CN108690535B - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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Publication number
CN108690535B
CN108690535B CN201710963801.1A CN201710963801A CN108690535B CN 108690535 B CN108690535 B CN 108690535B CN 201710963801 A CN201710963801 A CN 201710963801A CN 108690535 B CN108690535 B CN 108690535B
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adhesive layer
adhesive
meth
group
acrylate
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CN108690535A (en
Inventor
长仓毅
吉田弘幸
铃木史惠
大津贺健太郎
菱沼昌世
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The invention provides a surface resistivity of 2.0 x 10 with an adhesive layer+9An adhesive composition having extremely excellent antistatic performance of not more than omega/□ and not damaging durability, and an adhesive film using the same. The adhesive composition contains an acrylic polymer, and further contains (E) an ammonium antistatic agent having a fluorine-containing anion, (F) a crosslinking agent composed of a trifunctional or higher isocyanate compound or a bifunctional or higher epoxy compound, and (G) a silane coupling agent containing a functional group selected from an epoxy group, a mercapto group, and an acid anhydride group, wherein the acrylic polymer is a copolymer obtained by copolymerizing (A) n-butyl acrylate, (B) at least one selected from tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, (C) a copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group, and (D) a copolymerizable vinyl monomer containing an aromatic group.

Description

Adhesive composition and adhesive film
Technical Field
The present invention relates to an adhesive composition and an adhesive film that can be used for bonding to an In-cell screen panel having a touch panel function, In which an adherend is a liquid crystal panel, for example.
In particular to a surface resistivity of 2.0 x 10 which can not be achieved by the prior art and is provided with an adhesive layer+9An adhesive composition having extremely excellent antistatic properties of not more than omega/□, and an adhesive film using the adhesive composition.
Background
Various adhesive films for bonding optical members such as a polarizing plate and a retardation plate to an adherend such as a liquid crystal cell via an adhesive layer have been proposed (for example, see patent documents 1 to 2).
Patent document 1 describes an optical adhesive composition containing an acrylic polymer obtained by copolymerizing a monomer containing butyl acrylate or the like as a main component with an acrylamide compound or the like.
Patent document 2 describes an optical adhesive composition containing an acrylic polymer obtained by copolymerizing a carboxyl group-containing monomer and a nitrogen-containing vinyl monomer with a monomer containing, as a main component, (meth) acrylate having an alkyl group having 4 to 8 carbon atoms.
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent publication No. 2012-177022
Patent document 2: japanese unexamined patent publication No. 2012-201734
Disclosure of Invention
Technical problem to be solved by the invention
However, In the adhesive layer for bonding a polarizing plate and a liquid crystal panel, when the liquid crystal panel is an In-cell panel having a function as a touch panel, the surface resistivity of the adhesive layer is required to be lower than that of the conventional one.
Therefore, the adhesive layer for bonding the polarizing plate to the liquid crystal panel is required to have a surface resistivity of 2.0 × 10+9Omega/□ or less. However, in the prior art, it is very difficult to exhibit such high antistatic performance.
In addition, even if such a high antistatic performance can be exhibited, it is difficult to simultaneously maintain the durability of the adhesive layer.
The technical problem of the invention is to provide a surface resistivity of 2.0 x 10 with an adhesive layer+9An adhesive composition having extremely excellent antistatic performance of not more than omega/□ and not impairing durability, and an adhesive film using the adhesive composition.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the technical problem that it is difficult to achieve both such high antistatic performance and durability at the same time. As a result, the above-mentioned problems can be solved by forming an acrylic polymer composed of a copolymer obtained by copolymerizing two or more kinds of alkyl (meth) acrylates in a specific combination by limiting the number of carbon atoms of the alkyl group of the alkyl (meth) acrylate constituting the acrylic polymer of the adhesive composition to a specific range, and further forming an adhesive composition containing a specific antistatic agent.
The present inventors have found that an adhesive composition having extremely excellent antistatic performance, no deposition of an antistatic agent, and excellent durability against deterioration with time can be obtained as compared with conventional adhesive compositions by containing the acrylic polymer and an ammonium antistatic agent having a fluorine-containing anion in an amount exceeding 15 parts by weight based on 100 parts by weight of the acrylic polymer, and have completed the present invention.
The adhesive composition of the present invention has a surface resistivity of 2.0X 10 for the adhesive layer+9Omega/□ or less, and contains an ammonium antistatic agent having a fluorine-containing anion in an amount of more than 15 parts by weight based on 100 parts by weight of the acrylic polymer. As described above, in the present invention, the content of the antistatic agent is increased in order to obtain an extremely excellent antistatic performance which cannot be achieved by the conventional techniques.
The technical idea of the adhesive composition according to the present invention is that an acrylic polymer contained in the adhesive composition is copolymerized by selecting a monomer having good copolymerizability with n-Butyl Acrylate (BA) mainly, in order to form an adhesive layer capable of maintaining durability without precipitation of an ammonium antistatic agent having a fluorine-containing anion contained in a large amount in the adhesive layer from the surface of the adhesive layer after a durability test in a high-temperature and high-humidity environment of the adhesive layer.
