WO2023176834A1

WO2023176834A1 - Adhesive composition, adhesive layer, and adhesive sheet

Info

Publication number: WO2023176834A1
Application number: PCT/JP2023/009852
Authority: WO
Inventors: 大輔水野; 武史仲野
Original assignee: 日東電工株式会社
Priority date: 2022-03-16
Filing date: 2023-03-14
Publication date: 2023-09-21
Also published as: JP2023136273A; TW202346515A

Abstract

The purpose of the present invention is to provide an adhesive agent composition capable of forming and adhesive agent layer that exhibits low surface resistivity and has excellent antistatic performance.　An adhesive agent composition according to the present invention contains a block copolymer. The block copolymer includes an adhesive segment (A) and a conductive segment (B). The adhesive agent composition has a sea-island structure that has been phase separated into a continuous phase and a non-continuous phase.

Description

Adhesive composition, adhesive layer, and adhesive sheet

The present invention relates to an adhesive composition, an adhesive layer, and an adhesive sheet. More specifically, the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, and a pressure-sensitive 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 been widely used in various fields. In the manufacture of these display devices and input devices, adhesive sheets are used for bonding optical members together. For example, transparent adhesive sheets are used to bond optical members in various display devices such as touch panels.

In the manufacture of these display devices and input devices, when attaching the adhesive sheet to the display device, the release liner that protects the adhesive layer is peeled off, but static electricity is generated in the adhesive layer at this time. The generated static electricity affects the orientation of the display cells of the display device and causes display defects. As a means to suppress the generation of static electricity, antistatic agents are added to reduce the surface resistivity of the adhesive layer (for example, Patent Documents 1 to 3).

In recent years, as image quality has improved, the influence of static electricity on display devices with high-density display cells has increased.In order to efficiently remove static electricity, it is necessary to further reduce the surface resistivity of the adhesive sheet ( For example, about 10 ¹⁰ Ω/□) is required. In addition, the demand for thinner and lighter display devices has led to demands for thinner adhesive sheets, and in order to achieve thinner adhesive sheets with lower surface resistivity, it is necessary to incorporate large amounts of antistatic agents. It is being

However, when a large amount of antistatic agent is blended into the adhesive layer, there is a problem that the antistatic agent is deposited on the surface of the adhesive layer and metal wiring such as copper wiring corrodes. Further, there was also a problem that the antistatic agent migrated from the adhesive layer to other optical members in a moist heat environment, increasing the surface resistance value and reducing the antistatic property. Furthermore, the compatibility between the adhesive layer and the antistatic agent decreases, which may result in defects in transparency and appearance such as clouding, or in some cases, foaming or peeling, especially in a moist heat environment.

As a means to solve the above-mentioned problems caused by incorporating an antistatic agent into the adhesive layer, we developed an adhesive from an antistatic adhesive composition containing a (meth)acrylic polymer containing a reactive ionic liquid as a monomer unit. A method of forming a drug layer is known (for example, Patent Documents 4 and 5). In the adhesive layer formed from this antistatic adhesive composition, the reactive ionic liquid is incorporated into the skeleton of the (meth)acrylic polymer, so concerns about bleed-out are suppressed and the contamination property is low. It is said to be excellent in

Japanese Patent Application Publication No. 2020-187365 JP2019-56115A WO2018/008712 publication Japanese Patent Application Publication No. 2014-141649 Japanese Patent Application Publication No. 2014-189787

In Patent Documents 4 and 5, since the ionic component is uniformly dispersed in the adhesive layer, there is a problem that it is difficult to form a path for imparting conductivity, and the antistatic property is reduced.

Therefore, an object of the present invention is to provide an adhesive composition that can form an adhesive layer that exhibits low surface resistivity and has excellent antistatic performance.
Another object of the present invention is to provide an adhesive layer that exhibits low surface resistivity and has excellent antistatic performance.
Another object of the present invention is to provide a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer that exhibits low surface resistivity and has excellent antistatic performance.

Therefore, as a result of intensive studies in order to solve the above problems, the present inventor found that sea islands containing a block copolymer containing an adhesive segment and a conductive segment and phase-separated into a continuous phase and a discontinuous phase. We discovered that in an adhesive composition in which a structure is formed, paths for imparting conductivity can be efficiently formed, and an adhesive layer can be formed that exhibits low surface resistivity and has excellent antistatic performance. Completed the invention.

That is, the first aspect of the present invention contains a block copolymer, the block copolymer includes an adhesive segment (A) and a conductive segment (B), and has a continuous phase and a discontinuous phase. A pressure-sensitive adhesive composition having a separated sea-island structure is provided. In this specification, the adhesive composition of the first aspect of the present invention may be referred to as "the adhesive composition of the present invention".

Further, a second aspect of the present invention provides an adhesive layer formed from the adhesive composition of the present invention. In this specification, the adhesive layer of the second aspect of the present invention may be referred to as "the adhesive layer of the present invention". Further, a third aspect of the present invention provides a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer of the present invention. In this specification, the adhesive sheet of the third aspect of the present invention may be referred to as the "adhesive sheet of the present invention".
Since the pressure-sensitive adhesive layer of the present invention and the pressure-sensitive adhesive sheet of the present invention are formed from the pressure-sensitive adhesive composition of the present invention, they exhibit low surface resistivity and have excellent antistatic performance.

The adhesive composition of the present invention contains a block copolymer. In the pressure-sensitive adhesive composition of the present invention, this block copolymer is included as a base polymer constituting the pressure-sensitive adhesive composition of the present invention. In this specification, the block copolymer contained as a base polymer in the pressure-sensitive adhesive composition of the present invention may be referred to as "the block copolymer of the present invention."

In the adhesive composition of the present invention, the block copolymer of the present invention includes an adhesive segment (A) and a conductive segment (B). In the block copolymer of the present invention, the adhesive segment (A) is a segment that imparts adhesiveness to the adhesive layer of the present invention. Further, in the block copolymer of the present invention, the conductive segment (B) is a segment that imparts conductivity to the adhesive layer of the present invention and has an antistatic function.

The adhesive composition of the present invention has a sea-island structure separated into a continuous phase and a discontinuous phase. The configuration in which the pressure-sensitive adhesive composition of the present invention has a sea-island structure efficiently forms a path for imparting conductivity in the continuous phase, and the pressure-sensitive adhesive layer of the present invention exhibits low surface resistivity. , is preferable in that it has excellent antistatic performance.

In the pressure-sensitive adhesive composition of the present invention, the continuous phase (marine) preferably includes the conductive segment (B). The configuration in which the continuous phase (aquatic part) includes the conductive segment (B) efficiently forms a path for imparting conductivity in the continuous phase, and the adhesive layer of the present invention has a low surface area. It is preferable because it shows resistivity and has excellent antistatic performance.

In the adhesive composition of the present invention, the weight ratio of the conductive segment (B) to the adhesive segment (A) (conductive segment (B)/adhesive segment (A)) is 50/50 to 99/ It is preferable that it is 1. The configuration in which the weight ratio is 50/50 or more means that the pressure-sensitive adhesive composition of the present invention forms a sea-island structure in which a continuous phase and a discontinuous phase are separated, and the continuous phase (sea area) is This is preferable in that it can be configured to include a conductive segment (B). It is also preferable that the sea-island structure constitutes nano-scale microphase separation. Further, the configuration in which the weight ratio is 99/1 or less is suitable in that excellent adhesiveness can be imparted to the adhesive layer of the present invention.

In the adhesive composition of the present invention, the conductive segment (B) preferably contains an ionic compound having a radically polymerizable substituent as a monomer unit. Moreover, it is preferable that the said adhesive segment (A) contains a radically polymerizable compound as a monomer unit. These configurations are preferred in that the block copolymer of the present invention can be efficiently prepared.

The adhesive layer of the present invention preferably has a storage modulus of 3×10 ⁴ Pa or more and 5×10 ⁶ Pa or less at 25° C. and 1 Hz. It is preferable that the adhesive layer of the present invention has a storage modulus of 3×10 ⁴ Pa or more at 25° C. and 1 Hz because it is less likely to cause dents during handling. Further, the storage modulus of the adhesive layer of the present invention at 25° C. and 1 Hz is preferably 5×10 ⁶ Pa or less from the viewpoint of step followability.

The total light transmittance (according to JIS K7361-1) of the adhesive layer of the present invention is preferably 90% or more. Further, the haze (according to JIS K7136) of the adhesive layer of the present invention is preferably 3% or less. These structures are preferable in that excellent transparency and excellent appearance can be obtained.

The thickness of the adhesive sheet of the present invention is preferably 12 to 350 μm. A configuration in which the thickness is at least a certain level is preferable because peeling at the stepped portion is less likely to occur. Further, a configuration in which the thickness is below a certain level is preferable because it makes it easier to maintain an excellent appearance during manufacturing.

According to the pressure-sensitive adhesive composition of the present invention, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet can be obtained that exhibit low surface resistivity and have excellent antistatic performance.

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

The adhesive composition of the present invention contains a block copolymer, and the block copolymer includes an adhesive segment (A) and a conductive segment (B), and is phase-separated into a continuous phase and a discontinuous phase. This is an adhesive composition having a sea-island structure.

Moreover, the adhesive layer of the present invention is an adhesive layer formed from the adhesive composition of the present invention. Furthermore, the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer of the present invention.

[1. Adhesive composition]
The adhesive composition of the present invention may have any form, such as a solvent type, an emulsion type, a hot melt type, a solvent-free type (active energy ray-curable type), etc. It will be done. In particular, the adhesive composition of the present invention is preferably a solvent type. This is preferred because a stable sea-island structure can be formed when a solvent-based adhesive composition is heated and/or dried to obtain an adhesive layer. In this specification, the adhesive composition means a composition used to form an adhesive layer, and includes 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, but examples include hydrocarbon solvents such as cyclohexane, hexane, and heptane; aromatic solvents such as toluene and xylene; ethyl acetate, methyl acetate, etc. Ester solvents; ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, butanol, and isopropyl alcohol. Note that the organic solvent may be a mixed solvent containing two or more types of organic solvents.

[1-1. Block copolymer of the present invention]
The adhesive composition of the present invention contains a block copolymer. In the pressure-sensitive adhesive composition of the present invention, the block copolymer of the present invention is included as a base polymer constituting the pressure-sensitive adhesive composition of the present invention.

The content (total amount) of the block copolymer of the present invention in the adhesive composition of the present invention is not particularly limited, but is preferably 75% by weight or more (for example, 75 to 100% by weight), more preferably 85% by weight. or more (for example, 85 to 99.99% by weight).

In the adhesive composition of the present invention, the block copolymer of the present invention includes an adhesive segment (A) and a conductive segment (B). In the block copolymer of the present invention, the adhesive segment (A) is a segment that imparts adhesiveness to the adhesive layer of the present invention. Further, in the block copolymer of the present invention, the conductive segment (B) is a segment that imparts conductivity to the adhesive layer of the present invention and has an antistatic function. Note that the "segment" in the adhesive segment (A) and the conductive segment (B) refers to a partial structure that constitutes each block unit of the block copolymer.

The structure of the block copolymer of the present invention may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a block copolymer may be appropriately selected depending on the desired physical properties of the block copolymer, but from the viewpoint of cost and ease of manufacture, a linear block copolymer is preferable. Furthermore, the linear block copolymer may have any structure (sequence), such as (AB) _n type, (AB) _n -A type (n is an integer of 1 or more, for example, 1 to 3). A block copolymer having at least one structure selected from the group consisting of (integer) is preferable. In these structures, A and B refer to segments composed of different monomer compositions. In this specification, the segment represented by A constituting the linear block copolymer may be referred to as an "A segment", and the segment represented by B may be referred to as a "B segment".

Among these, from the viewpoint of ease of production etc., AB type diblock copolymers represented by AB and ABA type triblock copolymers represented by ABA are preferred, and ABA type triblock copolymers are more preferred. It is. It is thought that the ABA type triblock copolymer is capable of expressing a sea-island structure in which the A segment and the B segment are microphase-separated on a nanometer scale due to pseudo-crosslinking between the A segments at both ends. In addition, in the ABA type triblock copolymer, the two A segments located at both ends may be the same or different.

When the block copolymer of the present invention is an ABA type triblock copolymer, at least one of two A segments and one B segment (total of three) is an adhesive segment (A), and at least the other one is electrically conductive. Segment (B) is sufficient. From the viewpoint of ease of production, an ABA triblock copolymer in which the A segment is the adhesive segment (A) and the B segment is the conductive segment (B) is preferred. In that case, an ABA type triblock copolymer in which at least one of the two A segments is an adhesive segment (A) and a B segment is a conductive segment (B) is preferred, and both of the two A segments are adhesive. More preferred is an ABA type triblock copolymer in which the segment (A) is the conductive segment (B) and the B segment is the conductive segment (B).

The block copolymer of the present invention is composed of a plurality of segments (including an adhesive segment (A) and a conductive segment (B)) obtained by polymerizing monomer components, and is easy to prepare. From this viewpoint, it is preferable that the monomer component contains a radically polymerizable compound (a compound having a radically polymerizable substituent).

The radically polymerizable substituent in the radically polymerizable compound is not particularly limited, but includes, for example, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, a styryl group, and the like. Among these, (meth)acryloyloxy group and (meth)acryloylamino group are preferable, and from the viewpoint of ease of preparation of block copolymers, monomers having (meth)acryloyloxy group as a radically polymerizable substituent ((meth)acrylic monomers) are particularly preferred.

Note that "(meth)acrylic" means "acrylic" and/or "methacrylic" (one or both of "acrylic" and "methacrylic"), and the same applies below. In addition, "(meth)acryloyl group" means "acryloyl group" and/or "methacryloyl group" (one or both of "acryloyl group" and "methacryloyl group"), and the same applies below.

The block copolymer of the present invention or each segment thereof (including the adhesive segment (A) and the conductive segment (B)) contains a (meth)acrylic monomer in an amount of 70% by weight or more based on the total amount of monomer components (100% by weight). The content is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 90% by weight or more.

The block copolymer of the present invention or each segment thereof (including the adhesive segment (A) and the conductive segment (B)) is a (meth)acrylic having a linear or branched alkyl group as an essential monomer unit. It is preferable to contain a monomer component derived from an acid alkyl ester (hereinafter sometimes simply referred to as "(meth)acrylic acid alkyl ester") as the main monomer unit.

Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate ((meth)acrylate, ) n-butyl acrylate), isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylate ) Decyl acrylate, Isodecyl (meth)acrylate, Undecyl (meth)acrylate, Dodecyl (meth)acrylate, Tridecyl (meth)acrylate, Tetradecyl (meth)acrylate, Pentadecyl (meth)acrylate, (Meth) The alkyl group has 1 to 20 carbon atoms, such as hexadecyl acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Examples include (meth)acrylic acid alkyl esters. In addition, (meth)acrylic acid alkyl ester may be used individually or in combination of 2 or more types.

Among these, (meth)acrylic acid alkyl esters are preferably (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 18 carbon atoms, from the viewpoint of obtaining strong adhesiveness and adjusting residual stress. are methyl methacrylate (MMA), butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isostearyl acrylate (ISTA).

