TW202342675A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet - Google Patents

Abstract

A purpose of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer which is less apt to have failures in durability (particularly stability of non-corrosiveness and resistivity stability), shows a low surface resistivity, and has excellent antistatic performance. This pressure-sensitive adhesive composition comprises: a pressure-sensitive adhesive polymer (A); and an electroconductive polymer (B), a mixture of monomer ingredients for constituting the electroconductive polymer (B), or a product of partial polymerization of the mixture. The monomer ingredients for constituting the electroconductive polymer (B) include an ionic compound (B1) having a functional group (b1) in the molecule and a compound (B2) having, in the molecule, a functional group (b2) capable of reacting with the functional group (b1) to form a covalent bond. The electroconductive polymer (B) has a three-dimensional network structure. The pressure-sensitive adhesive layer formed from this pressure-sensitive adhesive composition has an interpenetration polymer network or semi-interpenetration polymer network formed by the entanglement of the three-dimensional network structure of the electroconductive polymer (B) with the pressure-sensitive adhesive polymer (A).

Description

Adhesive composition, adhesive layer, and adhesive sheet

The invention relates to an adhesive composition, an adhesive layer, and an adhesive sheet. More specifically, the invention relates to an adhesive composition, an adhesive layer, and an adhesive sheet having excellent antistatic properties.

In recent years, display devices such as liquid crystal displays (LCDs) and input devices such as touch panels have become widely used in various fields. In the manufacture of such display devices and input devices, adhesive sheets are used for bonding optical components. For example, transparent adhesive sheets are used for bonding optical components of various display devices such as touch panels.

In the manufacture of these display devices or input devices, when the adhesive sheet is attached to the display device, the release liner protecting the adhesive layer is peeled off, but at this time, static electricity is generated in the adhesive layer. The generated static electricity affects the alignment of the display unit of the display device and causes display defects. As a method of suppressing the generation of such static electricity, an antistatic agent is prepared to reduce the surface resistivity of the adhesive layer (for example, Patent Documents 1 to 3). Prior technical literature patent documents

Patent Document 1: Japanese Patent Application Publication No. 2020-187365 Patent Document 2: Japanese Patent Application Publication No. 2019-56115 Patent Document 3: Publication No. WO2018/008712

[Problem to be solved by the invention]

In recent years, due to the improvement of image quality, display devices with high-density display units are increasingly affected by static electricity. In order to effectively remove static electricity, it is required to further reduce the surface resistivity of the adhesive sheet (for example, 10 ¹² Ω/□ about). In addition, due to the requirements for thinner and lighter display devices, the adhesive sheet is also required to be thinner. In order to realize a thin adhesive sheet with a lower surface resistivity, a large amount of antistatic agent is required.

However, if a large amount of antistatic agent is blended into the adhesive layer, there will be the following problem: the antistatic agent will precipitate on the surface of the adhesive layer, causing corrosion of metal wiring such as copper wiring. In addition, there is also the following problem: in a humid and hot environment, the antistatic agent migrates from the adhesive layer to other optical components, causing the surface resistance to increase and the antistatic property to decrease. Furthermore, there may be cases where the compatibility between the adhesive layer and the antistatic agent decreases, resulting in poor transparency or appearance such as white turbidity, foaming or peeling, especially in hot and humid environments.

Therefore, the object of the present invention is to provide an adhesive layer that can form an adhesive layer that is durable (especially corrosion resistance stability, resistance value stability) and is not prone to defects, exhibits low surface resistivity, and has excellent antistatic properties. agent composition. Furthermore, another object of the present invention is to provide an adhesive layer that is less likely to suffer from defects in durability (especially corrosion resistance stability and resistance value stability), has lower surface resistivity, and has excellent antistatic properties. Furthermore, another object of the present invention is to provide an adhesive layer with an adhesive layer that is durable (especially corrosion resistance stability and resistance value stability) and is not prone to defects, exhibits low surface resistivity, and has excellent antistatic properties. Sheet. [Technical means to solve problems]

The inventors of the present invention have conducted intensive research to solve the above-mentioned problems, and as a result, they have discovered that the adhesiveness of a polymer containing an adhesive polymer, a conductive polymer of a specific composition, a mixture of monomer components constituting the conductive polymer, or a part of the mixture is In the agent composition, the above-mentioned adhesive polymer and the above-mentioned conductive polymer form an interpenetrating polymer network or a semi-interpenetrating polymer network, thereby forming durability (especially corrosion resistance stability, resistance value stability) that is not easily produced The adhesive layer is defective, exhibits low surface resistivity, and has excellent antistatic properties, thereby completing the present invention.

That is, the first aspect of the present invention provides an adhesive composition for forming an adhesive layer, which contains an adhesive polymer (A) and a conductive polymer (B) and constitutes the conductive polymer. The monomer component of (B) contains an ionic compound (B1) having a functional group (b1) in the molecule, and a functional group (b2) having a functional group (b1) in the molecule that can react with the above-mentioned functional group (b1) to form a covalent bond. ) compound (B2), the above-mentioned conductive polymer (B) has a three-dimensional network structure, and the above-mentioned three-dimensional network structure of the above-mentioned conductive polymer (B) intertwines with the above-mentioned adhesive polymer (A) to form interpenetration. Polymer network or semi-interpenetrating polymer network. In this specification, the adhesive composition of the first aspect of the present invention may be referred to as "adhesive composition (1)".

Furthermore, a second aspect of the present invention provides an adhesive composition containing an adhesive polymer (A) and a mixture of monomer components constituting the conductive polymer (B) or the conductive polymer (B). A partial polymer of a mixture of monomer components, and as a monomer component constituting the conductive polymer (B), an ionic compound (B1) having a functional group (b1) in the molecule, and an ionic compound (B1) having a functional group (b1) in the molecule. A compound (B2) that can react with the above-mentioned functional group (b1) to form a covalent bond with the functional group (b2), the functional group (b1) of the above-mentioned ionic compound (B1) and the functional group (b2) of the above-mentioned compound (B2) ) reacts to form covalent bonds to form the above-mentioned conductive polymer (B) with a three-dimensional network structure. The above-mentioned three-dimensional network structure is intertwined with the above-mentioned adhesive polymer (A) to form an interpenetrating polymer network or semi- Interpenetrating polymer networks. In this specification, the adhesive composition of the second aspect of the present invention may be referred to as "adhesive composition (2)". Moreover, the adhesive composition (1) and the adhesive composition (2) may be collectively called "the adhesive composition of this invention."

Furthermore, a third aspect of the present invention provides an adhesive layer formed of the adhesive composition (adhesive composition (1) or (2)) of the present invention. In this specification, the adhesive layer of the third aspect of the present invention is sometimes referred to as the "adhesive layer of the present invention." Furthermore, a fourth aspect of the present invention provides an adhesive sheet having the adhesive layer of the present invention. In this specification, the adhesive sheet of the fourth aspect of the present invention may be referred to as "the adhesive sheet of the present invention." The adhesive layer of the present invention and the adhesive sheet of the present invention are formed from the adhesive composition of the present invention (adhesive composition (1) or (2)). Therefore, durability (especially corrosion resistance stability, resistance value stability) ) is less prone to defects, shows lower surface resistivity, and has excellent antistatic properties.

The adhesive composition (1) of the present invention is an adhesive composition for forming an adhesive layer containing an adhesive polymer (A) and a conductive polymer (B). In the adhesive composition (1) of the present invention, the adhesive polymer (A) functions as a base polymer that imparts adhesiveness to the adhesive layer of the present invention, and the conductive polymer (B) functions as a base polymer that imparts adhesiveness to the adhesive layer of the present invention. The adhesive layer has a polymer component that imparts antistatic properties to function.

The adhesive composition (2) of the present invention contains an adhesive polymer (A) and a mixture of monomer components constituting the conductive polymer (B) or a mixture of monomer components constituting the conductive polymer (B). Some polymers. In the adhesive composition (2) of the present invention, the adhesive polymer (A) functions as a base polymer that imparts adhesiveness to the adhesive layer of the present invention. "The single unit constituting the conductive polymer (B) "The mixture of monomer components" and "the partial polymer of the mixture of monomer components constituting the conductive polymer (B)" are polymerized to form the precursor (raw material mixture) of the conductive polymer (B), so The formed conductive polymer (B) functions as a polymer component that imparts antistatic properties to the adhesive layer of the present invention.

The adhesive composition (adhesive composition (1) and (2)) of the present invention contains an ionic compound (B1) having a functional group (b1) in the molecule, and an ionic compound (B1) having a functional group (b1) in the molecule that can interact with the above-mentioned functional group (b1). ) reacts to form a covalently bonded functional group (b2), the compound (B2) serves as a monomer component constituting the conductive polymer (B). The ionic compound (B1) is a monomer component used to impart an antistatic function to the conductive polymer (B), and the compound (B2) is a monomer that together with the ionic compound (B1) constitutes the conductive polymer (B). Element. The functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, and a polymerization reaction proceeds to form the conductive polymer (B).

In the adhesive layer formed from the adhesive composition (1) of the present invention, the conductive polymer (B) has a three-dimensional network structure, and the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A ) are intertwined to form an interpenetrating polymer network or a semi-interpenetrating polymer network. As this structure, the adhesive polymer (A) provides adhesiveness to the adhesive layer of the present invention, the conductive polymer (B) provides antistatic properties to the adhesive layer of the present invention, and the conductive polymer (B) is used to impart antistatic properties to the adhesive layer. The three-dimensional network structure of the flexible polymer (B) is intertwined with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network, thereby preventing the antistatic agent from precipitating on the surface of the adhesive layer. It also causes corrosion of metal wiring and other defects, and inhibits the migration of antistatic agents from the adhesive layer to other optical components in hot and humid environments, suppresses the increase in surface resistance, and maintains excellent antistatic properties, thereby effectively The ground forms a conductive path in the adhesive layer. Therefore, the adhesive composition (1) of the present invention can form an adhesive that is durable (especially corrosion resistance stability, resistance value stability) and is not prone to defects, exhibits low surface resistivity, and has excellent antistatic properties. layer.

In the adhesive composition (2) of the present invention, the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, forming a three-dimensional network structure. The conductive polymer (B), the above-mentioned three-dimensional network structure and the adhesive polymer (A) are intertwined to form an interpenetrating polymer network or a semi-interpenetrating polymer network. The adhesive composition (2) of the present invention contains a mixture of an ionic compound (B1) and a compound (B2), or a partial polymer containing a mixture of an ionic compound (B1) and a compound (B2). The ionic compound ( The functional group (b1) of B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, and a polymerization reaction proceeds, thereby forming a conductive polymer (B) with a three-dimensional network structure. During the course of the polymerization reaction, the above-mentioned three-dimensional network structure is entangled with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. By forming an interpenetrating polymer network or a semi-interpenetrating polymer network, defects such as corrosion of metal wiring caused by the precipitation of the antistatic agent on the surface of the adhesive layer are less likely to occur. In addition, the antistatic agent is inhibited from occurring in hot and humid environments. The migration of the adhesive layer to other optical components suppresses the increase in surface resistance and maintains excellent antistatic properties. Furthermore, a path showing conductivity can be effectively formed in the adhesive layer. Therefore, the adhesive composition (2) of the present invention can form an adhesive that is durable (especially corrosion resistance stability, resistance value stability) and is not prone to defects, exhibits low surface resistivity, and has excellent antistatic properties. layer.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the ionic compound (B1) preferably has two or more functional groups (b1) in the molecule. The structure in which the ionic compound (B1) has two or more functional groups (b1) in the molecule can efficiently form the conductive polymer (B) by performing the above-mentioned polymerization reaction with the compound (B2). good.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the functional group (b1) is preferably selected from the group consisting of hydroxyl group, carboxyl group, amino group, mercapto group, and (meth)acryloxy group. At least one functional group from the group consisting of, (meth)acrylamide group, vinyl group, allyl group, and styrene group. It is preferable that the functional group (b1) is selected from these functional groups so that the polymerization reaction with the functional group (b2) is easy and the conductive polymer (B) can be formed efficiently.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the compound (B2) preferably has three or more functional groups (b2) in the molecule. The compound (B2) having three or more functional groups (b2) in the molecule undergoes the above-mentioned polymerization reaction with the ionic compound (B1), thereby efficiently forming the above-mentioned three-dimensional network of the conductive polymer (B). Better in terms of structure.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the functional group (b2) is preferably selected from the group consisting of isocyanate group, thioisocyanate group, epoxy group, nitrogen A group consisting of propidyl, ethanozolinyl, carbodiimide, (meth)acryloxy, (meth)acrylamide, vinyl, allyl, and styrene groups At least one of the functional groups. The functional group (b2) is preferably selected from the composition of these functional groups in that it is easy to polymerize with the functional group (b1), thereby efficiently forming the three-dimensional network structure of the conductive polymer (B).

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the content ratio of the conductive polymer (B) to the adhesive polymer (A) (conductive polymer (B) )/adhesive polymer (A)) is preferably 0.05 to 0.5. The above-mentioned content ratio is preferably 0.05 or more in terms of imparting excellent antistatic properties to the adhesive layer of the present invention. Moreover, the structure in which the said content ratio is 0.5 or less is preferable in terms of providing excellent adhesiveness to the adhesive layer of this invention.

The thickness of the adhesive sheet of the present invention is preferably 10 to 350 μm. The thickness of the adhesive sheet of the present invention is preferably at least a certain level in order to prevent peeling at the step portion from easily occurring. In addition, the thickness of the adhesive sheet of the present invention is preferably below a certain level in order to easily maintain an excellent appearance during production. [Effects of the invention]

According to the adhesive composition of the present invention, durability (especially corrosion resistance stability, resistance value stability) is obtained, which is less likely to cause defects, shows lower surface resistivity, and has an adhesive layer and adhesive sheet with excellent antistatic properties. material.

The adhesive composition (1) of the present invention is an adhesive composition that is used to form an adhesive layer, contains an adhesive polymer (A) and a conductive polymer (B), and serves as a component of the above-mentioned conductive The monomer component of polymer (B) contains an ionic compound (B1) having a functional group (b1) in the molecule, and a functional group in the molecule that can react with the above-mentioned functional group (b1) to form a covalent bond. In the compound (B2) of (b2), the conductive polymer (B) has a three-dimensional network structure, and the three-dimensional network structure of the conductive polymer (B) is entangled with the adhesive polymer (A) to form Interpenetrating polymer network or semi-interpenetrating polymer network.

Furthermore, the adhesive composition (2) of the present invention is an adhesive composition containing an adhesive polymer (A) and a mixture of monomer components constituting the conductive polymer (B) or a conductive polymer. (B) is a partial polymer of a mixture of monomer components, and contains, as a monomer component constituting the conductive polymer (B), an ionic compound (B1) having a functional group (b1) in the molecule, and A compound (B2) having a functional group (b2) in the molecule that can react with the above-mentioned functional group (b1) to form a covalent bond, the functional group (b1) of the above-mentioned ionic compound (B1) and the function of the above-mentioned compound (B2) The base (b2) reacts to form a covalent bond to form the above-mentioned conductive polymer (B) with a three-dimensional network structure. The above-mentioned three-dimensional network structure is intertwined with the above-mentioned adhesive polymer (A) to form an interpenetrating polymer. Network or semi-interpenetrating polymer network.

In addition, in this specification, the above-mentioned "mixture of monomer components" includes the case of including a single monomer component and the case of including two or more monomer components. In addition, the above-mentioned "partial polymerization of a mixture of monomer components" refers to a composition in which one or two or more monomer components among the monomer components constituting the above-mentioned "mixture of monomer components" are partially polymerized.

Furthermore, the adhesive layer of the present invention is an adhesive layer formed from the adhesive composition (1) or adhesive composition (2) of the present invention. Furthermore, the adhesive sheet of this invention is an adhesive sheet which has the adhesive layer of this invention.

[1. Adhesive composition] The adhesive composition of the present invention can have any form, and examples include: solvent type, emulsion type, hot melt type (hot melt type), solvent-free type (active energy ray hardening type), etc. In particular, the adhesive composition of the present invention is preferably solvent-based. When the adhesive layer is obtained by heating and/or drying the solvent-based adhesive composition, the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form Covalent bonds form the above-mentioned conductive polymer (B) with a three-dimensional network structure. The above-mentioned three-dimensional network structure is intertwined with the above-mentioned adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. Network, so it is better. In this specification, adhesive composition refers to a composition used to form an adhesive layer, including the meaning of a composition used to form an adhesive.

The organic solvent is not particularly limited as long as it is an organic compound used as a solvent. Examples thereof include hydrocarbon solvents such as cyclohexane, hexane, and heptane; aromatic solvents such as toluene and xylene; and acetic acid. Ester-based solvents such as ethyl ester and methyl acetate; ketone-based solvents such as acetone and methyl ethyl ketone; alcohol-based solvents such as methanol, ethanol, butanol, isopropyl alcohol, etc. Furthermore, the above-mentioned organic solvent may be a mixed solvent containing two or more organic solvents.

[1-1. Adhesive polymer (A)] In the adhesive composition of the present invention, the adhesive polymer (A) functions as a base polymer that imparts adhesiveness to the adhesive layer of the present invention. The adhesive polymer (A) is not particularly limited, and examples thereof include an acrylic polymer contained in an acrylic adhesive composition as a base polymer and a rubber adhesive composition (natural rubber adhesive). composition or synthetic rubber adhesive composition, etc.) as a base polymer, a rubber-based polymer, a polysilicone-based adhesive composition containing as a base polymer a polysilicone-based polymer, a polyester-based adhesive The agent composition contains a polyester polymer as a base polymer, a urethane adhesive composition contains a urethane polymer as a base polymer, and a polyamide adhesive composition. The polyamide-based polymer and the epoxy-based adhesive composition are contained as the base polymer. The epoxy-based polymer and the vinyl alkyl ether-based adhesive composition are contained as the base polymer. The vinyl alkyl ether polymer and the fluorine-based adhesive composition contain fluorine-based polymers as the base polymer. Among them, as the above-mentioned adhesive polymer (A), in terms of transparency, weather resistance, adhesion reliability, and the ease of functional design of solvent-based compositions due to a rich variety of monomers, acrylic-based polymers are preferred. polymer. That is, the adhesive composition of the present invention is preferably an acrylic adhesive composition containing an acrylic polymer as the adhesive polymer (A). In addition, the adhesive polymer (A) can use the said base polymer individually or in combination of 2 or more types. In this specification, the acrylic polymer contained as an adhesive polymer (A) may be called "acrylic polymer (A)".

The content of the adhesive polymer (A) in the adhesive composition of the present invention is not particularly limited, but is preferably 70 to 95% by weight, more preferably 75 to 93% by weight, and even more preferably 80 to 90% by weight. . A composition in which the content of the adhesive polymer (A) is 70% by weight or more is preferable in terms of imparting excellent adhesiveness to the adhesive layer of the present invention. In addition, a composition in which the content of the adhesive polymer (A) is 95% by weight or less is preferable in that it contains the conductive polymer (B) and can provide excellent antistatic properties to the adhesive layer of the present invention.

[1-2. Acrylic polymer (A)] Hereinafter, the acrylic polymer (A) contained as the adhesive polymer (A) will be described, but the present invention is not limited to this embodiment. The content of the acrylic polymer (A) in the adhesive composition of the present invention is not particularly limited. It is preferably 70 to 95% by weight relative to the total amount of the adhesive composition of the present invention (total weight, 100% by weight). %, more preferably 75 to 93% by weight, still more preferably 80 to 90% by weight. A composition in which the content of the acrylic polymer (A) is 70% by weight or more is preferable in terms of imparting excellent adhesiveness to the adhesive layer of the present invention. In addition, a composition in which the content of the acrylic polymer (A) is 95% by weight or less is preferable in that it contains the conductive polymer (B) and can provide excellent antistatic properties to the adhesive layer of the present invention.

The adhesive composition forming the adhesive layer containing the acrylic polymer (A) as a main component is not particularly limited. Examples thereof include: a composition containing the acrylic polymer (A) as an essential component; A mixture of monomer components of the acrylic polymer (A) (sometimes referred to as a "monomer mixture") or a composition in which a partial polymer thereof is an essential component, etc. Examples of the former include, but are not limited to, so-called solvent-based compositions, water-dispersed compositions (emulsion-type compositions), etc. Examples of the latter include, but are not limited to, so-called active energy ray curable combinations. Things etc. Among them, the above-mentioned adhesive composition is preferably a solvent-based composition. Furthermore, the above-mentioned adhesive composition may contain other additives if necessary.