Further, in order to solve the above-mentioned problems, the present invention provides an adhesive composition comprising an acrylic polymer and an antistatic agentThe acrylic polymer is an acrylic polymer having a weight average molecular weight of 100 to 300 ten thousand, which is a copolymer obtained by copolymerizing the following monomers: (A) n-butyl acrylate, (B) at least one member selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate, (C) at least one member selected from the group consisting of copolymerizable vinyl monomers containing a hydroxyl group and/or a carboxyl group, and (D) at least one member selected from the group consisting of copolymerizable vinyl monomers containing an aromatic group; the adhesive composition contains an ammonium antistatic agent having a fluorine-containing anion as the (E) antistatic agent in a proportion of more than 15 parts by weight and 40 parts by weight or less relative to 100 parts by weight of the acrylic polymer; the adhesive composition contains at least one or more crosslinking agents selected from the group consisting of trifunctional or higher isocyanate compounds and bifunctional or higher epoxy compounds as the (F) crosslinking agent; the adhesive composition further comprises (G) a monomeric or oligomeric silane coupling agent containing at least one or more functional groups selected from epoxy groups, mercapto groups, and acid anhydride groups; the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 2.0 x 10+9Omega/□ or less; after the adhesive layer was subjected to a durability test in a test environment of 85 ℃ x 750hr or in a test environment of 60 ℃ x 90% RH x 750hr, the antistatic agent was not precipitated on the surface of the adhesive layer.
Further, it is preferable that the antistatic agent is an ionic compound formed of a fluorine-containing anion and an ammonium cation and having a melting point of 25 ℃ or higher; the fluorine-containing anion is one selected from the group consisting of pentafluorobenzene sulfonate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, and trifluoromethanesulfonate.
Preferably, the acrylic polymer contains the n-butyl acrylate (A) in a proportion of 40 to 89 parts by weight and the (B) at least one selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate in a proportion of 5 to 40 parts by weight in total, based on 100 parts by weight of the acrylic polymer, and the ratio (A)/(B) of (A) to (B) is 1.0 to 17.8.
Preferably, when a polarizing plate having a total thickness of 80 μm is bonded to alkali-free glass via an adhesive layer having a thickness of 20 μm obtained by crosslinking the adhesive composition, the adhesive layer has an adhesive force of 1.0 to 6.0N/25mm with respect to the alkali-free glass; a test piece obtained by bonding a polarizing plate having a total thickness of 80 μm in a 10cm square to an alkali-free glass via an adhesive layer having a thickness of 20 μm obtained by crosslinking the adhesive composition was free from blistering and peeling after a durability test in a test environment of 85 ℃ x 750hr or a durability test in a test environment of 60 ℃ x 90% RH x 750 hr.
The (C) copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group is preferably at least one selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group; the copolymerizable monomer containing hydroxyl is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; the carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
Preferably, the initial surface resistivity of the adhesive layer and the surface resistivity after the durability test in the test environment of 85 ℃ x 750hr are both 2.0 x 10+9Omega/□ or less.
The present invention also provides an adhesive film comprising a resin film and, laminated on one surface thereof, an adhesive layer obtained by crosslinking the adhesive composition.
The present invention also provides an adhesive film for a polarizing plate, which uses the adhesive film.
The present invention also provides the adhesive film for a polarizing plate, which is used for bonding a polarizing plate to an In-cell panel.
The present invention also provides an adhesive film having a structure of a release film/an adhesive layer/a release film, wherein the adhesive layer obtained by crosslinking the adhesive composition is formed on one surface of the release film in a thickness of 1 to 25 μm.
The present invention also provides an optical film with an adhesive layer, which is characterized in that the optical film is formed by laminating an adhesive layer obtained by crosslinking the adhesive composition on at least one surface of the optical film.
The present invention also provides a polarizing plate with an adhesive layer, wherein the polarizing plate is obtained by laminating an adhesive layer obtained by crosslinking the adhesive composition on one surface of a polarizing plate.
The present invention also provides a liquid crystal panel using the above polarizing plate with an adhesive layer.
In addition, the present invention provides an In-cell type liquid crystal panel using the polarizing plate with an adhesive layer.
