizing film 3 shrinks. Therefore, as described above, it is technically significant to keep the storage elastic modulus of the pressure-sensitive adhesive layer 2 at 80 ° C. within a predetermined range. This is especially noticeable.

Here, the single shrinkage rate P (%) = ((Xp-Yp) / Xp) × 100 of the polarizing film 3 is defined. Xp is the dimension in the stretch axis direction of the polarizing film 3 after the polarizing film 3 is left alone in the environment of 23 ° C. and 50% RH, and Yp is the dimension of the polarizing film 3 alone in the environment of 80 ° C. It is the dimension in the drawing axis direction of the polarizing film 3 after leaving for 72 hours and letting it cool for 10 minutes in the environment of 23 degreeC 50% RH.

The single shrinkage rate P is, for example, 0.01 to 10%, preferably 1 to 8%. Specifically, the single shrinkage rate P is, for example, 0.01, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10%, and is exemplified here. It may be within the range between any two of the given numerical values.

1-7. High-temperature holding power The adhesive polarizing film 1 preferably has excellent holding power at high temperatures. Specifically, when the adhesive surface 1a of the adhesive polarizing film 1 is attached to a glass plate (preferably a non-alkali glass plate) with an area of 10 mm × 10 mm, and a load of 800 g is applied in the shearing direction in an environment of 80 ° C. In addition, it is preferable that the amount of displacement of the adhesive layer with respect to the glass plate 1 hour after the start of load application is 2.0 mm or less. In this case, as shown in FIG. 2, when the adhesive polarizing film 1 is attached to the image display element 6, the adhesive polarizing film 1 is prevented from being displaced from the image display element 6. This deviation is, for example, 0 to 2.0 mm, specifically, for example, 0, 0.5, 1.0, 1.5, 2.0 mm, and is between any two of the numerical values exemplified here. It may be within the range of.

2. 2. As shown in FIG. 2, the image display device laminate 5 according to the embodiment of the present invention is configured by attaching the adhesive polarizing film 1 to the image display element 6.

The adhesive polarizing film 1 can be attached to the image display element 6 so that the adhesive surface 1a comes into contact with the image display element 6 in a state where the release film 4 is peeled off to expose the adhesive surface 1a.

The image display element 6 is an element for displaying an image. The image display element 6 is preferably an element having a glass plate on the surface to which the adhesive polarizing film 1 is attached. The glass plate is preferably a non-alkali glass plate. Examples of such an image display element 6 include a liquid crystal cell.

The liquid crystal cell is preferably a liquid crystal cell constituting an in-cell or on-cell type touch panel input / output device. Incel is a method of incorporating a touch panel function into the pixels of a liquid crystal display. On-cell is a method in which a touch panel function is built in between a color filter substrate and a polarizing film.

In such a method, the touch sensor does not work normally due to static electricity generated near the cover glass, and touch failure often occurs. Therefore, by using a pressure-sensitive adhesive composition having a low surface resistivity in which the conductive polymer of the present invention is blended in the pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer neutralizes and disperses static electricity generated in the vicinity of the cover glass. It is possible to suppress touch defects.

The thickness of the glass plate is, for example, 0.3 to 3 mm, specifically, for example, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 mm. Yes, it may be within the range between any two of the numerical values exemplified here.

The thickness of the image display element 6 is, for example, 0.5 to 6 mm, specifically, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3 It is 5.5, 4.0, 4.5, 5.0, 5.5, 6.0 mm, and may be within the range between any two of the numerical values exemplified here.

Here, the shrinkage rate S (%) of the polarizing film 3 in the laminate 5 is defined as ((Xs—Ys) / Xs) × 100. Xs is the dimension of the polarizing film 3 in the laminated body 5 in the state after the laminated body 5 is left in the environment of 23 ° C. and 50% RH, and Ys is the dimension of the laminated body 5 in the environment of 80 ° C. It is the dimension in the stretch axis direction of the polarizing film 3 in the laminated body 5 after leaving it for 72 hours, and then letting it cool for 10 minutes in the environment of 23 degreeC 50% RH.