The above-mentioned "monomer mixture" includes a case of containing a single monomer component constituting the acrylic polymer (A) and a case of containing two or more monomer components constituting the acrylic polymer (A). In addition, the above-mentioned "partial polymer" refers to a composition in which one or two or more components of the monomer mixture constituting the acrylic polymer (A) are partially polymerized. In this specification, when simply referred to as "acrylic polymer (A)", unless otherwise mentioned, it includes "acrylic polymer (A)" and "monomer components constituting acrylic polymer (A)". "Mixture", and "Partial polymer of a mixture of monomer components constituting the acrylic polymer (A)".

The acrylic polymer (A) is a polymer containing an acrylic monomer as an essential monomer unit (monomer unit). In other words, the acrylic polymer (A) is a polymer containing a structural unit derived from an acrylic monomer as a structural unit. That is, the acrylic polymer (A) is a polymer composed (formed) of an acrylic monomer as an essential monomer component. In addition, in this specification, "(meth)acrylyl group" means either or both of "acrylyl group" and "methacrylyl group", and the others are the same. The weight average molecular weight of the acrylic polymer (A) is not particularly limited, but is preferably 100,000 to 5,000,000.

The acrylic polymer (A) preferably contains a (meth)acrylic acid alkyl ester (hereinafter, sometimes simply referred to as "(meth)acrylic acid alkyl ester") having a linear or branched alkyl group. A polymer of monomer units.

Examples of the alkyl (meth)acrylate include: (methyl)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Butyl methacrylate (n-butyl (meth)acrylate), isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (meth) Amyl acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Isooctyl methacrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecane (meth)acrylate ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, (meth)acrylate ) Cetyl acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate , (meth)acrylic acid alkyl ester and other alkyl (meth)acrylate, the carbon number of the alkyl group is 1 to 20, etc. In addition, alkyl (meth)acrylate can be used individually or in combination of 2 or more types.

Among them, the alkyl (meth)acrylate is preferably an alkyl (meth)acrylate in which the number of carbon atoms in the alkyl group is 1 to 18 in terms of obtaining strong adhesion and adjusting residual stress. , more preferably methyl methacrylate (MMA), butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isostearyl acrylate (ISTA).

The content (ratio) of the alkyl (meth)acrylate in all the monomer units of the acrylic polymer (A) (the total amount of monomer components constituting the acrylic polymer (A)) is not particularly limited. In terms of adhesion reliability, especially adhesion reliability at low temperatures, 30 to 100 parts by weight relative to the total amount of monomer components constituting the acrylic polymer (A) (100 parts by weight) is more preferable, and more preferably The amount is 35 to 90 parts by weight, and more preferably 40 to 85 parts by weight.

The acrylic polymer (A) is a (meth)acrylic acid alkoxyalkyl ester containing a linear or branched alkoxyalkyl group (hereinafter, sometimes referred to as "(meth)acrylic acid alkoxy group"). Alkyl ester") is also preferred when the polymer is a necessary monomer unit.

Examples of the (meth)acrylic acid alkoxyalkyl ester include: (meth)acrylic acid 2-methoxyethyl ester, (meth)acrylic acid 2-ethoxyethyl ester, (meth)acrylic acid Methoxytriethylene glycol, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (meth)acrylate (meth)alkoxyalkyl acrylate, etc., such as 4-ethoxybutyl acrylate, which has an alkoxy group with 1 to 20 carbon atoms substituted with an alkyl group with 1 to 20 carbon atoms. . In addition, (meth)acrylic acid alkoxyalkyl ester can be used individually or in combination of 2 or more types.

Among them, as the above-mentioned alkoxyalkyl (meth)acrylate, in terms of obtaining strong adhesiveness and adjusting residual stress, it is preferable that the alkoxy group having 1 to 18 carbon atoms is substituted with 1 to 18 carbon atoms. The alkyl (meth)acrylic acid alkoxyalkyl ester of 18 is more preferably 2-methoxyethyl acrylate (MEA).

There is no particular content (ratio) of the above-mentioned alkoxyalkyl (meth)acrylate in all the monomer units of the acrylic polymer (A) (the total amount of monomer components constituting the acrylic polymer (A)). It is limited to 30 to 100 parts by weight relative to the total amount of monomer components constituting the acrylic polymer (A) (100 parts by weight) in terms of adhesive reliability, especially at low temperatures. , more preferably 35 to 90 parts by weight, still more preferably 40 to 85 parts by weight.

The acrylic polymer (A) may contain a copolymerizable monomer (copolymerizable monomer) as a monomer unit in addition to the above-mentioned (meth)acrylic acid alkyl ester and (meth)acrylic acid alkoxyalkyl ester. That is, the acrylic polymer (A) may contain a copolymerizable monomer as a constituent monomer component. In addition, the copolymerizable monomer can be used alone or in combination of two or more types.

Preferable examples of the copolymerizable monomer include hydroxyl-containing monomers. If the acrylic polymer (A) contains a hydroxyl-containing monomer as a monomer unit, polymerization is easy when the monomer components are polymerized, and good cohesion is easily obtained. Therefore, it is easy to obtain strong adhesion, and by increasing the gel fraction, it is easy to obtain excellent foaming and peeling resistance. Furthermore, it is easy to suppress the whitening of the adhesive sheet that sometimes occurs in a high-humidity environment. Furthermore, the hydroxyl group may also serve as a reaction point with the following cross-linking agent.

The content (ratio) of the hydroxyl-containing monomer relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A) is not particularly limited. If the amount of the hydroxyl-containing monomer is at least a certain level, the whitening of the adhesive sheet that sometimes occurs in a high-humidity environment can be further suppressed, and transparency such as humidification whitening resistance can be ensured. The lower limit of the content of the above-mentioned hydroxyl-containing monomer is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, or 4 parts by weight or more. , 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, and more preferably 10 parts by weight or more. In addition, the upper limit of the content of the above-mentioned hydroxyl-containing monomer is preferably 40 parts by weight or less, and more preferably 40 parts by weight or less in terms of cohesive force and ease of obtaining adhesion, foaming and peeling resistance, and other adhesion reliability. 35 parts by weight or less, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, or 31 parts by weight or less, and more preferably 30 parts by weight or less.

Furthermore, a preferable example of the copolymerizable monomer is a monomer containing a nitrogen atom. If the acrylic polymer (A) contains a nitrogen atom-containing monomer as a monomer unit, appropriate cohesive force can be easily obtained. Therefore, by increasing the 180° peel-off adhesion to the glass plate and the 180° peel-off adhesion to the acrylic plate, it is easy to obtain strong adhesion, and by increasing the gel fraction, it is easy to obtain excellent hair resistance. Bubble peelability. Furthermore, it is easy to obtain appropriate flexibility in the adhesive layer, adjust the 300% tensile residual stress within a specific range, and obtain excellent stress relaxation and excellent step following properties.

The content (ratio) of the nitrogen atom-containing monomer relative to the total amount of monomer components constituting the acrylic polymer (A) (100 parts by weight) is not particularly limited, but is preferably 1 part by weight or more. The lower limit of the content of the above-mentioned nitrogen atom-containing monomer is, in terms of cohesion, adhesiveness, and foaming and peeling resistance, relative to the total amount of monomer components constituting the acrylic polymer (A) (100 parts by weight). ), preferably 2 parts by weight or more, more preferably 3 parts by weight or more, further preferably 5 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more. In addition, as the upper limit of the content of the above-mentioned nitrogen atom-containing monomer, it is easier to obtain appropriate flexibility in the adhesive layer, and it is easier to obtain excellent stress relaxation properties and excellent step following properties. It is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, still more preferably 30 parts by weight or less.

The above-mentioned acrylic polymer (A) can be obtained by polymerizing the above-mentioned monomer units (monomer components) using a known or commonly used polymerization method. Examples of the polymerization method of the acrylic polymer (A) include a solution polymerization method, an emulsion polymerization method, a block polymerization method, a polymerization method by active energy ray irradiation (active energy ray polymerization method), and the like. Among them, in terms of transparency, water resistance, cost, etc. of the adhesive layer, the solution polymerization method and the active energy ray polymerization method are preferred, and the active energy ray polymerization method is more preferred.

Examples of the active energy rays irradiated during the active energy ray polymerization (photopolymerization) include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron beams, or ultraviolet rays, and ultraviolet rays are particularly preferred. In addition, the irradiation energy, irradiation time, irradiation method, etc. of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated and the monomer components can react.

When polymerizing the acrylic polymer (A), various common solvents can be used. Examples of such solvents include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane; Alicyclic hydrocarbons such as hexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone and other organic solvents. In addition, the solvent can be used individually or in combination of 2 or more types.

When the acrylic polymer (A) is polymerized, a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction. In addition, the polymerization initiator can be used alone or in combination of two or more types.

The above-mentioned photopolymerization initiator is not particularly limited, and examples thereof include: benzoin ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, α-ketool-based photopolymerization initiator, aromatic Sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzoyl chloride photopolymerization initiator, benzophenone photopolymerization initiator, acetate Ketone photopolymerization initiator, 9-oxosulfide It is a photopolymerization initiator, etc. In addition, the photopolymerization initiator can be used alone or in combination of two or more types.

Examples of the benzoin ether photopolymerization initiator include: benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2- Diphenylethan-1-one, anisole methyl ether, etc. Examples of the acetophenone-based photopolymerization initiator include: 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxyacetophenone. Hexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-(tert-butyl)dichloroacetophenone, etc. Examples of the α-ketool photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane. -1-one etc. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride and the like. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime and the like. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzyl-based photopolymerization initiator include benzoyl and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and polyethylene. benzophenone, α-hydroxycyclohexyl phenyl ketone, etc. Examples of the ketal-based photopolymerization initiator include benzyl dimethyl ketal and the like. As the above 9-oxosulfide𠮿 It is a photopolymerization initiator, for example: 9-oxosulfide , 2-chloro-9-oxosulfide𠮿 , 2-Methyl-9-oxosulfide𠮿 , 2,4-dimethyl-9-oxosulfide𠮿 , isopropyl-9-oxosulfide𠮿 , 2,4-diisopropyl-9-oxysulfide𠮿 , dodecyl-9-oxosulfide𠮿 wait.

The usage amount of the above-mentioned photopolymerization initiator is not particularly limited, for example, relative to 100 parts by weight of all monomer units of the acrylic polymer (A) (the total amount of monomer components constituting the acrylic polymer (A)), the amount is less than 100 parts by weight. Preferably, it is 0.001-1 part by weight, More preferably, it is 0.01-0.50 part by weight.

In addition, the thermal polymerization initiator is not particularly limited, and examples thereof include azo-based polymerization initiators, peroxide-based polymerization initiators (such as dibenzoyl peroxide, butylene peroxide). tert-butyl diacid, etc.), redox polymerization initiator, etc. Among them, the azo polymerization initiator disclosed in Japanese Patent Application Laid-Open No. 2002-69411 is preferred. Examples of the azo polymerization initiator include: 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as "AIBN"), 2,2'-azobis-2-methylbutane Nitrile (hereinafter sometimes referred to as "AMBN"), 2,2'-azobis(2-methylpropionic acid)dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, etc.

The usage amount of the above-mentioned thermal polymerization initiator is not particularly limited. For example, in the case of the above-mentioned azo polymerization initiator, it is ) 100 parts by weight, preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight.

[1-3. Carboxyl group-containing monomers, etc.] Examples of copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers include carboxyl group-containing monomers. The above-mentioned carboxyl group-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth)acryl group or vinyl group and a carboxyl group. Examples of the above-mentioned carboxyl group-containing monomer include: (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc. In addition, the above-mentioned carboxyl group-containing monomer Examples of monomers also include monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride. Furthermore, the carboxyl group-containing monomer can be used alone or in combination of two or more.

When the acrylic polymer (A) contains the above-mentioned carboxyl group-containing monomer as a monomer component constituting the polymer, the above-mentioned content in all monomer components (100% by weight) constituting the acrylic polymer (A) The ratio of the carboxyl monomer is not particularly limited, but in terms of improving durability and obtaining higher bonding reliability, it is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1% by weight. %above. In addition, the upper limit of the ratio of the carboxyl group-containing monomer is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 10% by weight or less, in order to obtain an adhesive layer with moderate flexibility. 1% by weight or less.

[1-4. Monomers containing basic groups] Furthermore, the adhesive composition of the present invention preferably does not contain or substantially does not contain a monomer containing a basic group as a monomer component constituting the base polymer. For example, in the case where the adhesive composition of the present invention is an acrylic adhesive composition containing an acrylic polymer (A) as a base polymer, it is preferred that the acrylic acid-containing monomer substantially does not contain a basic group. It is a monomer component of polymers other than polymer (A). Even if it is not a monomer component constituting various polymers, it is better if the above-mentioned adhesive composition does not substantially contain a monomer containing a basic group. good. Specifically, the content of the basic group-containing monomer is preferably 0.05 parts by weight or less (for example, 0 to 0.05 parts by weight) relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (A). , more preferably 0.01 parts by weight or less (for example, 0 to 0.01 parts by weight), and still more preferably 0.001 parts by weight or less (for example, 0 to 0.001 parts by weight), it can be said to be substantially free.

[1-5. Hydroxyl-containing monomer] The so-called hydroxyl-containing monomer refers to a monomer having at least one hydroxyl group in the molecule. Furthermore, a carboxyl group-containing monomer, which is a monomer having at least one hydroxyl group in the molecule and at least one carboxyl group in the molecule, is not a hydroxyl group-containing monomer. The above-mentioned hydroxyl-containing monomer is not particularly limited, and specific examples include: (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 2 -Hydroxybutyl ester, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, (meth)acrylate )Hydroxydecyl acrylate, hydroxylauryl (meth)acrylate, (meth)acrylate (4-hydroxymethylcyclohexyl) ester and other hydroxyl-containing (meth)acrylates; vinyl alcohol, allyl alcohol, etc. Among them, the above-mentioned hydroxyl-containing monomer is preferably a hydroxyl-containing (meth)acrylate, more preferably 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl (meth)acrylate (HPA), 4-Hydroxybutyl acrylate (4HBA). Furthermore, the hydroxyl-containing monomer can be used alone or in combination of two or more.

[1-6. Monomers containing nitrogen atoms] The so-called monomer containing nitrogen atoms refers to a monomer having at least one nitrogen atom in the molecule (within one molecule). Wherein, the above-mentioned hydroxyl-containing monomer does not include the above-mentioned nitrogen atom-containing monomer. That is, in this specification, a monomer having a hydroxyl group and a nitrogen atom in the molecule is included in a monomer containing a nitrogen atom. Furthermore, a carboxyl group-containing monomer having at least one nitrogen atom in the molecule and at least one carboxyl group in the molecule is not a nitrogen atom-containing monomer.

As the above-mentioned nitrogen atom-containing monomer, from the viewpoint of improving foaming and peeling resistance, N-vinyl cyclic amide, (meth)acrylamide, etc. are preferred. Furthermore, the nitrogen atom-containing monomer may be used alone or in combination of two or more.

The N-vinyl cyclic amide is preferably an N-vinyl cyclic amide represented by the following formula (1). [Chemical 1] (In formula (1), R ¹ represents a divalent organic group)

R ¹ in the above formula (1) is a divalent organic group, preferably a divalent saturated hydrocarbon group or an unsaturated hydrocarbon group, more preferably a divalent saturated hydrocarbon group (such as an alkylene group with 3 to 5 carbon atoms, etc.) .

As the N-vinyl cyclic amide represented by the above formula (1), from the viewpoint of further improving the foaming and peeling resistance, N-vinyl-2-pyrrolidone (NVP), N- Vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-𠰌linone, N-vinyl-1,3-㗁𠯤-2-one, N- Vinyl-3,5-𠰌lindione, etc., more preferably N-vinyl-2-pyrrolidinone, N-vinyl-2-caprolactam, even more preferably N-vinyl-2- Pyrrolidone.

Examples of the (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide. wait. Examples of the N-alkyl(meth)acrylamide include N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-butyl( Methyl acrylamide, N-octyl acrylamide, etc. Furthermore, the above-mentioned N-alkyl(meth)acrylamide also includes dimethylaminoethyl(meth)acrylamide, diethylaminoethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, Propyl(meth)acrylamide is a (meth)acrylamide with an amine group. Examples of the N,N-diamino(meth)acrylamide include N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide. Amine, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide , N,N-di(tert-butyl)(meth)acrylamide, etc.

In addition, the above-mentioned (meth)acrylamides also include various N-hydroxyalkyl (meth)acrylamides, for example. Examples of the N-hydroxyalkyl(meth)acrylamide include N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide , N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide Amine, N-methyl-N-2-hydroxyethyl (meth)acrylamide, etc.

Moreover, the said (meth)acrylamides also include various N-alkoxyalkyl (meth)acrylamide, for example. Examples of the N-alkoxyalkyl(meth)acrylamide include N-methoxymethyl(meth)acrylamide and N-butoxymethyl(meth)acrylamide. Amines etc.

Moreover, examples of nitrogen atom-containing monomers other than the above-mentioned N-vinyl cyclic amide and the above-mentioned (meth)acrylamides include: (meth)aminoethyl acrylate, (methyl) Amino-containing monomers such as dimethylaminoethyl acrylate, dimethylaminopropyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate; acrylonitrile, methacrylonitrile, etc. contain cyanide Monomer of base; (meth)acrylyl pyroline, N-vinyl piperazoline, N-vinylpyrrole, N-vinylimidazole, N-vinyl pyroline, N-vinyl pyroline, N- Vinyl pyrazole, vinyl pyridine, vinyl pyrimidine, vinyl 㗁azole, vinyl isothiazole, vinyl thiazole, vinyl isothiazole, vinyl pyrrolidine, (meth)acrylylpyrrolidone, ( Meth)acrylylpyrrolidine, (meth)acrylylpiperidine, N-methylvinylpyrrolidone and other heterocyclic-containing monomers; N-cyclohexylmaleimide, N- Isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and other maleimide monomers, N-methyl Ikonimide, N-Ethyl Iconimide, N-Butyl Iconimide, N-Octyl Iconimide, N-2-Ethylhexyl Iconimide, N -Iconidimine-based monomers such as lauryl itonimide and N-cyclohexyl itonimide, N-(meth)acryloxymethylenesuccinimide, N-( Meth)acryl-6-oxyhexamethylene succinimide, N-(meth)acryl-8-oxyoctamethylene succinimide and other succinimines They are monomers containing acyl imide groups; monomers containing isocyanate groups such as 2-(meth)acryloyloxyethyl isocyanate.

[1-7. Monomers containing aromatic ring structures] Examples of copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers include aromatic ring structure-containing monomers. The aromatic ring structure-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth)acryl group or a vinyl group and has an aromatic ring structure. For example, (meth)acrylic acid alkyl ester having a phenyl group is included in the above-mentioned aromatic ring structure-containing monomer. Examples of the aromatic ring structure-containing monomer include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate. Furthermore, the aromatic ring structure-containing monomer can be used alone or in combination of two or more types.

When the acrylic polymer (A) contains the above-mentioned aromatic ring structure-containing monomer as a monomer component constituting the polymer, among all the monomer components (100% by weight) constituting the acrylic polymer (A) The ratio of the aromatic ring structure-containing monomer is not particularly limited, but in terms of improving durability and obtaining higher bonding reliability, it is preferably 5% by weight or more, and more preferably 10% by weight or more. In addition, the upper limit of the ratio of the aromatic ring structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably less than 50% by weight, in order to obtain an adhesive layer with moderate flexibility. Preferably, it is less than 30% by weight.

[1-8. Monomers containing alicyclic structures] Examples of copolymerizable monomers other than nitrogen atom-containing monomers and hydroxyl group-containing monomers include alicyclic structure-containing monomers. The alicyclic structure-containing monomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth)acryl group or a vinyl group and has an alicyclic structure. For example, alkyl (meth)acrylate having a cycloalkyl group is included in the above-mentioned alicyclic structure-containing monomer. Furthermore, the alicyclic structure-containing monomer can be used alone or in combination of two or more types.