Effects of the invention
According to the present invention, it is possible to provide a pressure-sensitive adhesive composition having an adhesive layer and having a surface resistivity of 2.0X 10 which has not been achieved by the conventional techniques+9An adhesive composition having extremely excellent antistatic performance of not more than omega/□ and not impairing durability, and an adhesive film using the adhesive composition.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present embodiment comprises an acrylic polymer, an antistatic agent, andand a crosslinking agent, wherein the acrylic polymer is a copolymer obtained by copolymerizing (A), (B), (C) and (D), and has a weight average molecular weight of 100 to 300 ten thousand, wherein (A) is n-butyl acrylate, (B) is at least one selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate, (C) is at least one of copolymerizable vinyl monomers containing a hydroxyl group and/or a carboxyl group, and (D) is at least one of copolymerizable vinyl monomers containing an aromatic group; the adhesive composition contains an ammonium antistatic agent having a fluorine-containing anion as the (E) antistatic agent in a proportion of more than 15 parts by weight and 40 parts by weight or less relative to 100 parts by weight of the acrylic polymer; the adhesive composition contains at least one or more crosslinking agents selected from the group consisting of trifunctional or higher isocyanate compounds and bifunctional or higher epoxy compounds as the (F) crosslinking agent; the adhesive composition further comprises (G) a monomeric or oligomeric silane coupling agent containing at least one or more functional groups selected from epoxy groups, mercapto groups, and acid anhydride groups; the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 2.0 x 10+9Omega/□ or less; after the adhesive layer was subjected to a durability test in a test environment of 85 ℃ x 750hr or in a test environment of 60 ℃ x 90% RH x 750hr, the antistatic agent was not precipitated on the surface of the adhesive layer.
(A) N-butyl acrylate, and (B) at least one selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, all of which are used as the alkyl (meth) acrylate monomer. In the adhesive composition of the present embodiment, the alkyl (meth) acrylate monomer constituting the acrylic polymer is preferably a combination of two or more specific types of (a) and (B).
The acrylic polymer of the present embodiment is mainly composed of (a) n-butyl acrylate, and preferably contains (a) n-butyl acrylate in a proportion of 40 to 89 parts by weight with respect to 100 parts by weight of the acrylic polymer, for example. The acrylic polymer further preferably contains (B) at least one or more selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate as an alkyl (meth) acrylate monomer other than (A) n-butyl acrylate in a total amount of 5 to 40 parts by weight. The ratio (A)/(B) of (A) to (B) is preferably 1.0 to 17.8 in terms of weight ratio.
The copolymerizable vinyl monomer having a hydroxyl group and/or a carboxyl group (C) includes at least one selected from the group consisting of a copolymerizable monomer having a hydroxyl group (hydroxyl group-containing monomer) and a copolymerizable monomer having a carboxyl group (carboxyl group-containing monomer). That is, either one of the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be selected and copolymerized, or both the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be copolymerized.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; or at least one kind of hydroxyl group-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.
The hydroxyl group-containing monomer contained in the adhesive composition according to the present embodiment can be used as a copolymerizable monomer for reducing the content of a carboxyl group-containing monomer that affects the corrosiveness of the obtained adhesive layer to a corrodible adherend such as an ITO surface of a transparent conductive film. Therefore, the hydroxyl group-containing monomer can function to improve the adhesion of the adhesive layer and reduce the corrosiveness. The proportion of the hydroxyl group-containing monomer contained in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.1 to 5.0 parts by weight, more preferably 0.1 to 4.4 parts by weight, and particularly preferably 0.1 to 3.8 parts by weight, based on 100 parts by weight of the acrylic polymer.
Examples of the carboxyl group-containing monomer include at least one of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
In addition, the carboxyl group-containing monomer contained in the adhesive composition according to the present embodiment can impart a necessary cohesive force to the obtained adhesive layer. The proportion of the carboxyl group-containing monomer in the adhesive composition according to the present embodiment is preferably 0 to 5.0 parts by weight (it is permissible not to copolymerize the carboxyl group-containing monomer) per 100 parts by weight of the acrylic polymer, and in the case of copolymerizing the carboxyl group-containing monomer, the proportion is more preferably 0.01 to 5.0 parts by weight, particularly preferably 0.01 to 3.3 parts by weight, and most preferably 0.01 to 2.8 parts by weight.
Examples of the aromatic group-containing copolymerizable vinyl monomer (D) include at least one member selected from benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, 2- (1-naphthyloxy) ethyl (meth) acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate, 6- (1-naphthyloxy) hexyl (meth) acrylate, 6- (2-naphthyloxy) hexyl (meth) acrylate, 8- (1-naphthyloxy) octyl (meth) acrylate, and 8- (2-naphthyloxy) octyl (meth) acrylate. When an aromatic group-containing (meth) acrylate monomer is contained as the (D) aromatic group-containing copolymerizable vinyl monomer, it is preferable because it has excellent copolymerizability with an alkyl (meth) acrylate monomer composed of a combination of (a) and (B).
In order to obtain an adhesive layer having a high refractive index, it is preferable to blend at least one or more aromatic group-containing (meth) acrylate monomers into the adhesive composition according to the present embodiment. By copolymerizing these aromatic group-containing (meth) acrylate monomers with an acrylic polymer, the refractive index of the obtained adhesive agent layer can be increased and adjusted, the refractive index difference between optical members can be reduced, and the total light transmittance can be increased by reducing total reflection. The pressure-sensitive adhesive composition according to the present embodiment contains the aromatic group-containing (meth) acrylate monomer in an amount of preferably 5 to 30 parts by weight, more preferably 6 to 28 parts by weight, and particularly preferably 6 to 24 parts by weight, based on 100 parts by weight of the acrylic polymer.