The content (ratio) of the above-mentioned (meth)acrylic acid alkyl ester in all monomer units (total amount of monomer components constituting the block copolymer) of the block copolymer of the present invention is not particularly limited, but from the viewpoint of adhesive reliability, The amount is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, even more preferably 5 to 30 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the invention.

The block copolymer of the present invention or each segment thereof (including the adhesive segment (A) and the conductive segment (B)) is a (meth)acrylic having a linear or branched alkoxyalkyl group as an essential monomer unit. It is also preferable to contain an acid alkoxyalkyl ester (hereinafter sometimes simply referred to as "(meth)acrylic acid alkoxyalkyl ester").

Examples of the (meth)acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-methacrylate (meth)acrylate. - An alkoxy group having 1 to 20 carbon atoms such as methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, etc. Examples include (meth)acrylic acid alkyl esters having an alkoxyalkyl group substituted with an alkyl group. Note that the (meth)alkoxyacrylic acid alkyl esters may be used alone or in combination of two or more.

Among these, the above-mentioned (meth)acrylic acid alkoxyalkyl ester has an alkoxy group having 1 to 18 carbon atoms substituted with an alkyl group having 1 to 18 carbon atoms in order to obtain strong adhesive properties and adjust residual stress. Preferred are meth)acrylic acid alkoxyalkyl esters, and more preferred is 2-methoxyethyl acrylate (MEA).

The content (proportion) of the (meth)acrylic acid alkoxyalkyl ester in all monomer units (total amount of monomer components constituting the block copolymer) of the block copolymer of the present invention is not particularly limited, but in terms of adhesive reliability, The amount is preferably 30 to 99 parts by weight, more preferably 40 to 95 parts by weight, even more preferably 50 to 90 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention.

The block copolymer of the present invention may contain a copolymerizable monomer (copolymerizable monomer) in addition to the above-mentioned (meth)acrylic acid alkyl ester and (meth)acrylic acid alkoxyalkyl ester as a monomer unit. . That is, the block copolymer of the present invention may contain a copolymerizable monomer as a constituent monomer component. Note that the copolymerizable monomers may be used alone or in combination of two or more types.

As the above-mentioned copolymerizable monomer, carboxyl group-containing monomers are preferably mentioned. When the block copolymer of the present invention contains a carboxyl group-containing monomer as a monomer unit, it becomes easier to obtain good cohesive force. For this reason, it becomes easier to obtain strong adhesion. Furthermore, the carboxyl group can also serve as a reaction site with the crosslinking agent described below.

The content (ratio) of the carboxyl group-containing monomer to the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention is not particularly limited. The content of the carboxyl group-containing monomer is preferably 0.1 to 20 parts by weight from the viewpoint of cohesive force, adhesiveness, ease of obtaining adhesive reliability, and reactivity with the crosslinking agent, More preferably 0.3 to 10 parts by weight, still more preferably 0.5 to 5 parts by weight.

As the above-mentioned copolymerizable monomer, hydroxyl group-containing monomers are preferably mentioned. When the block copolymer of the present invention contains a hydroxyl group-containing monomer as a monomer unit, it becomes easier to polymerize the constituent monomer components, and it becomes easier to obtain good cohesive force. Therefore, it becomes easier to obtain strong adhesive properties, and by increasing the gel fraction, it becomes easier to obtain excellent foam peeling resistance. Furthermore, it becomes easier to suppress whitening of the pressure-sensitive adhesive sheet, which may occur in a high-humidity environment. Furthermore, the hydroxyl group can also serve as a point of reaction with the crosslinking agent described below.

The content (ratio) of the hydroxyl group-containing monomer to the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention is not particularly limited. When the amount of the hydroxyl group-containing monomer is above a certain level, whitening of the pressure-sensitive adhesive sheet that may occur in a high-humidity environment can be further suppressed, and transparency such as resistance to humid clouding can be ensured. The lower limit of the content of the hydroxyl group-containing monomer is preferably 1 part by weight or more, more preferably 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more. The amount is at least 8 parts by weight, more preferably at least 10 parts by weight. Further, the upper limit of the content of the hydroxyl group-containing monomer is preferably 40 parts by weight or less, and 35 parts by weight, from the viewpoint of cohesive force, adhesion, and ease of obtaining adhesive reliability such as foam peeling resistance. Hereinafter, the amount is more preferably 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 even more preferably 30 parts by weight or less.

Further, as the copolymerizable monomer, nitrogen atom-containing monomers are preferably mentioned. When the block copolymer of the present invention contains a nitrogen atom-containing monomer as a monomer unit, it becomes easier to obtain an appropriate cohesive force. Therefore, by increasing the 180° peel adhesion force to the glass plate and the 180° peel adhesion force to the acrylic plate, it is easier to obtain strong adhesion, and by increasing the gel fraction, excellent It becomes easier to obtain foam peeling resistance. Furthermore, it becomes easier to obtain appropriate flexibility in the adhesive layer, adjust the 300% tensile residual stress within a specific range, and easily obtain excellent stress relaxation properties and excellent step followability.

Although the content (ratio) of the nitrogen atom-containing monomer to the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention is not particularly limited, it is preferably 0.1 parts by weight or more. The lower limit of the content of the nitrogen atom-containing monomer is set at 0.5 parts by weight based on the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention, from the viewpoint of cohesive force, adhesiveness, and foaming peeling resistance. It is preferably at least 0.8 parts by weight, more preferably at least 0.8 parts by weight, even more preferably at least 1 part by weight. In addition, the upper limit of the content of the nitrogen atom-containing monomer is set at 10 parts by weight, since it makes it easier to obtain appropriate flexibility in the adhesive layer, as well as excellent stress relaxation properties and excellent step followability. It is preferably at most 8 parts by weight, more preferably at most 8 parts by weight, even more preferably at most 5 parts by weight.

[1-2. Carboxyl group-containing monomer]
It is preferable to contain a carboxyl group-containing monomer as a monomer component constituting the block copolymer of the present invention. By containing a carboxyl group-containing monomer as a monomer component constituting the block copolymer of the present invention, it becomes a reaction point with the crosslinking agent described below to form a crosslinked structure, and the sea-island structure described below can be efficiently formed. In this respect, it is preferable. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, etc.; , itaconic anhydride and other acid anhydride group-containing monomers are also included. Note that the carboxyl group-containing monomers may be used alone or in combination of two or more types.

[1-3. Hydroxyl group-containing monomer]
The hydroxyl group-containing monomer means a monomer having at least one hydroxyl group in the molecule. Further, a monomer having at least one hydroxyl group in the molecule and at least one carboxyl group in the molecule is a carboxyl group-containing monomer, not a hydroxyl group-containing monomer. The hydroxyl group-containing monomer is not particularly limited, but specifically includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 3-hydroxypropyl meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylic acid Examples include hydroxyl group-containing (meth)acrylic acid esters such as hydroxylauryl and (meth)acrylic acid (4-hydroxymethylcyclohexyl); vinyl alcohol, allyl alcohol, and the like. Among these, the hydroxyl group-containing monomer is preferably a hydroxyl group-containing (meth)acrylic ester, more preferably 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl (meth)acrylate (HPA), or 4-acrylic acid. -Hydroxybutyl (4HBA). Note that the hydroxyl group-containing monomers may be used alone or in combination of two or more types.

[1-4. Nitrogen atom-containing monomer]
A nitrogen atom-containing monomer means a monomer having at least one nitrogen atom in the molecule (in one molecule). However, the hydroxyl group-containing monomer does not include the nitrogen atom-containing monomer. That is, in this specification, monomers having a hydroxyl group and a nitrogen atom in the molecule are included in nitrogen atom-containing monomers. Further, a monomer having at least one nitrogen atom in the molecule and having at least one carboxyl group in the molecule is a carboxyl group-containing monomer and not a nitrogen atom-containing monomer.

As the nitrogen atom-containing monomer, N-vinyl cyclic amides, (meth)acrylamides, heterocycle-containing monomers, etc. are preferable from the viewpoint of improving foaming and peeling resistance. Note that the nitrogen atom-containing monomers may be used alone or in combination of two or more types.

The above-mentioned heterocycle-containing monomers include (meth)acryloylmorpholine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, N-vinylpyrazine, N-vinylmorpholine, N-vinylpyrazole, vinylpyridine, vinylpyrimidine, Examples include vinyloxazole, vinylisoxazole, vinylthiazole, vinylisothiazole, vinylpyridazine, (meth)acryloylpyrrolidone, (meth)acryloylpyrrolidine, (meth)acryloylpiperidine, and N-methylvinylpyrrolidone.

Examples of the N-vinyl cyclic amide include N-vinyl cyclic amide represented by the following formula (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 (e.g. 3 to 5 alkylene groups, etc.).

As the N-vinyl cyclic amide represented by the above formula (1), N-vinyl-2-pyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl -2-caprolactam, N-vinyl-3-morpholinone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, etc. are preferred, and N-vinyl-2- Pyrrolidone, N-vinyl-2-caprolactam, and more preferably N-vinyl-2-pyrrolidone.

Examples of the above (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, and the like. Examples of the N-alkyl (meth)acrylamide include N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, and N-octylacrylamide. Furthermore, the above-mentioned N-alkyl (meth)acrylamide also includes (meth)acrylamide having an amino group such as dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and dimethylaminopropyl (meth)acrylamide. Examples of the N,N-dialkyl(meth)acrylamide include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl Examples include (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide, and the like.

Furthermore, the above-mentioned (meth)acrylamides include, for example, various N-hydroxyalkyl (meth)acrylamides. Examples of the N-hydroxyalkyl (meth)acrylamide include N-methylol (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, Examples include N-(4-hydroxybutyl)(meth)acrylamide and N-methyl-N-2-hydroxyethyl(meth)acrylamide.

Furthermore, the above (meth)acrylamides include, for example, various N-alkoxyalkyl (meth)acrylamides. Examples of the N-alkoxyalkyl (meth)acrylamide include N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and the like.

In addition, examples of nitrogen atom-containing monomers other than the above-mentioned heterocycle-containing monomers, N-vinyl cyclic amides, and the above-mentioned (meth)acrylamides include aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and ) Amino group-containing monomers such as dimethylaminopropyl acrylate and t-butylaminoethyl (meth)acrylate; Cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide , maleimide monomers such as N-phenylmaleimide, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-laurylitaconimide, N- - Itaconimide monomers such as cyclohexyl itaconimide, succinimides such as N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyoctamethylene succinimide, etc. Imide group-containing monomers such as system monomers; isocyanate group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate;

[1-5. Alicyclic structure-containing monomer]
Copolymerizable monomers other than carboxyl group-containing monomers, nitrogen atom-containing monomers, and hydroxyl group-containing monomers further 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)acryloyl group or a vinyl group, and has an alicyclic structure. For example, alkyl (meth)acrylates having a cycloalkyl group are included in the alicyclic structure-containing monomers. Note that the alicyclic structure-containing monomers can be used alone or in combination of two or more.

The alicyclic structure in the alicyclic structure-containing monomer is a cyclic hydrocarbon structure, and preferably has 5 or more carbon atoms, more preferably 6 to 24 carbon atoms, even more preferably 6 to 15 carbon atoms, and 6 to 10 are particularly preferred.

Examples of the alicyclic structure-containing monomer include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, Isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, HPMPA represented by the following formula (2), TMA-2 represented by the following formula (3), HCPA represented by the following formula (4), etc. Examples include (meth)acrylic monomers. In addition, in the following formula (4), the bonding position between the cyclohexyl ring connected by a line and the structural formula in parentheses is not particularly limited. Among these, isobornyl (meth)acrylate is preferred.

When the block copolymer of the present invention contains the alicyclic structure-containing monomer as a monomer component constituting the polymer, the alicyclic structure-containing monomer is Although the proportion is not particularly limited, it is preferably 10% by weight or more from the viewpoint of improving durability and obtaining high adhesion reliability. Further, the upper limit of the proportion of the alicyclic structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, from the viewpoint of obtaining an adhesive layer with appropriate flexibility. It is.

[1-6. Other copolymerizable monomers]
In addition to the above-mentioned carboxyl group-containing monomers, nitrogen atom-containing monomers, and hydroxyl group-containing monomers, examples of copolymerizable monomers in the block copolymer of the present invention include epoxy group-containing monomers [e.g., glycidyl (meth)acrylate, (meth) ) Methylglycidyl acrylate, etc.]; Sulfonic acid group-containing monomers [e.g., sodium vinyl sulfonate, etc.]; Phosphate group-containing monomers; (meth)acrylic acid esters having aromatic hydrocarbon groups [e.g., (meth)acrylic acid phenyl, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, etc.]; vinyl esters [e.g., vinyl acetate, vinyl propionate, etc.]; aromatic vinyl compounds [e.g., styrene, vinyltoluene, etc.]; olefins or dienes [for example, ethylene, propylene, butadiene, isoprene, isobutylene, etc.]; vinyl ethers [for example, vinyl alkyl ether, etc.]; vinyl chloride, and the like.

Furthermore, examples of the copolymerizable monomer in the block copolymer of the present invention include polyfunctional monomers. The polyfunctional monomer acts as a crosslinking component. Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene 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, Examples include allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Note that the polyfunctional monomers may be used alone or in combination of two or more types.

The content (proportion) of the polyfunctional monomer in all the monomer units of the block copolymer of the present invention is not particularly limited, but is 0.00% relative to the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention. The amount is preferably 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 even more preferably 0 to 0.3 parts by weight. When the content of the polyfunctional monomer is 0.5 parts by weight or less, the adhesive layer has a suitable cohesive force, and the adhesive force and level difference absorbability are easily improved, which is preferable. Note that when a crosslinking agent is used, it is not necessary to use a polyfunctional monomer, but when a crosslinking 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 0.35 parts by weight, still more preferably 0.002 to 0.3 parts by weight.

[1-7. Adhesive segment (A)]
In the block copolymer of the present invention, the adhesive segment (A) is a segment that imparts adhesiveness to the adhesive layer of the present invention. As the monomer component constituting the adhesive segment (A), the above-mentioned radically polymerizable compounds are preferred.

As a monomer component constituting the adhesive segment (A), the above-mentioned (meth)acrylic acid alkyl ester and nitrogen atom-containing monomer may be included as essential monomers from the viewpoint of cohesive force, adhesiveness, and foaming peeling resistance. preferable. As the nitrogen atom-containing monomer, a heterocycle-containing monomer is preferable, and (meth)acryloylmorpholine is more preferable from the viewpoint of cohesive force, adhesiveness, and foaming peeling resistance.

The content (ratio) of the above (meth)acrylic acid alkyl ester in all monomer units of the adhesive segment (A) (the total amount of monomer components constituting the adhesive segment (A)) is not particularly limited, but it is determined by adhesive reliability. From this point of view, it is preferably 30 to 95 parts by weight, more preferably 35 to 90 parts by weight, even more preferably 40 to 85 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the adhesive segment (A). It is.

The content (ratio) of the nitrogen atom-containing monomer (in particular, the heterocycle-containing monomer) in all monomer units of the adhesive segment (A) (total amount of monomer components constituting the adhesive segment (A)) is not particularly limited. However, from the viewpoint of cohesive force, adhesiveness, and foaming peeling resistance, it is preferably 5 to 40 parts by weight, more preferably 7 to 35 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the block copolymer of the present invention. Parts by weight, more preferably 10 to 30 parts by weight.