The alicyclic structure in the above-mentioned alicyclic structure-containing monomer is a cyclic hydrocarbon structure, preferably having a carbon number of 5 or more, more preferably a carbon number of 6 to 24, further preferably a carbon number of 6 to 15, and particularly preferably Carbon number 6 to 10.

Examples of the alicyclic structure-containing monomer include: (meth)cyclopropyl acrylate, (meth)cyclobutyl acrylate, (meth)cyclopentyl acrylate, and (meth)cyclohexyl acrylate. , (meth)acrylic acid cycloheptyl ester, (meth)acrylic acid cyclooctyl ester, (meth)acrylic acid isoester, (meth)acrylic acid ester dicyclopentyl ester, HPMPA represented by the following formula (2), (Meth)acrylic monomers such as TMA-2 represented by the following formula (3) and HCPA represented by the following formula (4). In addition, in the following formula (4), the bonding site between the cyclohexyl ring connected by a line and the structural formula in parentheses is not particularly limited. Among these, iso(meth)acrylate is preferred. [Chemicalization 2] [Chemical 3] [Chemical 4]

When the acrylic polymer (A) contains the above-mentioned alicyclic structure-containing monomer as a monomer component constituting the polymer, 100 parts by weight of all monomer components constituting the acrylic polymer (A) The ratio of the alicyclic structure-containing monomer is not particularly limited, but in terms of improving durability and obtaining higher bonding reliability, it is preferably 10% by weight or more. In addition, the upper limit of the ratio of the alicyclic structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably less than 50% by weight, in order to obtain an adhesive layer with moderate flexibility. Preferably, it is less than 30% by weight.

[1-9. Other copolymerizable monomers] As the copolymerizable monomer in the acrylic polymer (A), in addition to the above-mentioned nitrogen atom-containing monomers and hydroxyl group-containing monomers, for example, epoxy group-containing monomers [such as (meth)acrylic acid Glycidyl ester, methyl glycidyl (meth)acrylate, etc.]; monomers containing sulfonic acid groups [such as sodium vinyl sulfonate, etc.]; monomers containing phosphate groups; vinyl esters [such as vinyl acetate, Vinyl propionate, etc.]; aromatic vinyl compounds [such as styrene, vinyl toluene, etc.]; olefins or dienes [such as ethylene, propylene, butadiene, isoprene, isobutylene, etc.]; vinyl ethers Class [such as vinyl alkyl ether, etc.]; vinyl chloride, etc.

Furthermore, examples of the copolymerizable monomer in the acrylic polymer (A) include polyfunctional monomers. The polyfunctional monosystem functions as a cross-linking component. Examples of the polyfunctional monomer include: hexylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate , trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy Acrylic, polyester acrylate, acrylic urethane, etc. In addition, the polyfunctional monomer can be used alone or in combination of two or more types.

The content (ratio) of the above-mentioned polyfunctional monomer in all the monomer units of the acrylic polymer (A) is not particularly limited. ), preferably 0.5 parts by weight or less (for example, 0 to 0.5 parts by weight), more preferably 0 to 0.35 parts by weight, and still more preferably 0 to 0.3 parts by weight. If the content of the polyfunctional monomer is 0.5 parts by weight or less, the adhesive layer will have moderate cohesion and will easily improve the adhesive force or step absorption, so it is preferable. Furthermore, when a cross-linking agent is used, the polyfunctional monomer does not need to be used. However, when a cross-linking agent is not used, the content of the polyfunctional monomer is preferably 0.001 to 0.5 parts by weight, more preferably 0.001 to 0.5 parts by weight. 0.35 parts by weight, more preferably 0.002 to 0.3 parts by weight.

[1-10. Acrylic polymer (B)] When the adhesive composition of the present invention contains an acrylic polymer (A) as a base polymer, the adhesive composition of the present invention preferably contains the acrylic polymer (A) with a weight average molecular weight of 1,000 ~30000 acrylic polymer (B). If the acrylic polymer (B) is contained, the adhesion of the interface of the adhesive sheet to the adherend is improved, so it is easy to obtain strong adhesion and excellent foaming and peeling resistance. In addition, in this specification, "the acrylic polymer (B) with a weight average molecular weight of 1,000-30,000" may be simply called "acrylic polymer (B)". Furthermore, when the adhesive composition of the present invention contains an acrylic polymer (B) as a base polymer, the acrylic polymer (B) may also be combined with the acrylic polymer (A) and the conductive polymer. The three-dimensional network structure of (B) is intertwined to form an interpenetrating polymer network or a semi-interpenetrating polymer network.

As the above-mentioned acrylic polymer (B), an acrylic polymer composed of (meth)acrylate having a cyclic structure in the molecule as an essential monomer component can be preferably exemplified. Example: Acrylic polymerization consisting of (meth)acrylate having a cyclic structure in the molecule and alkyl (meth)acrylate having a linear or branched alkyl group as essential monomer components things. That is, as the acrylic polymer (B), an acrylic polymer containing (meth)acrylate having a cyclic structure in the molecule as a monomer unit can be preferably exemplified. : An acrylic polymer containing (meth)acrylate having a cyclic structure in the molecule and (meth)acrylic acid alkyl ester having a linear or branched alkyl group as monomer units.

The cyclic structure (ring) of the (meth)acrylate (hereinafter, sometimes referred to as "ring-containing (meth)acrylate") having a cyclic structure in the molecule (within one molecule) may be aromatic. There is no particular limitation on either the aromatic ring or the non-aromatic ring. Examples of the aromatic ring include aromatic carbocyclic rings [for example, monocyclic carbocyclic rings such as benzene rings or condensed carbocyclic rings such as naphthalene rings], various aromatic heterocyclic rings, and the like. Examples of the non-aromatic ring include non-aromatic aliphatic rings (non-aromatic alicyclic rings) [for example, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring] Cycloalkane rings such as cyclohexene rings; cycloalkene rings such as cyclohexene rings, etc.], non-aromatic bridged rings [such as bicyclic hydrocarbon rings such as pinane, pinene, 𦯉ane, nor𦯉ane, nor𦯉ene, etc.; diamond Aliphatic hydrocarbon rings with three or more rings (bridged hydrocarbon rings) such as alkanes, etc.], non-aromatic heterocyclic rings [such as epoxy ring, oxolane ring, oxetane ring, etc.], etc.

Examples of the above-mentioned tricyclic or higher aliphatic hydrocarbon ring (tricyclic or higher bridged hydrocarbon ring) include: dicyclopentyl represented by the following formula (5a), dicyclopentyl represented by the following formula (5b) Cyclopentenyl group, adamantyl group represented by the following formula (5c), tricyclopentenyl group represented by the following formula (5d), tricyclopentenyl group represented by the following formula (5e), etc. [Chemistry 5]

That is, examples of the ring-containing (meth)acrylate include: (meth)cyclopentyl acrylate, (meth)cyclohexyl acrylate, (meth)cycloheptyl acrylate, (meth)acrylate (Meth)acrylic acid cycloalkyl esters such as cyclooctyl acrylate; (meth)acrylate and other aliphatic hydrocarbon ring having a bicyclic aliphatic hydrocarbon ring; (meth)acrylic acid dicyclopentyl ester , dicyclopentoxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate , 2-ethyl-2-adamantyl (meth)acrylate and other (meth)acrylates with three or more aliphatic hydrocarbon rings; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate , (meth)aryloxyalkyl acrylates such as phenoxyethyl (meth)acrylate, aryloxyalkyl (meth)acrylates such as benzyl (meth)acrylate, etc. with aromatic rings ( Meth)acrylate, etc. Among them, as the above-mentioned ring-containing (meth)acrylate, a non-aromatic ring-containing (meth)acrylate is particularly preferred, and more preferred is cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHA), CHMA), dicyclopentyl acrylate (DCPA), dicyclopentyl methacrylate (DCPMA), and more preferably dicyclopentyl acrylate (DCPA) or dicyclopentyl methacrylate (DCPMA). Furthermore, the ring-containing (meth)acrylate can be used alone or in combination of two or more.

When a (meth)acrylate having an aliphatic hydrocarbon ring of three or more rings (especially a bridged hydrocarbon ring of three or more rings) is used among the above-mentioned non-aromatic ring-containing (meth)acrylates, In particular, it is preferable in that it does not easily cause polymerization inhibition. Also, when using a dicyclopentyl group represented by the above formula (5a), an adamantyl group represented by the above formula (5c), and a tricyclopentyl group represented by the above formula (5d) that does not have an unsaturated bond In the case of meth)acrylate, the foaming and peeling resistance can be further improved, and the adhesion to low-polarity adherends such as polyethylene or polypropylene can be significantly improved.

The content (ratio) of the above-mentioned ring-containing (meth)acrylate in all the monomer units of the acrylic polymer (B) (the total amount of monomer components constituting the acrylic polymer (B)) is not particularly limited. It is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight relative to the total amount of monomer components constituting the acrylic polymer (B) (100 parts by weight). When the content of the above-mentioned ring-containing (meth)acrylate is 10 parts by weight or more, it is easy to improve the foaming and peeling resistance, so it is preferable. In addition, when the content is 90 parts by weight or less, the adhesive layer has moderate softness, and it is easy to improve the adhesive force, step absorption, etc., so it is preferable.

Moreover, as the (meth)acrylic acid alkyl ester having a linear or branched alkyl group as the monomer unit of the acrylic polymer (B), for example, (meth)acrylic acid methyl ester, Ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, butyl(meth)acrylate Ester, tert-butyl (meth)acrylate, amyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Isodecyl methacrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate Ester, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, (meth) Alkyl (meth)acrylate with an alkyl group having 1 to 20 carbon atoms, such as nonadecyl acrylate and eicosanyl (meth)acrylate. Among them, methyl methacrylate (MMA) is preferred in terms of good compatibility with the acrylic polymer (A). In addition, the said (meth)acrylic acid alkyl ester can be used individually or in combination of 2 or more types.

The above-mentioned alkyl (meth)acrylate having a linear or branched alkyl group in all the monomer units of the acrylic polymer (B) (the total amount of monomer components constituting the acrylic polymer (B)) The content (ratio) is not particularly limited, but in terms of foaming and peeling resistance, it is preferably 10 to 90 parts by weight relative to the total amount of monomer components (100 parts by weight) constituting the acrylic polymer (B). parts, more preferably 20 to 80 parts by weight, still more preferably 20 to 60 parts by weight. If the content is 10 parts by weight or more, it is particularly easy to improve the adhesion to an adherend made of acrylic resin or polycarbonate, so it is preferable.

As the monomer unit of the acrylic polymer (B), in addition to the above-mentioned ring-containing (meth)acrylate and (meth)acrylic acid alkyl ester having a linear or branched alkyl group, it may also contain Monomers copolymerized with these monomers (copolymerizable monomers). In addition, the content (ratio) of the above-mentioned copolymerizable monomer in all the monomer units of the acrylic polymer (B) (the total amount of monomer components constituting the acrylic polymer (B)) is not particularly limited. The total amount of monomer components constituting the acrylic polymer (B) (100 parts by weight) is preferably 49.9 parts by weight or less (for example, 0 to 49.9 parts by weight), and more preferably 30 parts by weight or less. Moreover, a copolymerizable monomer can be used individually or in combination of 2 or more types.

Examples of the copolymerizable monomer that is the monomer unit of the acrylic polymer (B) (the copolymerizable monomer constituting the acrylic polymer (B)) include: (meth)acrylic acid alkoxyalkane esters [such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, (meth)acrylic acid 3 -Methoxypropyl ester, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, etc.]; contains hydroxyl group (hydroxyl) monomer [such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate and other hydroxyalkyl (meth)acrylates, vinyl alcohol, allyl alcohol, etc.]; monomers containing amide groups [For example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide amide, N-butoxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, etc.]; monomers containing amine groups [such as aminoethyl (meth)acrylate , dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, etc.]; monomers containing cyano groups [such as acrylonitrile, methacrylonitrile, etc.]; containing sulfonic acid groups monomers [such as sodium vinyl sulfonate, etc.]; monomers containing phosphate groups [such as 2-hydroxyethylacryl phosphate, etc.]; monomers containing isocyanate groups [such as 2-methyl isocyanate] Acryloxyethyl ester, etc.], monomers containing acyl imine groups [cyclohexyl maleic acid imide, isopropyl maleic acid imide, etc.], etc.

As mentioned above, the acrylic polymer (B) preferably contains a (meth)acrylate having a cyclic structure in the molecule and a (meth)acrylic acid alkyl ester having a linear or branched alkyl group. Acrylic polymer with monomer units. Among these, an acrylic polymer containing a ring-containing (meth)acrylate and the above-mentioned alkyl (meth)acrylate having a linear or branched alkyl group as monomer units is preferred. In the above-mentioned acrylic polymer containing ring-containing (meth)acrylate and (meth)acrylic acid alkyl ester having a linear or branched alkyl group as monomer units, relative to the composition of the acrylic polymer The amount of ring-containing (meth)acrylate in the total monomer component (100 parts by weight) of (B) is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight. Moreover, the content of the alkyl (meth)acrylate having a linear or branched alkyl group is not particularly limited, but is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, and still more preferably 20 to 60 parts by weight.

Furthermore, a particularly preferred specific structure of the acrylic polymer (B) includes (1) a polymer selected from the group consisting of dicyclopentyl acrylate, dicyclopentyl methacrylate, cyclohexyl acrylate, and methacrylic acid. An acrylic polymer having at least one monomer in the group consisting of cyclohexyl ester and (2) methyl methacrylate as the monomer unit. In the above-mentioned particularly preferred acrylic polymer (B), all monomer units of the acrylic polymer (B) include (1) dicyclopentyl acrylate, dicyclopentyl methacrylate, and cyclohexyl acrylate. The content of ester and cyclohexyl methacrylate (when two or more are contained, the total amount thereof) is smaller than the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer (B). Preferably, it is 30 to 70 parts by weight. The content of (2) methyl methacrylate is preferably 30 to 70 parts by weight. However, the acrylic polymer (B) is not limited to the specific configuration described above.

The acrylic polymer (B) can be obtained by polymerizing the above-mentioned monomer components using a known or conventional polymerization method. Examples of the polymerization method of the acrylic polymer (B) include a solution polymerization method, an emulsion polymerization method, a block polymerization method, a polymerization method by active energy ray irradiation (active energy ray polymerization method), and the like. Among them, the block polymerization method and the solution polymerization method are preferred, and the solution polymerization method is more preferred.

When polymerizing the acrylic polymer (B), various common solvents can be used. Examples of the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane; alicyclic hydrocarbons such as alkanes; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. Furthermore, such solvents can be used alone or in combination of two or more.

Furthermore, when polymerizing the acrylic polymer (B), a known or commonly used polymerization initiator (for example, a thermal polymerization initiator or a photopolymerization initiator, etc.) can be used. In addition, the polymerization initiator can be used alone or in combination of two or more types.

Examples of the thermal polymerization initiator include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile (AMBN), 2,2' -Azobis(2-methylpropionic acid)dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis(4-methoxy-2,4 -dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2 '-Azobis(2,4,4-trimethylpentane) and other azo initiators; benzyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, peroxide Tert-butyl benzoate oxide, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis Peroxide-based initiators such as (tert-butylperoxy)cyclododecane, etc. Furthermore, when performing solution polymerization, it is preferable to use an oil-soluble polymerization initiator. Moreover, the thermal polymerization initiator can be used individually or in combination of 2 or more types.

The usage amount of the thermal polymerization initiator is not particularly limited, but may be, for example, 100 parts by weight relative to all monomer units of the acrylic polymer (B) (the total amount of monomer components constituting the acrylic polymer (B)). 0.1 to 15 parts by weight.

In addition, the photopolymerization initiator is not particularly limited, and examples thereof include the same photopolymerization initiator used in the polymerization of the acrylic polymer (A) exemplified above. . The usage amount of the above-mentioned photopolymerization initiator is not particularly limited and can be selected appropriately.

When polymerizing the acrylic polymer (B), a chain transfer agent can be used to adjust the molecular weight (specifically, to adjust the weight average molecular weight to 1,000 to 30,000). Examples of the chain transfer agent include: 2-mercaptoethanol, α-thioglycerol, 2,3-dimercapto-1-propanol, octylthiol, tertiary nonylthiol, dodecylthiol (lauryl sulfide) alcohol), tertiary-dodecanethiol, glycidyl mercaptan, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, sulfide tert-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, Ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate, α-methylstyrene dimer, etc. Among them, from the viewpoint of suppressing whitening of the adhesive sheet due to humidification, α-thioglycerin and methyl thioglycolate are preferred, and α-thioglycerin is particularly preferred. In addition, the chain transfer agent can be used alone or in combination of two or more types.

The content (usage amount) of the above-mentioned chain transfer agent is not particularly limited. It is less than 100 parts by weight of all monomer units of the acrylic polymer (B) (the total amount of monomer components constituting the acrylic polymer (B)). It is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and still more preferably 0.3 to 10 parts by weight. By setting the content (usage amount) of the chain transfer agent within the above range, an acrylic polymer having a weight average molecular weight controlled to 1,000 to 30,000 can be easily obtained.

The weight average molecular weight (Mw) of the acrylic polymer (B) is 1,000 to 30,000, preferably 1,000 to 20,000, more preferably 1,500 to 10,000, further preferably 2,000 to 8,000. Since the weight average molecular weight of the acrylic polymer (B) is 1,000 or more, the adhesive force or retention characteristics are improved, and the foaming and peeling resistance is improved. On the other hand, the weight average molecular weight of the acrylic polymer (B) is 30,000 or less, so it is easy to increase the adhesive force and improve the foaming and peeling resistance.

The weight average molecular weight (Mw) of the acrylic polymer (B) can be obtained in terms of polystyrene by GPC (Gel permeation chromatography) method. For example, a high-speed GPC device "HPLC-8120GPC" manufactured by Tosoh Co., Ltd. can be used, and measurement can be performed based on the following conditions. Column: TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000 Solvent: Tetrahydrofuran Flow rate: 0.6 ml/minute

The glass transition temperature (Tg) of the acrylic polymer (B) is not particularly limited, but is preferably 20 to 300°C, more preferably 30 to 300°C, and still more preferably 40 to 300°C. It is preferable that the glass transition temperature of the acrylic polymer (B) is 20° C. or higher because the foaming and peeling resistance is easily improved. In addition, if the glass transition temperature of the acrylic polymer (B) is 300°C or less, the adhesive layer will have moderate flexibility, and it will be easy to obtain good adhesion or good step absorption, and it will be easy to obtain excellent bonding reliability. , so it is better.

The glass transition temperature (Tg) of the acrylic polymer (B) is the glass transition temperature (theoretical value) represented by the following formula. 1/Tg＝W ₁ /Tg ₁ ＋W ₂ /Tg ₂ ＋・・・＋W _n /Tg _nIn the above formula, Tg represents the glass transition temperature (unit: K) of the acrylic polymer (B), and Tg _i represents the single unit The glass transition temperature (unit: K) when monomer i forms a homopolymer, _{and Wi} represents the weight fraction of the total monomer components of monomer i (i=1, 2,...n). As the Tg of the homopolymer of the monomer constituting the acrylic polymer (B), the values described in Table 1 below can be adopted. In addition, as the Tg of the homopolymer of the monomer not listed in Table 1, the value described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989) can be used. Furthermore, as the Tg of the homopolymer of the monomer that is not described in the above-mentioned literature, the value obtained by the above-mentioned measurement method (the peak temperature of tan δ based on the viscoelasticity test) can be used.

[Table 1] Table 1 composition Tg[℃] Homopolymer Methyl methacrylate (MMA) 105 Dicyclopentyl methacrylate (DCPMA) 175 Dicyclopentyl acrylate (DCPA) 120 Isopropyl methacrylate (IBXMA) 173 Isoacrylate (IBXA) 97 Cyclohexyl methacrylate (CHMA) 66 1-Adamantyl methacrylate (ADMA) 250 1-adamantyl acrylate (ADA) 153 copolymer DCPMA/MMA=60/40 144 Furthermore, the copolymer of "DCPMA/MMA=60/40" in Table 1 refers to a copolymer of 60 parts by weight of DCPMA and 40 parts by weight of MMA.