The method for producing the acrylic polymer contained in the adhesive composition according to the present embodiment is not particularly limited, and any suitable known polymerization method such as solution polymerization method or emulsion polymerization method can be used. The weight average molecular weight of the copolymer of the acrylic polymer is preferably 100 to 300 ten thousand.
The pressure-sensitive adhesive composition according to the present embodiment contains (E) an antistatic agent for obtaining antistatic performance. The (E) antistatic agent is preferably an ammonium antistatic agent having a fluorine-containing anion contained in an amount of more than 15 parts by weight and not more than 40 parts by weight, more preferably 16 to 40 parts by weight, and particularly preferably 16 to 38 parts by weight, based on 100 parts by weight of the acrylic polymer. The antistatic agent is an ionic compound formed by fluorine-containing anions and ammonium cations. Preferably, the ionic compound has a melting point of 25 ℃ or higher and is solid at ordinary temperature (e.g., 25 ℃). Further, the ionic compound is more preferably an ionic compound which is solid at a temperature of 25 ℃ and has a melting point of 25 to 80 ℃.
Examples of the fluorine-containing anion contained in the antistatic agent (E) include inorganic or organic fluorine-containing anions. Here, the fluoro group means a fluorine atom bonded to other atoms constituting the anion. As the inorganic fluorine-containing anion, PF is exemplified6 -、AsF6 -、SbF6 -、BF4 -、AlF4 -、(FSO2)2N-、FSO3 -And the like. Examples of the organic fluorine-containing anion include sulfonate anion (RSO) containing fluorine group3 -) Fluorine-containing carboxylate anion (RCOO)-) Fluorine-containing alkoxide (アルコキシド) or phenoxide (フェノキシド) anion (RO)-) Fluorine group-containing organic imide anion (R)2N-) And (R) a fluorine-containing methide (メチド)3C-) Anionic, fluorine-containing organic borate (R)4B-) In the anion, at least 1 or more of R are anions having an organic group having a fluorine-containing group. Examples of the organic group include at least one of an alkyl group, an alkoxy group, an aromatic group (such as an aryl group and an aralkyl group), an alkylcarbonyl group, an aromatic carbonyl group, an alkylsulfonyl group, and an aromatic sulfonyl group. When the anion has 2 or more R, the anion may have a bond between 2 or more R to form a cyclic group. Among them, one selected from the group consisting of pentafluorobenzene sulfonate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, and trifluoromethanesulfonate is preferable.
The ammonium cation contained in the antistatic agent (E) includes organic ammonium cations having 1 to 4 organic groups, and quaternary ammonium cation (R) is particularly preferable4N+). Examples of R include hydrocarbon groups such as acyclic or cyclic alkyl groups and aromatic groups (such as aryl groups and aralkyl groups). When the cation has 2 or more R, a cyclic structure may be formed with 2 or more R bonds.
The adhesive composition according to the present embodiment further contains at least one or more crosslinking agents selected from the group consisting of trifunctional or higher isocyanate compounds and bifunctional or higher epoxy compounds as the (F) crosslinking agent. The proportion of the crosslinking agent (F) is, for example, 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic polymer.
Examples of the trifunctional or higher isocyanate compound include biuret modified products and isocyanurate modified products of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate; and adducts with trihydric or higher polyhydric alcohols such as trimethylolpropane and glycerol.
Examples of the bifunctional or higher epoxy compound include diglycidyl ethers of dihydric alcohols, diglycidyl ethers of bisphenols, triglycidyl ethers of trihydric alcohols, diglycidyl esters of dicarboxylic acids, diglycidyl-substituted amines, and tetraglycidyl-substituted diamines.
The adhesive composition according to the present embodiment further contains (G) a silane coupling agent. The silane coupling agent (G) has at least one organic functional group and at least one hydrolyzable group in 1 molecule, and examples thereof include compounds in which the hydrolyzable group is an alkoxy group bonded to a silicon atom. (G) The silane coupling agent contains at least one functional group selected from an epoxy group, a mercapto group, and an acid anhydride group. (G) The silane coupling agent may be used in at least one of a monomeric type and an oligomeric type. The proportion of the silane coupling agent is, for example, 0.01 to 0.5 part by weight based on 100 parts by weight of the acrylic polymer.
Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 5, 6-epoxyhexyltrimethoxysilane, 5, 6-epoxyhexylmethyldimethoxysilane, 5, 6-epoxyhexylmethyldiethoxysilane, 5, 6-epoxyhexyltriethoxysilane, etc. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 3-mercaptopropyltriethoxysilane. Examples of the silane coupling agent having an acid anhydride group include 3-trimethoxysilylpropyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride. Further, an oligomeric alkoxy oligomer (siloxane alkoxy oligomer) or the like can also be used as the silane coupling agent.