S is preferably less than 3. That is, it is preferable that the following equation (1) is satisfied.
((Xs-Ys) / Xs) x 100 <3 ... (1)

In this case, since the shrinkage rate S is not large, the increase in the surface resistivity of the pressure-sensitive adhesive layer 2 due to the shrinkage of the polarizing film 3 is suppressed.

The laminate shrinkage rate S is, for example, 0.01 to 2.99, preferably 0.01 to 2.9, and even more preferably 0.01 to 2.0. Specifically, the shrinkage rate S is, for example, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9. , 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2 .2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.99, and the range between any two of the numerical values exemplified here. It may be inside.

The surface resistance of the adhesive layer 2 exposed by peeling the adhesive polarizing film 1 from the laminate 5 after leaving the laminate 5 in a 23 ° C. and 50% RH environment is set to Xr, and the laminate 5 is placed in an 80 ° C. environment. Let Yr be the surface resistance of the adhesive layer 2 exposed by peeling the adhesive polarizing film 1 from the laminate 5 after allowing it to cool for 10 minutes in an environment of 23 ° C. and 50% RH. And Yr are both preferably less than 1.0 × 10 ¹² . In this case, the laminate 5 having the pressure-sensitive adhesive layer 2 having a sufficiently low surface resistivity can be obtained at both normal temperature and high temperature.

For Xr and Yr, respectively, less than 5.0 × 10 ¹¹ is more preferable, less than 1.0 × 10 ¹¹ is further preferable, less than 5.0 × 10 ¹⁰ is further preferable, and less than 1.0 × 10 ¹⁰ is further preferable. , 5.0 × 10 ⁹ or less, more preferably 1.0 × 10 ⁹ or less.

It is preferable that Xr and Yr satisfy the following formula (2).
Yr / Xr <10 ... (2)

In this case, the increase in surface resistivity in a high temperature environment is suppressed. The value of Yr / Xr is, for example, 0.5 to 9.9, more preferably 1 to 5. Specifically, this value is, for example, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 9.9, and any of the numerical values exemplified here. It may be within the range between the two.

The present invention will be described in more detail in Examples, but the present invention is not limited to these Examples.

1. 1. Production of Conductive Polymers Conductive polymers C1 to C5 were produced by the methods shown below.

-Manufacturing example C1 (manufacturing of conductive polymer C1)
A 1 L flask was charged with 500 g of propylene carbonate, 3.4 g of 3,4-ethylenedioxythiophene (EDOT) and 3.0 g of dodecylbenzenesulfonic acid (DBS), and stirred for 0.25 hours. Then, under nitrogen purge, 0.04 g of iron (III) trisparatoluenesulfonate (Fe (PTS) ₃ ), 1.8 g of phthalaldehyde acid (PAA), 6.75 g of benzoyl peroxide, and 100 g of propylene carbonate were added, and the temperature was 40 ° C. Was stirred for 4 hours. Further, 1.25 g of DBS was added, and the mixture was stirred at 60 ° C. for 2 hours. After adding 30 g of an anion exchange resin substituted with propylene carbonate (manufactured by LANXESS MP62WS) and stirring for 24 hours, the anion exchange resin is removed, treated with an ultrasonic homogenizer, prepared with propylene carbonate, and the chemical formula (1). ) Was obtained as a propylene carbonate dispersion (nonvolatile content 1.0% by mass) of the conductive polymer C1 mainly containing the structural unit represented by).

R ¹ of the conductive polymer C 1 is represented by the chemical formula (5).

-Manufacturing example C2 (manufacturing of conductive polymer C2)
1.2 g of epoxyhexyl is added to the propylene carbonate dispersion obtained in Production Example C1, and the mixture is stirred at 80 ° C. for 6 hours to react the carboxyl group of the conductive polymer with the epoxy group of the epoxyhexyl to be alkyl-modified. A dispersion liquid of the conductive polymer C2 was obtained.

R ¹ of the conductive polymer C2 is represented by the chemical formula (6).