When the adhesive composition of the present invention contains acrylic polymers (A) and (B), the content of acrylic polymer (B) is not particularly limited. It is based on 100 parts by weight of the acrylic polymer (A). , preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and even more preferably 2 to 10 parts by weight. That is, the content of the acrylic polymer (B) in the adhesive composition of the present invention is not particularly limited, but is preferably 1 to 30 parts by weight based on 100 parts by weight of all monomer units of the acrylic polymer (A). Parts by weight are more preferably 2 to 20 parts by weight, and still more preferably 2 to 10 parts by weight. The content of the acrylic polymer (B) in the adhesive composition of the present invention is not particularly limited. For example, it is preferably 1 to 30 parts by weight, and more preferably 2 to 20 parts by weight based on 100 parts by weight of the above monomer mixture. parts, more preferably 2 to 10 parts by weight. If the content of the acrylic polymer (B) is 1 part by weight or more, it is easy to obtain excellent adhesiveness and excellent foaming and peeling resistance, so it is preferable. Moreover, when the content of the acrylic polymer (B) is 30 parts by weight or less, it is easy to obtain excellent transparency and adhesion reliability, so it is preferable.

[1-11. Conductive polymer (B)] The adhesive composition (1) of the present invention is an adhesive composition for forming an adhesive layer that also contains a conductive polymer (B) in addition to the adhesive polymer (A). In the adhesive composition (1) of the present invention, the conductive polymer (B) functions as a polymer component that imparts antistatic properties to the adhesive layer of the present invention.

In addition, the adhesive composition (2) of the present invention also contains, in addition to the adhesive polymer (A), a mixture of monomer components constituting the conductive polymer (B) or a monomer constituting the conductive polymer (B). A partial polymer of a mixture of ingredients. In the adhesive composition (2) of the present invention, "the mixture of monomer components constituting the conductive polymer (B)" and "the partial polymer of the mixture of monomer components constituting the conductive polymer (B)" A polymerization reaction is performed to form a precursor (raw material mixture) of conductive polymer (B). The formed conductive polymer (B) serves as a polymer component that imparts antistatic properties to the adhesive layer of the present invention. Functional person.

The above-mentioned "monomer mixture" includes a case of containing a single monomer component constituting the conductive polymer (B) and a case of containing two or more monomer components constituting the conductive polymer (B). In addition, the above-mentioned "partial polymer" refers to a composition in which one or two or more components of the monomer mixture constituting the conductive polymer (B) are partially polymerized. In this specification, when simply referred to as "conductive polymer (B)", unless otherwise mentioned, it includes "conductive polymer (B)" and "monomer components constituting conductive polymer (B)". "Mixture", and "a partial polymer of a mixture of monomer components constituting the conductive polymer (B)".

The adhesive composition (adhesive composition (1) and (2)) of the present invention contains an ionic compound (B1) having a functional group (b1) in the molecule, and an ionic compound (B1) having a functional group (b1) in the molecule that can interact with the above-mentioned functional group (b1). ) reacts to form a covalently bonded functional group (b2), the compound (B2) serves as a monomer component constituting the conductive polymer (B). The ionic compound (B1) is a monomer component used to impart an antistatic function to the conductive polymer (B), and the compound (B2) is a monomer that together with the ionic compound (B1) constitutes the conductive polymer (B). Element. The functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, and a polymerization reaction proceeds to form the conductive polymer (B).

In the adhesive layer formed from the adhesive composition (1) of the present invention, the conductive polymer (B) has a three-dimensional network structure. Furthermore, in the adhesive composition (2) of the present invention, the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, forming a three-dimensional network. Structure of conductive polymer (B). The above-mentioned "three-dimensional network structure" refers to a structure in which linear or branched polymers constituting the conductive polymer (B) are connected through a cross-linked structure to form a three-dimensional network structure.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the ionic compound (B1) preferably has two or more functional groups (b1) in the molecule. The structure in which the ionic compound (B1) has two or more functional groups (b1) in the molecule can efficiently form the conductive polymer (B) by performing the above-mentioned polymerization reaction with the compound (B2). good. In order to efficiently form the conductive polymer (B), the number of functional groups (b1) that the ionic compound (B1) has in the molecule is preferably 2 to 4, more preferably 2. ~3, and more preferably 2.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the functional group (b1) is preferably selected from the group consisting of hydroxyl group, carboxyl group, amino group, mercapto group, and (meth)acryloxy group. At least one functional group from the group consisting of, (meth)acrylamide group, vinyl group, allyl group, and styrene group. It is preferable that the functional group (b1) is selected from these functional groups so that the polymerization reaction with the functional group (b2) is easy and the conductive polymer (B) can be formed efficiently. In terms of efficiently forming the conductive polymer (B), the functional group (b1) is preferably a hydroxyl group, a carboxyl group, an amino group or a mercapto group, more preferably a hydroxyl group or a carboxyl group, and still more preferably a hydroxyl group. Furthermore, the ionic compound (B1) may have one functional group (b1), or may have two or more functional groups (b1) in combination. Furthermore, the amine group includes -NH ₂ and -NHR (R is an alkyl group having 1 to 6 carbon atoms).

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the compound (B2) preferably has three or more functional groups (b2) in the molecule. The compound (B2) having three or more functional groups (b2) in the molecule undergoes the above-mentioned polymerization reaction with the ionic compound (B1), thereby efficiently forming the above-mentioned three-dimensional network of the conductive polymer (B). Better in terms of structure. In order to efficiently form the above-mentioned three-dimensional network structure of the conductive polymer (B), the number of functional groups (b2) contained in the molecule of the compound (B2) is preferably 3 to 8. More preferably, they are 3 to 6, still more preferably 3 to 5, still more preferably 3 or 4.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the functional group (b2) is preferably selected from the group consisting of isocyanate group, thioisocyanate group, epoxy group, nitrogen A group consisting of propidyl, ethanozolinyl, carbodiimide, (meth)acryloxy, (meth)acrylamide, vinyl, allyl, and styrene groups At least one of the functional groups. It is preferable that the functional group (b2) is selected from these functional groups so as to be easily polymerized with the functional group (b1), thereby efficiently forming the conductive polymer (B). In terms of effectively forming the conductive polymer (B), the functional group (b2) is preferably an isocyanate group, a thioisocyanato group or an epoxy group, more preferably an isocyanate group or a cyclic group. Oxygen group, more preferably isocyanate group. Furthermore, compound (B2) may have one functional group (b2), or may have two or more functional groups (b2) in combination.

The functional group (b1) and the functional group (b2) can react to form a covalent bond. That is, the functional group (b1) of the ionic compound (B1) and the functional group (b2) of the compound (B2) react sequentially to form a covalent bond, and a polymerization reaction proceeds, thereby forming a conductive structure with a three-dimensional network structure Polymer (B). The combination of functional group (b1) and functional group (b2) is not particularly limited as long as it can react with each other to form a covalent bond. Examples include: hydroxyl group and isocyanato group, amine group and isocyanate group. Acid group, thiol group and isocyanate group, hydroxyl group and thioisocyanate group, amine group and thioisocyanato group, thiol group and thioisocyanate group, carboxyl group and epoxy group, carboxyl group and aziridinyl group , carboxyl and tetrazolinyl, mercapto and tetrazolinyl, carboxyl and tetrazolinyl, selected from (meth)acryloxy, (meth)acrylamine, vinyl, allyl, and a combination of one styrene group and one selected from the group consisting of (meth)acryloxy group, (meth)acrylamide group, vinyl group, allyl group, and styrene group. Among these, the combination of a hydroxyl group and an isocyanato group, and the combination of a carboxyl group and an epoxy group are preferable from the viewpoint that the reactivity is high and the conductive polymer (B) can be formed efficiently. Among them, from the viewpoint of ease of material acquisition and high reactivity, a combination in which the functional group (b1) is a hydroxyl group and the functional group (b2) is an isocyanate group is most preferred. Hereinafter, a mode using an ionic compound (B1) having a hydroxyl group as a functional group (b1) and a compound (B2) having an isocyanato group as a functional group (b2) will be described. However, the present invention is not limited to this embodiment. Way.

The ionic compound (B1) is an essential monomer component for constituting the conductive polymer (B) and is a monomer component for imparting an antistatic function to the conductive polymer (B). The ionic compound (B1) is an ionic compound having a functional group (b1) in the cation part and/or the anion part (either or both) constituting the ionic compound (B1) in the molecule. Furthermore, the ionic compound (B1) is preferably a liquid (liquid state) at any temperature within the range of 0 to 150° C., a non-volatile molten salt, and a transparent compound (ionic liquid). In addition, the ionic compound (B1) can be used individually or in combination of 2 or more types.

By containing the ionic compound (B1) as a monomer component, the conductive polymer (B) can incorporate the ionic compound (B1) into the molecules of the conductive polymer (B), so it can be used in harsh environments such as hot and humid environments. Under certain conditions, it can also inhibit the leakage of antistatic components, making it less likely to cause corrosion of metal wiring and other defects caused by the precipitation of antistatic agents on the surface of the adhesive layer. In addition, even under severe conditions such as hot and humid environments, the antistatic agent can be inhibited from migrating from the adhesive layer to other optical components, thereby inhibiting the increase in surface resistance, thereby maintaining excellent antistatic properties. Furthermore, it is easy to maintain transparency without impairing compatibility, suppress foaming and peeling on the surface of the adhesive layer, and is less likely to cause durability defects such as appearance or bonding reliability. Therefore, the adhesive layer of the present invention including the conductive polymer (B) containing the ionic compound (B1) as a monomer component can satisfy excellent antistatic properties and durability (especially corrosion resistance stability and resistance value stability). ),it works.

The cation part of the ionic compound (B1) can be used without particular limitation, and examples thereof include quaternary ammonium cation, imidazolium cation, pyridinium cation, piperidinium cation, pyrrolidinium cation, and quaternary phosphonium cation. Trialkyl sulfonium cation, pyrrole cation, pyrazolium cation, guanidium cation, etc., among which, quaternary ammonium cation, imidazolium cation, pyridinium cation, piperidinium cation, pyrrolidinium cation, quaternary ammonium cation, etc. are more preferably used. Phosphonium cations, trialkyl sulfonium cations, and more preferably quaternary ammonium cations are used.

Moreover, in the anion part constituting the ionic compound (B1), examples of the anions include SCN ^- , BF ₄ ^- , PF ₆ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- and CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (FSO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ³ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , F(HF) _n ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ ) (CF ₃ CO)N ^- , B(CN) ₄ ^- , C(CN) ₃ ^- , N(CN) ₂ ^- , CH ₃ OSO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₄ H ₉ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , p-toluenesulfonate anion, 2-(2-methoxyethyl)ethylsulfate anion, (C ₂ F ₅ ) ₃ PF ₃ ^- etc., especially anionic components containing fluorine atoms (fluorine-containing anions) are preferred in terms of obtaining an ionic compound with a low melting point and excellent antistatic properties. Furthermore, as anions, chloride ions, bromide ions, etc. are corrosive and therefore are preferably not used.

The ionic compound (B1) having two or more hydroxyl groups as functional groups (b1) in the molecule is preferably the following general formula (B1) in terms of efficiently forming the conductive polymer (B). B) represents the ionic compound. [Chemical 6]

In the above formula (B), X ⁺ is a cation part. Y ^- is an anion. Z ¹ and Z ² are the same or different, and are a single bond, an alkylene group having 1 to 16 carbon atoms, or a polyoxyalkylene group. n ¹ is 1, n ² is an integer from 1 to 3. When n ² is 2 or more, the two or more Z ² in parentheses may be the same or different.

Examples of the cation part (X ⁺ ) constituting the ionic compound represented by the general formula (B) include: quaternary ammonium group, imidazolium group, pyridinium group, piperidinium group, pyrrolidinium group, and pyrrolyl group , quaternary phosphonium group, trialkyl sulfonyl group, pyrazolium group, guanidium group, etc. Among these, in particular, the case of a quaternary ammonium group is excellent in transparency and is preferred for electronic and optical applications. In addition, when quaternary ammonium is cured by ultraviolet (UV), it is less likely to hinder normal radical polymerization reactions and is presumed to have higher curing properties, so it is preferable.

As the above-mentioned quaternary ammonium group, when n ¹ + n ² is 2, examples thereof include: dimethylammonium group, diethylammonium group, dipropylammonium group, methylethylammonium group, methylpropyl ammonium group methyl ammonium group, methyl benzylammonium group, ethyl benzylammonium group, methyl octadecyl ammonium group, ethyl octadecyl ammonium group, methyl oleyl ammonium group, ethyl oleyl ammonium group, etc. , among them, dimethylammonium group and methyloleyl ammonium group are particularly preferred in terms of easy access to cheap industrial materials.

Among the anions (parts) (Y ^- ) constituting the ionic compound represented by the general formula (B), examples of the anions include SCN ^- , BF ₄ ^- , PF ₆ ^- , NO ₃ ^- and CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (FSO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- ,SbF ₆ ^- ,NbF ₆ ^- ,TaF ₆ ^- ,F(HF) _n ^- ,(CN) ₂ N ^- ,C ₄ F ₉ SO ₃ ^- ,(C ₂ F ₅ SO ₂ ) ₂ N ^- ,C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , B(CN) ₄ ^- , C(CN) ₃ ^- , N(CN) ₂ ^- , CH ₃ OSO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , C ₄ H ₉ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , p-toluenesulfonate anion, 2-(2-methoxyethyl)ethyl sulfate anion, (C ₂ F ₅ ) ₃ PF ₃ ^- and the like, especially anionic components containing fluorine atoms (fluorine-containing anions) are preferred in terms of obtaining an ionic compound with a low melting point and excellent antistatic properties. Furthermore, as anions, chloride ions, bromide ions, etc. are corrosive and therefore are preferably not used.

Z ¹ and Z ² constituting the ionic compound represented by the above general formula (B) are a single bond, an alkylene group having 1 to 16 carbon atoms, or a polyoxyalkylene group. The alkylene group having 1 to 16 carbon atoms is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. . Specific examples include methylene, ethylidene, trimethylene, methylethylidene, etc., and ethylidene and trimethylene are preferred. As the polyoxyalkylene group, a polyoxyalkylene group in which an oxyalkylene unit having 2 to 4 carbon atoms is polymerized with a degree of polymerization of 2 to 8 is preferred. Furthermore, Z ¹ and Z ² may be the same or different.

In the above general formula (B), specific examples of the group represented by -Z ¹ -OH or -Z ² -OH include: hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyl Hydroxyalkyl groups such as hexyl group, polyoxyalkylene groups such as polyoxyethylene group and polyoxypropylene group, etc. In addition, the groups represented by -Z ¹ -OH and -Z ² -OH may be the same or different.

In the ionic compound represented by the above general formula (B), a specific example in which X ⁺ is a quaternary ammonium group, n ¹ is 1, n ² is 1, and Z ¹ and Z ² are an alkylene group can be Examples: bis(2-hydroxyethyl)-dimethylammonium bis(fluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-butylammonium bis(trifluoromethanesulfonate) Bis(2-hydroxyethyl)-methyl-octyl ammonium bis(trifluoromethanesulfonyl)amide imide, bis(2-hydroxyethyl)-methyl-decyl ammonium bis(trifluoromethanesulfonyl)amide (Trifluoromethanesulfonyl)amide, bis(2-hydroxyethyl)-methyl-dodecyl ammonium bis(trifluoromethanesulfonyl)amide, bis(2-hydroxyethyl) -Methyl-tetradecyl ammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-cetadecylammonium bis(trifluoromethanesulfonyl)imide Amine, bis(2-hydroxyethyl)-methyl-octadecyl ammonium bis(trifluoromethanesulfonyl)imide, bis(2-hydroxyethyl)-methyl-(9-ene-deca Octalkyl) ammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-octyl ammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis (2-hydroxyethyl)-decyl ammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-dodecyl ammonium bis(trifluoromethanesulfonyl)imide acyl imine, ethyl-bis(2-hydroxyethyl)-tetradecyl ammonium bis(trifluoromethanesulfonyl) acyl imine, ethyl-bis(2-hydroxyethyl)-hexadecyl ammonium Ammonium bis(trifluoromethanesulfonyl)imide, ethyl-bis(2-hydroxyethyl)-octadecyl ammonium bis(trifluoromethanesulfonyl)imide, oleyl bis(2- Hydroxyethyl) methyl ammonium bis(trifluoromethanesulfonyl)imide, oleyl-ethyl-bis(2-hydroxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, etc.

Specific examples of the ionic compound represented by the above general formula (B) in which X ⁺ is a quaternary ammonium group, n ¹ is 1, n ² is 1, and Z ¹ and Z ² are polyoxyalkylene groups. , examples include: bis(polyoxyethylidene)-methyl-octyl ammonium bis(trifluoromethanesulfonyl)imide, bis(polyoxyethylidene)-methyl-decylammonium bis( Trifluoromethanesulfonyl)amide, bis(polyoxyethylidene)-methyl-dodecyl ammonium bis(trifluoromethanesulfonyl)amide, bis(polyoxyethylidene)- Methyl-tetradecyl ammonium bis(trifluoromethanesulfonyl)imide, bis(polyoxyethylidene)-methyl-cetadecylammonium bis(trifluoromethanesulfonyl)imide , bis(polyoxyethylidene)-methyl-octadecyl ammonium bis(trifluoromethanesulfonyl)imide, oleyl-bis(polyoxyethylidene)-methyl-octadecyl ammonium bis(trifluoromethyl) Methanesulfonyl)imide, etc.

The content (ratio) of the ionic compound (B1) relative to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, as long as it can provide sufficient resistance to the adhesive layer of the present invention. In terms of electrostatic properties, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and even more preferably 100 parts by weight of the total monomer components constituting the conductive polymer (B). 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more. The content of the ionic compound (B1) is not particularly limited. In terms of ensuring durability such as transparency, appearance, and adhesion reliability of the adhesive layer of the present invention, the content of the ionic compound (B1) is higher than that of the conductive polymer (B). The total amount of monomer components is 100 parts by weight, preferably 90 parts by weight or less, more preferably 85 parts by weight or less, and further preferably 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, or 65 parts by weight. portion or less.

The conductive polymer (B) may contain a non-ionic compound (B1') having two or more hydroxyl groups as functional groups (b1) in the molecule as a monomer component within a range that does not impair the effects of the present invention. .

As the compound (B1'), a known or commonly used polyhydric alcohol can be used without particular limitation. Examples thereof include: ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3- Butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxy C _2-4 alkylene glycol ( Polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.), bisphenol A and its alkylene oxide adducts, bisphenol F and its alkylene oxide adducts, hydrogenated bisphenol A and its ring Oxane adducts, hydrogenated bisphenol F and its alkylene oxide adducts, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, isosorbide, xylene glycol, polyester diol , polyether glycol, polycarbonate glycol and other glycols; glycerin, 1,1,1-tris(hydroxymethyl)propane, D-sorbitol, xylitol, D-mannitol (mannitol), D-Mannitol (Mannite), diglycerin, polyglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, cyclic Oxygen polyols, natural oil polyols, silicone polyols, fluorine polyols, polyolefin polyols, etc. are polyols with more than three hydroxyl groups in the molecule.

The content (ratio) of the ionic compound (B1') relative to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, so long as it can impart sufficient strength to the adhesive layer of the present invention. In terms of antistatic properties, it is preferably 30 parts by weight or less (for example, 0 to 30 parts by weight), more preferably 20 parts by weight, based on 100 parts by weight of the total monomer components constituting the conductive polymer (B). or less, and more preferably 10 parts by weight or less, 5 parts by weight or less, 1 part by weight or less, or 0.1 parts by weight or less. The lower limit of the content (ratio) of the ionic compound (B1') is not particularly limited, but may be 0.01 parts by weight or more.

Compound (B2) is an essential monomer component for constituting conductive polymer (B) together with ionic compound (B1). In particular, from the viewpoint that a three-dimensional cross-linked structure can be introduced into the polymer structure of the conductive polymer (B) to efficiently form a three-dimensional network structure, it is preferable to use a polymer having three or more functions in the molecule. The compound (B2) of group (b2) is particularly preferably a polyfunctional isocyanate having three or more isocyanate groups in the molecule. In addition, compound (B2) can be used individually or in combination of 2 or more types.