Moreover, it is preferable to contain a carboxyl group-containing monomer as a monomer component constituting the adhesive segment (A). By containing a carboxyl group-containing monomer as a monomer component constituting the adhesive segment (A), it becomes a reaction point with the crosslinking agent described below to form a crosslinked structure, and efficiently forms the sea-island structure described below. This is preferable because it can be done.

The content (ratio) of the carboxyl group-containing monomer to the total amount (100 parts by weight) of the monomer components constituting the adhesive segment (A) is not particularly limited, but it is determined based on the cohesive force, adhesiveness, and ease of obtaining adhesive reliability. From the viewpoint of strength and reactivity with the crosslinking agent, the amount is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and still more preferably 3 to 10 parts by weight.

[1-8. Conductive segment (B)]
In the block copolymer of the present invention, the conductive segment (B) is a segment that imparts conductivity to the adhesive layer of the present invention and has an antistatic function. As the monomer component constituting the conductive segment (B), the above-mentioned radically polymerizable compounds are preferred.

The monomer component constituting the conductive segment (B) preferably contains the above-mentioned (meth)acrylic acid alkoxyalkyl ester as an essential monomer unit from the viewpoint of easily imparting conductivity.

The content (proportion) of the above (meth)acrylic acid alkoxyalkyl ester in all monomer units of the conductive segment (B) (total amount of monomer components constituting the conductive segment (B)) is not particularly limited, but may have a sea-island structure. From the viewpoint of efficient formation, the amount is preferably 50 to 99 parts by weight, more preferably 70 to 98 parts by weight, and even more preferably The amount is 80 to 95 parts by weight.

In addition to the above-mentioned radically polymerizable compounds, the monomer components constituting the conductive segment (B) include ionic compounds having radically polymerizable substituents (hereinafter referred to as "ionic monomers" in this specification). It is preferable to include the following. The ionic monomer is a monomer component that imparts conductivity to the conductive segment (B) and imparts an antistatic function.

The ionic monomer is a monomer component that has a radically polymerizable substituent in the cation part and/or anion part (either or both) constituting the ionic monomer. Further, the ionic monomer is preferably a nonvolatile molten salt that is liquid (liquid) at a temperature of 0 to 150° C. and is transparent (ionic liquid). Note that the ionic monomers can be used alone or in combination of two or more.

When the conductive segment (B) contains an ionic monomer as a monomer component, the ionic monomer is incorporated into the molecule of the conductive segment (B), which improves compatibility in the adhesive layer of the present invention. is not impaired, making it easier to maintain transparency. In addition, it is possible to suppress bleed-out of antistatic components even under harsh conditions such as humid heat environments, making it difficult for defects such as corrosion of metal wiring to occur, and suppressing increases in surface resistance under humid heat environments. This is preferable because excellent antistatic properties can be maintained. Furthermore, precipitation, foaming, and peeling on the surface of the adhesive layer are suppressed, and durability defects such as appearance and adhesion reliability are less likely to occur. Therefore, the adhesive layer formed from the adhesive composition of the present invention containing the block copolymer of the present invention containing the conductive segment (B) has excellent antistatic properties, transparency, moist heat resistance, and low staining properties. Satisfied and useful.

The cation moiety of the ionic monomer can be used without particular limitation, but includes quaternary ammonium cations, imidazolium cations, pyridinium cations, piperidinium cations, pyrrolidinium cations, quaternary phosphonium cations, and trialkylsulfonium cations. cations, pyrrole cations, pyrazolium cations, guanidium cations, etc. Among them, quaternary ammonium cations, imidazolium cations, pyridinium cations, piperidinium cations, pyrrolidinium cations, quaternary phosphonium cations. , it is more preferred to use trialkylsulfonium cations.

Furthermore, among the anion moieties constituting the ionic monomer, the anions include SCN ^- , BF ₄ ^- , PF ₆ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , _CF3SO3- ^, ₍ _FSO2 ⁾ _2N- , ( _CF3SO2 ₎ ^2N- ^, ( _CF3SO2 ₎ _3C- ^, ^AsF6- _, ^SbF6- _, ^NbF6- _, _TaF6- ^, 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 Examples include 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 in particular, fluorine Anion components containing atoms (fluorine-containing anions) are preferred because they yield ionic compounds with low melting points and are excellent in antistatic properties. Note that, as anions, it is preferable not to use chloride ions, bromide ions, etc., since they have corrosive properties.

Examples of the radically polymerizable substituent that the ionic monomer has include a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, an allyl group, and a styryl group. Among these, a (meth)acryloyloxy group and a (meth)acryloylamino group are preferred, and a (meth)acryloyloxy group is particularly preferred.

The number of radically polymerizable substituents that the ionic monomer has is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. When the number of radically polymerizable substituents is two or more, the two or more radically polymerizable substituents may be the same or different. Note that when the number of radically polymerizable substituents is two or more, the ionic monomer can also function as a crosslinking agent that crosslinks two or more polymers.

The ionic monomer can be used without any particular limitation, but is preferably an ionic compound represented by the following general formula (A).

In the above general formula (A), X ⁺ is a cation moiety. Y ^- is an anion. Z ¹ and Z ² are the same or different and are a single bond or an alkylene group having 1 to 16 carbon atoms. A ¹ and A ² are the same or different and are radically polymerizable substituents. n ¹ is 0 or 1, n ² is 0 or 1, provided that n ¹ +n ² is 1 or 2.

The cation moiety (X ⁺ ) constituting the ionic monomer represented by the above general formula (A) includes a quaternary ammonium group, an imidazolium group, a pyridinium group, a piperidinium group, a pyrrolidinium group, a pyrrole group, and a quaternary phosphonium group. group, trialkylsulfonium group, pyrazolium group, guanidium group, etc. Among these, a quaternary ammonium group is particularly preferred because it has excellent transparency and is suitable for electronic and optical applications. Moreover, a quaternary ammonium group is suitable because it is assumed that it is unlikely to inhibit a general radical polymerization reaction and has high curability during ultraviolet (UV) curing.

When n ¹ + n ² is 1, the quaternary ammonium group includes a trimethylammonium group, a triethylammonium group, a tripropylammonium group, a methyldiethylammonium group, an ethyldimethylammonium group, a methyldipropylammonium group, and a dimethylbenzyl group. Examples include ammonium group, diethylbenzylammonium group, methyldibenzylammonium group, ethyldibenzylammonium group, dimethyloctadecylammonium group, dimethyloleylammonium group, among others, trimethylammonium group and dimethylbenzylammonium group are inexpensive industrial This is a preferred embodiment since the material is easily available.

When n ¹ + n ² is 2, the quaternary ammonium group includes dimethylammonium group, diethylammonium group, dipropylammonium group, methylethylammonium group, methylpropylammonium group, methylbenzylammonium group, ethylbenzylammonium group. Among them, dimethylammonium group and methyloleylammonium group are particularly preferred because they are easy to obtain inexpensive industrial materials. It becomes a mode.

Among the anions (sites) (Y ^- ) constituting the ionic monomer represented by the above general formula (A), the anions include SCN ^- , BF ₄ ^- , PF ₆ ^- , NO ₃ ^- , 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 ^- , ( _CF3SO2 ₎ ( _CF3CO )N- ^, ^B (CN ₎ _4- ^, _C ₍ CN) _3- ^, N ₍ CN) _2- ^, CH3OSO3- ^, _C2H5OSO3- , 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 Examples include PF ₃ ^- , and in particular, an anion component containing a fluorine atom (fluorine-containing anion) is preferable because an ionic compound with a low melting point can be obtained and it has excellent antistatic properties. Note that, as anions, it is preferable not to use chloride ions, bromide ions, etc., since they have corrosive properties.

Z ¹ and Z ² constituting the ionic monomer represented by the above general formula (A) are a single bond or an alkylene group having 1 to 16 carbon atoms. 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 group, ethylene group, trimethylene group, methylethylene group, etc., with ethylene group and trimethylene group being preferred. When n ¹ +n ² is 2, Z ¹ and Z ² may be the same or different.

A ¹ and A ² constituting the ionic monomer represented by the above general formula (A) are radically polymerizable substituents, specifically, (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, allyl group, styryl group, etc. Among these, a (meth)acryloyloxy group and a (meth)acryloylamino group are preferred, and a (meth)acryloyloxy group copolymerizable with the radically polymerizable compound is particularly preferred. When n ¹ +n ² is 2, A ¹ and A ² may be the same or different.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a quaternary ammonium group, n ¹ is 1, n ² is 0, A ¹ is a vinyl group, (meth)acryloyl Specific examples of embodiments in which it is an oxy group or a (meth)acryloylamino group include N,N,N-trialkyl-N-vinylammonium tetrafluoroborate, N,N,N-trialkyl-N-vinylammonium trifluoride, Fluoroacetate, N,N,N-trialkyl-N-vinylammonium heptafluorobutyrate, N,N,N-trialkyl-N-vinylammonium trifluoromethanesulfonate, N,N,N-trialkyl-N-vinyl Ammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-vinylammonium bis(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammonium bis(pentafluoroethanesulfonyl)imide, N, N,N-trialkyl-N-vinylammonium tris(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-vinylammonium hexafluorophosphate, N,N,N-trialkyl-N-vinylammonium ( N,N,N-trialkyl- such as trifluoromethanesulfonyl) trifluoroacetamide, N,N,N-trialkyl-N-vinylammonium dicyanamide, N,N,N-trialkyl-N-vinylammonium thiocyanate, etc. N-vinylammonium cation-containing ionic compound; N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium tetrafluoroborate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium Trifluoroacetate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium heptafluorobutyrate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium trifluoromethanesulfonate, N , N,N-trialkyl-N-(meth)acryloyloxyalkylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium bis(trifluoromethanesulfonyl)imide, N,N , N-trialkyl-N-(meth)acryloyloxyalkylammonium bis(pentafluoroethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium tris(trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium hexafluorophosphate, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N , N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium dicyanamide, N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium thiocyanate, etc. Alkyl-N-(meth)acryloyloxyalkylammonium cation-containing ionic compound; N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium tetrafluoroborate, N,N,N-trialkyl-N- (meth)acryloylaminoalkylammonium trifluoroacetate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium heptafluorobutyrate, N,N,N-trialkyl-N-(meth)acryloylamino Alkylammonium trifluoromethanesulfonate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium perfluorobutanesulfonate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium bis(trifluoromethane) sulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium bis(pentafluoroethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium tris (trifluoromethanesulfonyl)imide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium hexafluorophosphate, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium (trifluoromethane) sulfonyl) trifluoroacetamide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium dicyanamide, N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium thiocyanate, etc. Examples include ionic compounds containing N,N,N-trialkyl-N-(meth)acryloylaminoalkylammonium cations. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a quaternary ammonium group, n ¹ is 1, n ² is 0, and A ¹ is a (meth)acryloyloxy group. Preferred specific examples of certain embodiments include (meth)acryloyloxypropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxypropyldimethylbenzylammoniumbis(trifluoromethanesulfonyl)imide, and (meth)acryloyloxyethyltrimethylammonium. Bis(trifluoromethanesulfonyl)imide, (meth)acryloyloxyethyldimethylbenzylammoniumbis(trifluoromethanesulfonyl)imide,(meth)acryloyloxyethyltrimethylammoniumbis(fluorosulfonyl)imide,(meth)acryloyloxyethyldimethylbenzylammoniumbis (Fluorosulfonyl)imide, (meth)acryloyloxyethyltrimethylammonium trifluoromethanesulfonic acid, (meth)acryloyloxyethyldimethylbenzylammonium trifluoromethanesulfonic acid, and the like.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a quaternary ammonium group, n ¹ is 1, n ² is 0, and A ¹ is a (meth)acryloylamino group. Preferred specific examples of certain embodiments include (meth)acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide, (meth)acryloylaminopropyldimethylbenzylammoniumbis(trifluoromethanesulfonyl)imide, and (meth)acryloylaminopropyltrimethylammonium. Bis(fluorosulfonyl)imide, (meth)acryloylaminopropyldimethylbenzylammonium bis(fluorosulfonyl)imide, (meth)acryloylaminopropyltrimethylammonium trifluoromethanesulfonic acid, (meth)acryloylaminopropyldimethylbenzylammonium trifluoromethanesulfonic acid, etc. can be mentioned.

Among the ionic monomers represented by the above general formula (A), X ⁺ is an imidazolium group, n ¹ is 1, n ² is 0 or 1, and A ¹ and A ² are vinyl groups. Specific examples of the embodiment include 1-alkyl-3-vinylimidazolium tetrafluoroborate, 1-alkyl-3-vinylimidazolium trifluoroacetate, 1-alkyl-3-vinylimidazolium heptafluorobutyrate, 1-alkyl -3-vinylimidazolium trifluoromethanesulfonate, 1-alkyl-3-vinylimidazolium perfluorobutanesulfonate, 1-alkyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium bis (pentafluoroethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium tris(trifluoromethanesulfonyl)imide, 1-alkyl-3-vinylimidazolium hexafluorophosphate, 1-alkyl-3-vinylimidazolium (trifluoromethane) 1-alkyl-3-vinylimidazolium cation-containing ionic compounds such as sulfonyl) trifluoroacetamide, 1-alkyl-3-vinylimidazolium dicyanamide, 1-alkyl-3-vinylimidazolium thiocyanate; 1,2- Dialkyl-3-vinylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-vinylimidazolium dicyanamide, 1, 1,2-Dialkyl-3-vinylimidazolium cation-containing ionic compounds such as 2-dialkyl-3-vinylimidazolium thiocyanate; 2-alkyl-1,3-divinylimidazolium bis(fluorosulfonyl)imide, 2-alkyl 2-alkyl- such as -1,3-divinylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-divinylimidazolium dicyanamide, 2-alkyl-1,3-divinylimidazolium thiocyanate, etc. 1,3-Divinylimidazolium cation-containing ionic compound; 1-vinylimidazolium bis(fluorosulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium dicyanamide, 1-vinyl Examples include ionic compounds containing 1-vinylimidazolium cations such as imidazolium thiocyanate.