-Manufacturing example C3 (manufacturing of conductive polymer C3)
In the same manner as in Production Example C2, 1.2 g of epoxy hexyl used for modification in Production Example C2 was changed to 56.4 g of one-ended epoxy silicone (“X-22-173DX” manufactured by Shin-Etsu Chemical Co., Ltd.). A dispersion liquid of the conductive polymer C3 was obtained. The conductive polymer C3 is silicone-modified by reacting the carboxyl group of the conductive polymer before modification with the epoxy group of X-22-173DX.

R ¹ of the conductive polymer C3 is represented by the chemical formula (7).

-Manufacturing example C4 (manufacturing of conductive polymer C4)
30 g of one-ended epoxy organosiloxane (X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd.), 1.98 g of sodium 2-mercaptoethanesulfonate, 23 g of isopropyl alcohol, and 0.3 g of triethylamine are charged in a 1 L flask, mixed, and heated under reflux. It was allowed to react for 15 hours. Water was added to the reaction product and isopropyl alcohol was removed by distillation under reduced pressure to obtain an emulsion of an acid-modified silicone compound (nonvolatile content 12.6%).

Next, 142.5 g of the emulsion of the acid-modified silicone compound, 3.2 g of concentrated hydrochloric acid of 1.6 g of ethylenedioxythiophene (EDOT), and 0.09 g of iron sulfate were mixed in the reaction apparatus, and the mixture was mixed at 30 ° C. for 30 minutes. Stirred. Then, an aqueous solution prepared by dissolving 5.9 g of ammonium persulfate in 50 g of ion-exchanged water was added dropwise to the above mixture over 1 hour. Then, the reaction was carried out for 5 hours while maintaining the state of 30 ° C. By solid-liquid separation of the obtained reaction solution, a wet product of the conductive polymer C4 was obtained. The wet product was freeze-dried at 0 ° C. for 24 hours to obtain a dry powder of the conductive polymer C4. Next, the dry powder of the conductive polymer C4 is mixed at a ratio of 1.5% of the non-volatile content to the methyl ethyl ketone, treated with a probe-type ultrasonic homogenizer, and dispersed in an organic solvent of the conductive polymer C4. Obtained liquid.

-Manufacturing example C5 (manufacturing of conductive polymer C5)
In a 2L flask, 50 g of 2-sodium sulfoethyl methacrylate (2-NaSEMA), 55 g of benzyl methacrylate (BzMA), 47 g of 2-ethylhexyl methacrylate (2-EHA), 150 g of water and 300 g of isopropyl alcohol are charged and raised to the reflux temperature. After warming, 0.7 g of azobisisobutyronitrile (AIBN) was added, and the polymerization reaction was carried out for 18 hours in a reflux state. After completion of the reaction, the mixture was cooled to room temperature to obtain a polymerization solution.

Next, 500 g of hexane was added to the 2 L flask containing the polymerization solution to obtain a mixed solution. Using a separating funnel, impurities in the oil layer were removed from the mixed solution by liquid separation extraction. 1 kg of methanol was added dropwise to the aqueous layer after the liquid separation over 1 hour to precipitate the solid content, and the solid content was filtered off. The obtained solid material was dried under reduced pressure at 100 ° C. for 24 hours and then pulverized in a mortar to obtain a powder of a polymer compound.

Next, 16.1 g of the polymer compound, 200 g of ion-exchanged water and 6 g of a 35% aqueous hydrochloric acid solution were weighed into one flask and heated and stirred at 60 ° C. to obtain a uniform aqueous solution of the polymer compound. After cooling the aqueous solution of the polymer compound, 4.65 g of aniline was weighed and added. When this mixture was stirred and dissolved, a uniform emulsion was obtained. Separately, 30 g of water and 10 g of ammonium peroxodisulfate were weighed and mixed, and the mixture was added dropwise at 0 ° C. over 2 hours into a flask containing an emulsion. After completion of the dropping, the temperature was returned to room temperature (25 ° C.), and the mixture was stirred for 48 hours.