The polyfunctional isocyanate having three or more isocyanate groups in the molecule can be either aromatic or aliphatic, and can efficiently form the three-dimensional conductive polymer (B) due to its reactivity. From the viewpoint of network structure, aromatic isocyanate, aliphatic isocyanate, and alicyclic isocyanate are preferred, and in particular, polyol adducts of aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate are more preferred. , or a polymer of aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate.

Examples of polyol adducts of aromatic diisocyanates, aliphatic diisocyanates, or alicyclic diisocyanates include polyols and toluene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate. , excess amount of aromatic diisocyanates such as benzidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-propylene diisocyanate Butyl diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, dodecylmethylene diisocyanate, lysine diisocyanate and other carbon numbers (in NCO Excess amount of aliphatic diisocyanate (excluding carbon atoms) 2 to 12, or cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, Compounds containing terminal isocyanates obtained by reacting excess amounts of alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, dimer diisocyanate, norphenylene diisocyanate, etc. Among these, from the viewpoint of reactivity and efficient formation of a three-dimensional network structure of the conductive polymer (B), toluene diisocyanate, xylylene diisocyanate, and 1,6-hexane diisocyanate are preferred. Polyol adducts of methylene diisocyanate, hydrogenated xylylene diisocyanate or isophorone diisocyanate. Examples of the polyol here include aliphatic polyols such as glycerin, trimethylolpropane, pentaerythritol, di-trimethylolpropane, and dipentaerythritol, and trimethylolpropane is preferred. .

Examples of polymers of aromatic diisocyanates, aliphatic diisocyanates or alicyclic diisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and toluidine diisocyanate. , xylylene diisocyanate, tetramethylxylylene diisocyanate and other aromatic diisocyanates, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamide Methyl diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Butyl diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, dodecyl methylene diisocyanate, lysine diisocyanate and other fats with carbon numbers (excluding the carbon in NCO) of 2 to 12 Group diisocyanates, or cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, dimer diisocyanate Tri- to hexamers of alicyclic diisocyanates such as isocyanate and nor-phenylene diisocyanate, and trimers (for example, isocyanurate bodies) can be used particularly suitably. In addition, an isocyanurate body and a modified body in which the isocyanurate body is polymerized can also be used.

As the polyfunctional isocyanate having three or more isocyanate groups in the molecule, commercially available products can be used. For example, the isocyanurate adduct of hexamethylene diisocyanate [manufactured by Tosoh Corporation, commercial product] Name "Coronate HX"], trimethylolpropane/toluene diisocyanate adduct [manufactured by Tosoh Corporation, trade name "Coronate L"], trimethylolpropane/hexamethylene diisocyanate adduct [Japan Polyurethane Manufactured by Kogyo Co., Ltd., trade name "Coronate HL"], trimethylolpropane/xylylenediisocyanate adduct [manufactured by Mitsui Chemicals Co., Ltd., trade name "Takenate D-110N"], toluene diisocyanate isocyanurate [manufactured by Mitsui Chemicals Co., Ltd., trade name "Takenate D-262"], trimethylolpropane adduct of toluene diisocyanate [manufactured by Mitsui Chemicals Co., Ltd., trade name "Takenate D" -101E"] etc.

The content (ratio) of the compound (B2) relative to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, so that the conductive polymer (B) can be formed efficiently. From the viewpoint of the three-dimensional network structure, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and still more preferably 100 parts by weight of the total monomer components constituting the conductive polymer (B). It may contain more than 15 parts by weight, more than 20 parts by weight, more than 25 parts by weight, more than 30 parts by weight or more than 35 parts by weight. The content of the compound (B2) is not particularly limited. In order to easily ensure the flexibility and stress relaxation properties of the adhesive layer of the present invention, the content of the compound (B2) is 100% by weight based on the total amount of the monomer components constituting the conductive polymer (B). Parts, preferably 90 parts by weight or less, more preferably 85 parts by weight or less, further preferably 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less or 65 parts by weight or less.

The content (ratio) of the polyfunctional isocyanate having three or more isocyanate groups in the molecule relative to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, as long as From the viewpoint of efficiently forming the three-dimensional network structure of the conductive polymer (B), it is preferable to contain 5 parts by weight or more based on 100 parts by weight of the total amount of monomer components constituting the conductive polymer (B). More preferably, it can contain 10 parts by weight or more, and still more preferably, it can contain 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more. The content of the polyfunctional isocyanate having three or more isocyanate groups in the molecule is not particularly limited. In order to easily ensure the flexibility and stress relaxation of the adhesive layer of the present invention, the content of the polyfunctional isocyanate that constitutes the conductive polymer is The total amount of monomer components of substance (B) is 100 parts by weight, preferably 90 parts by weight or less, more preferably 85 parts by weight or less, and further preferably 80 parts by weight or less, 75 parts by weight or less, or 70 parts by weight. or less than 65 parts by weight.

The conductive polymer (B) may contain a non-ionic compound (B2') having two or more isocyanato groups as functional groups (b2) in the molecule, within a range that does not impair the effects of the present invention. Monomeric components. Examples of the compound (B2') include the above-mentioned aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate.

The content (ratio) of the ionic compound (B2') relative to the total amount (100 parts by weight) of the monomer components constituting the conductive polymer (B) is not particularly limited, and the conductive polymer (B) can be efficiently formed. From the viewpoint of the three-dimensional network structure of B), it is preferably 30 parts by weight or less (for example, 0 to 30 parts by weight) based on 100 parts by weight of the total monomer components constituting the conductive polymer (B), and more preferably It is 20 parts by weight or less, more preferably 10 parts by weight or less, 5 parts by weight or less, 1 part by weight or less, or it may be 0.1 part by weight or less. The lower limit of the content (ratio) of the ionic compound (B2') is not particularly limited, but may be 0.01 parts by weight or more.

In the conductive polymer (B), the ratio of the ionic compound (B1) to the compound (B2) (ionic compound (B1)/compound (B2)) is not particularly limited, and the adhesive layer of the present invention can be provided with In terms of sufficient antistatic performance, it is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, and may be 0.4 or more, 0.5 or more, or 0.6 or more. Moreover, from the viewpoint of efficiently forming the three-dimensional network structure of the conductive polymer (B), the above ratio is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, and may be is less than 2.5 or less than 2.

The above "mixture of monomer components constituting the conductive polymer (B)" can be prepared by adding the ionic compound (B1) and the compound (B2) at room temperature or while heating as needed. The compounds (B1') and (B2') are mixed while stirring.

The above-mentioned "partial polymer of the mixture of monomer components constituting the conductive polymer (B)" can be prepared by cross-linking the above-mentioned "mixture of monomer components constituting the conductive polymer (B)" The polymerization reaction proceeds in the presence of a catalyst, in the presence or absence of a cross-linking retardant.

As the cross-linking catalyst that can be used when obtaining the above partial polymer, any suitable catalyst can be used. Examples of such a catalyst include tertiary amine compounds, organic metal compounds, and the like.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU), and the like.

Examples of organometallic compounds include tin-based compounds, non-tin-based compounds, and the like.

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, sulfide Dibutyltin, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethanol, tributyltin ethanol, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethyltin hexanoate, etc. .

Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride; lead oleate, lead 2-ethylhexanoate, and benzene. Lead-based compounds such as lead formate and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylpyruvate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate , zinc 2-ethylhexanoate and other zinc compounds; zirconium naphthenate and other zirconium compounds; etc.

The usage amount of the above-mentioned cross-linking catalyst is preferably 0.01 to 1.0% by weight relative to the mixture of monomer components.

When obtaining the above-mentioned partial polymer, a cross-linking retardant can be used together with the above-mentioned cross-linking catalyst. By using a cross-linking retardant, the effect of extending the pot life of the adhesive composition can be achieved. As the cross-linking retardant, a compound generating keto-enol tautomerism can be suitably used. As compounds that produce keto-enol tautomerism, various β-dicarbonyl compounds can be used. For example, β-diketones (acetyl acetone, 2,4-hexanedione, etc.) or acetyl acetates (methyl acetyl acetate, ethyl acetate acetate, etc.) can be preferably used. The crosslinking retardant can be used alone or in combination of two or more. The usage amount of the crosslinking retardant may be, for example, 0.1 to 30 parts by weight, or 0.5 to 25 parts by weight based on 100 parts by weight of the mixture of monomer components.

The reaction temperature when obtaining the above-mentioned partial polymer is preferably less than 100°C, more preferably 50°C to 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and cross-linked structure, and it may be difficult to obtain the above-mentioned partial polymer having a predetermined molecular weight. The reaction time is not particularly limited and can be selected from 1 hour to 72 hours.

The content of the conductive polymer (B) in the adhesive composition of the present invention is not particularly limited, but is preferably 5 to 30% by weight, more preferably 7 to 25% by weight, and even more preferably 10 to 20% by weight. . A composition in which the content of the conductive polymer (B) is 5% by weight or more is preferable in that it can impart sufficient antistatic properties to the adhesive layer of the present invention. In addition, a composition in which the content of the conductive polymer (B) is 30% by weight or less is preferable in that it can impart excellent adhesiveness to the adhesive layer of the present invention.

In the adhesive composition (adhesive composition (1) and (2)) of the present invention, the content ratio of the conductive polymer (B) to the adhesive polymer (A) (conductive polymer (B) )/adhesive polymer (A)) is preferably 0.05 to 0.5. The above-mentioned content ratio is preferably 0.05 or more in terms of imparting excellent antistatic properties to the adhesive layer of the present invention. In order to impart excellent antistatic properties to the adhesive layer of the present invention, the content ratio is preferably 0.07 or more, more preferably 0.08 or more, and still more preferably 0.1 or more. Moreover, the structure in which the said content ratio is 0.5 or less is preferable in terms of providing excellent adhesiveness to the adhesive layer of this invention. In order to impart excellent adhesiveness to the adhesive layer of the present invention, the content ratio is preferably 0.4 or less, more preferably 0.3 or less.

[1-11. Antistatic agent] The adhesive composition of the present invention may contain an antistatic agent within the range that does not impair the effects of the present invention. Examples of the antistatic agent include materials that can provide antistatic properties, such as ionic compounds, ionic surfactants, conductive polymers, and conductive fine particles. Among these, in terms of compatibility with the adhesive polymer (A) and the conductive polymer (B) and the transparency of the adhesive layer, an ionic compound is preferred.

As the ionic compound, inorganic cation anion salts and/or organic cation anion salts can be preferably used, and in particular, the use of inorganic cation anion salts is preferred. Ionic compounds containing inorganic cations (inorganic cation anion salts) are more preferable than organic cation anion salts because they can suppress a decrease in the adhesiveness (gripping power) of the adhesive layer during use. Furthermore, the so-called "inorganic cation anion salt" in the present invention generally refers to an alkali metal salt formed from an alkali metal cation and anion. As the alkali metal salt, organic salts and inorganic salts of alkali metals can be used. In addition, the so-called "organic cation anion salt" in the present invention refers to an organic salt whose cation part contains an organic substance, and the anion part may be an organic substance or an inorganic substance. "Organic cation anion salt" is also called ionic liquid or ionic solid. In addition, as the anion component constituting the ionic compound, it is preferable to use anion containing fluorine in terms of antistatic function.

Examples of the alkali metal ions constituting the cation part of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.

The anion part of the alkali metal salt may contain an organic substance or an inorganic substance. As the anion part constituting the organic salt, for example, CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , C ₄ F ₉ SO ₃ ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- , PF ₆ ^- , CO ₃ ^2- , or the following general formula (1) to (4) (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (n is an integer from 1 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (where m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer from 1 to 10), (4): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (where p and q are integers from 1 to 10), and those represented by (FSO ₂ ) ₂ N ^- , etc. In particular, an anionic part containing a fluorine atom can be preferably used because an ionic compound with good ion dissociation properties can be obtained. As the anion part constituting the inorganic salt, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ - , ClO ₄ ^- , NO ₃ ^{- ,} AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , etc. Among the anions containing a fluorine atom, a fluorine-containing acyl imine anion is preferred, and among these, a bis(trifluoromethanesulfonyl) acyl imine anion and a bis(fluorosulfonyl) acyl imine anion are preferred. In particular, bis(fluorosulfonyl)imide anion is preferable because it can be added in a smaller amount to impart excellent antistatic properties, maintain adhesive properties, and is beneficial to durability in humidified or heated environments.

Specific examples of organic salts of alkali metals include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, KO ₃ S(CF ₂ ) ₃ SO ₃ K , LiO ₃ S(CF ₂ ) ₃ SO ₃ K, etc., among them, LiCF ₃ SO ₃ , Li(FSO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, etc., more preferably Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N and other fluorine-containing lithium imide salts, especially lithium bis(trifluoromethanesulfonyl)imide and bis(fluoromethanesulfonyl)imide Lithium amide.

Moreover, examples of inorganic salts of alkali metals include lithium perchlorate and lithium iodide.

The organic cation anion salt contains a cation component and an anion component, and the cation component contains an organic substance. Specific examples of the cationic component include: pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having a pyrroline skeleton, cation having a pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium Cation, pyrazolium cation, pyrazolinium cation, tetraalkyl ammonium cation, trialkyl sulfonium cation, tetraalkyl phosphonium cation, etc.

As anionic components, for example, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ - , NO ₃ ^{- ,} CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ² ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ - , TaF ₆ ^{- ,} (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , C ₃ F ₇ COO ^- , ((CF ₃ SO ₂ )(CF ₃ CO)N ^- , ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- , or the following general formula (1) to (4) (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (where n is an integer from 1 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- ( Where, m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (where, l is an integer from 1 to 10), (4): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (where p and q are integers from 1 to 10), and those represented by (FSO ₂ ) ₂ N ^- , etc. Among them, anions containing fluorine atoms are especially (Fluorine-containing anions) can be preferably used because ionic compounds with good ion dissociation properties can be obtained. Among the anions containing fluorine atoms, fluorine-containing amide anions are preferred, and among these, bis(tris) is preferred. Fluoromethanesulfonyl)amide anion and bis(fluoromethanesulfonyl)amide anion. In particular, bis(fluoromethanesulfonyl)amide anion can be added in a smaller amount to impart excellent antistatic properties and maintain The adhesive properties are good for durability in humidified or heated environments, so they are better.

In addition, as the ionic compound, in addition to the above-mentioned inorganic cation anion salts (alkali metal salts) and organic cation anion salts, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, and ferric chloride can also be exemplified. , ammonium sulfate and other inorganic salts. This plasma compound can be used individually or in combination of multiple types.

Examples of ionic surfactants include cationic surfactants (for example, quaternary ammonium salt type, phosphonium salt type, sulfonate salt type, etc.), anionic surfactants (carboxylic acid type, sulfonate type, sulfate type, phosphate type, etc.) , phosphite type, etc.), zwitterionic system (sulfobetaine type, alkyl betaine type, alkyl imidazolium betaine type, etc.) or non-ionic system (polyol derivatives, β-cyclodextrin inclusion compounds, sorbitan fatty acid monoesters/diesters, polyalkylene oxide derivatives, amine oxides, etc.).

Examples of the conductive polymer include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoline-based polymers. Among these, polyaniline, polythiophene, and the like are preferably used. Particularly preferred are polythiophenes.

Examples of the conductive fine particles include metal oxides such as tin oxide type, antimony oxide type, indium oxide type, and zinc oxide type. Among these, the tin oxide type is preferable. Examples of the tin oxide system include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide complex, oxide Titanium-tin oxide complex, etc. The average particle diameter of the fine particles is about 1 to 100 nm, preferably 2 to 50 nm.

Examples of antistatic agents other than the above include acetylene black, Ketjen black, natural graphite, artificial graphite, titanium black, cationic (quaternary ammonium salts, etc.), zwitterionic (betaine compounds, etc.), and anionic. (Sulfonate, etc.) or nonionic (glycerin, etc.) homopolymers of monomers with ion conductive groups or copolymers of the above monomers and other monomers, derived from acrylic acid with quaternary ammonium salt groups Polymers with ionic conductivity such as polymers containing esters or methacrylates; permanent antistatic agents that are alloyed with hydrophilic polymers such as polyethylene methacrylate copolymer and acrylic resins.

When the adhesive composition of the present invention contains the above-mentioned antistatic agent, its content is not particularly limited. From the perspective of ensuring durability such as transparency, appearance, and connection reliability of the adhesive layer of the present invention, it is relatively Based on 100 parts by weight of the total amount of adhesive polymer (A) and conductive polymer (B), it is preferably 1 part by weight or less, more preferably 0.5 part by weight or less, and may also be 0.4 part by weight or less or 0.3 part by weight. or less than 0.2 parts by weight. When the adhesive composition of the present invention contains the above-mentioned antistatic agent, the lower limit of the content is not particularly limited, but is based on 100 parts by weight of the total amount of adhesive polymer (A) and conductive polymer (B). , can be 0.01 parts by weight or more or 0.05 parts by weight or more.

[1-12.Additives] If necessary, the adhesive composition of the present invention may contain a cross-linking agent, a cross-linking accelerator, a silane coupling agent, a tackifying resin (rosin derivative, polyterpene resin, etc.) within the scope that does not impair the characteristics of the present invention. Petroleum resin, oil-soluble phenol, etc.), anti-aging agent, filler, colorant (pigment or dye, etc.), ultraviolet absorber, antioxidant, chain transfer agent, plasticizer, softener, surfactant, anti-rust agent and other well-known additives. Furthermore, such additives may be used alone or in combination of two or more.

If the adhesive layer contains a cross-linking agent, the base polymer will be cross-linked, the gel fraction will be increased, and the foaming and peeling resistance will be easily improved. For example, by crosslinking the acrylic polymer (A), the control of the gel fraction can be easily increased, and therefore the foaming and peeling resistance can be easily improved. Moreover, the acrylic polymer (A) and the conductive polymer (B) can form a covalent bond via a crosslinking agent.

Examples of the cross-linking agent include, in addition to isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, and peroxide-based cross-linking agents, urea-based cross-linking agents and metal alkoxides. Physical cross-linking agent, metal chelate cross-linking agent, metal salt cross-linking agent, carbodiimide cross-linking agent, oxazoline cross-linking agent, aziridine cross-linking agent, amine cross-linking agent Cross-linking agents, etc. Among them, when the adhesive layer contains an acrylic polymer (A) as a base polymer, in terms of improving foaming and peeling resistance, it is preferable to use an isocyanate cross-linking agent, a cyclic polymer, or an isocyanate-based cross-linking agent. Oxygen-based cross-linking agent, more preferably isocyanate-based cross-linking agent. In addition, the cross-linking agent can be used alone or in combination of two or more types.

Examples of the isocyanate cross-linking agent (polyfunctional isocyanate compound) include 1,2-ethylidene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, and the like. Lower aliphatic polyisocyanates; alicyclic polyisocyanates such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated xylene diisocyanate; 2,4-toluene Aromatic polyisocyanates such as diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Furthermore, examples of the isocyanate-based crosslinking agent include: trimethylolpropane/toluene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"], trimethylolpropane /Hexamethylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL"], trimethylolpropane/xylylene diisocyanate adduct [manufactured by Mitsui Chemicals Co., Ltd., Trade name "Takenate D-110N"] and other commercial products.

Examples of the above-mentioned epoxy cross-linking agent (polyfunctional epoxy compound) include: N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1, 3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol Sugar alcohol anhydride polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tris(2-hydroxyethyl)triglycidyl isocyanurate , resorcin diglycidyl ether, bisphenol S-diglycidyl ether, in addition to epoxy resins having two or more epoxy groups in the molecule, etc. Examples of the above-mentioned epoxy cross-linking agent include commercially available products such as "Tetrad C" manufactured by Mitsubishi Gas Chemical Co., Ltd. under the trade name.

The content of the cross-linking agent in the adhesive composition of the present invention is not particularly limited. For example, it is preferably 0.001 parts by weight based on 100 parts by weight of the total amount of adhesive polymer (A) and conductive polymer (B). ~10 parts by weight, more preferably 0.01~5 parts by weight. If the content of the cross-linking agent is 0.001 parts by weight or more, it is easy to improve the foaming and peeling resistance, so it is preferable. On the other hand, if the content of the cross-linking agent is 10 parts by weight or less, the adhesive layer has moderate flexibility and the adhesive force is easily improved, so it is preferable.