Among the ionic monomers represented by the above general formula (A), X ⁺ is an imidazolium group, n ¹ is 1, n ² is 0 or 1, and A ¹ and A ² are (meth)acryloyl Specific examples of oxy groups include 1-alkyl-3-(meth)acryloyloxyalkylimidazolium tetrafluoroborate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium trifluoroacetate, 1-alkyl -3-(meth)acryloyloxyalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium perfluorobutane Sulfonate, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl -3-(meth)acryloyloxyalkylimidazolium tris(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium hexafluorophosphate, 1-alkyl-3-(meth)acryloyloxyalkylimidazo 1-alkyl-3 such as trifluoroacetamide, 1-alkyl-3-(meth)acryloyloxyalkylimidazolium dicyanamide, and 1-alkyl-3-(meth)acryloyloxyalkylimidazolium thiocyanate. -(Meth)acryloyloxyalkylimidazolium cation-containing ionic compound; 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyl Oxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium dicyanamide, 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium thiocyanate, etc. 1,2-dialkyl-3-(meth)acryloyloxyalkylimidazolium cation-containing ionic compound; 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl -1,3-di(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium dicyanamide, 2-alkyl-1,3 - Ionic compounds containing 2-alkyl-1,3-di(meth)acryloyloxyalkylimidazolium cations such as di(meth)acryloyloxyimidazolium thiocyanate; 1-(meth)acryloyloxyalkylimidazolium bis(fluorosulfonyl) 1-( such as imide, 1-(meth)acryloyloxyalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(meth)acryloyloxyalkylimidazolium dicyanamide, 1-(meth)acryloyloxyalkylimidazolium thiocyanate, etc. Examples include ionic compounds containing meth)acryloyloxyalkylimidazolium cations. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is an imidazolium group, n ¹ is 1, n ² is 0 or 1, and A ¹ and A ² are (meth)acryloyl Specific examples of amino groups include 1-alkyl-3-(meth)acryloylaminoalkylimidazolium tetrafluoroborate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium trifluoroacetate, 1-alkyl -3-(meth)acryloylaminoalkylimidazolium heptafluorobutyrate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium trifluoromethanesulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium perfluorobutane Sulfonate, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium bis(pentafluoroethanesulfonyl)imide, 1-alkyl -3-(meth)acryloylaminoalkylimidazolium tris(trifluoromethanesulfonyl)imide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium hexafluorophosphate, 1-alkyl-3-(meth)acryloylaminoalkylimidazo 1-alkyl-3 such as trifluoroacetamide (trifluoromethanesulfonyl), 1-alkyl-3-(meth)acryloylaminoalkylimidazolium dicyanamide, 1-alkyl-3-(meth)acryloylaminoalkylimidazolium thiocyanate, etc. -(Meth)acryloylaminoalkylimidazolium cation-containing ionic compound; 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 1,2-dialkyl-3-(meth)acryloyl Aminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium dicyanamide, 1,2-dialkyl-3-(meth)acryloylaminoalkylimidazolium thiocyanate, etc. 1,2-Dialkyl-3-(meth)acryloylaminoalkylimidazolium cation-containing ionic compound; 2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl)imide, 2-alkyl -1,3-di(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium dicyanamide, 2-alkyl-1,3 -2-alkyl-1,3-di(meth)acryloylaminoalkylimidazolium cation-containing ionic compounds such as di(meth)acryloylaminoimidazolium thiocyanate; 1-(meth)acryloylaminoalkylimidazolium bis(fluorosulfonyl) 1-( such as imide, 1-(meth)acryloylaminoalkylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(meth)acryloylaminoalkylimidazolium dicyanamide, 1-(meth)acryloylaminoalkylimidazolium thiocyanate, etc. Examples include ionic compounds containing meth)acryloylaminoalkylimidazolium cations. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a pyridinium group, n ¹ is 1, n ² is 0, A ¹ is a vinyl group, a (meth)acryloyloxy group, or (meth)acryloylamino group, 1-vinylpyridinium bis(fluorosulfonyl)imide, 1-vinylpyridiniumbis(trifluoromethanesulfonyl)imide, 1-vinylpyridiniumdicyanamide, 1-vinyl 1-vinylpyridinium cation-containing ionic compounds such as pyridinium thiocyanate; 1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 1- 1-(meth)acryloyloxyalkylpyridinium cation-containing ionic compounds such as (meth)acryloyloxyalkylpyridinium dicyanamide, 1-(meth)acryloyloxyalkylpyridinium thiocyanate; 1-(meth)acryloylaminoalkylpyridinium bis( 1- of fluorosulfonyl)imide, 1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 1-(meth)acryloylaminoalkylpyridinium dicyanamide, 1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. (Meth)acryloylaminoalkylpyridinium cation-containing ionic compound; 2-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 2-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1- 2-alkyl-1-vinylpyridinium cation-containing ionic compounds such as vinylpyridinium dicyanamide, 2-alkyl-1-vinylpyridinium thiocyanate; 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl) imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 2-alkyl-1-(meth)acryloyl Ionic compounds containing 2-alkyl-1-(meth)acryloyloxyalkylpyridinium cations such as oxyalkylpyridinium thiocyanate; 2-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl)imide, 2-alkyl- 1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 2-alkyl-1-(meth)acryloylaminoalkylpyridinium thiocyanate, etc. 2-alkyl-1-(meth)acryloylaminoalkylpyridinium cation-containing ionic compound; 3-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-vinylpyridinium bis(trifluoromethanesulfonyl)imide , 3-alkyl-1-vinylpyridinium dicyanamide, 3-alkyl-1-vinylpyridinium thiocyanate, and other 3-alkyl-1-vinylpyridinium cation-containing ionic compounds; 3-alkyl-1-(meth)acryloyloxy Alkylpyridinium bis(fluorosulfonyl)imide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 3-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanamide, 3-alkyl -3-alkyl-1-(meth)acryloyloxyalkylpyridinium cation-containing ionic compounds such as 1-(meth)acryloyloxyalkylpyridinium thiocyanate; 3-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(fluorosulfonyl) imide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 3-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 3-alkyl-1-(meth)acryloyl Ionic compounds containing 3-alkyl-1-(meth)acryloylaminoalkylpyridinium cations such as aminoalkylpyridinium thiocyanate; 4-alkyl-1-vinylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-vinylpyridinium bis 4-alkyl-1-vinylpyridinium cation-containing ionic compounds such as (trifluoromethanesulfonyl)imide, 4-alkyl-1-vinylpyridinium dicyanamide, 4-alkyl-1-vinylpyridinium thiocyanate; 4-alkyl-1- (meth)acryloyloxyalkylpyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium bis(trifluoromethanesulfonyl)imide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium dicyanide amide, 4-alkyl-1-(meth)acryloyloxyalkylpyridinium cation-containing ionic compounds such as 4-alkyl-1-(meth)acryloyloxyalkylpyridinium thiocyanate; 4-alkyl-1-(meth)acryloylaminoalkyl Pyridinium bis(fluorosulfonyl)imide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium bis(trifluoromethanesulfonyl)imide, 4-alkyl-1-(meth)acryloylaminoalkylpyridinium dicyanamide, 4-alkyl- Examples include ionic compounds containing 4-alkyl-1-(meth)acryloylaminoalkylpyridinium cations such as 1-(meth)acryloylaminoalkylpyridinium thiocyanate. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a piperidinium group, n ¹ is 1, n ² is 0, A ¹ is a vinyl group, a (meth)acryloyloxy group, or (meth)acryloylamino group, 1-alkyl-1-vinylalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpiperidinium bis(trifluoromethanesulfonyl) ) 1-alkyl-1-vinylalkylpiperidinium cation-containing ionic compounds such as imide, 1-alkyl-1-vinylalkylpiperidinium dicyanamide, 1-alkyl-1-vinylalkylpiperidinium thiocyanate; 1 -Alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-alkyl-1- Ionic compounds containing 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium cations such as (meth)acryloyloxyalkylpiperidinium dicyanamide and 1-alkyl-1-(meth)acryloyloxyalkylpiperidinium thiocyanate. Compound; 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-alkyl 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium cations such as -1-(meth)acryloylaminoalkylpiperidinium dicyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpiperidinium thiocyanate, etc. Examples include ionic compounds contained therein. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a pyrrolidinium group, n ¹ is 1, n ² is 0, A ¹ is a vinyl group, a (meth)acryloyloxy group, or (meth)acryloylamino group, 1-alkyl-1-vinylalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-vinylalkylpyrrolidinium bis(trifluoromethanesulfonyl) ) 1-alkyl-1-vinylalkylpyrrolidinium cation-containing ionic compounds such as imide, 1-alkyl-1-vinylalkylpyrrolidinium dicyanamide, 1-alkyl-1-vinylalkylpyrrolidinium thiocyanate; 1-Alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-alkyl-1 -Containing 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium cations such as (meth)acryloyloxyalkylpyrrolidinium dicyanamide, 1-alkyl-1-(meth)acryloyloxyalkylpyrrolidinium thiocyanate, etc. Ionic compound; 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(fluorosulfonyl)imide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1 -1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium dicyanamide, 1-alkyl-1-(meth)acryloylaminoalkylpyrrolidinium thiocyanate, etc. Examples include ionic compounds containing nium cations. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a trialkylsulfonium group, n ¹ is 1, n ² is 0, A ¹ is a vinyl group, (meth)acryloyloxy Specific examples of embodiments in which the group is a group or a (meth)acryloylamino group include dialkyl(vinyl)sulfonium bis(fluorosulfonyl)imide, dialkyl(vinyl)sulfoniumbis(trifluoromethanesulfonyl)imide, dialkyl(vinyl)sulfonium dicyanide. Ionic compounds containing dialkyl(vinyl)sulfonium cations such as amido, dialkyl(vinyl)sulfonium thiocyanate, etc.; dialkyl((meth)acryloyloxyalkyl)sulfonium bis(fluorosulfonyl)imide, dialkyl((meth)acryloyloxyalkyl)sulfonium bis (trifluoromethanesulfonyl)imide, dialkyl((meth)acryloyloxyalkyl)sulfonium dicyanamide, dialkyl((meth)acryloyloxyalkyl)sulfonium thiocyanate, and other dialkyl((meth)acryloyloxyalkyl)sulfonium cation-containing ionic compounds; Dialkyl ((meth)acryloylaminoalkyl)sulfonium bis(fluorosulfonyl)imide, dialkyl((meth)acryloylaminoalkyl)sulfonium bis(trifluoromethanesulfonyl)imide, dialkyl((meth)acryloylaminoalkyl)sulfonium dicyanamide, dialkyl Examples include dialkyl((meth)acryloylaminoalkyl)sulfonium cation-containing ionic compounds such as ((meth)acryloylaminoalkyl)sulfonium thiocyanate. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

Among the ionic monomers represented by the above general formula (A), X ⁺ is a quaternary phosphonium group, n ¹ is 1, n ² is 0, A ¹ is a vinyl group, (meth)acryloyl Specific examples of embodiments in which it is an oxy group or a (meth)acryloylamino group include trialkyl(vinyl)phosphonium bis(fluorosulfonyl)imide, trialkyl(vinyl)phosphoniumbis(trifluoromethanesulfonyl)imide, and trialkyl(vinyl)phosphoniumbis(trifluoromethanesulfonyl)imide. ) Ionic compounds containing trialkyl(vinyl)phosphonium cations such as phosphonium dicyanamide, trialkyl(vinyl)phosphonium thiocyanate; trialkyl((meth)acryloyloxyalkyl)phosphonium bis(fluorosulfonyl)imide, trialkyl( Trialkyl ((meth)acryloyloxyalkyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl((meth)acryloyloxyalkyl)phosphonium dicyanamide, trialkyl((meth)acryloyloxyalkyl)phosphonium thiocyanate, etc. Ionic compounds containing acryloyloxyalkyl)phosphonium cations; trialkyl ((meth)acryloylaminoalkyl)phosphonium bis(fluorosulfonyl)imide, trialkyl((meth)acryloylaminoalkyl)phosphonium bis(trifluoromethanesulfonyl)imide, trialkyl Examples include ionic compounds containing trialkyl((meth)acryloylaminoalkyl)phosphonium cations such as ((meth)acryloylaminoalkyl)phosphonium dicyanamide and trialkyl((meth)acryloylaminoalkyl)phosphonium thiocyanate. The alkyl substituent is preferably an alkyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.

The content (ratio) of the ionic monomer in all the monomer units of the conductive segment (B) (the total amount of monomer components constituting the conductive segment (B)) is not particularly limited, but it is important that the adhesive layer of the present invention is excellent. From the viewpoint of imparting an antistatic function, the amount is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, and more preferably 3 to 15 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the conductive segment (B). Preferably it is 5 to 10 parts by weight.

The content (ratio) of the ionic monomer in all monomer units (total amount of monomer components constituting the block copolymer) of the block copolymer of the present invention is not particularly limited, but the content (proportion) of the ionic monomer in the total monomer units of the block copolymer of the present invention is not particularly limited, but the content (ratio) of the ionic monomer in the total monomer units of the block copolymer of the present invention is not particularly limited. In terms of the ability to add, it is preferably 0.01 part by weight or more, more preferably 0.05 part by weight or more, even more preferably 0.1 part by weight or more, 0. .5 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, 3.0 parts by weight or more, 4.0 parts by weight or more, or 5.0 parts by weight or more. Further, the content (proportion) of the ionic monomer is not particularly limited, but from the viewpoint of easily ensuring durability such as transparency, appearance, and adhesion reliability in the adhesive layer of the present invention, the content (ratio) of the ionic monomer is Preferably 50 parts by weight or less, more preferably 40 parts by weight or less, even more preferably 30 parts by weight or less, 25 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less, based on 100 parts by weight of the copolymer block copolymer. You can stay there.

[1-9. Preparation method of block copolymer of the present invention]
The block copolymer of the present invention can be produced by the living radical polymerization method of the monomer components described above. Living radical polymerization maintains the simplicity and versatility of conventional radical polymerization, while preventing termination reactions and chain transfer, and allowing growth without deactivation of growing terminals, allowing precise control and uniformity of molecular weight distribution. This is preferable because it is easy to produce a polymer having a specific composition.

In the living radical polymerization method, the adhesive segment (A) may be produced first, and the monomer of the conductive segment (B) may be polymerized to the adhesive segment (A); the conductive segment (B) may be produced first. The monomer of the adhesive segment (A) may be polymerized onto the conductive segment (B).

When the block copolymer of the present invention is an ABA type triblock copolymer, from the viewpoint of ease of production, it is preferable to produce the A segment first and then polymerize the monomer of the B segment onto the A segment.

For the living radical polymerization method, any known method can be used without particular limitation, and depending on the method of stabilizing the polymer growth terminal, there may be a method using a transition metal catalyst (ATRP method); a sulfur-based reversible addition method; There are methods such as a method using a cleavage chain transfer agent (RAFT agent) (RAFT method) and a method using an organic tellurium compound (TERP method). Among these methods, it is preferable to use the RAFT method from the viewpoints of the diversity of monomers that can be used, the ease of controlling the molecular weight, and the fact that no metal remains in the adhesive composition.

For the RAFT method, any known method can be used without particular limitation. For example, step 1 (first RAFT polymerization ), and Step 2 (Step 2) in which a monomer component different from the monomer composition in Step 1 is further added and polymerized to the first segment obtained in Step 1 to add the second segment to the first segment. 2 RAFT polymerization). After the second RAFT polymerization, third, fourth, etc. RAFT polymerizations may be performed in the same manner as the second RAFT polymerization, and third, fourth, etc. segments may be further added.

The steps 1 and 2 can be carried out by a known and commonly used method, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method using heat or active energy ray irradiation (thermal polymerization method, active energy ray polymerization). method), etc. Among these, the solution polymerization method is preferred in terms of transparency, water resistance, cost, and the like. Note that the polymerization is preferably carried out while avoiding contact with oxygen in order to suppress polymerization inhibition caused by oxygen. For example, it is preferable to carry out the polymerization under a nitrogen atmosphere.

When the block copolymer of the present invention is an ABA type triblock copolymer, it is preferable to prepare an A segment in step 1, and add a B segment to the obtained A segment in step 2. In this case, the A segment is preferably an adhesive segment (A), and the B segment is preferably a conductive segment (B).