The pressure-sensitive adhesive composition of the present embodiment may contain, as optional components, known additives such as an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a crosslinking catalyst, a crosslinking retarder, a curing retarder, a processing aid, and an antioxidant. These arbitrary components may be used alone or in combination of two or more.
The surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is preferably 2.0 × 10+9Omega/□ or less, more preferably 1.0X 10+9Omega/□ or less, particularly preferably 8.0X 10+8Omega/□ or less. Preferably, the initial surface resistivity of the adhesive layer and the surface resistivity after the durability test are both 2.0X 10+9Omega/□ or less, more preferably 1.0X 10+9Omega/□ or less, particularly preferably 8.0X 10+8Omega/□ or less. Here, the initial surface resistivity refers to the surface resistivity of the adhesive layer before the durability test. The surface resistivity after the durability test is the surface resistivity after subjecting the adhesive layer to the durability test in the test environment of 85 ℃ x 750 hr. Here, the test environment at 85 ℃ C.. times.750 hr may be dry conditions.
After the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is subjected to a durability test in a test environment of 85℃ × 750hr and a durability test in a test environment of 60℃ × 90% RH × 750hr, (E) the antistatic agent is not precipitated on the surface of the adhesive layer. Here, the test environment at 85 ℃ C.. times.750 hr may be dry conditions.
With respect to the performance of preventing the deposition of the (E) antistatic agent in the adhesive composition of the present embodiment, two or more samples of the adhesive layer obtained by crosslinking the same adhesive composition were prepared, and after one sample was subjected to a durability test under a test environment of 85℃ × 750hr, (E) the antistatic agent was not deposited, and after the other sample was subjected to a durability test under a test environment of 60℃ × 90% RH × 750hr, (E) the antistatic agent was not deposited.
The adhesive composition of the embodiment of the crosslinked adhesive layer preferably via the thickness of 20 u m adhesive layer, the total thickness of 80 u m polarizer is bonded to alkali-free glass, adhesive layer to alkali-free glass adhesion is 1.0 ~ 6.0N/25 mm.
Further, it is preferable that a test piece obtained by bonding a polarizing plate having a total thickness of 80 μm in a 10cm square direction to an alkali-free glass via an adhesive layer having a thickness of 20 μm is free from bubbling and peeling after being subjected to a durability test in a test environment of 85 ℃ x 750hr and a durability test in a test environment of 60 ℃ x 90% RH x 750 hr.
Regarding the non-foaming and non-peeling performance of the adhesive composition of the present embodiment, two or more test pieces manufactured using the same adhesive composition were manufactured, and after one test piece was subjected to a durability test under a test environment of 85℃ × 750hr, foaming and peeling were not generated, and after another test piece was subjected to a durability test under a test environment of 60℃ × 90% RH × 750hr, foaming and peeling were not generated.
The adhesive agent layer according to the present embodiment can be obtained by applying the adhesive agent composition of the present embodiment to a substrate such as a resin film or a release film and then crosslinking the adhesive agent composition.
When the adhesive layer according to the present embodiment is used for lamination between layers of optical members or the like, it is desirable that the difference in refractive index is as small as possible in order to reduce reflection of light at the interface between the adhesive layer and the optical member. Therefore, the refractive index of the adhesive layer is preferably 1.47 to 1.50.
The adhesive film according to the present embodiment can be produced by forming the adhesive layer according to the present embodiment on one surface of a substrate such as a resin film or a release film. As the resin film or release film (separator) to be used as the substrate, a resin film such as a polyester film or the like can be used. The release film may be subjected to a release treatment on the surface of the release film that is bonded to the pressure-sensitive adhesive layer with a silicone or fluorine-based release agent. The resin film to be a substrate may be subjected to an anti-fouling treatment with a silicone or fluorine-based release agent or coating agent, silica fine particles, or the like, or an antistatic treatment with an antistatic agent such as coating or kneading, on the surface of the resin film opposite to the side on which the adhesive agent layer is formed. The thickness of the adhesive layer is, for example, 1 to 25 μm.
The structure of "release film/adhesive layer/release film" may be formed by bonding the release-treated surfaces of the release films to both surfaces of one adhesive layer. In this case, the release films on both sides are peeled off sequentially or simultaneously to expose the adhesive surface, whereby the optical member such as an optical film can be bonded. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an anti-glare (anti-glare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film. Examples of the device to which the optical member is applied include a liquid crystal panel, an organic EL panel, a touch panel, and an In-cell type liquid crystal panel.
The adhesive film of the present embodiment is suitable as an adhesive film for a polarizing plate. In particular, it can be used for attaching a polarizing plate to an In-cell panel. Further, an optical film with an adhesive layer may be formed by laminating the adhesive layer on at least one surface of the optical film. Further, by using the above adhesive film on one surface of a polarizing plate, a polarizing plate with an adhesive layer can be provided. A liquid crystal panel such as an In-cell type liquid crystal panel can be provided by using the above-described polarizing plate with an adhesive layer.