If the adhesive composition of the present invention contains a silane coupling agent, it is easy to obtain excellent adhesion to glass (especially, excellent adhesion reliability to glass under high temperature and high humidity), so it is preferable. The silane coupling agent is not particularly limited, and examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-aminopropyltrimethoxysilane. Silane, N-phenyl-aminopropyltrimethoxysilane, etc. Among them, γ-glycidoxypropyltrimethoxysilane is preferred. Furthermore, examples of the silane coupling agent include commercially available products with the trade name "KBM-403" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Furthermore, the silane coupling agent can be used alone or in combination of two or more.

The content of the above-mentioned silane coupling agent in the adhesive composition of the present invention is not particularly limited. In terms of improving the bonding reliability to glass, relative to the adhesive polymer (A) and the conductive polymer (B) The total amount is 100 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 parts by weight.

If the adhesive composition of the present invention contains a colorant (pigment, dye, etc.), it can prevent reflection caused by metal oxides such as metal wiring or ITO (Indium Tin Oxides, indium tin oxide), and can also help prevent RGB is better for mixing colors or improving contrast.

The above-mentioned colorant may be a dye or a pigment as long as it is dissolved or dispersed in the adhesive composition of the present invention. Dyes are preferred because low haze can be achieved with a small amount of addition, and they do not have sedimentation properties like pigments and can be easily distributed evenly. In addition, pigments are also preferable in terms of high color expression even when added in a small amount. When a pigment is used as a colorant, one with low conductivity or no conductivity is preferred. Moreover, when using a dye, it is preferable to use it together with antioxidant etc.

Examples of pigments include "9050BLACK", "UVBK-0001" manufactured by TOKUSHIKI, carbon black, titanium black, etc. Examples of dyes include "VALIFAST BLACK 3810" and "NUBIAN Black PA-2802" manufactured by Orient Chemical Industries.

The content of the colorant in the adhesive composition of the present invention is, for example, about 0.01 to 20 parts by weight relative to 100 parts by weight (total amount) of the adhesive polymer (A) and the conductive polymer (B). It can be set appropriately according to the type of colorant or the color tone and light transmittance of the adhesive layer. Colorants can be added to the composition as a solution or dispersion dissolved or dispersed in a suitable solvent.

[1-13. Interpenetrating polymer network or semi-interpenetrating polymer network] In the adhesive layer formed from the adhesive composition (1) of the present invention, the three-dimensional network structure of the conductive polymer (B) is intertwined with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. Wearing polymer networks. As this structure, the adhesive polymer (A) provides adhesiveness to the adhesive layer of the present invention, the conductive polymer (B) provides antistatic properties to the adhesive layer of the present invention, and the conductive polymer (B) is used to impart antistatic properties to the adhesive layer. The three-dimensional network structure of the flexible polymer (B) is intertwined with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network, thereby preventing the antistatic agent from precipitating on the surface of the adhesive layer. It also causes corrosion of metal wiring and other defects, and inhibits the migration of antistatic agents from the adhesive layer to other optical components in hot and humid environments, suppresses the increase in surface resistance, and maintains excellent antistatic properties, thereby effectively The ground forms a conductive path in the adhesive layer. Therefore, the adhesive composition (1) of the present invention can form an adhesive that is durable (especially corrosion resistance stability, resistance value stability) and is not prone to defects, exhibits low surface resistivity, and has excellent antistatic properties. layer.

Furthermore, in the adhesive composition (2) of the present invention, the functional group (b1) of the ionic compound (B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, forming a three-dimensional network. The conductive polymer (B) of the structure, the above-mentioned three-dimensional network structure and the adhesive polymer (A) are intertwined to form an interpenetrating polymer network or a semi-interpenetrating polymer network. The adhesive composition (2) of the present invention contains a mixture of an ionic compound (B1) and a compound (B2), or a partial polymer containing a mixture of an ionic compound (B1) and a compound (B2). The ionic compound ( The functional group (b1) of B1) reacts with the functional group (b2) of the compound (B2) to form a covalent bond, and a polymerization reaction proceeds, thereby forming a conductive polymer (B) with a three-dimensional network structure. During the course of the polymerization reaction, the above-mentioned three-dimensional network structure is entangled with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. By forming an interpenetrating polymer network or a semi-interpenetrating polymer network, defects such as corrosion of metal wiring caused by the precipitation of the antistatic agent on the surface of the adhesive layer are less likely to occur. In addition, the antistatic agent is inhibited from occurring in hot and humid environments. The migration of the adhesive layer to other optical components suppresses the increase in surface resistance and maintains excellent antistatic properties. Furthermore, a path showing conductivity can be effectively formed in the adhesive layer. Therefore, the adhesive composition (2) of the present invention can form an adhesive that is durable (especially corrosion resistance stability, resistance value stability) and is not prone to defects, exhibits low surface resistivity, and has excellent antistatic properties. layer.

"Interpenetrating polymer network (IPN)" is a material containing two or more polymer network structures that are at least partially combined at the molecular level, but are not covalently bonded to each other and cannot be separated as long as the chemical bonds are not broken. , refers to the form in which the cross-linked structures of two or more polymers with cross-linked structures are intertwined with each other. That is, the interpenetrating polymer network (IPN) formed by the entanglement of the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) means that the adhesive polymer (A) has a cross-linked structure. A form in which the cross-linked structure and the three-dimensional network structure of the conductive polymer (B) are intertwined.

On the other hand, "semi-interpenetrating polymer network (Semi-IPN)" is a material that contains more than one polymer network structure and more than one linear or branched polymer. Materials characterized by at least one network structure connected at the molecular level by at least a few linear or branched giant molecules refer to more than one polymer chain without a cross-linked structure and those with a cross-linked structure. A form in which the cross-linked structures of more than one polymer are intertwined. That is, the semi-interpenetrating polymer network (Semi-IPN) formed by the entanglement of the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A) means that the adhesive polymer (A) has no interpenetrating The chain structure is intertwined with the three-dimensional network structure of the conductive polymer (B).

Semi-interpenetrating polymer networks can separate linear or branched polymers from their constituent polymer network structures without breaking chemical bonds, so they are different from interpenetrating polymer networks. Furthermore, the form in which the conductive polymer (B) and the adhesive polymer (A) are cross-linked by, for example, the above-mentioned cross-linking agent or the like and further by covalent bonds are also included in the interpenetrating polymer network of the present invention. in semi-interpenetrating polymer networks.

The formation method of the "interpenetrating polymer network" in the present invention is not particularly limited. For example, it can be carried out by: A mixture of components such as functional monomers that can impart a cross-linked structure to the adhesive polymer (A), a mixture containing the monomer components constituting the conductive polymer (B) or a partial polymer thereof, and the above-mentioned cross-linking catalyst , and a mixture of the above-mentioned cross-linking retarder if necessary, simultaneously or sequentially under the condition that the adhesive polymer (A) and the conductive polymer (B) react but do not form a cross-linked form with each other through covalent bonds. The polymerization reaction of the adhesive polymer (A) and the polymerization reaction of the conductive polymer (B).

The formation method of the "semi-interpenetrating polymer network" of the present invention is not particularly limited. For example, it can be carried out by the following method: containing the monomer components constituting the adhesive polymer (A) and not containing the above-mentioned cross-linking agent , a mixture of components such as polyfunctional monomers that can impart a cross-linked structure to the adhesive polymer (A) and a mixture containing the monomer components constituting the conductive polymer (B) or a partial polymer thereof, the above-mentioned cross-linked contact A mixture of media and, if necessary, the above-mentioned cross-linking retardant, in a state in which the adhesive polymer (A) and the conductive polymer (B) react without forming cross-links with each other through covalent bonds, at the same time or in accordance with The polymerization reaction of the adhesive polymer (A) and the polymerization reaction of the conductive polymer (B) are carried out sequentially.

The above-mentioned "polymerization reaction of the adhesive polymer (A)" can be performed in the same manner as the above-mentioned "polymerization method of the acrylic polymer (A)". In addition, the above-mentioned "polymerization reaction of the conductive polymer (B)" can be performed in the same manner as the above-mentioned "method of obtaining a partial polymer of a mixture of monomer components constituting the conductive polymer (B)". Furthermore, the above-mentioned "polymerization method of acrylic polymer (A)" and/or "polymerization reaction of conductive polymer (B)" can be performed after the following adhesive layer is formed.

The specific method for forming the "interpenetrating polymer network formed by the entanglement of the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A)" of the present invention preferably includes the following steps. (1) A mixture containing the monomer components constituting the adhesive polymer (A), the above-mentioned cross-linking agent, polyfunctional monomers, and other components that can impart a cross-linked structure to the adhesive polymer (A) is subjected to polymerization. react to form an adhesive polymer (A) with a cross-linked structure. (2) Prepare a mixture of the formed adhesive polymer (A) and the monomer components constituting the conductive polymer (B) or a partial polymer thereof, the above-mentioned cross-linking catalyst, and an optional cross-linking retarder, By the above "method of obtaining a partial polymer of a mixture of monomer components constituting the conductive polymer (B)", a conductive polymer (B) having a three-dimensional network structure is formed. The three-dimensional network structure of the conductive polymer (B) formed by step (2) is intertwined with the cross-linked structure of the adhesive polymer (A) formed by step (1), thereby forming the present invention. "Interpenetrating polymer network".

The specific method for forming the "semi-interpenetrating polymer network formed by the entanglement of the three-dimensional network structure of the conductive polymer (B) and the adhesive polymer (A)" of the present invention preferably includes the following steps. (1') A mixture containing the monomer components constituting the adhesive polymer (A) and not containing the above-mentioned cross-linking agent, polyfunctional monomer and other components that can impart a cross-linked structure to the adhesive polymer (A) It is sent to polymerization reaction to form a linear or branched adhesive polymer (A) without a cross-linked structure. (2') Prepare a mixture of the formed adhesive polymer (A) and the monomer components constituting the conductive polymer (B) or a partial polymer thereof, the above-mentioned cross-linking catalyst, and an optional cross-linking retardant , through the above-mentioned "method of obtaining a partial polymer of a mixture of monomer components constituting the conductive polymer (B)", a conductive polymer (B) having a three-dimensional network structure is formed. The linear or branched adhesive polymer (A) formed in step (1') penetrates the three-dimensional network structure of the conductive polymer (B) formed in step (2'). And entangled, thereby forming the "semi-interpenetrating polymer network" of the present invention.

[2. Adhesive layer] The adhesive layer of the present invention is an adhesive layer formed from the adhesive composition of the present invention. The adhesive layer of the present invention has excellent antistatic properties. Therefore, when the image display device and the optical component are bonded together through the adhesive layer of the present invention, display defects caused by static electricity can be suppressed. In this way, the adhesive layer of the present invention can be preferably used in the manufacture of image display devices.

The surface resistivity (according to JIS K 6271) of the adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) is preferably 1.0×10 ¹³ from the viewpoint of excellent antistatic performance. Ω/□ or less, more preferably 0.5×10 ¹³ Ω/□ or less, further preferably 1.0×10 ¹² Ω/□ or less, but also 0.5×10 ¹² Ω/□ or less or 1.0×10 ¹¹ Ω/□ or less . The lower limit of the surface resistivity of the adhesive layer of the present invention is not particularly limited, and may be 1.0×10 ⁵ Ω/□ or more or 0.5×10 ⁵ Ω/□ or more.

The adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) can inhibit the migration of the antistatic agent from the adhesive layer to other optical components and inhibit the increase in surface resistance value even in a humid and hot environment. Can maintain excellent antistatic properties. Therefore, even in a humid and hot environment after the image display device and the optical component are bonded via the adhesive layer of the present invention, display defects caused by static electricity can be suppressed. In this way, the adhesive layer of the present invention can be preferably used in the manufacture of image display devices.

As an example, the adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) is placed in an environment of 85°C and 85%RH for 168 hours and taken out, and then placed in an environment of 23°C and 50%RH for 72 hours. From the perspective of maintaining excellent antistatic properties, the surface resistivity of the adhesive layer surface after temperature and humidity control is preferably 1.0×10 ¹³ Ω/□ or less, and more preferably 0.5×10 ¹³ Ω/ □ or less, more preferably 1.0×10 ¹² Ω/□ or less, and may be 0.5×10 ¹² Ω/□ or less or 1.0×10 ¹¹ Ω/□ or less. The lower limit value of the surface resistivity of the adhesive layer of the present invention after the above humidification test is not particularly limited, and may be 1.0×10 ⁵ Ω/□ or more or 0.5×10 ⁵ Ω/□ or more.

The surface resistivity of the adhesive layer of the present invention and the surface resistivity after the humidification test can be measured by the methods described in the examples disclosed below. The surface resistivity of the adhesive layer of the present invention and the surface resistivity after the humidification test can be determined by the composition of the monomers constituting the adhesive polymer (A), the amount of the cross-linking agent, and the amount of the conductive polymer (B). Adjust the type or ratio of the ionic compound (B1) and the compound (B2), the quantity ratio of the adhesive polymer (A) and the conductive polymer (B), the type or quantity of other additives, hardening conditions, etc.

The adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) is transparent or has transparency. Therefore, the visibility and appearance through the adhesive layer of the present invention are excellent. In this way, the adhesive layer of the present invention can be preferably used for optical purposes.

The haze (according to JIS K7136) of the adhesive layer of the present invention (the adhesive layer formed from the adhesive composition of the present invention) is not particularly limited, but is preferably 3% or less, more preferably 1% or less, and 0.7% or less. , or it can be less than 0.6%. If the haze is 3% or less, excellent transparency or excellent appearance can be obtained, which is preferable. Furthermore, the above-mentioned haze can be measured, for example, by the following method: prepare an adhesive layer (thickness: 100 μm), let it stand for at least 24 hours under normal conditions (23°C, 50%RH), and then attach it to the carrier. A glass slide (for example, one with a total light transmittance of 92% and a haze of 0.2%) is used as a sample and measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HM-150N").

The total light transmittance (according to JIS K7361-1) of the adhesive layer of the present invention in the visible light wavelength range is not particularly limited, but is preferably more than 90%, more preferably more than 91%, or may be more than 92%. If the total light transmittance is 90% or more, excellent transparency or excellent appearance is obtained, which is preferable. Furthermore, the above-mentioned total light transmittance can be measured, for example, by: preparing an adhesive layer (thickness: 100 μm), leaving it to stand for at least 24 hours under normal conditions (23°C, 50%RH), and then In the case of peeling off the liner, peel it off, attach it to a glass slide (for example, with a total light transmittance of 92% and a haze of 0.2%), use it as a sample, and use a haze meter (Murakami Color Research Laboratory Co., Ltd. Manufactured by, trade name "HM-150N") and measured.

The total light transmittance and haze of the adhesive layer of the present invention can be measured according to JIS K7136 and JIS K7361-1 respectively. The total light transmittance and haze of the adhesive layer of the present invention can be determined by the monomer composition constituting the adhesive polymer (A), the amount of cross-linking agent, and the ionic compound (B1) constituting the conductive polymer (B). ), the type or ratio of compound (B2), the quantity ratio of adhesive polymer (A) and conductive polymer (B), the type or quantity of other additives, hardening conditions, etc.

The gel fraction (ratio of solvent-insoluble components) of the adhesive layer of the present invention is not particularly limited, but is preferably 40 to 95%, more preferably 50 to 92%, and further preferably 55 to 90%. If the gel fraction is more than 40%, the cohesion of the above-mentioned adhesive layer will increase, resulting in foaming or peeling of the interface with the adherend in a high temperature environment, dents during operation, or contamination of the ends during processing. This is preferable because it is easier to obtain excellent foaming and peeling resistance by suppressing it. In addition, if the gel fraction is 95% or less, moderate softness is obtained, and adhesiveness and step followability are further improved, which is preferable.

The above-mentioned gel fraction (ratio of solvent-insoluble components) is a value calculated by the following "Measurement Method of Gel Fraction" specifically, for example.

The adhesive layer of the self-adhesive sheet: about 0.1 g is wrapped in a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nitto Denko Co., Ltd.) with an average pore size of 0.2 μm, and then tied tightly with a kite string, and the value is measured. The weight at that time was taken as the weight before immersion. Furthermore, the weight before immersion is the total weight of the adhesive layer (the adhesive layer adopted above), the PTFE sheet and the kite string. In addition, the total weight of the tetrafluoroethylene sheet and the kite string was also measured in advance, and this weight was used as the weight of the packaging bag. Next, the adhesive layer wrapped with a tetrafluoroethylene sheet and tied with a kite string (called a "sample") was placed into a 50 ml container filled with ethyl acetate and left to stand at 23°C for 7 days. Thereafter, the sample (after treatment with ethyl acetate) was taken out from the container, moved to an aluminum cup, and dried in a dryer at 130° C. for 2 hours. After removing the ethyl acetate, the weight was measured, and this weight was used as the weight after immersion. . Next, the gel fraction was calculated from the following formula. Gel fraction [%(weight%)]=(X-Y)/(Z-Y)×100

Furthermore, the above-mentioned gel fraction can be determined by, for example, the monomer composition constituting the adhesive polymer (A), the amount of the cross-linking agent, the ionic compound (B1) and the compound (B2) constituting the conductive polymer (B). ), the amount ratio of adhesive polymer (A) and conductive polymer (B), the type or amount of other additives, hardening conditions, etc.

The storage modulus of the adhesive layer of the present invention at 25°C and 1 Hz is not particularly limited, but is preferably 3×10 ⁴ Pa or more. The adhesive layer of the present invention preferably has a storage modulus of 3×10 ⁴ Pa or more at 25° C. and 1 Hz in that it is less likely to cause dents during handling. In order to suppress the dents of the adhesive layer of the present invention, the storage modulus of the adhesive layer of the present invention at 25°C and 1 Hz is more preferably 5×10 ⁴ Pa or more, and may also be 1×10 ⁵ Pa or more. The upper limit of the storage modulus at 25°C and 1 Hz of the adhesive layer of the present invention is not particularly limited. From the perspective of the step followability of the adhesive layer of the present invention, 5×10 ⁶ is preferred. Pa or less, or 1×10 ⁶ Pa or less.

The above-mentioned storage modulus at 25°C and 1 Hz of the adhesive sheet of the present invention can be measured by dynamic viscoelasticity measurement. The above-mentioned storage modulus at 25°C and 1 Hz of the adhesive sheet of the present invention can be determined by the monomer composition constituting the adhesive polymer (A), the amount of cross-linking agent, and the ions constituting the conductive polymer (B). The type or ratio of the adhesive compound (B1) and the compound (B2), the quantity ratio of the adhesive polymer (A) and the conductive polymer (B), the type or quantity of other additives, the hardening conditions, etc.

The adhesive layer of the present invention is not particularly limited, preferably 5-250 μm, more preferably 7-240 μm, 10-230 μm, 12-220 μm, 15-210 μm, 20-200 μm, 23-175 μm μm, or it can be 25-150 μm. If the thickness is at least a certain level, it is preferable because the step followability and the bonding reliability are improved. In addition, when the thickness is equal to or less than a certain value, the workability and manufacturability are particularly excellent, so it is preferable.

The method for producing the adhesive layer of the present invention is not particularly limited. For example, it can be produced by preparing the adhesive composition (precursor composition) of the present invention, and irradiating active energy rays, heating and drying, etc. if necessary. Specific examples include the following steps: adding to an adhesive polymer (A), a conductive polymer (B), a mixture of monomer components constituting the conductive polymer (B), or part of the polymer as needed. Additives, etc. and mix. Furthermore, after forming the adhesive layer of the present invention, the above-mentioned "polymerization method of acrylic polymer (A)" and/or "polymerization reaction of conductive polymer (B)" can be performed.

The manufacturing method of the adhesive layer of the present invention is not particularly limited. For example, the above-mentioned adhesive composition is coated (coated) on the base material or release liner, and dried, hardened or dried as necessary. and hardening.

In addition, a known coating method can be used for coating (coating) of the said adhesive composition. For example, gravure roll coaters, reverse roll coaters, contact roll coaters, dip roll coaters, rod coaters, blade coaters, spray coaters, and notch wheel coaters can be used. , direct coater and other coating machines.

[3.Adhesive sheet] The adhesive sheet of the present invention is an adhesive sheet having the adhesive layer of the present invention. The adhesive sheet of the present invention is not particularly limited as long as it has the adhesive layer of the present invention (an adhesive layer formed from the adhesive composition of the present invention).