After completion of the reaction, the polymerization solution was separated by filtration, the obtained crystals were redispersed in water, washed, and filtered again. The solid substance containing water obtained by repeating the above washing four times was taken out and dried at 40 ° C. under reduced pressure for 96 hours to obtain a dry powder of the conductive polymer C5.
The dry powder of the conductive polymer C5 is mixed at a ratio of 1.5% of the non-volatile content to the methyl ethyl ketone and treated with a probe-type ultrasonic homogenizer to obtain an organic solvent dispersion of the conductive polymer C5. rice field.

2. 2. Example of Manufacture / Production of (Meta) Acrylic Polymer A1 (Manufacturing of (Meta) Acrylic Polymer A1)
Butyl acrylate: 96.8 parts by mass, acrylic acid: 0.2 parts by mass, 2-hydroxyethyl acrylate: 3 parts by mass in a reaction device equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube. After charging, ethyl acetate was charged in an amount of 50% by mass of the monomer concentration. Next, 0.1 part by mass of 2,2'-azobisisobutyronitrile was added to 100 parts by mass of the total monomer components, and the mixture was stirred while replacing the air in the reaction vessel with nitrogen gas to raise the temperature to 60 ° C. After warming, it was reacted for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate to obtain a solution of (meth) acrylic polymer A1 (nonvolatile content 15%). The weight average molecular weight (Mw) of the (meth) acrylic polymer A1, Mw / Mn, and the storage elastic modulus of the polymer alone at 80 ° C. are as shown in Table 1.

Production Examples A2 to A9 (Production of (meth) acrylic polymers A2 to A9)
The (meth) acrylic polymers A2 to A9 were polymerized by the same method as in Production Example A1 except that the composition ratio of the monomers was changed as shown in Table 1, and Mw, Mw / Mn, 80 ° C. was used by the method shown below. The storage elastic modulus was measured. The results are shown in Table 1.

The meanings of the abbreviations in the table are as follows.
BA: Butyl acrylate MEA: 2-methoxyethyl acrylate MA: Methyl acrylate BzA: Benzyl acrylate 2EHA: 2-ethylhexyl acrylate AA: 2HEA acrylate: 2-hydroxyethyl acrylate

<Mw, Mn>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by the gel permeation chromatography method (GPC method) under the following conditions.
-Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)
-GPC column configuration: The following 4-column column (all manufactured by Tosoh Corporation)
(1) TSKgel HxL-H (guard column)
(2) TSKgel GMHxL
(3) TSKgel GMHxL
(4) TSKgel G2500HxL
・ Flow velocity: 1.0 mL / min
-Column temperature: 40 ° C
-Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran)
・ Mobile phase solvent: Tetrahydrofuran ・ Standard polystyrene conversion

<80 ° C storage elastic modulus>
The 80 ° C. storage elastic modulus in the table was measured by the following method.
On a stripped polyethylene terephthalate film (PET film), a measurement sample (here, a (meth) acrylic polymer) was placed on a polyethylene terephthalate film (PET film) so that the film thickness after drying was 25 μm, and the liquid temperature was 25 ° C. using a doctor blade. And dried at 90 ° C. for 3 minutes to obtain an adhesive sheet. Only a plurality of pressure-sensitive adhesive layers obtained from the pressure-sensitive adhesive sheet were prepared, and these were laminated to prepare a test piece having a thickness of 1 mm. Using this test piece, the storage elastic modulus at 80 ° C. was measured using a modular compact reometer MCR300 manufactured by AntonioPaar. The measurement frequency was 1 Hz.

3. 3. Production of Adhesive Composition A pressure-sensitive adhesive composition for evaluation was produced by mixing various components shown in Tables 2 to 5 with the formulations (parts by mass) shown in Tables 2 to 5. The conductive polymer and the (meth) acrylic polymer were mixed in the state of the dispersion liquid or the solution obtained in the above-mentioned production example. The blending amount of the conductive polymer and the (meth) acrylic polymer indicates the amount of the solid content in the dispersion liquid or the solution.