Specific examples of such a laminated structure of an optical film with an adhesive layer include "release film/adhesive layer/optical film", "release film/adhesive layer/optical film/adhesive layer/release film", "optical film/adhesive layer/optical film", "optical film/adhesive layer", "adhesive layer/optical film/adhesive layer", and the like. Specific examples of the laminated structure of the polarizing plate with an adhesive layer include "release film/adhesive layer/polarizing plate", "release film/adhesive layer/polarizing plate/adhesive layer/release film", "polarizing plate/adhesive layer", "adhesive layer/polarizing plate/adhesive layer", and the like. As a partial structure of a liquid crystal panel or the like, an optical film with an adhesive layer or a polarizing plate with an adhesive layer may be provided.
In addition, like "release film/adhesive layer/optical film", "release film/adhesive layer/polarizing plate", and the like, in the case where a release film is included in a laminated structure, after the release film is peeled off, the optical film or polarizing plate is bonded to an adherend via the adhesive layer.
Examples
The present invention will be specifically described below with reference to examples.
< preparation of acrylic Polymer >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, 70 parts by weight of n-butyl acrylate, 15 parts by weight of n-butyl methacrylate, 2.0 parts by weight of 8-hydroxyoctyl acrylate, 15 parts by weight of benzyl acrylate, and a solvent (ethyl acetate) were charged into the reaction apparatus. Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65 ℃ for 6 hours to obtain a solution of the acrylic polymer used in example 1.
Examples 2 to 6 and comparative examples 1 to 3
Acrylic polymer solutions used in examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as in example 1 above, except that the monomer compositions were as shown in (a) to (D) in table 1.
Further, although the measurement results are not particularly shown, the weight average molecular weight of the copolymer contained in the acrylic polymer solutions of examples 1 to 6 and comparative examples 1 to 3 is in the range of 100 to 300 ten thousand.
< production of adhesive film >
[ example 1]
To the acrylic polymer solution of example 1 prepared as described above, cyclohexyltrimethylammonium bis (trifluoromethanesulfonyl) imide was added in a proportion of 20 parts by weight, the crosslinking agent (D-110N) was added in a proportion of 0.1 parts by weight, and the silane coupling agent (X-12-967C) was added in a proportion of 0.05 parts by weight, followed by stirring and mixing to obtain the adhesive composition of example 1.
The adhesive composition was applied to a release film formed of a silicone resin-coated polyethylene terephthalate (PET) film so that the thickness of the dried adhesive layer became 20 μm, and then dried at 90 ℃ to remove the solvent. Then, the adhesive film of example 1 having a structure of a release film/an adhesive layer/a release film having an adhesive layer obtained by crosslinking an adhesive composition on one surface of a release film was obtained by curing at 23 ℃ and 50% RH for 7 days.
Examples 2 to 6 and comparative examples 1 to 3
Adhesive films of examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the adhesive film of example 1 described above, except that the additive compositions were as shown in (E) to (G) in table 1.
[ Table 1]
Figure GDA0003022415620000151
In Table 1, the numerical values added after the abbreviations of the respective components represent parts by weight. The weight parts are determined by assuming that the total amount of (A), (B) and (D) is 100 weight parts. Further, the compound names of the abbreviations used for the respective components in table 1 are shown in table 2. For simplicity, the IOA is included in (B). (C) In (1), the monomer having a hydroxyl group is classified as "(C) OH", and the monomer having a carboxyl group is classified as "(C) COOH".
[ Table 2]
Figure GDA0003022415620000161
In Table 2, CORONATE (registered trademark) L is a trade name of TOSOH CORPORATION, D-110N is a trade name of Mitsui Chemicals, Inc., and TETRAD (registered trademark) -X is a trade name of MITSUBISHI GAS CHEMICAL COMPANY, INC. In addition, TDI refers to toluene diisocyanate, TMP refers to trimethylolpropane, and XDI refers to xylylene diisocyanate. Furthermore, KBM-403, X-12-967C, X-41-1805, and KBM-503 are trade names of Shin-Etsu Chemical Co., Ltd.
< test method and evaluation >
The release film (silicone resin-coated PET film) was peeled from the adhesive films of examples 1 to 6 and comparative examples 1 to 3, and one surface of the adhesive layer of the adhesive film was exposed. Then, the adhesive film was bonded to one surface of a polarizing plate (resin film) having a thickness of 80 μm via the adhesive layer, thereby obtaining an adhesive layer-equipped polarizing plate having a structure of a release film/adhesive layer/polarizing plate.