As the RAFT agent, any known agent can be used without particular limitation. For example, a compound represented by the following formula (a), formula (b), or formula (c) (trithiocarbonate, dithioester, dithiocarbonates) are preferred.

In formula (a), formula (b), or formula (c) [formulas (a) to (c)], R ^1a and R ^1b are the same or different and represent a hydrogen atom, a hydrocarbon group, or a cyano group. show. R ^1c represents a hydrocarbon group which may have a cyano group. Examples of the hydrocarbon groups as R ^1a , R ^1b , and R ^1c include hydrocarbon groups having 1 to 20 carbon atoms (linear, branched, or cyclic saturated or unsaturated hydrocarbon groups, etc.). Among them, hydrocarbon groups having 1 to 12 carbon atoms are preferred. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, dodecyl group, octadecyl group, etc. straight chain, branched, or cyclic alkyl group having 1 to 18 carbon atoms (preferably 1 to 12 carbon atoms); aryl group having 6 to 12 carbon atoms such as phenyl group; total carbon atoms such as benzyl group and phenethyl group Examples include 7 to 10 arylalkyl groups. Examples of the hydrocarbon group having a cyano group as R ^1c include a group in which 1 to 3 of the hydrogen atoms of the above-mentioned hydrocarbon group are substituted with a cyano group.

In formulas (a) to (c), R ² represents a hydrocarbon group or a group in which some of the hydrogen atoms of the hydrocarbon group are substituted with carboxyl groups (eg, carboxyalkyl group). Examples of the above-mentioned hydrocarbon groups include hydrocarbon groups having 1 to 20 carbon atoms (linear, branched, or cyclic saturated or unsaturated hydrocarbon groups, etc.); Hydrocarbon groups are preferred. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, dodecyl group, octadecyl group, etc. Examples include linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms (preferably 1 to 12 carbon atoms); arylalkyl groups having 7 to 10 carbon atoms in total, such as benzyl and phenethyl groups.

In the RAFT method, the raw material monomer reacts to be inserted between the sulfur atom in the RAFT agent shown in formulas (a) to (c) and the methylene group adjacent to the sulfur atom, and polymerization proceeds.

Many of the above RAFT agents are commercially available. Those that are not commercially available can be easily synthesized by known or conventional methods. In addition, in this invention, RAFT agent can also be used individually by 1 type, and can also be used in combination of 2 or more types.

Examples of RAFT agents include trithiocarbonates such as dibenzyltrithiocarbonate and S-cyanomethyl-S-dodecyltrithiocarbonate; cyanoethyl dithiopropionate, benzyl dithiopropionate, benzyl dithiobenzoate, acetoxyethyl dithiobenzoate, etc. Dithioesters; O-ethyl-S-(1-phenylethyl)dithiocarbonate, O-ethyl-S-(2-propoxyethyl)dithiocarbonate, O-ethyl-S-(1-cyano-1-methylethyl) Examples include dithiocarbonates such as dithiocarbonate, among which trithiocarbonates are preferred, and trithiocarbonates having a bilaterally symmetrical structure in formula (a) are more preferred, particularly dibenzyltrithiocarbonate, bis{4 -[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl}trithiocarbonate is preferred.

The step 1 can be performed by polymerizing monomer components in the presence of a RAFT agent. In step 1, the amount of the RAFT agent used is usually 0.05 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total amount of monomer components. With such an amount used, it is easy to control the reaction, and it is also easy to control the weight average molecular weight of the obtained segment.
The step 2 can be carried out by adding a monomer component to the polymerization reaction mixture obtained in the step 1 and further polymerizing the mixture.

The RAFT method is preferably carried out in the presence of a polymerization initiator. Examples of the polymerization initiator include ordinary organic polymerization initiators, and specific examples include peroxides and azo compounds. Among these, azo compounds are preferred. One kind of polymerization initiator can be used alone or two or more kinds can be used.

Examples of peroxide-based polymerization initiators include benzoyl peroxide and tert-butyl permaleate.
Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropyl propionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile) , 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis( N,N'-dimethyleneisobutyramidine), 2,2'-azobis(isobutyramide) dihydrate, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-cyanopropanol), Examples include dimethyl-2,2'-azobis(2-methylpropionate) and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

The amount of the polymerization initiator used is usually 0.001 to 2 parts by weight, preferably 0.002 to 1 part by weight, based on 100 parts by weight of the total amount of monomer components. With such a usage amount, it is easy to control the weight average molecular weight of the obtained segment.

Although the RAFT method may be bulk polymerization without using a polymerization solvent, it is preferable to use a polymerization solvent. Examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, cyclohexane, cycloheptane, and cyclopentane; Alicyclic hydrocarbons such as octane; halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole , phenylethyl ether, diphenyl ether, etc.; esters such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone; N,N-dimethylformamide, N , N-dimethylacetamide, and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethyl sulfoxide and sulfolane. The polymerization solvent can be used alone or in combination of two or more.

The amount of the polymerization solvent used is not particularly limited, and for example, it is preferably 0.01 mL or more, more preferably 0.05 mL or more, still more preferably 0.1 mL or more, and 50 mL or less per 1 g of monomer component. It is preferably 1 mL or less, more preferably 1 mL or less.

The reaction temperature in the RAFT method is usually 60 to 120°C, preferably 70 to 110°C, and is usually carried out under an inert gas atmosphere such as nitrogen gas. This reaction can be carried out under normal pressure, increased pressure or reduced pressure, and is usually carried out under normal pressure. Further, the reaction time is usually 1 to 20 hours, preferably 2 to 14 hours.

The polymerization reaction conditions of the RAFT method described above can be applied to Step 1 and Step 2, respectively.

After the completion of the polymerization reaction, the solvent used, residual monomers, etc. can be removed from the obtained reaction mixture by ordinary separation and purification means, and the target block copolymer of the present invention can be separated.

When the adhesive segment (A) or the conductive segment (B) of the block copolymer of the present invention is prepared in step 1, the weight average molecular weight (Mw) of the adhesive segment (A) or the conductive segment (B) is: Although not particularly limited, it is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and still more preferably 100,000 to 300,000. It is suitable for the Mw of the adhesive segment (A) or the conductive segment (B) to be within this range for the above-mentioned effects of the present invention.
When the block copolymer of the present invention has two or more adhesive segments (A) or conductive segments (B), the above Mw is the sum of the adhesive segments (A) or conductive segments (B).

The weight average molecular weight (Mw) of the block copolymer of the present invention is not particularly limited, but is preferably 200,000 (200,000) or more, more preferably 300,000 to 5,000,000, even more preferably 400,000, 000 to 2,500,000. It is suitable for the Mw of the block copolymer of the present invention to be within this range for the above-mentioned effects of the present invention.

The molecular weight distribution (Mw/Mn) of the block copolymer of the present invention is not particularly limited, but is preferably larger than 1, more preferably 1.5 or more, still more preferably 2 or more, and particularly preferably 2.5 or more. It is preferably 5 or less, more preferably 4.5 or less, even more preferably 4 or less, particularly preferably 3.5 or less.

Note that the above weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are measured by the GPC method.

The content of the adhesive segment (A) in all monomer units (the total amount of monomer components constituting the block copolymer) of the block copolymer of the present invention is not particularly limited, but is preferably 1 to 50% by weight, more preferably The amount is 3 to 45% by weight, more preferably 5 to 40% by weight. A structure in which the content of the adhesive segment (A) is 1% by weight or more is suitable in that excellent adhesiveness can be imparted to the adhesive layer of the present invention. Further, the configuration in which the content of the adhesive segment (A) is 50% by weight or less is such that the adhesive composition of the present invention can form a sea-island structure in which a continuous phase and a discontinuous phase are separated. , is suitable.

The content of the conductive segment (B) in all monomer units (the total amount of monomer components constituting the block copolymer) of the block copolymer of the present invention is not particularly limited, but is preferably 50 to 99% by weight, more preferably It is 55 to 97% by weight, more preferably 60 to 95% by weight. The configuration in which the content of the conductive segment (B) is 50% by weight or more is preferable because the pressure-sensitive adhesive composition of the present invention can form a sea-island structure in which a continuous phase and a discontinuous phase are separated. It is. Further, a configuration in which the content of the conductive segment (B) is 99% by weight or less is suitable in that excellent adhesiveness can be imparted to the adhesive layer of the present invention.

In the block copolymer of the present invention, the weight ratio of the conductive segment (B) to the adhesive segment (A) (conductive segment (B)/adhesive segment (A)) is from 50/50 to 99/1. It is preferable that there be. The configuration in which the weight ratio is 50/50 or more is preferable in that the pressure-sensitive adhesive composition of the present invention can form a sea-island structure in which a continuous phase and a discontinuous phase are separated, and more preferably 55/45. The ratio is more preferably 60/40 or more, particularly preferably 65/35 or more. Further, the configuration in which the weight ratio is 99/1 or less is suitable in that excellent adhesiveness can be imparted to the adhesive layer of the present invention, more preferably 97/3 or less, and even more preferably 95/3 or less. /5 or less, particularly preferably 93/7 or less.

The content of each segment and their ratio can be calculated from the amount of monomer components used in each step of the RAFT method, and can be controlled by the charging ratio of monomers and the polymerization rate of each monomer when forming each segment. can do.

[1-10. Antistatic agent]
The adhesive composition of the present invention may contain an antistatic agent to the extent that the effects of the present invention are not impaired.
Examples of the antistatic agent include materials that can impart antistatic properties, such as ionic compounds, ionic surfactants, conductive polymers, and conductive fine particles. Among these, ionic compounds are preferred from the viewpoint of compatibility with the block copolymer of the present invention and transparency of the adhesive layer.

As the ionic compound, an inorganic cation anion salt and/or an organic cation anion salt can be preferably used, and it is a particularly preferable embodiment to use an inorganic cation anion salt. Ionic compounds containing inorganic cations (inorganic cation anion salts) are more preferable than organic cation anion salts because they can suppress a decrease in adhesiveness (anchoring force) of the pressure-sensitive adhesive layer when used. In the present invention, the term "inorganic cation anion salt" generally refers to an alkali metal salt formed from an alkali metal cation and an anion, and the alkali metal salt refers to an alkali metal organic salt and an inorganic salt. Can be used. Furthermore, the term "organic cation anion salt" as used in the present invention refers to an organic salt in which the cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. It's okay. "Organic cation anion salts" are also referred to as ionic liquids and ionic solids. Further, as the anion component constituting the ionic compound, it is preferable to use a fluorine-containing anion from the viewpoint of antistatic function.

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

The anion part of the alkali metal salt may be composed of an organic substance or an inorganic substance. Examples of the anion moiety constituting ^the organic salt include 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- , and 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 (FSO ₂ ) ₂ N ^- The following expressions are used. In particular, an anion moiety containing a fluorine atom is preferably used because an ionic compound with good ionic dissociation properties can be obtained. The anion parts constituting the inorganic salt include 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. are used. Among the anions containing a fluorine atom, fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable. In particular, bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability under humidified and heated environments.

Examples of organic salts of alkali metals include sodium acetate, sodium alginate, sodium ligninsulfonate, 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, Examples include LiO ₃ S(CF ₂ ) ₃ SO ₃ K, among which 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. are preferred, and 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 the like are more preferred, and lithium bis(trifluoromethanesulfonyl) imide and lithium bis(fluorosulfonyl) imide are particularly preferred.

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

An organic cation anion salt is composed of a cation component and an anion component, and the cation component is composed of an organic substance. Specifically, the cation components include pyridinium cations, piperidinium cations, pyrrolidinium cations, cations having a pyrroline skeleton, cations having a pyrrole skeleton, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, Examples include pyrazolium cations, pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations, and tetraalkylphosphonium cations.

Examples of anion components include Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- ^, _CH3SO3- ^, _CF3SO3- _, ( _CF3SO2 ⁾ _3C- ^, _AsF6- ^, ^SbF6- _, _NbF6- ^, _TaF6- ^, ( _CN ) _2N- ^, _C4F ₉ SO ₃ ^- , C ₃ F ₇ COO ^- , ((CF ₃ SO ₂ ) (CF ₃ CO) N ^- , ^- O ₃ S (CF ₂ ) ₃ SO ₃ ^- , and the following general formulas (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 (FSO ₂ ) ₂ N ^- The following expressions are used. Among these, anions containing a fluorine atom (fluorine-containing anions) are particularly preferably used because an ionic compound with good ionic dissociation properties can be obtained. Among the anions containing a fluorine atom, fluorine-containing imide anions are preferable, and among these, bis(trifluoromethanesulfonyl)imide anions and bis(fluorosulfonyl)imide anions are preferable. In particular, bis(fluorosulfonyl)imide anion is preferable because it can impart excellent antistatic properties even when added in a relatively small amount, maintains adhesive properties, and is advantageous for durability under humidified and heated environments.

In addition to the above-mentioned inorganic cation anion salts (alkali metal salts) and organic cation anion salts, examples of ionic compounds include inorganic compounds such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. Salt is an example. These ionic compounds can be used alone or in combination.

Examples of ionic surfactants include cationic surfactants (for example, quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.) and anionic surfactants (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.) , zwitterionic (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic type (polyhydric alcohol derivatives, β-cyclodextrin inclusion compounds, sorbitan fatty acid monoesters/diesters, polyalkylene oxide derivatives, amines) oxides, etc.).

Examples of the conductive polymer include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers, among which polyaniline, polythiophene, etc. are preferably used. Particularly preferred is polythiophene.

Examples of the conductive fine particles include metal oxides such as tin oxide, antimony oxide, indium oxide, and zinc oxide. Among these, tin oxide type is preferred. Examples of tin oxide-based compounds 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, and titanium oxide. Examples include tin oxide complexes. The average particle size of the fine particles is about 1 to 100 nm, preferably 2 to 50 nm.

Furthermore, antistatic agents other than those mentioned above include acetylene black, Ketjen black, natural graphite, artificial graphite, titanium black, cationic type (quaternary ammonium salts, etc.), amphoteric type (betaine compounds, etc.), anionic type (sulfonic acid homopolymers of monomers with nonionic (glycerin, etc.) ion-conductive groups or copolymers of the above monomers with other monomers, acrylates or methacrylates with quaternary ammonium bases Examples include permanent antistatic agents such as polymers having ionic conductivity such as polymers having a derived site; and permanent antistatic agents of a type in which a hydrophilic polymer such as a polyethylene methacrylate copolymer is alloyed with an acrylic resin or the like.

When the adhesive composition of the present invention contains the antistatic agent, its content is not particularly limited, but from the viewpoint of ensuring durability such as transparency, appearance, contact reliability, etc. of the adhesive layer of the present invention. Based on 100 parts by weight of the total amount of the block copolymer of the present invention, the amount is preferably 1 part by weight or less, more preferably 0.5 part by weight or less, 0.4 part by weight or less, 0.3 part by weight or less, or 0. It may be 2 parts by weight or less. When the adhesive composition of the present invention contains the antistatic agent, the lower limit of the content is not particularly limited, but is 0.01 part by weight or more based on 100 parts by weight of the block copolymer of the present invention; Alternatively, it may be 0.05 parts by weight or more.