4. Production of Adhesive Polarizing Film The adhesive composition obtained in "3. Production of Adhesive Composition" is placed on a peel-treated polyethylene terephthalate film (PET film) so that the film thickness after drying is 25 μm. The film was applied at a liquid temperature of 25 ° C. using a doctor blade and dried at 90 ° C. for 3 minutes to obtain an adhesive sheet.

Next, the obtained adhesive sheet and the polarizing films shown in Tables 2 to 5 were bonded together so that the coating film and the polarizing film were in contact with each other, and allowed to stand for 7 days under the conditions of 23 ° C./50% RH. , An adhesive polarizing film of Examples and Comparative Examples was obtained.

Details of the components and members described in the above table are as follows.

((Meta) acrylic polymer)
(Meta) Acrylic Polymers A1 to A9: Manufactured by Production Examples A1 to A9

(Conductive polymer)
-Conductive polymers C1 to C5: Manufactured by Production Examples C1 to C5

(Hydrogenated block copolymer)
The details of the rubber-based polymers 1 and 2 are as follows. Mw and the 80 ° C. storage elastic modulus were measured by the method described in "2. Production of (meth) acrylic polymer".
-Rubber polymer 1 (mixture of SEPS 50% by mass and SEP 50% by mass, hydrogenation rate over 90%, styrene content 15% by mass, Mw: 130,000, 80 ° C storage elastic modulus: 720 kPa)
-Rubber polymer 2 (mixture of SEPS 50% by mass and SEP 50% by mass, hydrogenation rate over 90%, styrene content 20% by mass, Mw: 150,000, 80 ° C storage elastic modulus: 920 kPa)

(Adhesive-imparting resin)
FMR-0150 (aromatic adhesive-imparting resin with softening point of 145 ° C: manufactured by Mitsui Chemicals)
TH-130 (softening point 130 ° C. terpene phenol-type adhesive-imparting resin: manufactured by Yasuhara Chemical Co., Ltd.)
・ FTR-6100 (Aromatic adhesive resin with softening point of 95 ° C: manufactured by Mitsui Chemicals)

(Softener)
LV-100 (Mn500 polybutene: made by ENEOS)
HV-300 (Mn1400 polybutene: manufactured by ENEOS)

(Other ingredients)
-Crosslinking agent: "Coronate L" manufactured by Tosoh Corporation
-Silane coupling agent: "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.
-Antioxidant: ADEKA STAB AO-330 (Hindered phenolic antioxidant: ADEKA)

(Polarizing film)
As the polarizing film, the one having the configuration shown in Table 6 was used.

The meaning of the abbreviation of the protective layer member is as follows.
COP: Cycloolefin Polymer PMMA: Polymethylmethacrylate PET: Polyethylene terephthalate TAC: Triacetylcellulose

The single shrinkage of the polarizing film was measured by the following method.
A test piece was prepared by cutting the polarizing film into a size of 160 mm (MD direction) × 25 mm (TD direction). This test piece was left alone in an environment of 23 ° C. and 50% RH for 10 minutes, and then the dimension (Xp) in the long side direction of the test piece was measured. Next, the test piece was left alone under the condition of 80 ° C. for 72 hours, then allowed to cool for 10 minutes in an environment of 23 ° C. and 50% RH, and the dimension (Yp) in the long side direction of the polarizing film was measured. ..
The single shrinkage rate (((Xp-Yp) / Xp) × 100) was calculated from the obtained Xp and Yp.

5. Preparation of laminated body for test A test piece was prepared by cutting an adhesive polarizing film into a size of 160 mm (MD direction) × 25 mm (TD direction). The PET film is peeled off from the test piece, and a pressure-sensitive adhesive layer and a non-alkali glass plate are formed on one side of a liquid crystal panel having a 2 mm-thick non-alkali glass plate as a glass substrate using a laminator roll. The contact-bonded material was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes to prepare a laminated body for testing.

6. Evaluation Various evaluations were performed according to the following criteria. The results are shown in Tables 2 to 5.

Comparing Examples and Comparative Examples, the laminated body of the example has a smaller shrinkage rate, Xr, Yr, Yr / Xr of the laminated body than the laminated body of the comparative example, and is excellent in heat resistance and durability at 80 ° C. You can see that.