< method for measuring adhesive force >
The release film of the polarizing plate with the adhesive layer obtained above was peeled off, and the polarizing plate with the adhesive layer was bonded to a surface of alkali-free glass (EAGLE XG (registered trademark) manufactured by Corning Incorporated) cleaned with acetone by a pressure roller through the adhesive layer, thereby producing a test piece. Then, the test piece was subjected to autoclave treatment at 50 ℃ for 0.5 MPa.times.20 minutes. Thereafter, the pressure-sensitive adhesive layer was returned to the atmosphere of 23 ℃ x 50% RH, and the peel strength of the polarizing plate with the pressure-sensitive adhesive layer after 1 hour had elapsed was measured by a tensile tester in accordance with JIS Z0237 "adhesive tape/adhesive sheet test method", and the peel strength when the pressure-sensitive adhesive layer was peeled at a speed of 0.3 m/min in the direction of 180 ° was taken as the adhesion of the pressure-sensitive adhesive layer to alkali-free glass.
< method for measuring surface resistivity >
The surface resistivity (Ω/□) of the adhesive layer was measured using a resistivity meter HIRESTA (registered trademark) UP-HT450 (manufactured by Mitsubishi Chemical analytical co., ltd.) to obtain the initial surface resistivity of the adhesive layer-carrying polarizing plate obtained above. The same polarizing plate with an adhesive layer was subjected to a durability test under a test environment of 85 ℃ x 750hr, and then the surface resistivity was measured in the same manner, and the surface resistivity after the durability test was obtained.
< method for testing durability >
In the same manner as in the measurement of the adhesive force, a 10cm square release film of the polarizing plate with the adhesive layer was peeled off and bonded to the acetone-cleaned surface of the alkali-free glass, to produce a test piece. Then, the test piece was subjected to a durability test in a test environment of 85℃ × 750hr and a durability test in a test environment of 60℃ × 90% RH × 750hr, and then taken out to an atmosphere of 23℃ × 50% RH, and after 1 hour, the state of the adhesive layer was visually observed, and the durability was determined.
O: without foaming and peeling of the adhesive layer.
And (delta): a part of the adhesive layer is foamed and peeled off.
X: the adhesive layer was foamed and peeled off as a whole.
< method for evaluating precipitation State of antistatic agent >
In the same manner as in the measurement of the adhesive force, a 10cm square release film of the polarizing plate with the adhesive layer was peeled off and bonded to the acetone-cleaned surface of the alkali-free glass, to produce a test piece. Then, the test piece was subjected to a durability test in a test environment of 85℃ × 750hr and a durability test in a test environment of 60℃ × 90% RH × 750hr, and then taken out to an atmosphere of 23℃ × 50% RH, and after 1 hour, the state of the adhesive layer was visually observed, and the state of deposition of the antistatic agent on the surface of the adhesive layer was determined.
O: there was no precipitation of the antistatic agent on the surface of the adhesive layer.
And (delta): precipitation of the antistatic agent occurs on a part of the surface of the adhesive agent layer.
X: the antistatic agent is precipitated on the entire surface of the adhesive agent layer.
The evaluation results are shown in table 3.
[ Table 3]
Figure GDA0003022415620000191
The adhesive films of examples 1 to 6 had an adhesive force to alkali-free glass of 1.0 to 6.0N/25mm, and the initial surface resistivity of the adhesive layer and the surface resistivity after the durability test in the test environment of 85 ℃ C. × 750hr were each 2.0 × 10+9Omega/□ or less, and has no foam and peeling off, durability and no deposition of antistatic agent on the surface of the adhesive agent layer after a durability test in a test environment of 85 ℃ x 750hr and a durability test in a test environment of 60 ℃ x 90% RH x 750 hr. That is, the evaluation results of the adhesive films of examples 1 to 6 confirmed that the technical problem of the present invention could be solved.
In the adhesive film of comparative example 1, the alkyl (meth) acrylate monomer copolymerized in the acrylic polymer was not any of TBA, IBA, BMA, and MA, and the aromatic group-containing copolymerizable vinyl monomer (D) was not copolymerized. Therefore, the adhesive layer of the adhesive film of comparative example 1 before the durability test had too large an adhesive force and had poor durability. In addition, in the adhesive film of comparative example 1, since the content ratio of the (E) antistatic agent is large, the surface resistivity of the adhesive layer is low, but the antistatic agent is precipitated on the entire surface of the adhesive layer after the durability test.
The adhesive film of comparative example 2 contains (G) a silane coupling agent, but does not contain at least one or more functional groups selected from epoxy groups, mercapto groups, and acid anhydride groups. Therefore, the adhesive layer of the adhesive film of comparative example 2 had poor durability, and the antistatic agent was observed on the surface of the adhesive layer after the durability test.
In the adhesive film of comparative example 3, the alkyl (meth) acrylate monomer copolymerized in the acrylic polymer was not any of TBA, IBA, BMA, and MA, and the aromatic group-containing copolymerizable vinyl monomer (D) was not copolymerized. Therefore, even if the adhesive film of comparative example 3 does not contain the (G) silane coupling agent, the adhesive force of the adhesive layer before the durability test is too large, and the durability is poor. Further, since the content ratio of the antistatic agent (E) is small, the adhesive film of comparative example 3 has no deposition of the antistatic agent on the surface of the adhesive layer after the durability test, but the surface resistivity of the adhesive layer becomes high.