[1-11. Additive]
The adhesive composition of the present invention may optionally include a crosslinking agent, a crosslinking accelerator, a silane coupling agent, a tackifier resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, etc.), an antiaging agent, Known additives such as fillers, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, rust preventives, etc. may enhance the properties of the present invention. It may be included as long as it does not cause any damage. Note that such additives may be used alone or in combination of two or more.

When the adhesive composition of the present invention contains a crosslinking agent, the block copolymer of the present invention is crosslinked to increase the gel fraction, and the foaming and peeling resistance is easily improved. Furthermore, it becomes easier to efficiently form a sea-island structure, which will be described later. For example, the block copolymer of the present invention can be crosslinked to easily increase the control of the gel fraction, making it easier to improve foam peeling resistance.

Examples of the crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal Examples include salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, and amine crosslinking agents. Among these, when the adhesive composition of the present invention is an adhesive layer containing an acrylic polymer as a base polymer, isocyanate-based crosslinking agents and epoxy-based crosslinking agents are preferred, and more preferred from the viewpoint of improving foaming peeling resistance. is an isocyanate-based crosslinking agent. In addition, a crosslinking agent may be used individually or in combination of 2 or more types.

Examples of the isocyanate crosslinking agent (polyfunctional isocyanate compound) include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate; , cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and other alicyclic polyisocyanates; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and aromatic polyisocyanates such as xylylene diisocyanate. Examples of the isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct [manufactured by Japan Polyurethane Industries Co., Ltd., trade name "Coronate L"], trimethylolpropane/hexamethylene diisocyanate adduct [Japan Polyurethane Commercially available products such as Kogyo Co., Ltd., trade name "Coronate HL"] and trimethylolpropane/xylylene diisocyanate adduct [Mitsui Chemicals, Ltd., trade name "Takenate D-110N"] can also be mentioned.

Examples of the epoxy crosslinking agent (polyfunctional epoxy compound) include N,N,N',N'-tetraglycidyl-m-xylene diamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl (aminomethyl) 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, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2) -hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. Examples of the epoxy crosslinking agent include commercially available products such as "Tetrad C" manufactured by Mitsubishi Gas Chemical Co., Ltd.

The content of the crosslinking agent in the adhesive composition of the present invention is not particularly limited, but is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the block copolymer of the present invention. 01 to 5 parts by weight. It is preferable that the content of the crosslinking agent is 0.001 parts by weight or more, since the foaming peeling resistance tends to improve. On the other hand, when the content of the crosslinking agent is 10 parts by weight or less, the adhesive layer has appropriate flexibility and the adhesive strength is easily improved, which is preferable.

It is preferable that the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent because it facilitates obtaining excellent adhesion to glass (especially excellent adhesion reliability to glass at high temperature and high humidity). Examples of the silane coupling agent include, but are not limited to, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-aminopropyltrimethoxysilane. etc. Among these, γ-glycidoxypropyltrimethoxysilane is preferred. Furthermore, examples of the silane coupling agent include commercially available products such as the trade name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.). Note that the silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent in the adhesive composition of the present invention is not particularly limited, but for example, when the adhesive composition of the present invention is an adhesive layer containing an acrylic polymer as a base polymer, glass From the viewpoint of improving adhesion reliability to the block copolymer of the present invention, the amount is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight, based on 100 parts by weight of the block copolymer of the present invention.

When the adhesive composition of the present invention contains a coloring agent (pigment, dye, etc.), it prevents reflection from metal wiring and metal oxides such as ITO, and also contributes to preventing RGB color mixing and improving contrast. This is preferable in that it can be done.

The colorant may be a dye or a pigment as long as it can be dissolved or dispersed in the pressure-sensitive adhesive composition of the present invention. Dyes are preferred because they can achieve low haze even when added in small amounts, and are easy to distribute uniformly without settling unlike pigments. Pigments are also preferred because they provide high color development even when added in small amounts. If a pigment is used as a coloring agent, it is preferably one with low or no electrical conductivity. Moreover, when using a dye, it is preferable to use it together with an antioxidant or the like.

Examples of pigments include "9050BLACK" and "UVBK-0001" manufactured by Tokushiki, carbon black, titanium black, and the like. Examples of the dye include "VALIFAST BLACK 3810" and "NUBIAN Black PA-2802" manufactured by Orient Chemical Industry Co., Ltd.

The content of the colorant in the pressure-sensitive adhesive composition of the present invention is, for example, about 0.01 to 20 parts by weight based on 100 parts by weight of the block copolymer of the present invention. It may be set appropriately depending on the color tone, light transmittance, etc. The colorant may be added to the composition as a solution or dispersion dissolved or dispersed in a suitable solvent.

[1-12. Sea-island structure]
The pressure-sensitive adhesive composition of the present invention has a sea-island structure separated into a continuous phase and a discontinuous phase. The configuration in which the pressure-sensitive adhesive composition of the present invention has a sea-island structure efficiently forms a path for imparting conductivity in the continuous phase, and the pressure-sensitive adhesive layer of the present invention exhibits low surface resistivity. , is preferable in that it has excellent antistatic performance.

The above-mentioned "sea-island structure" refers to a structure in which a discontinuous phase (island part) made of at least one of two or more polymers is dispersed in a continuous phase (sea part) made of another type of polymer. represent. The sea-island structure can be confirmed by observing a thin section prepared from a frozen sample using a transmission electron microscope (TEM).

In the block copolymer contained in the pressure-sensitive adhesive composition of the present invention, the sea-island structure is such that the adhesive segments (A) are brought together by pseudo-crosslinking, and the conductive segments (B) are brought together by pseudo-crosslinking, and each of them is mutually coupled. It is thought that it is formed by forming and separating. There is no particular limitation on whether the phase derived from the adhesive segment (A) or the phase derived from the conductive segment (B) forms the continuous phase (sea area) or the discontinuous phase (island area), but block copolymers It can be adjusted by adjusting the type, monomer composition and amount, the type of each segment of the adhesive segment (A) and the conductive segment (B), the monomer composition and amount, the type and amount of the crosslinking agent, etc. .

In the pressure-sensitive adhesive composition of the present invention, the continuous phase (marine) preferably includes the conductive segment (B). The configuration in which the continuous phase (Ama) includes the conductive segment (B) efficiently forms a path for imparting conductivity in the continuous phase (Ama), and the adhesive layer of the present invention , is preferable because it shows low surface resistivity and has excellent antistatic performance.

In the adhesive composition of the present invention, it is preferable that the discontinuous phase (island portion) includes the adhesive segment (A). The configuration in which the discontinuous phase (island portion) includes the adhesive segment (A) is advantageous in that excellent adhesiveness can be imparted to the adhesive layer of the present invention without impairing the excellent antistatic performance. ,preferable.

The configuration in which the continuous phase (sea area) includes the conductive segment (B) and the configuration in which the discontinuous phase (island area) includes the adhesive segment (A) are based on the adhesive composition of the present invention. This can be achieved by adjusting the type of block copolymer in the product, monomer composition and amount, type of adhesive segment (A) and conductive segment (B), monomer composition and amount, type and amount of crosslinking agent, etc. can do.

[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 performance. Therefore, when an image display device and an optical member are bonded together via the adhesive layer of the present invention, display defects due to static electricity can be suppressed. As described above, the adhesive layer of the present invention is suitably used for manufacturing an image display device.

The surface resistivity (according to JIS K 6271) of the adhesive layer of the present invention (adhesive layer formed from the adhesive composition of the present invention) is preferably 1.0× from the viewpoint of excellent antistatic performance. 10 ¹¹ Ω/□ or less, more preferably 0.5×10 ¹¹ Ω/□ or less, even more preferably 1.0×10 ¹⁰ Ω/□ or less, 0.5×10 ¹⁰ Ω/□ It is as follows. The lower limit of the surface resistivity of the adhesive layer of the present invention is not particularly limited, but 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 can be measured by the method described in Examples below. The surface resistivity of the adhesive layer of the present invention is determined by the type of block copolymer, monomer composition and amount, type of each segment of adhesive segment (A) and conductive segment (B), monomer composition and amount, and type of crosslinking agent. It can be adjusted by adjusting the quantity and quantity.

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, visibility and appearance through the adhesive layer of the present invention are excellent. Thus, the adhesive layer of the present invention is suitably used for optical applications.

The haze of the adhesive layer of the present invention (adhesive layer formed from the adhesive composition of the present invention) is not particularly limited (according to JIS K7136), but is preferably 3% or less, more preferably 1%. Below, it may be 0.7% or less, or 0.6% or less. A haze of 3% or less is preferable because excellent transparency and excellent appearance can be obtained. The above-mentioned haze can be applied, for example, to an adhesive layer (thickness: 100 μm), which is allowed to stand for at least 24 hours under normal conditions (23° C., 50% RH), and then applied to a slide glass (for example, with a total light transmittance of 92%, It is possible to measure using a haze meter (manufactured by Murakami Color Research Institute Co., Ltd., trade name "HM-150N") by using a sample pasted onto a glass plate (having a haze of 0.2%).

The total light transmittance of the adhesive layer of the present invention in the visible wavelength region (according to JIS K7361-1) is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. You can. It is preferable that the total light transmittance is 90% or more because excellent transparency and excellent appearance can be obtained. Note that the above total light transmittance is determined by, for example, using an adhesive layer (thickness: 100 μm), leaving it for at least 24 hours under normal conditions (23°C, 50% RH), and then removing it if it has a release liner. The sample was peeled off and bonded to a slide glass (for example, one with a total light transmittance of 92% and a haze of 0.2%), and a haze meter (manufactured by Murakami Color Research Institute Co., Ltd., product name "HM-150N") was used. ”).

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 are determined by the type of block copolymer, monomer composition and amount, type of each segment of adhesive segment (A) and conductive segment (B), monomer composition and amount, crosslinking. It can be adjusted depending on the type and amount of the agent.

The gel fraction (proportion 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%, even more preferably 55 to 90%. When the gel fraction is 40% or more, the cohesive force of the pressure-sensitive adhesive layer will be improved, and it will cause problems such as foaming and peeling at the interface with the adherend in high-temperature environments, dents during handling, and edges during processing. This is preferable because it suppresses contamination of the parts and makes it easier to obtain excellent foam peeling resistance. In addition, it is preferable that the gel fraction is 95% or less, since appropriate flexibility can be obtained and adhesiveness and step followability can be further improved.

Specifically, the above gel fraction (proportion of solvent-insoluble components) is a value calculated by, for example, the following "method for measuring gel fraction".

Adhesive layer: Approximately 0.1 g was collected from the adhesive sheet, wrapped in a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nitto Denko Corporation) with an average pore diameter of 0.2 μm, and tied with a kite string. The weight at that time is measured, and this weight is taken as the weight before immersion. The weight before dipping is the total weight of the adhesive layer (the adhesive layer collected above), the tetrafluoroethylene sheet, and the kite string. In addition, the total weight of the tetrafluoroethylene sheet and the kite string is also measured, and this weight is taken as the weight of the package.
Next, the adhesive layer wrapped in a tetrafluoroethylene sheet and tied with a kite string (referred to as a "sample") is placed in a 50 ml container filled with ethyl acetate and left to stand at 23° C. for 7 days. Thereafter, the sample (after ethyl acetate treatment) was taken out of the container, transferred to an aluminum cup, dried in a dryer at 130°C for 2 hours to remove ethyl acetate, then weighed, and the weight was transferred to an aluminum cup. After weight.
Then, the gel fraction is calculated from the following formula.
Gel fraction [% (weight %)] = (X-Y) / (Z-Y) x 100

In addition, the above gel fraction depends on, for example, the type of block copolymer, the monomer composition and amount, the type of each segment of the adhesive segment (A) and the conductive segment (B), the monomer composition and amount, and the type and amount of the crosslinking agent. It can be adjusted by

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. It is preferable that the adhesive layer of the present invention has a storage modulus of 3×10 ⁴ Pa or more at 25° C. and 1 Hz because dents are less likely to occur during handling. In terms of suppressing dents in the adhesive layer of the present invention, the storage elastic 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 1×10 ⁵ Pa or more. You can. The upper limit of the storage modulus of the adhesive layer of the present invention at 25° C. and 1 Hz is not particularly limited, but from the viewpoint of the step followability of the adhesive layer of the present invention, it is preferably 5×10 ⁶ Pa or less, and 1× It may be 10 ⁶ Pa or less.

The storage modulus of the pressure-sensitive adhesive sheet of the present invention at 25° C. and 1 Hz can be measured by dynamic viscoelasticity measurement. The storage elastic modulus of the pressure-sensitive adhesive sheet of the present invention at 25°C and 1Hz depends on the type of block copolymer, monomer composition and amount, type of each segment of adhesive segment (A) and conductive segment (B), monomer composition, The amount can be adjusted depending on the type and amount of the crosslinking agent.

The thickness of the adhesive layer of the present invention is not particularly limited, but is preferably 5 to 250 μm, more preferably 7 to 240 μm, 10 to 230 μm, 12 to 220 μm, 15 to 210 μm, 20 to 200 μm, 23 to 175 μm, or 25 μm. It may be ~150 μm. It is preferable that the thickness is at least a certain level because it improves step followability and adhesion reliability. In addition, it is preferable that the thickness is below a certain level because it is particularly excellent in handleability and manufacturability.

The method for producing the adhesive layer of the present invention is not particularly limited. For example, it can be produced by producing the adhesive composition (precursor composition) of the present invention, and performing irradiation with active energy rays, heat drying, etc., as necessary. Specifically, the block copolymer of the present invention may be produced by adding and mixing the above-mentioned crosslinking agent, additives, etc., if necessary.

The method for producing the adhesive layer of the present invention is not particularly limited, but for example, the above-mentioned adhesive composition is applied (coated) onto a base material or a release liner, and if necessary, dried, cured, or dried. and curing.

Note that a known coating method may be used for applying (coating) the above-mentioned pressure-sensitive adhesive composition. For example, coaters such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater may be used.

[3. Adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention. The pressure-sensitive adhesive sheet of the present invention is not particularly limited in other respects as long as it has the pressure-sensitive adhesive layer of the present invention (an adhesive layer formed from the pressure-sensitive adhesive composition of the present invention).

The pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet in which both surfaces are adhesive layer surfaces, or may be a single-sided pressure-sensitive adhesive sheet in which only one surface is a pressure-sensitive adhesive layer surface. Among these, from the viewpoint of bonding two members together, a double-sided adhesive sheet is preferable. Note that in this specification, the term "adhesive sheet" includes a tape-shaped sheet, that is, "adhesive tape." Further, in this specification, the surface of the adhesive layer may be referred to as the "adhesive surface".

A release liner may be provided on the adhesive surface of the adhesive sheet of the present invention until use.