<80 ° C storage elastic modulus of adhesive layer>
The 80 ° C. storage elastic modulus of the pressure-sensitive adhesive layer was measured by the method described in "2. Production of (meth) acrylic polymer" using the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer as a measurement sample.

<Amount of deviation of the adhesive layer at 80 ° C>
The adhesive polarizing film is cut into a width of 10 mm × a length of 100 mm, the PET film is peeled off, and the adhesive layer is attached onto the non-alkali glass so that the adhesive layer is in contact with the glass and has a bonding area of 10 mm × 10 mm. Together, a test piece for measurement was obtained.

The test piece for measurement was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes, and allowed to stand for 1 hour in a 23 ° C. and 50% RH environment. Next, the test piece was set in the chamber BOX of a microcreep measuring machine (model name: TA.TX.PLUS manufactured by Eiko Seiki Co., Ltd.) with a length of 15 mm for the fixing chuck portion.

After heating the inside of the chamber BOX to 80 ° C. and allowing it to stand at the measurement temperature for 40 minutes, the pressure-sensitive polarizing film on the test piece was subjected to the polarizing film and the glass under a tensile load of 800 g and a tension time of 1 hour. It was pulled parallel to the bonding surface with the polarizing film and in the length direction of the polarizing film, and the amount of deviation (μm) of the bonded portion between the glass and the polarizing film in the test piece was measured.

<Layer shrinkage rate>
The laminated body for the test was allowed to cool for 10 minutes in an environment of 23 ° C. and 50% RH, and the dimensions (Xs) in the long side direction of the polarizing film in the laminated body were measured. Next, the laminate was left to stand at 80 ° C. for 72 hours and then allowed to cool for 10 minutes in an environment of 23 ° C. and 50% RH to determine the dimensions (Ys) of the polarizing film in the laminate in the long side direction. It was measured. The laminate shrinkage rate (((Xs—Ys) / Xs) × 100) was calculated from the obtained Xs and Ys.

<Surface resistivity>
The surface of the pressure-sensitive adhesive layer exposed by allowing the test laminate to cool in an environment of 23 ° C. and 50% RH for 10 minutes and peeling off the adhesive polarizing film from the liquid crystal panel at a peeling angle of 90 ° and a peeling speed of 300 mm / min. The resistivity (Xr) was measured using a resistivity meter (High Resta UX MCP-HT800, Mitsubishi Chemical Analytical) at an applied voltage of 1000 V according to JIS-K-6911.

Further, the laminate was left to stand at 80 ° C. for 72 hours and then allowed to cool for 10 minutes in an environment of 23 ° C. and 50% RH to peel off the adhesive polarizing film from the liquid crystal panel at a peeling angle of 90 ° and a peeling speed of 300 mm. The surface resistivity (Yr) was measured in the same manner as the surface resistivity (Xr) except that it was peeled off at / min.

<80 ° C dry heat resistance durability>
After the test laminate was left at a temperature of 80 ° C. dry for 500 hours, the state of the laminate was visually observed, and the heat resistance and durability of the laminate at 80 ° C. dry was evaluated according to the following criteria.
◯: No wrinkles, foaming, or peeling in the adhesive layer Δ: Wrinkles are present in the adhesive layer, but no foaming or peeling is present ×: Foaming or peeling is present in the adhesive layer

Claims (11)