Thus, the adhesive films of comparative examples 1 to 3 could not solve the technical problems of the present invention.
According to the present invention, a surface resistor having an adhesive layer can be providedThe ratio is 2.0 × 10 which can not be achieved in the prior art+9An adhesive composition having extremely excellent antistatic properties of not more than omega/□ and not impairing durability, and an adhesive film using the same. Therefore, the adhesive composition and the adhesive film using the same according to the present invention have extremely excellent antistatic properties and durability as the adhesive composition for bonding a polarizing plate and a liquid crystal panel and the adhesive film using the same, and thus have a large industrial value.

Claims (14)

1. An adhesive composition comprising an acrylic polymer, an antistatic agent, and a crosslinking agent, characterized in that,
the acrylic polymer is a copolymer obtained by copolymerizing the following monomers, and the weight-average molecular weight of the copolymer is 100-300 ten thousand: (A) n-butyl acrylate, (B) at least one member selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate, (C) at least one member selected from the group consisting of copolymerizable vinyl monomers containing a hydroxyl group and/or a carboxyl group, and (D) at least one member selected from the group consisting of copolymerizable vinyl monomers containing an aromatic group;
the adhesive composition contains an ammonium antistatic agent having a fluorine-containing anion as the (E) antistatic agent in a proportion of more than 15 parts by weight and 40 parts by weight or less relative to 100 parts by weight of the acrylic polymer;
the adhesive composition contains at least one or more crosslinking agents selected from the group consisting of trifunctional or higher isocyanate compounds and bifunctional or higher epoxy compounds as the (F) crosslinking agent;
the adhesive composition further comprises (G) a monomeric or oligomeric silane coupling agent containing at least one or more functional groups selected from epoxy groups, mercapto groups, and acid anhydride groups;
the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 2.0 x 10+9Omega/□ or less;
after the adhesive layer was subjected to a durability test in a test environment of 85 ℃ x 750hr or in a test environment of 60 ℃ x 90% RH x 750hr, the antistatic agent was not precipitated on the surface of the adhesive layer.
2. The adhesive composition according to claim 1, wherein the antistatic agent is an ionic compound having a melting point of 25 ℃ or higher, which is formed from a fluorine-containing anion and an ammonium cation;
the fluorine-containing anion is one selected from the group consisting of pentafluorobenzene sulfonate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, and trifluoromethanesulfonate.
3. The adhesive composition according to claim 1 or 2, wherein the acrylic polymer comprises 40 to 89 parts by weight of the n-butyl acrylate (A) and 5 to 40 parts by weight in total of at least one selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate (B) per 100 parts by weight of the acrylic polymer, and the ratio (A)/(B) of (A) to (B) is 1.0 to 17.8.
4. The adhesive composition according to claim 1 or 2, wherein when a polarizing plate having a total thickness of 80 μm is bonded to an alkali-free glass via an adhesive layer having a thickness of 20 μm obtained by crosslinking the adhesive composition, the adhesive layer has an adhesive force of 1.0 to 6.0N/25mm with respect to the alkali-free glass;
a test piece obtained by bonding a polarizing plate having a total thickness of 80 μm in a 10cm square to an alkali-free glass via an adhesive layer having a thickness of 20 μm obtained by crosslinking the adhesive composition was free from blistering and peeling after a durability test in a test environment of 85 ℃ x 750hr or a durability test in a test environment of 60 ℃ x 90% RH x 750 hr.
5. The adhesive composition according to claim 1 or 2, wherein the (C) copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group is at least one or more selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group;
the copolymerizable monomer containing hydroxyl is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide;
the carboxyl group-containing copolymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
6. The adhesive composition according to claim 1 or 2, wherein the initial surface resistivity of the adhesive layer and the surface resistivity after the durability test in the test environment of 85 ℃ x 750hr are both 2.0 x 10+9Omega/□ or less.
7. An adhesive film comprising a resin film and, laminated on one surface thereof, an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 6.
8. An adhesive film for a polarizing plate, which comprises the adhesive film according to claim 7.
9. The adhesive film for a polarizing plate according to claim 8, which is used for bonding a polarizing plate to an In-cell panel.
10. An adhesive film characterized by having a structure of a release film/an adhesive layer/a release film, wherein the adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 6 is formed on one surface of a release film with a thickness of 1 to 25 μm.
11. An optical film with an adhesive layer, characterized in that the optical film is formed by laminating an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 6 on at least one surface of an optical film.
12. A polarizing plate with an adhesive layer, characterized in that the polarizing plate is obtained by laminating an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 6 on one surface of a polarizing plate.
13. A liquid crystal panel, wherein the adhesive layer-attached polarizing plate according to claim 12 is used.
14. An In-cell type liquid crystal panel, characterized In that the polarizing plate with an adhesive layer described In claim 12 is used.
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