The adhesive sheet of the present invention may be a double-sided adhesive sheet in which both sides are exposed to the adhesive layer, or may be a single-sided adhesive sheet in which only one side is exposed to the adhesive layer. Among them, from the viewpoint of bonding two members to each other, a double-sided adhesive sheet is preferred. In addition, in this specification, when it is described as "adhesive sheet", it also includes a belt-shaped one, that is, "adhesive tape". In addition, in this specification, the surface of the adhesive layer may be called "adhesive surface".

The adhesive sheet of the present invention can be provided with a release liner on the adhesive surface until use.

The adhesive sheet of the present invention may be a so-called "base material-less type" adhesive sheet that does not have a base material (base material layer) (hereinafter sometimes referred to as a "base material-less adhesive sheet"), or may have a base material layer. Type of adhesive sheet with base material (hereinafter sometimes referred to as "adhesive sheet with base material"). Examples of the base-less adhesive sheet include a double-sided adhesive sheet including only the adhesive layer, or an adhesive layer including the adhesive layer and an adhesive layer other than the adhesive layer (sometimes referred to as "other"). "Adhesive layer") double-sided adhesive sheet, etc. On the other hand, examples of the adhesive sheet with a base material include an adhesive sheet having the above-mentioned adhesive layer on at least one side of the base material. Among them, a substrate-free adhesive sheet (substrate-free double-sided adhesive sheet) is preferred, and a substrate-free double-sided adhesive sheet including only the above-mentioned adhesive layer is more preferred. In addition, the above-mentioned "base material (base material layer)" does not include a release liner that is peeled off when the adhesive sheet is used (attached). The adhesive sheet of the present invention is preferably a base-free adhesive sheet.

One embodiment of the adhesive sheet of the present invention (adhesive sheet without base material) is shown in Figure 1 . In the adhesive sheet in Figure 1, 10 is an adhesive layer, and 11 and 12 are release liners.

[3-1. Various physical properties of adhesive sheets] The adhesive sheet of the present invention has a 180° peel adhesion to the glass plate at 23° C. (especially, the adhesive surface provided by the above-mentioned adhesive layer (the adhesive layer formed from the adhesive composition of the present invention) to the glass plate (180° peeling adhesion force at 23°C) is not particularly limited. From the perspective that the higher the adhesion force is, the more sufficient adhesion is obtained, it is preferably 4 N/20 mm or more, and more preferably 6 N/20 mm. or above, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more. If the adhesive sheet of the present invention has a 180° peeling adhesion to a glass plate at 23° C. of a certain value or above, the adhesion to the glass and the ability to suppress step bulging will be even better. Furthermore, the upper limit of the 180° peeling adhesion force of the adhesive sheet of the present invention to the glass plate at 23°C is not particularly limited. For example, 28 N/20 mm, 27 N/20 mm or 26 N is preferred. /20 mm, preferably 25 N/20 mm, 24 N/20 mm, 23 N/20 mm, 22 N/20 mm, 21 N/20 mm or 20 N/20 mm.

The adhesive sheet of the present invention has a 180° peel adhesion to a glass plate at 80° C. (especially, the adhesive surface provided by the above-mentioned adhesive layer (the adhesive layer formed from the adhesive composition of the present invention) to the glass plate (180° peeling adhesion force at 80°C) is not particularly limited. From the perspective that the higher the adhesion force, the more sufficient adhesion is obtained, it is preferably 4 N/20 mm or more, and more preferably 6 N/20 mm. or above, more preferably 8 N/20 mm or more, still more preferably 10 N/20 mm or more. If the adhesive sheet of the present invention has a 180° peeling adhesion to a glass plate at 80° C. of a certain value or above, the adhesion to the glass and the ability to suppress step bulging will be even better. Furthermore, the upper limit of the 180° peeling adhesion force of the adhesive sheet of the present invention to the glass plate at 80°C is not particularly limited. For example, 18 N/20 mm is preferred, and 16 N/20 mm is more preferred. . The 180° peel adhesion strength of a glass plate at 23°C or 80°C is determined by the following 180° peel adhesion strength measurement method.

The glass plate is not particularly limited, and an example thereof is “soda lime glass #0050” with a trade name (manufactured by Matsunami Glass Ind.). Moreover, alkali-free glass, chemically strengthened glass, etc. can also be mentioned.

(A-1. Measuring method of 180° peel adhesion strength) Place the adhesive surface of the adhesive sheet onto the adherend, press it with a 2 kg roller and 1 reciprocating press, and age it in an environment of 23°C and 50% RH for 30 minutes or 240 hours. After aging, according to JIS Z 0237, in an environment of 23℃ or 80℃, 50%RH, with a stretching speed of 300 mm/min and a peeling angle of 180°, peel the adhesive sheet from the adherend and measure 180° peel adhesion force (N/20 mm).

(B.Thickness) The thickness (total thickness) of the adhesive sheet of the present invention is not particularly limited, but is preferably 10 to 350 μm, more preferably 12 to 350 μm, further preferably 15 to 330 μm, 18 to 325 μm, or 18 to 320 μm. μm, 20-300 μm, 23-300 μm, 25-275 μm, or 30-250 μm. If the thickness is at least a certain level, peeling at the step portion is less likely to occur, which is preferable. In addition, if the thickness is below a certain level, it is easy to maintain an excellent appearance during production, so it is preferable. Furthermore, in the case of an adhesive sheet with a base material, the thickness of the adhesive sheet of the present invention includes the thickness of the base material, but does not include the thickness of the release liner.

(C. Haze) The haze (according to JIS K7136) of the adhesive sheet of the present invention is not particularly limited, but is preferably 3% or less, more preferably 1% or less, 0.7% or less, or may be 0.6% or less. If the haze is 3% or less, excellent transparency or excellent appearance is obtained, which is preferable. Furthermore, the above-mentioned haze can be measured by, for example, the following method: After leaving the adhesive sheet to stand for at least 24 hours under normal conditions (23°C, 50%RH), peel it off with a release liner, and laminate it. Use a glass slide (for example, a total light transmittance of 92% and a haze of 0.2%) as a sample and measure it using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HM-150N") .

(D. Total light transmittance) The total light transmittance (according to JIS K7361-1) of the adhesive sheet of the present invention in the visible light wavelength range is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or may be 92% or more. If the total light transmittance is 90% or more, excellent transparency or excellent appearance is obtained, which is preferable. Furthermore, the above-mentioned total light transmittance can be measured by, for example, the following method: after leaving the adhesive sheet standing under normal conditions (23°C, 50%RH) for at least 24 hours, peeling it off with a release liner, Place it on a glass slide (for example, with a total light transmittance of 92% and a haze of 0.2%), use it as a sample, and use a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HM-150N") Make a determination.

The above-mentioned adhesive strength, total light transmittance and haze of the adhesive sheet of the present invention can be measured in accordance with JIS K7136 and JIS K7361-1. The above-mentioned adhesive strength, total light transmittance and haze of the adhesive sheet of the present invention can be determined by the monomer composition constituting the adhesive polymer (A), the amount of the cross-linking agent, and the ions constituting the conductive polymer (B). The type or ratio of the adhesive compound (B1) and the compound (B2), the quantity ratio of the adhesive polymer (A) and the conductive polymer (B), the type or quantity of other additives, the hardening conditions, etc.

[3-2. Manufacturing method of adhesive sheet] The manufacturing method of the adhesive sheet of the present invention is not particularly limited, and is preferably manufactured according to a known or commonly used manufacturing method. For example, when the adhesive sheet of the present invention is a base-less adhesive sheet, it can be obtained by forming the adhesive layer on a release liner using the above method. In addition, when the adhesive sheet of the present invention is an adhesive sheet with a base material, it can be obtained by directly forming the above-mentioned adhesive layer on the surface of the base material (direct printing method), or it can be obtained by the following method: The above-mentioned adhesive layer is temporarily formed on a release liner and then transferred (laminated) to the base material, whereby the above-mentioned adhesive layer is provided on the base material (transfer method).

[3-3. Other layers of adhesive sheet] In addition to the above-mentioned adhesive layer, the adhesive sheet of the present invention may also have other layers. Examples of the other layers include: other adhesive layers (adhesive layers other than the above-mentioned adhesive layers (adhesive layers other than the adhesive layer formed from the adhesive composition of the present invention)), intermediate layers, and primer layers wait. Furthermore, the adhesive sheet of the present invention may have two or more other layers.

[3-4. Base material of adhesive sheet] When the adhesive sheet of the present invention is an adhesive sheet with a base material, the base material is not particularly limited. Examples thereof include various optical films such as plastic films, anti-reflection (AR) films, polarizing plates, and phase difference plates. membrane. Examples of materials for the above-mentioned plastic films include polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, and triethylene. Acetocellulose (TAC), polypropylene, polyarylate, polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name "ARTON" (cyclic olefin polymerization Plastic materials such as cyclic olefin-based polymers such as "ZEONOR (cyclic olefin-based polymer, manufactured by Nippon Zeon Co., Ltd.)" and "ZEONOR (cyclic olefin-based polymer, manufactured by Nippon Zeon Co., Ltd.)". Furthermore, these plastic materials can be used alone or in combination of two or more. In addition, the above-mentioned "base material" refers to the part that is attached to the adherend together with the adhesive layer when the adhesive sheet is attached to the adherend. The release liner (release liner) that is peeled off when the adhesive sheet is used (when attached) is not included in the "base material".

The above-mentioned base material is preferably transparent. The total light transmittance (according to JIS K7361-1) of the above-mentioned base material in the visible light wavelength range is not particularly limited, but is preferably 85% or more, and more preferably 88% or more. In addition, the haze (based on JIS K7136) of the above-mentioned base material is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less. Examples of such a transparent base material include PET film, non-aligned films such as the trade name "ARTON" and the trade name "ZEONOR".

The thickness of the above-mentioned base material is not particularly limited, but is preferably 1 to 500 μm, for example. Furthermore, the above-mentioned base material may have any form of a single layer or a multi-layer. In addition, known and conventional surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as primer treatment can be appropriately performed on the surface of the above-mentioned base material.

[3-5. Release liner for adhesive sheet] The adhesive sheet of the present invention can be provided with a release liner on the adhesive surface until use. Furthermore, when the adhesive sheet of the present invention is a double-sided adhesive sheet, each adhesive surface can be protected by two release liners, or one release liner with both sides serving as release surfaces. Protected by being rolled into a drum shape. The release liner is used as a protective material for the adhesive layer and is peeled off when attached to the adherend. Furthermore, when the adhesive sheet of the present invention is a substrate-less adhesive sheet, the release liner also serves as a support for the adhesive layer. Furthermore, the release liner is not required.

As the above-mentioned release liner, conventional release paper and the like can be used. Specifically, for example, in addition to a base material having a release-treated layer with a release treatment agent on at least one surface, a fluorine-based polymer (for example, Polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.) low-adhesion substrate, Or a low-adhesion base material containing a non-polar polymer (for example, an olefin resin such as polyethylene or polypropylene).

As the release liner, for example, a release liner in which a release treatment layer is formed on at least one surface of a release liner base material can be suitably used. Examples of the base material for such a release liner include polyester films (polyethylene terephthalate films, etc.), olefin resin films (polyethylene films, polypropylene films, etc.), polyvinyl chloride films, Polyimide film, polyimide film (nylon film), rayon film and other plastic base films (synthetic resin film) or paper (high-grade paper, Japanese paper, kraft paper, cellophane, synthetic paper, topcoat paper, etc. ), there can also be exemplified those which are laminated by lamination or co-extrusion (a composite of 2 to 3 layers).

The release treatment agent constituting the release treatment layer is not particularly limited, and examples thereof include polysiloxane release treatment agents, fluorine-based release treatment agents, long-chain alkyl release treatment agents, and the like. The peeling treatment agent can be used alone or in combination of two or more.

The thickness of the release liner is not particularly limited, and can be appropriately selected from the range of 5 to 100 μm.

In order to prevent damage to adherends such as image display panels, the release liner may form an antistatic layer on at least one surface of the release liner base material. The antistatic layer may be formed on one side of the release liner (release treated side or untreated side), or may be formed on both sides of the release liner (release treated side and untreated side).

The antistatic layer is not particularly limited, but may be an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a release liner. Specifically, for example, the antistatic layer is formed by coating a conductive coating liquid containing a conductive polymer on a release liner (release treated surface and/or untreated surface). Specific coating methods include roll coating, rod coating, gravure coating, and the like.

As the conductive polymer, polymers such as polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoline-based polymers can be used.

The thickness of the antistatic layer is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm. The above-mentioned antistatic layer may be only one layer, or may be two or more layers.

[3-6. Uses of adhesive sheets, etc.] The adhesive sheet of the present invention has the above-mentioned adhesive layer (an adhesive layer formed from the adhesive composition of the present invention), and therefore has excellent antistatic properties. Therefore, when used for lamination of an image display device, display defects caused by static electricity are less likely to occur. In addition, even under severe conditions such as hot and humid environments, the antistatic component can be inhibited from leaking out, making it less likely to cause defects such as corrosion of metal wiring due to precipitation of the antistatic agent on the surface of the adhesive layer. In addition, even under severe conditions such as hot and humid environments, the antistatic agent can be inhibited from migrating from the adhesive layer to other optical components, thereby inhibiting the increase in surface resistance, thereby maintaining excellent antistatic properties. In addition, a path showing conductivity can be efficiently formed in the adhesive layer. Furthermore, it is easy to maintain transparency without impairing compatibility, suppress foaming and peeling on the surface of the adhesive layer, and is less likely to cause durability defects such as appearance or bonding reliability. Therefore, the adhesive layer formed from the adhesive composition of the present invention can satisfy excellent antistatic properties, transparency, moisture and heat resistance, and low contamination properties, and is useful in the manufacture of image display devices.

Furthermore, the adhesive layer of the present invention is excellent in adhesion, foaming and peeling resistance, and stress relaxation properties, and is excellent in step following properties, adhesion reliability, and especially adhesion reliability at high temperatures. In addition, the appearance is excellent. Therefore, the adhesive sheet of the present invention can be preferably used for adherends that are prone to foaming at the interface at high temperatures. For example, polymethyl methacrylate resin (PMMA) sometimes contains unreacted monomers and is prone to foaming caused by foreign matter at high temperatures. In addition, polycarbonate (PC) is prone to outgassing of water and carbon dioxide at high temperatures. The adhesive sheet of the present invention has excellent foaming and peeling resistance, so it can be preferably used for plastic adherends containing this resin.

In addition, the adhesive sheet of the present invention can be preferably used on adherends with a small linear expansion coefficient, and can also be preferably used on adherends with a large linear expansion coefficient. Furthermore, the adherend having a small linear expansion coefficient is not particularly limited. Examples include: glass plate (linear expansion coefficient: 0.3×10 ^-5 ~ 0.8×10 ^-5 /°C), polyparaphenylene Ethylene diformate base material (PET film, linear expansion coefficient: 1.5×10 ^-5 ~ 2×10 ^-5 /℃), etc. In addition, the adherend having a large linear expansion coefficient is not particularly limited. For example, a resin base material with a large linear expansion coefficient can be exemplified. More specifically, a polycarbonate resin base material ( PC, linear expansion coefficient: 7×10 ^-5 ~ 8×10 ^-5 /℃), polymethyl methacrylate resin base material (PMMA, linear expansion coefficient: 7×10 ^-5 ~ 8×10 ^-5 /℃ ), cycloolefin polymer base material (COP, linear expansion coefficient: 6×10 ^-5 ~ 7×10 ^-5 /℃), trade name "ZEONOR" (manufactured by Nippon Zeon Co., Ltd.), trade name "ARTON" ( Manufactured by JSR Co., Ltd.), etc.

The adhesive sheet of the present invention can be preferably used to bond an adherend with a small linear expansion coefficient to an adherend with a large linear expansion coefficient. Specifically, the adhesive sheet of the present invention can be preferably used for bonding glass adherends (such as glass plates, chemically strengthened glass, glass lenses, etc.) and the above-mentioned resin substrates with large linear expansion coefficients.

In this way, the adhesive sheet of the present invention is useful for bonding adherends of various materials, and is particularly suitable for bonding glass adherends and plastic adherends. Furthermore, the plastic adherend may be an optical film such as a plastic film having an ITO (oxide of indium and tin) layer on the surface.

Furthermore, the adhesive sheet of the present invention can be preferably used not only for adherends with smooth surfaces, but also for adherends with stepped surfaces. In particular, even if at least one of the glass adherend and the above-mentioned resin substrate with a large linear expansion coefficient has a step difference on the surface, the adhesive sheet of the present invention can be preferably used for the glass adherend and the above-mentioned linear expansion coefficient. Lamination of resin substrates with larger coefficients.

The adhesive sheet of the present invention can be preferably used in the manufacture of portable electronic devices. Examples of the above-mentioned portable electronic equipment include: mobile phones, PHS (personal handyphone systems, personal portable phone systems), smart phones, tablets (tablet computers), mobile computers (Mobile PC), and portable information terminals (PDA), electronic notepad, portable transceiver such as portable TV or portable radio, portable game console, portable audio and video player, portable DVD (Digital Versatile Disc, digital versatile disc) player, Cameras such as digital cameras, camcorder-type video cameras, etc.

The adhesive sheet of the present invention can be preferably used, for example, for attaching components or modules constituting a portable electronic device to each other, or for fixing components or modules constituting a portable electronic device to a casing. More specifically, examples include: the bonding of the cover glass or lens (especially the glass lens) and the touch panel or touch sensor, the fixation of the cover glass or lens (especially the glass lens) on the housing, Fixing of the display panel on the casing, fixing of input devices such as sheet keyboards or touch panels on the casing, fitting of the protective panel of the information display part and the casing, fitting of the casings to each other, casing and decoration The lamination of sheets, the fixation or lamination of various components or modules that constitute portable electronic devices, etc. Furthermore, in this specification, the so-called display panel refers to a structure including at least a lens (especially a glass lens) and a touch panel. In addition, the concept of lens in this specification includes both a transparent body showing refraction of light and a transparent body without refraction of light. That is, the lens in this specification also includes a simple window panel without refraction.

Furthermore, the adhesive sheet of the present invention can be preferably used for optical applications. That is, the adhesive sheet of the present invention is preferably an optical adhesive sheet used for optical applications. More specifically, for example, the use for bonding optical members (for optical member bonding) or the use for manufacturing products using the above-mentioned optical members (optical products) are preferred.

[4. Optical components] The adhesive sheet of the present invention can be preferably used for bonding optical components. Furthermore, the above-mentioned adhesive sheet may be provided with a release liner on the adhesive surface until use. However, the above-mentioned adhesive sheet in the optical component of the present invention is an adhesive sheet during use, and therefore does not have a release liner.

The so-called optical components refer to components with optical properties (such as polarization, light refraction, light scattering, light reflectivity, light transmittance, light absorption, light diffraction, optical rotation, visibility, etc.). The substrate constituting the optical member is not particularly limited, and examples thereof include substrates constituting equipment (optical equipment) such as display devices (image display devices) and input devices, or substrates used in such equipment. For example, For example: polarizing plate, wave plate, phase difference plate, optical compensation film, brightness enhancement film, light guide plate, reflective film, anti-reflective film, hard coating film (hard coating treatment is implemented on at least one side of plastic films such as PET film film), transparent conductive film (such as a plastic film with an ITO layer on the surface (preferably ITO film of PET-ITO, polycarbonate, cyclic olefin polymer, etc.), etc.), design film, decorative film, surface protection board , lenses, lenses, color filters, transparent substrates (glass sensors, glass display panels (LCD, etc.), glass substrates such as glass plates with transparent electrodes, etc.), or substrates laminated with these (there are These are collectively referred to as "functional films"), etc. In addition, these films may have a metal nanowire layer or a conductive polymer layer. In addition, thin metal lines can be screen-printed on these films. Furthermore, the above-mentioned "plate" and "film" respectively include plate-like, film-like, sheet-like and other forms. For example, "polarizing film" includes "polarizing plate" and "polarizing sheet". In addition, "film" includes film sensors and the like.

Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper. Moreover, as the said input device, a touch panel etc. are mentioned.