1. In an adhesive polarizing film formed by laminating an adhesive layer and a polarizing film,
   The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive and a conductive polymer.
   An adhesive polarizing film having a storage elastic modulus (G') of the pressure-sensitive adhesive layer at 80 ° C. of 20 to 1000 kPa.
2. The adhesive polarizing film according to claim 1, wherein the adhesive polarizing film is used.
   The pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive.
   The acrylic pressure-sensitive adhesive contains a (meth) acrylic polymer and a cross-linking agent.
   The (meth) acrylic polymer is a polymer of a monomer mixture, and is
   The monomer mixture has a content of the first monomer of 0.05 to 10% by mass and a content of the second monomer of 51 to 99.5% by mass.
   The first monomer is a crosslinkable functional group-containing monomer, and is
   The second monomer is not the first monomer, but a (meth) acrylic acid alkyl ester having a homopolymer glass transition temperature of −60 to 20 ° C. and a homopolymer having a glass transition temperature of −60 to 20 ° C. (meth). ) At least one selected from acrylic acid alkoxyalkyl esters,
   An adhesive polarizing film having a weight average molecular weight of 600,000 or more of the (meth) acrylic polymer.
3. The adhesive polarizing film according to claim 1, wherein the adhesive polarizing film is used.
   The pressure-sensitive adhesive is a rubber-based pressure-sensitive adhesive.
   The rubber-based pressure-sensitive adhesive contains a hydrogenated block copolymer, a tack-imparting resin, and a softening agent.
   The hydrogenated block copolymer has a segment composed of a polymer component of an aromatic vinyl monomer and a segment composed of a polymer component of a conjugated diene monomer.
   The tackifier resin has a softening point of 80 ° C. or higher and has a softening point of 80 ° C. or higher.
   The softener is an adhesive polarizing film that is liquid at 23 ° C.
4. The adhesive polarizing film according to any one of claims 1 to 3.
   The conductive polymer is an adhesive polarizing film having at least one of the structural units represented by the chemical formula (1) or (2).
   

   

   

   (R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms and having 1 to 12 carbon atoms, and a phenyl group which may have a substituent. , A heterocyclic group which may have a substituent, or a fused ring group which may have a substituent, R ² is an oxygen atom or a sulfur atom, respectively, and R ³ is a hydrogen atom or a hydrogen atom, respectively. It is an organic group. A ⁻ is a monoanion derived from a dopant. N is 2 or more and 300 or less.)
5. The adhesive polarizing film according to claim 4, wherein the adhesive polarizing film is used.
   An adhesive polarizing film in which R ¹ of the conductive polymer (B) has an ester bond.
6. The adhesive polarizing film according to any one of claims 1 to 5.
   The pressure-sensitive adhesive composition is a pressure-sensitive polarizing film containing a silane coupling agent.
7. The adhesive polarizing film according to any one of claims 1 to 6.
   When the adhesive surface of the adhesive polarizing film is attached to a glass plate with an area of 10 mm × 10 mm and a load of 800 g is applied in the shearing direction in an environment of 80 ° C., the adhesive surface adheres to the glass plate 1 hour after the start of load application. An adhesive polarizing film having a displacement of 2.0 mm or less in the agent layer.
8. A laminate for an image display device configured by attaching the adhesive polarizing film according to any one of claims 1 to 7 to an image display element.
9. The laminated body according to claim 8.
   A laminated body that satisfies the following formula (1).
   ((Xs-Ys) / Xs) x 100 <3 ... (1)
   (Xs is the dimension in the stretch axis direction of the polarizing film in the laminate in a state after the laminate is left in a 23 ° C. and 50% RH environment, and Ys is a dimension in which the laminate is placed in an 80 ° C. environment. It is the dimension in the stretch axis direction of the polarizing film in the laminated body after leaving it under the structure for 72 hours and then allowing it to cool for 10 minutes in an environment of 23 ° C. and 50% RH.)
10. The laminated body according to claim 8 or 9.
    A laminate in which both Xr and Yr are less than 1.0 × 10 ¹² .
    (Xr is the surface resistance of the adhesive layer exposed by peeling the adhesive polarizing film from the laminate after leaving the laminate in a 23 ° C. and 50% RH environment, and Yr is the surface resistance of the laminate. The surface resistance of the pressure-sensitive adhesive layer exposed by peeling the adhesive polarizing film from the laminate after leaving the body in an environment of 80 ° C. for 72 hours and then allowing it to cool in an environment of 23 ° C. and 50% RH for 10 minutes. Is.)
11. The laminated body according to claim 10.
    A laminated body that satisfies the following formula (2).
    Yr / Xr <10 ... (2)

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