The adhesive sheet of the present invention may be a so-called "base material-less type" adhesive sheet (hereinafter sometimes referred to as "base material-less adhesive sheet") that does not have a base material (base material layer). , a type of adhesive sheet having a base material (hereinafter sometimes referred to as "adhesive sheet with base material") may be used. Examples of the base material-less adhesive sheet include a double-sided adhesive sheet consisting only of the adhesive layer, the adhesive layer and an adhesive layer other than the adhesive layer (sometimes referred to as "another adhesive layer"). ) and the like. On the other hand, examples of the pressure-sensitive adhesive sheet with a base material include a pressure-sensitive adhesive sheet having the above-mentioned pressure-sensitive adhesive layer on at least one side of the base material. Among these, a substrate-less adhesive sheet (substrate-less double-sided adhesive sheet) is preferable, and a substrate-less double-sided adhesive sheet consisting only of the above-mentioned adhesive layer is more preferable. Note that the above-mentioned "base material (base material layer)" does not include a release liner that is peeled off when the pressure-sensitive adhesive sheet is used (applied). The pressure-sensitive adhesive sheet of the present invention is preferably a base material-less pressure-sensitive adhesive sheet.

An embodiment of the adhesive sheet of the present invention (substrate-less adhesive sheet) is shown in FIG. In the adhesive sheet of FIG. 1, 10 is an adhesive layer, and 11 and 12 are release liners.

[3-1. Various physical properties of adhesive sheet]
The 180° peeling adhesive strength of the adhesive sheet of the present invention to a glass plate at 23°C (particularly the adhesive surface of the glass provided by the adhesive layer (adhesive layer formed from the adhesive composition of the present invention)) The adhesive strength (180° peeling strength against the plate at 23°C) is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive strength is high, it is preferably 4 N/20 mm or more, more preferably 6 N. /20mm or more, more preferably 8N/20mm or more, even more preferably 10N/20mm or more. If the adhesive strength of the pressure-sensitive adhesive sheet of the present invention to a glass plate when peeled off at 180 degrees at 23° C. is a certain value or more, the adhesive sheet will be more excellent in adhesion to glass and prevention of lifting at steps. The upper limit of the 180° peeling adhesive strength of the adhesive sheet of the present invention to a glass plate at 23°C is not particularly limited, but is preferably, for example, 28N/20mm, 27N/20mm, or 26N/20mm, and more preferably. is 25N/20mm, 24N/20mm, 23N/20mm, 22N/20mm, 21N/20mm, or 20N/20mm.

The 180° peeling adhesive strength of the adhesive sheet of the present invention to a glass plate at 80°C (particularly the adhesive surface of the glass provided by the adhesive layer (adhesive layer formed from the adhesive composition of the present invention)) The adhesive strength (180° peeling strength against the plate at 80°C) is not particularly limited, but from the viewpoint that sufficient adhesion can be obtained if the adhesive strength is high, it is preferably 4N/20mm or more, more preferably 6N. /20mm or more, more preferably 8N/20mm or more, even more preferably 10N/20mm or more. If the adhesive strength of the pressure-sensitive adhesive sheet of the present invention to a glass plate when peeled off at 180° at 80° C. is a certain value or more, it will have better adhesion to glass and prevention of lifting at steps. The upper limit of the 180° peeling adhesive strength of the adhesive sheet of the present invention to a glass plate at 80° C. is not particularly limited, but is preferably, for example, 18 N/20 mm, more preferably 16 N/20 mm. The 180° peel adhesive strength to a glass plate at 23° C. or 80° C. is determined by the following 180° peel adhesive strength measuring method.

The above-mentioned glass plate is not particularly limited, but includes, for example, the product name "Soda Lime Glass #0050" (manufactured by Matsunami Glass Industries Co., Ltd.). Other examples include alkali-free glass and chemically strengthened glass.

(A-1. 180° peeling adhesive strength measurement method)
The adhesive side of the adhesive sheet is pasted onto the adherend, pressed with a 2 kg roller in one reciprocation, and aged in an atmosphere of 23° C. and 50% RH for 30 minutes or 240 hours. After aging, in accordance with JIS Z 0237, the adhesive sheet was peeled off from the adherend in an atmosphere of 23°C or 80°C, 50% RH, a tensile speed of 300 mm/min, and a peeling angle of 180°. Measure the peeling adhesive force (N/20mm).

(B. Thickness)
The thickness (total thickness) of the adhesive sheet of the present invention is not particularly limited, but is preferably 12 to 350 μm, more preferably 15 to 330 μm, 18 to 325 μm, 18 to 320 μm, 20 to 300 μm, 23 to 300 μm, 25 to 275 μm. , or 30 to 250 μm. It is preferable that the thickness is at least a certain level because peeling at the stepped portion is less likely to occur. In addition, it is preferable that the thickness is below a certain level because it makes it easier to maintain an excellent appearance during manufacturing. Note that, in the case of a pressure-sensitive adhesive sheet with a base material, the thickness of the pressure-sensitive adhesive sheet of the present invention includes the thickness of the base material, but does not include the thickness of the release liner.

(C. Hayes)
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 0.6% or less. . A haze of 3% or less is preferable because excellent transparency and excellent appearance can be obtained. The above-mentioned haze can be obtained by, for example, leaving the pressure-sensitive adhesive sheet for at least 24 hours under normal conditions (23°C, 50% RH), then peeling off the release liner if it has a release liner, and applying it to a slide glass (for example, total light transmittance). 92%, haze 0.2%) as a sample, and can be measured using a haze meter (manufactured by Murakami Color Research Institute Co., Ltd., trade name "HM-150N").

(D. Total light transmittance)
The total light transmittance of the adhesive sheet of the present invention in the visible wavelength region (according to JIS K7361-1) is not particularly limited, but is preferably 90% or more, more preferably 91% or more, or 92% or more. Good too. It is preferable that the total light transmittance is 90% or more because excellent transparency and excellent appearance can be obtained. The above total light transmittance is determined by, for example, leaving the adhesive sheet at normal conditions (23°C, 50% RH) for at least 24 hours, then peeling off the release liner if it has a release liner, and applying it to the slide glass (for example, completely A haze meter (manufactured by Murakami Color Research Institute Co., Ltd., product name "HM-150N") can be used to measure the haze using a sample pasted onto a material (with a light transmittance of 92% and a haze of 0.2%). can.

The total light transmittance and haze of the adhesive sheet of the present invention can be measured according to JIS K7136 and JIS K7361-1, respectively. The adhesive strength, total light transmittance, and haze of the adhesive sheet of the present invention are determined by the type of block copolymer, the monomer composition and amount, the type of each segment of the adhesive segment (A) and the conductive segment (B), and the monomer composition. The amount can be adjusted depending on the type and amount of the crosslinking agent.

[3-2. Adhesive sheet manufacturing method]
The adhesive sheet of the present invention is preferably manufactured according to a known or commonly used manufacturing method, although it is not particularly limited. For example, when the pressure-sensitive adhesive sheet of the present invention is a base material-less pressure-sensitive adhesive sheet, it can be obtained by forming the pressure-sensitive adhesive layer on a release liner by the method described above. In addition, when the adhesive sheet of the present invention is an adhesive sheet with a base material, the adhesive layer may be obtained by directly forming the adhesive layer on the surface of the base material (direct copying method), or the adhesive layer may be obtained by directly forming the adhesive layer on the surface of the base material (direct copying method), or once the adhesive layer is formed on the release liner. After forming the adhesive layer, the adhesive layer may be provided on the base material by transferring (bonding) onto the base material (transfer method).

[3-3. Other layers of adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention may have other layers in addition to the pressure-sensitive adhesive layer described above. Other layers include, for example, other adhesive layers (adhesive layers other than the above-mentioned adhesive layers (adhesive layers other than the adhesive layer formed by the adhesive composition of the present invention)), intermediate layers, and undercoats. Examples include layers. Note that the pressure-sensitive adhesive sheet of the present invention may have two or more other layers.

[3-4. Adhesive sheet base material]
When the adhesive sheet of the present invention is an adhesive sheet with a base material, the base material is not particularly limited, but examples thereof include various optical films such as plastic films, antireflection (AR) films, polarizing plates, and retardation plates. It will be done. Examples of materials for the plastic film include polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, product name "ARTON (cyclic olefin polymer, manufactured by JSR Corporation)", product name "ZEONOR (cyclic olefin polymer, manufactured by JSR Corporation)" Examples include plastic materials such as cyclic olefin-based polymers such as "Made in Japan". In addition, these plastic materials may be used individually or in combination of 2 or more types. Moreover, the above-mentioned "base material" is a part that is attached to an adherend together with an adhesive layer when the adhesive sheet is attached to an adherend. The release liner that is peeled off when the adhesive sheet is used (applied) is not included in the "base material."

It is preferable that the base material is transparent. The total light transmittance of the base material in the visible light wavelength region (according to JIS K7361-1) is not particularly limited, but is preferably 85% or more, more preferably 88% or more. Further, the haze (according to JIS K7136) of the base material is not particularly limited, but is preferably 1.0% or less, more preferably 0.8% or less. Examples of such transparent substrates include PET films and non-oriented films such as those under the trade name "Arton" and "Zeonor".

The thickness of the base material is not particularly limited, but is preferably, for example, 1 to 500 μm. In addition, the said base material may have either a single layer or a multilayer form. Further, the surface of the base material may be appropriately subjected to known and commonly used surface treatments such as physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as undercoat treatment.

[3-5. Adhesive sheet release liner]
The pressure-sensitive adhesive sheet of the present invention may have a release liner provided on its pressure-sensitive adhesive surface until it is used. In addition, when the adhesive sheet of the present invention is a double-sided adhesive sheet, each adhesive surface may be protected by two release liners, or one release liner with release surfaces on both sides may protect the adhesive surface from the roll. It may be protected by being wound into a shape. The release liner is used as a protective material for the adhesive layer and is peeled off when it is applied to an adherend. Further, when the adhesive sheet of the present invention is a base material-less adhesive sheet, the release liner also plays a role as a support for the adhesive layer. Note that the release liner does not necessarily have to be provided.

As the above-mentioned release liner, a conventional release paper or the like can be used, and specifically, in addition to a base material having a release treatment layer formed by a release agent on at least one surface, fluorine-based polymers (such as polytetrafluorocarbon ethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.), and non-polar A low adhesive base material made of a polymer (for example, an olefin resin such as polyethylene or polypropylene) can be used.

As the above-mentioned 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. Such base materials for release liners include polyester films (polyethylene terephthalate films, etc.), olefin resin films (polyethylene films, polypropylene films, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon films), and rayon films. In addition to plastic base films (synthetic resin films) such as (composite of two to three layers).

The release agent constituting the release layer is not particularly limited, and for example, a silicone release agent, a fluorine release agent, a long chain alkyl release agent, or the like can be used. The release agent can be used alone or in combination of two or more.

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

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

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

As the conductive polymer, polyaniline-based, polythiophene-based, polypyrrole-based, polyquinoxaline-based polymers, etc. can be used.

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

[3-6. Applications of adhesive sheets, etc.]
Since the pressure-sensitive adhesive sheet of the present invention has the above-mentioned pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention), it has excellent antistatic performance. Therefore, when used for bonding together image display devices, display defects due to static electricity are less likely to occur. Therefore, the adhesive layer formed from the adhesive composition of the present invention can satisfy excellent antistatic properties, transparency, moist heat resistance, and low staining properties, and is useful for manufacturing image display devices.

Furthermore, the adhesive layer of the present invention has excellent adhesiveness, foam peeling resistance, and stress relaxation properties, and is excellent in step followability and adhesion reliability, especially adhesion reliability at high temperatures. It also has excellent appearance. Therefore, the pressure-sensitive adhesive sheet of the present invention is useful for adherends that tend to foam at the interface at high temperatures. For example, polymethyl methacrylate resin (PMMA) may contain unreacted monomers and tends to foam due to foreign matter at high temperatures. Further, polycarbonate (PC) tends to generate outgas of water and carbon dioxide at high temperatures. Since the pressure-sensitive adhesive sheet of the present invention has excellent foaming peeling resistance, it can also be usefully used for plastic adherends containing such resins.

Further, the pressure-sensitive adhesive sheet of the present invention can be usefully used not only for adherends having a small coefficient of linear expansion but also for adherends having a large coefficient of linear expansion. Note that the adherend having a small coefficient of linear expansion is not particularly limited, but includes, for example, a glass plate (coefficient of linear expansion: 0.3×10 ^-5 to 0.8×10 ^-5 /°C), a polyethylene terephthalate group, etc. (PET film, coefficient of linear expansion: 1.5×10 ^-5 to 2×10 ^-5 /°C), etc. Further, the adherend having a large coefficient of linear expansion is not particularly limited, but includes, for example, a resin base material having a large coefficient of linear expansion, and more specifically, a polycarbonate resin base material (PC, coefficient of linear expansion: 7×10 ^-5 to 8×10 ^-5 /℃), polymethyl methacrylate resin base material (PMMA, coefficient of linear expansion: 7×10 ^-5 to 8×10 ^-5 /℃), cycloolefin polymer base material ( COP, coefficient of linear expansion: 6×10 ^-5 to 7×10 ^-5 /°C), product name "Zeonor" (manufactured by Nippon Zeon Co., Ltd.), product name "Arton" (manufactured by JSR Corporation), etc.

The pressure-sensitive adhesive sheet of the present invention is useful for bonding an adherend with a small coefficient of linear expansion and an adherend with a large coefficient of linear expansion. Specifically, the pressure-sensitive adhesive sheet of the present invention is preferably used for bonding a glass adherend (for example, a glass plate, chemically strengthened glass, glass lens, etc.) to the above resin base material having a large coefficient of linear expansion.

As described above, the pressure-sensitive adhesive sheet of the present invention is useful for bonding adherends made of various materials, and is particularly useful for bonding glass adherends and plastic adherends. Note that the plastic adherend may be an optical film such as a plastic film having an ITO (indium and tin oxide) layer on the surface.

Furthermore, the pressure-sensitive adhesive sheet of the present invention can be usefully used not only for adherends with smooth surfaces but also for adherends with steps on the surface. In particular, the pressure-sensitive adhesive sheet of the present invention can be used even if at least one of the glass adherend and the resin base material having a large linear expansion coefficient has a step on the surface. Useful for bonding with large resin base materials.

The pressure-sensitive adhesive sheet of the present invention is preferably used for manufacturing portable electronic devices. Examples of the above-mentioned portable electronic devices include mobile phones, PHSs, smartphones, tablets (tablet computers), mobile computers (mobile PCs), personal digital assistants (PDAs), electronic notebooks, portable televisions, portable radios, and other portable electronic devices. Examples include type broadcast receivers, portable game consoles, portable audio players, portable DVD players, cameras such as digital cameras, and camcorder type video cameras.

The adhesive sheet of the present invention is preferably used, for example, for pasting together members or modules that make up a portable electronic device, or for fixing members or modules that make up a portable electronic device to a housing. More specifically, bonding a cover glass or lens (especially a glass lens) to a touch panel or touch sensor, fixing a cover glass or lens (especially a glass lens) to a housing, fixing a display panel to a housing, Fixing input devices such as sheet keyboards and touch panels to the housing, pasting together the protective panel of the information display section and the housing, pasting together housings, pasting the housing and decorative sheets, mobile electronics, etc. Examples include fixing and bonding various components and modules that make up equipment. Note that in this specification, a display panel refers to a structure that includes at least a lens (particularly a glass lens) and a touch panel. Furthermore, the term "lens" in this specification includes both a transparent body that exhibits a light refraction effect and a transparent body that does not have a light refraction effect. That is, the lens in this specification also includes a simple window panel that does not have a refractive effect.