The substrate constituting the optical member is not particularly limited, and examples thereof include substrates (such as sheets) containing glass, acrylic resin, polycarbonate, polyethylene terephthalate, cycloolefin polymers, metal films, etc. shaped or film-shaped, plate-shaped substrates, etc.). Furthermore, as mentioned above, the "optical member" of the present invention also includes members (design film, decorative film, surface protection film, etc.) that maintain the visibility of the display device or input device and play a role of decoration or protection.

If the adhesive sheet of the present invention is an adhesive sheet with a base material, and the above-mentioned adhesive sheet constitutes a component with optical properties, then the above-mentioned base material can be equivalent to the above-mentioned substrate, and it can be considered that the above-mentioned adhesive sheet is also an optical component of the present invention. .

When the adhesive sheet of the present invention is an adhesive sheet with a base material, and the above-mentioned functional film is used as the above-mentioned base material, the adhesive sheet of the present invention can also be used as at least one side of the functional film having The "adhesive functional film" of the above-mentioned adhesive layer. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples in any way.

Manufacturing example 1 ＜Preparation of acrylic polymer P1＞ In a reaction vessel equipped with a mixer, a thermometer, a reflux condenser and a nitrogen introduction pipe, 100 parts by mass of n-butyl acrylate (BA) and 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator were placed ) 0.2 parts by mass and 122 parts by mass of ethyl acetate as a solvent were stirred at 60° C. in a nitrogen atmosphere for 7 hours (polymerization reaction). Thereby, a polymer solution containing acrylic polymer P1 was obtained.

Manufacturing example 2 ＜Preparation of acrylic polymer P2＞ In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, 100 parts by mass of 2-methoxyethyl acrylate (2-MEA) and 2,2'-azo as a polymerization initiator were placed A mixture of 0.2 parts by mass of diisobutyronitrile (AIBN) and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. in a nitrogen atmosphere for 7 hours (polymerization reaction). Thereby, a polymer solution containing acrylic polymer P2 was obtained.

Manufacturing example 3 ＜Preparation of acrylic polymer P3＞ In a reaction vessel equipped with a mixer, a thermometer, a reflux condenser and a nitrogen introduction pipe, 80.3 parts by mass of butyl acrylate (BA), 16 parts by mass of phenoxyethyl acrylate (PEA), and N-vinylpyrrolidone (NVP) 3 parts by mass, 0.5 parts by mass 4-hydroxybutyl acrylate (4-HBA), 0.2 parts by mass 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator, and 0.2 parts by mass as a solvent A mixture of 122 parts by mass of ethyl acetate was stirred at 60° C. in a nitrogen atmosphere for 7 hours (polymerization reaction). Thereby, a polymer solution containing acrylic polymer P3 was obtained.

Manufacturing example 4 ＜Preparation of Acrylic Polymer P4＞ In a reaction vessel equipped with a mixer, a thermometer, a reflux condenser and a nitrogen introduction pipe, 80.3 parts by mass of butyl acrylate (BA), 0.2 parts by mass of acrylic acid (AA), and 16 parts by mass of phenoxyethyl acrylate (PEA) , 3 parts by mass of N-vinylpyrrolidone (NVP), 0.5 parts by mass of 4-hydroxybutyl acrylate (4-HBA), 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator A mixture of 0.2 parts by mass and 122 parts by mass of ethyl acetate as a solvent was stirred at 60° C. in a nitrogen atmosphere for 7 hours (polymerization reaction). Thereby, a polymer solution containing acrylic polymer P4 was obtained.

Example 1 <Preparation of adhesive composition A> In the above polymer solution containing the acrylic polymer P1, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare adhesive composition A. ・Ionic compounds containing hydroxyl groups: N-oleyl-N,N-bis(2-hydroxyethyl)-N-methylammonium = bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd. )8.3 parts by mass ・Polyfunctional isocyanate additive: polyhexamethylene diisocyanate (trade name "Coronate HX", manufactured by Japan Polyurethane Co., Ltd.) 5.05 parts by mass ・Crosslinking catalyst: dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass ・Cross-linking retardant: 3 parts by mass of acetyl acetone (manufactured by Wako Pure Chemical Industries, Ltd.)

＜Manufacture of Adhesive Sheet A＞ Adhesive composition A was applied to a release liner (polyester film, thickness 38 μm, Mitsubishi Chemical Co., Ltd., MRF #38) with one side serving as the release surface to form a coating film. Next, the coating film was dried at 152°C for 3 minutes to form an adhesive layer A with a thickness of 25 μm. A release liner with a thickness of 38 μm (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Co., Ltd., MRF #38) was bonded to the adhesive layer so that one side of the polyester film would become the release surface. Thereafter, aging treatment is performed at 60° C. for 1 day, and a urethane reaction is performed in the adhesive layer to obtain an adhesive sheet A including a release liner/adhesive layer A/release liner.

Example 2 <Preparation of adhesive composition B> In the above polymer solution containing the acrylic polymer P2, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare adhesive composition B. ・Ionic compounds containing hydroxyl groups: N-oleyl-N,N-bis(2-hydroxyethyl)-N-methylammonium = bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd. )8.3 parts by mass ・Polyfunctional isocyanate additive: polyhexamethylene diisocyanate (trade name "Coronate HX", manufactured by Japan Polyurethane Co., Ltd.) 5.1 parts by mass ・Crosslinking catalyst: dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass ・Cross-linking retardant: 3 parts by mass of acetyl acetone (manufactured by Wako Pure Chemical Industries, Ltd.) ＜Manufacturing of Adhesive Sheet B＞ Except using adhesive composition B instead of adhesive composition A, in the same manner as in Example 1, an adhesive sheet B including a release liner/adhesive layer B/release liner was obtained.

Example 3 <Preparation of adhesive composition C> In the above polymer solution containing the acrylic polymer P2, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare the adhesive composition C. ・Ionic compounds containing hydroxyl groups: N-oleyl-N,N-bis(2-hydroxyethyl)-N-methylammonium = bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd. )8.3 parts by mass ・Polyfunctional isocyanate additive: Trimethylolpropane/toluene diisocyanate trimer adduct (trade name "Coronate L", manufactured by Tosoh Corporation) 8.6 parts by mass ・Crosslinking catalyst: dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass ・Cross-linking retardant: 3 parts by mass of acetyl acetone (manufactured by Wako Pure Chemical Industries, Ltd.) ＜Manufacture of Adhesive Sheet C＞ Except using adhesive composition C instead of adhesive composition A, in the same manner as in Example 1, an adhesive sheet C including a release liner/adhesive layer C/release liner was obtained.

Example 4 <Preparation of adhesive composition D> In the above polymer solution containing the acrylic polymer P2, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare an adhesive composition D. ・Ionic compounds containing hydroxyl groups: N-oleyl-N,N-bis(2-hydroxyethyl)-N-methylammonium = bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd. )8.3 parts by mass ・Polyfunctional isocyanate additive: isocyanurate body of toluene diisocyanate (trade name "Takenate D262", manufactured by Mitsui Chemicals Co., Ltd.) 14.3 parts by mass ・Crosslinking catalyst: dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass ・Cross-linking retardant: 3 parts by mass of acetyl acetone (manufactured by Wako Pure Chemical Industries, Ltd.) ＜Manufacture of adhesive sheet D＞ Except using adhesive composition D instead of adhesive composition A, in the same manner as in Example 1, an adhesive sheet D including a release liner/adhesive layer D/release liner was obtained.

Comparative example 1 <Preparation of adhesive composition E> In the above-mentioned polymer solution containing the acrylic polymer P1, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare the adhesive composition E. ・Antistatic agent: N-ethyl-N-(2-methoxyethyl)-N,N-dimethylammonium = bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) 5.25 parts by mass ＜Manufacturing of Adhesive Sheet E＞ Adhesive composition E was applied to a release liner (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Co., Ltd., MRF #38) that was used as the release surface on one side to form a coating film. Next, the coating film was dried at 152°C for 3 minutes to form an adhesive layer E with a thickness of 25 μm. A release liner with a thickness of 38 μm (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Co., Ltd., MRF #38) was bonded to one side of the polyester film to become the release surface. Thereafter, aging treatment was performed at 60° C. for 1 day to obtain an adhesive sheet E including a release liner/adhesive layer E/release liner.

Comparative example 2 <Preparation of adhesive composition F> In the above polymer solution containing the acrylic polymer P2, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare the adhesive composition F. ・Antistatic agent: N-ethyl-N-(2-methoxyethyl)-N,N-dimethylammonium = bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) 5.25 parts by mass ＜Manufacturing of Adhesive Sheet F＞ In the same manner as Comparative Example 1, except that adhesive composition F was used instead of adhesive composition E, an adhesive sheet F including a release liner/adhesive layer F/release liner was obtained.

Example 5 <Preparation of adhesive composition G> In the above polymer solution containing the acrylic polymer P3, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare the adhesive composition C. ・Ionic compounds containing hydroxyl groups: N-butyl-N,N-bis(2-hydroxyethyl)-N-methylammonium・Bis(trifluoromethanesulfonyl)imide (trade name "CIL- R10", manufactured by Carlit Holdings) 3 parts by mass ・Polyfunctional isocyanate additive: Trimethylolpropane/toluene diisocyanate trimer adduct (trade name "Coronate L", manufactured by Tosoh Corporation) 6.6 parts by mass ・Crosslinking catalyst: dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass ・Cross-linking retardant: 3 parts by mass of acetyl acetone (manufactured by Wako Pure Chemical Industries, Ltd.)

＜Manufacturing of adhesive sheet G＞ Adhesive composition G was applied to a release liner (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Co., Ltd., MRF #38) with one side serving as the release surface to form a coating film. Next, the coating film was dried at 152°C for 3 minutes to form an adhesive layer G with a thickness of 15 μm. A release liner with a thickness of 38 μm (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Co., Ltd., MRF #38) was bonded to the adhesive layer so that one side of the polyester film would become the release surface. Thereafter, aging treatment is performed at 60° C. for 1 day, and a urethane reaction is performed in the adhesive layer to obtain an adhesive sheet G including a release liner/adhesive layer G/release liner.

Example 6 <Preparation of adhesive composition H> In the above polymer solution containing the acrylic polymer P4, the following components were uniformly mixed per 100 parts by mass of the acrylic polymer (base polymer) to prepare an adhesive composition H. ・Ionic compounds containing hydroxyl groups: N-butyl-N,N-bis(2-hydroxyethyl)-N-methylammonium・Bis(trifluoromethanesulfonyl)imide (trade name "CIL- R10", manufactured by Carlit Holdings) 3 parts by mass ・Polyfunctional isocyanate additive: Trimethylolpropane/toluene diisocyanate trimer adduct (trade name "Coronate L", manufactured by Tosoh Corporation) 9.9 parts by mass ・Crosslinking catalyst: dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) 0.01 parts by mass ・Cross-linking retardant: 3 parts by mass of acetyl acetone (manufactured by Wako Pure Chemical Industries, Ltd.)

＜Manufacturing of adhesive sheet H＞ Adhesive composition H was applied to a release liner (polyester film, thickness 38 μm, Mitsubishi Chemical Co., Ltd., MRF #38) with one side serving as the release surface to form a coating film. Next, the coating film was dried at 152°C for 3 minutes to form an adhesive layer H with a thickness of 15 μm. A release liner with a thickness of 38 μm (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Co., Ltd., MRF #38) was bonded to the adhesive layer so that one side of the polyester film would become the release surface. Thereafter, aging treatment is performed at 60° C. for 1 day, and a urethane reaction is performed in the adhesive layer to obtain an adhesive sheet H including a release liner/adhesive layer H/release liner.

The following evaluations were performed using the adhesive sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 2 described above. The results are shown in Table 2.

<Resistance value stability> ・Measurement of initial surface resistance value SR ₁ After peeling off one release liner of the obtained adhesive sheet, the surface resistance value of the surface of the adhesive layer was measured. The measurement was performed in an environment of 23°C and 50% RH using MCP-HT450 manufactured by Mitsubishi Chemical ANALYTECH.・Measurement of the surface resistance value SR ₂ after storage at 85°C, 85%RH, and 168 hours. One release liner of the obtained adhesive sheet was peeled off, and then it was laminated to a 25 μm-thick triacetyl cellulose film (commercial product Name: KC2UA, manufactured by Konica Minolta Company). The sample containing the release liner/adhesive layer/triacetyl cellulose film in sequence was stored in a constant temperature and humidity machine at 85°C and 85%RH for 168 hours. After storage, let it stand for 72 hours in an environment of 23°C and 50% RH, and then measure the surface resistance value. The measurement was performed in an environment of 23°C and 50% RH using MCP-HT450 manufactured by Mitsubishi Chemical ANALYTECH.・Resistance value stability is determined by the difference between the common logarithm of SR ₂ , Log(SR ₂ ), and the common logarithm of SR ₁ , Log(SR ₁ ): Log(SR ₂ ) - Log(SR ₁ ) to evaluate the resistance value stability. If the difference is less than 0.5, the resistance value stability is considered to be excellent.

＜Corrosion resistance stability＞ After peeling off one release liner of the obtained adhesive sheet, it was bonded to the aluminum vapor deposition surface of the aluminum vapor deposition PET film 100 (trade name: Metalumy TS, manufactured by Toray Advanced Film Co., Ltd.). The sample containing the release liner/adhesive layer/aluminum evaporated PET film in sequence was stored in a constant temperature and humidity machine at 85°C and 85% R.H. for 168 hours. After storage, visually confirm whether there is corrosion on the metal surface. If there is no corrosion, it will be evaluated as 0, and if there is corrosion, it will be evaluated as ×.

[Table 2] (Table 2) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Surface resistance Initial resistance value SR ₁ 5.22×10 ¹¹ 7.82×10 ⁹ 1.00×10 ¹⁰ 1.61×10 ¹⁰ 2.02×10 ¹¹ 1.64×10 ¹¹ 1.97×10 ⁹ 3.65×10 ⁸ (Ω/□) Resistance value SR ₂ after 85℃, 85%RH, 168 hours 4.99×10 ¹¹ 9.25×10 ⁹ 9.11×10 ⁹ 9.11×10 ⁹ 1.78×10 ¹¹ 2.64×10 ¹¹ 4.49×10 ¹¹ 4.88×10 ⁸ Resistance value stability Log(SR ₂ )-Log(SR ₁ ) 0.029 0.076 0.029 0.034 0.055 0.207 2.353 0.117 Corrosion resistance stability after 85℃, 85%RH, 168 hours 〇 〇 〇 〇 〇 〇 × ×

Modifications of the present invention will be described below. [Note 1] An adhesive composition for forming an adhesive layer, containing an adhesive polymer (A) and a conductive polymer (B), and The monomer components constituting the conductive polymer (B) include an ionic compound (B1) having a functional group (b1) in the molecule and an ionic compound (B1) having a functional group (b1) in the molecule that can react with the functional group (b1) to form a co-containing compound. Compound (B2) of the functional group (b2) of the valence bond, The above-mentioned conductive polymer (B) has a three-dimensional network structure, The three-dimensional network structure of the conductive polymer (B) is entangled with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. [Note 2] An adhesive composition containing an adhesive polymer (A) and a mixture of monomer components constituting the conductive polymer (B) or a mixture of monomer components constituting the conductive polymer (B) part of the polymer, and The monomer components constituting the conductive polymer (B) include an ionic compound (B1) having a functional group (b1) in the molecule and an ionic compound (B1) having a functional group (b1) in the molecule that can react with the functional group (b1) to form a co-containing compound. Compound (B2) of the functional group (b2) of the valence bond, The functional group (b1) of the above-mentioned ionic compound (B1) reacts with the functional group (b2) of the above-mentioned compound (B2) to form a covalent bond, forming the above-mentioned conductive polymer (B) with a three-dimensional network structure, and the above-mentioned three-dimensional The network structure is intertwined with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. [Supplementary Note 3] The adhesive composition according to Appendix 1 or 2, wherein the ionic compound (B1) has two or more of the above-mentioned functional groups (b1) in the molecule. [Additional Note 4] The adhesive composition according to any one of Additional Notes 1 to 3, wherein the above-mentioned functional group (b1) is selected from the group consisting of hydroxyl group, carboxyl group, amino group, mercapto group, (meth)acryloxy group, (methyl) ) At least one functional group from the group consisting of acrylamino group, vinyl group, allyl group, and styrene group. [Appendix 5] The adhesive composition according to any one of Appendices 1 to 4, wherein the compound (B2) has three or more functional groups (b2) in the molecule. [Supplement 6] The adhesive composition according to any one of Appendix 1 to 5, wherein the above-mentioned functional group (b2) is selected from the group consisting of isocyanato group, thioisocyanate group, epoxy group, aziridinyl group, At least one of the group consisting of azozoline group, carbodiimide group, (meth)acryloxy group, (meth)acrylamide group, vinyl group, allyl group, and styryl group Functional group. [Appendix 7] The adhesive composition according to any one of Appendices 1 to 6, wherein the content ratio of the conductive polymer (B) to the adhesive polymer (A) is (conductive polymer (B)/ Adhesive polymer (A)) is 0.05 to 0.5. [Appendix 8] An adhesive layer formed from the adhesive composition according to any one of Appendices 1 to 7. [Appendix 9] An adhesive sheet having an adhesive layer as in Appendix 8. [Appendix 10] The thickness of the adhesive sheet as in Appendix 9 is 10 to 350 μm.

1: Adhesive sheet 10: Adhesive layer 11,12: Release liner

FIG. 1 is a schematic diagram (sectional view) showing one embodiment of the adhesive sheet of the present invention.

Claims (10)

An adhesive composition used to form an adhesive layer, containing an adhesive polymer (A) and a conductive polymer (B), and The monomer components constituting the conductive polymer (B) include an ionic compound (B1) having a functional group (b1) in the molecule and an ionic compound (B1) having a functional group (b1) in the molecule that can react with the functional group (b1) to form a co-containing compound. Compound (B2) of the functional group (b2) of the valence bond, The above-mentioned conductive polymer (B) has a three-dimensional network structure, The three-dimensional network structure of the conductive polymer (B) is entangled with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. An adhesive composition containing an adhesive polymer (A) and a mixture of monomer components constituting the conductive polymer (B) or a part of the polymer of the mixture of monomer components constituting the conductive polymer (B) ,and The monomer component constituting the conductive polymer (B) includes an ionic compound (B1) having a functional group (b1) in the molecule and an ionic compound (B1) having a functional group (b1) in the molecule that can react with the functional group (b1) to form a co-containing compound. Compound (B2) of the functional group (b2) of the valence bond, The functional group (b1) of the above-mentioned ionic compound (B1) reacts with the functional group (b2) of the above-mentioned compound (B2) to form a covalent bond, forming the above-mentioned conductive polymer (B) with a three-dimensional network structure, and the above-mentioned three-dimensional The network structure is intertwined with the adhesive polymer (A) to form an interpenetrating polymer network or a semi-interpenetrating polymer network. The adhesive composition of claim 1 or 2, wherein the ionic compound (B1) has two or more functional groups (b1) in the molecule. Such as the adhesive composition of claim 1 or 2, wherein the above-mentioned functional group (b1) is selected from the group consisting of hydroxyl group, carboxyl group, amine group, mercapto group, (meth)acryloxy group, (meth)acrylamide group, At least one functional group from the group consisting of vinyl, allyl, and styrene. The adhesive composition of claim 1 or 2, wherein the above-mentioned compound (B2) has more than 3 above-mentioned functional groups (b2) in the molecule. The adhesive composition of claim 1 or 2, wherein the above-mentioned functional group (b2) is selected from the group consisting of isocyanate group, thioisocyanato group, epoxy group, aziridinyl group, oxazoline group, carbon dioxide group, etc. At least one functional group from the group consisting of acyl imide group, (meth)acryloxy group, (meth)acrylamide group, vinyl group, allyl group, and styrene group. The adhesive composition of claim 1 or 2, wherein the content ratio of the conductive polymer (B) to the adhesive polymer (A) is (conductive polymer (B)/adhesive polymer (A) ) is 0.05~0.5. An adhesive layer formed from the adhesive composition of claim 1 or 2. An adhesive sheet having an adhesive layer as claimed in claim 8. For example, the thickness of the adhesive sheet of claim 9 is 10 to 350 μm.