Furthermore, the pressure-sensitive adhesive sheet of the present invention is 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, it is preferably used, for example, for bonding optical members together (for bonding optical members) or for manufacturing products (optical products) using the optical members.

[4. Optical components]
It can be suitably used for bonding the optical members of the present invention. Note that the adhesive sheet may have a release liner provided on its adhesive surface until it is used, but since the adhesive sheet in the optical member of the present invention is an adhesive sheet during use, it does not have a release liner.

Optical member refers to a member that has optical properties (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.) . The substrate constituting the optical member is not particularly limited, but includes, for example, a substrate constituting a device (optical device) such as a display device (image display device) or an input device, or a substrate used in these devices, For example, polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness enhancement films, light guide plates, reflective films, antireflection films, hard coat films (hard coat treatment is applied to at least one side of plastic films such as PET films). transparent conductive films (for example, plastic films having an ITO layer on the surface (preferably ITO films such as PET-ITO, polycarbonate, and cycloolefin polymer)), design films, decorative films, surface protection plates, prisms, etc. , lenses, color filters, transparent substrates (glass sensors, glass display panels (LCDs, etc.), glass substrates such as glass plates with transparent electrodes, etc.), and even substrates on which these are laminated (these are collectively referred to as " (sometimes referred to as "functional film"). Moreover, these films may have a metal nanowire layer, a conductive polymer layer, or the like. Further, these films may be printed with a mesh of fine metal wires. In addition, the above-mentioned "plate" and "film" each include forms such as plate, film, and sheet. For example, "polarizing film" includes "polarizing plate" and "polarizing sheet", etc. . Furthermore, "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, a touch panel etc. are mentioned as said input device.

The substrate constituting the optical member is not particularly limited, but includes, for example, a substrate made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, cycloolefin polymer, metal thin film, etc. (for example, a sheet-like, film-like, or plate-like substrate). etc.) etc. In addition, as mentioned above, the "optical member" in the present invention also includes members (design films, decorative films, surface protection films, etc.) that play the role of decoration and protection while maintaining the visibility of display devices and input devices. shall be held.

If the adhesive sheet of the present invention is an adhesive sheet with a base material, and the adhesive sheet constitutes a member having optical properties, the base material can be regarded as the same as the substrate, and the adhesive sheet can be used as the optical member of the present invention. It can be said that there is also.

When the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet with a base material and the above-mentioned functional film is used as the base material, the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer on at least one side of the functional film. It can also be used as an "adhesive functional film".

The present invention will be explained in more detail below based on Examples, but the present invention is not limited to these Examples in any way.

Manufacturing example 1
<Preparation of acrylic polymer solution 1>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 81.8 parts by mass of butyl acrylate, 5.5 parts by mass of acrylic acid, and acryloylmorpholine (KJ Chemicals Co., Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.75 parts by mass of trithiocarbonate=bis{4-[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl (manufactured by Wako Pure Chemical Industries, Ltd.) as a RAFT agent. A mixture containing 0.047 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) as an initiator and 100 parts by mass of ethyl acetate as a solvent was heated at 75°C. The mixture was stirred for 6 hours under a nitrogen atmosphere (Step 1 of RAFT polymerization reaction). Thereby, acrylic polymer solution 1 containing acrylic polymer P1 was obtained.

Example 1
<Preparation of block copolymer solution 2>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 30 parts by mass (solid content equivalent) of the acrylic polymer solution 1 containing the acrylic polymer P1 obtained in Production Example 1 were added. , 65 parts by mass of 2-methoxyethyl acrylate, 5 parts by mass of (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) as an ionic monomer, and as a polymerization initiator. A mixture containing 0.020 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts by mass of ethyl acetate as a solvent was heated at 75°C for 6 hours. , and stirred under a nitrogen atmosphere (Step 2 of RAFT polymerization reaction). Thereby, block copolymer solution 2 containing block copolymer P2 was obtained. Block copolymer P2 is an ABA type triblock copolymer, the A segment is an adhesive segment derived from acrylic polymer P1, and the B segment is (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide. It is a conductive segment contained as a monomer unit.
<Preparation of adhesive composition 1>
Adhesive composition 1 was prepared by uniformly mixing the following components per 100 parts by mass of block copolymer P2 (base polymer) into block copolymer solution 2 containing block copolymer P2 obtained above.
Crosslinking agent: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name "Tetrad C", manufactured by Mitsubishi Gas Chemical Co., Ltd.): 0.05 parts by mass <Production of adhesive sheet 1>
The adhesive composition 1 obtained above was applied to a release liner (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Corporation, MRF #38) having one side as a release surface to form a coating film. Next, this coating film was dried at 152° C. for 3 minutes to form an adhesive layer with a thickness of 25 μm. A release liner (polyester film, thickness 38 μm, manufactured by Mitsubishi Chemical Corporation, MRF #38) having a thickness of 38 μm and having one side of a polyester film serving as a release surface was bonded to this adhesive layer. Thereafter, an aging treatment was performed at 60° C. for one day to advance a crosslinking reaction in the adhesive layer, thereby obtaining an adhesive sheet 1.

Example 2
<Preparation of block copolymer solution 3>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 20 parts by mass (solid content equivalent) of the acrylic polymer solution 1 containing the acrylic polymer P1 obtained in Production Example 1 were added. , 75 parts by mass of 2-methoxyethyl acrylate, 5 parts by mass of (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) as an ionic monomer, and as a polymerization initiator. A mixture containing 0.014 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts by mass of ethyl acetate as a solvent was heated at 75°C for 6 hours. , and stirred under a nitrogen atmosphere (Step 2 of RAFT polymerization reaction). Thereby, block copolymer solution 3 containing block copolymer P3 was obtained. Block copolymer P3 is an ABA type triblock copolymer, the A segment is an adhesive segment derived from acrylic polymer P1, and the B segment is (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide. It is a conductive segment contained as a monomer unit.
<Preparation of adhesive composition 2>
Adhesive composition 2 was prepared in the same manner as in Example 1 except that block copolymer solution 3 containing block copolymer P3 obtained above was used instead of block copolymer solution 2.
<Manufacture of adhesive sheet 2>
A pressure-sensitive adhesive sheet 2 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition 2 obtained above was used instead of the pressure-sensitive adhesive composition 1.

Example 3
<Preparation of block copolymer solution 4>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 10 parts by mass (solid content equivalent) of the acrylic polymer solution 1 containing the acrylic polymer P1 obtained in Production Example 1 were added. , 85 parts by mass of 2-methoxyethyl acrylate, 5 parts by mass of (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.) as an ionic monomer, and as a polymerization initiator. A mixture containing 0.014 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts by mass of ethyl acetate as a solvent was heated at 75°C for 6 hours. , and stirred under a nitrogen atmosphere (Step 2 of RAFT polymerization reaction). Thereby, block copolymer solution 4 containing block copolymer P4 was obtained. Block copolymer P4 is an ABA type triblock copolymer, the A segment is an adhesive segment derived from acrylic polymer P1, and the B segment is (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide. It is a conductive segment contained as a monomer unit.
<Preparation of adhesive composition 3>
Adhesive composition 3 was prepared in the same manner as in Example 1 except that block copolymer solution 4 containing block copolymer P4 obtained above was used instead of block copolymer solution 2.
<Manufacture of adhesive sheet 3>
A pressure-sensitive adhesive sheet 3 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition 3 obtained above was used instead of the pressure-sensitive adhesive composition 1.

Comparative example 1
<Preparation of acrylic polymer solution 5>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 24.5 parts by mass of butyl acrylate, 1.7 parts by mass of acrylic acid, and acryloylmorpholine (KJ Chemicals Co., Ltd.) were added. 65 parts by mass of 2-methoxyethyl acrylate, and 5 parts by mass of (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by Wako Pure Chemical Industries, Ltd.). , 0.25 parts by mass of trithiocarbonate=bis{4-[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl (manufactured by Wako Pure Chemical Industries, Ltd.) as a RAFT agent, and 2,2'- as a polymerization initiator. A mixture containing 0.023 parts by mass of dimethyl azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts by mass of ethyl acetate as a solvent was stirred at 75°C for 6 hours under a nitrogen atmosphere. (Step 1 of RAFT polymerization reaction). Thereby, acrylic polymer solution 5 containing acrylic polymer P5 was obtained. Acrylic polymer P5 is not a block copolymer but a conductive polymer containing (2-acryloyloxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide as a monomer unit.
<Preparation of adhesive composition 4>
Adhesive composition 4 was prepared in the same manner as in Example 1, except that acrylic polymer solution 5 obtained above was used instead of block copolymer solution 1.
<Manufacture of adhesive sheet 4>
A pressure-sensitive adhesive sheet 4 was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition 4 containing the acrylic polymer P5 obtained above was used instead of the pressure-sensitive adhesive composition 1.

The following evaluations were performed using the pressure-sensitive adhesive sheets obtained in Examples 1 to 3 and Comparative Example 1 above. The results are listed in Table 1.

<Measurement of surface resistance value>
After peeling off one of the release liners of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, the surface resistance value of the surface of the pressure-sensitive adhesive layer was measured. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd. in an atmosphere of 23° C. and 50% RH.

<Presence or absence of micro phase separation structure>
The presence or absence of a microphase separation structure was confirmed for the adhesive layer of each adhesive sheet obtained in Examples and Comparative Examples as follows. First, a sample for observation with a transmission electron microscope (TEM) was prepared. Specifically, the adhesive layer was dyed and then rapidly frozen, and a thin section was cut from the adhesive layer using an ultramicrotome (manufactured by Leica). Then, the thin section was observed and photographed using a transmission electron microscope (trade name "HT7820", manufactured by Hitachi High-Technologies). Next, the obtained TEM image was analyzed and binarized using image analysis software to confirm the presence or absence of phase separation.

<Evaluation of total light transmittance and haze>
One release liner was peeled off from the adhesive sheets obtained in Examples 1 to 3 and Comparative Example 1, and the double-sided adhesive sheet was placed on a slide glass (manufactured by Matsunami Glass Industries Co., Ltd., "White Polish No. 1", thickness: 0.8 to 1.0 mm, total light transmittance 92%, haze 0.2%), and then peel off the other release liner to change the layer structure of double-sided adhesive sheet (adhesive layer)/slide glass. Prepare a test piece with The total light transmittance and haze of the above test piece in the visible light region are measured using a haze meter (equipment name "HM-150N", manufactured by Murakami Color Research Institute, Inc.).

<Shear storage modulus of adhesive layer>
The shear storage modulus of the adhesive layer of each adhesive sheet of Examples 1 to 3 and Comparative Example 1 is examined by dynamic viscoelasticity measurement (first measurement).

The sample for the first measurement is prepared as follows. First, for each adhesive layer to be measured, 60 adhesive layers (thickness: 25 μm) are laminated to obtain a laminated adhesive layer (thickness: 1.5 mm). Next, a cylindrical pellet (thickness 1.5 mm, diameter 7.9 mm) as a first measurement sample is obtained by punching the laminated adhesive layer.

For dynamic viscoelasticity measurement, a dynamic viscoelasticity measuring device (trade name "ARES", manufactured by Rheometric Co., Ltd.) is used. Specifically, after fixing a measurement sample to a parallel plate jig with a diameter of 7.9 mm, dynamic viscoelasticity measurement is performed using the above device. In this measurement, the measurement mode is shear mode, the measurement temperature range is -70°C to 250°C, the temperature increase rate is 5°C/min, and the frequency is 1Hz. The shear storage modulus (Pa) of the adhesive layer at 25°C is determined.

Even though the adhesive layers of Examples 1 to 3 and Comparative Example 1 contain the same 5% by weight of ionic monomer, the surface resistance values of the adhesive layers of Examples 1 to 3 are about half or less than that of Comparative Example 1. has declined to Therefore, the conductive segments of the block copolymer are more unevenly distributed in the continuous phase (sea area) than in the discontinuous phase (island area) of the phase-separated adhesive layers of Examples 1 to 3, allowing the conductive path to be efficiently It is thought that it is formed based on

Variations of the present invention are additionally described below.
[Appendix 1] An adhesive composition containing a block copolymer,
The block copolymer includes an adhesive segment (A) and a conductive segment (B),
An adhesive composition having a sea-island structure phase-separated into a continuous phase and a discontinuous phase.
[Additional Note 2] The pressure-sensitive adhesive composition according to Additional Note 1, wherein the continuous phase (marine) includes the conductive segment (B).
[Appendix 3] Additional note that the weight ratio of the conductive segment (B) to the adhesive segment (A) (conductive segment (B)/adhesive segment (A)) is from 50/50 to 99/1. 3. The pressure-sensitive adhesive composition according to 1 or 2.
[Appendix 4] The adhesive composition according to any one of Appendices 1 to 3, wherein the conductive segment (B) contains an ionic compound having a radically polymerizable substituent as a monomer unit.
[Appendix 5] The adhesive composition according to any one of Appendices 1 to 4, wherein the adhesive segment (A) contains a radically polymerizable compound as a monomer unit.
[Appendix 6] An adhesive layer formed from the adhesive composition according to any one of Appendices 1 to 5.
[Appendix 7] The adhesive layer according to Appendix 6, having a storage modulus of 3×10 ⁴ Pa or more and 5×10 ⁶ Pa or less at 25° C. and 1 Hz.
[Appendix 8] The adhesive layer according to Appendix 6 or 7, which has a total light transmittance (according to JIS K7361-1) of 90% or more.
[Appendix 9] The adhesive layer according to any one of Appendices 6 to 8, which has a haze (according to JIS K7136) of 3% or less.
[Appendix 10] A pressure-sensitive adhesive sheet having the adhesive layer according to any one of Appendices 6 to 9.
[Appendix 11] The pressure-sensitive adhesive sheet according to Appendix 10, having a thickness of 12 to 350 μm.

1 Adhesive sheet 10

Adhesive layer

11, 12 Release liner

Claims

An adhesive composition containing a block copolymer,
The block copolymer includes an adhesive segment (A) and a conductive segment (B),
An adhesive composition having a sea-island structure phase-separated into a continuous phase and a discontinuous phase.
The pressure-sensitive adhesive composition according to claim 1, wherein the continuous phase (marine) includes the conductive segment (B).
Claim 1 or 2, wherein the weight ratio of the conductive segment (B) to the adhesive segment (A) (conductive segment (B)/adhesive segment (A)) is from 50/50 to 99/1. The adhesive composition described in .
The adhesive composition according to any one of claims 1 to 3, wherein the conductive segment (B) contains an ionic compound having a radically polymerizable substituent as a monomer unit.
The adhesive composition according to any one of claims 1 to 4, wherein the adhesive segment (A) contains a radically polymerizable compound as a monomer unit.
An adhesive layer formed from the adhesive composition according to any one of claims 1 to 5.
The adhesive layer according to claim 6, having a storage elastic modulus of 3×10 4 Pa or more and 5×10 6 Pa or less at 25° C. and 1 Hz.
The adhesive layer according to claim 6 or 7, having a total light transmittance (according to JIS K7361-1) of 90% or more.
The adhesive layer according to any one of claims 6 to 8, having a haze (according to JIS K7136) of 3% or less.
A pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer according to any one of claims 6 to 9.
The adhesive sheet according to claim 10, having a thickness of 12 to 350 μm.