JP5133114B2 - Antistatic adhesive - Google Patents

Description

  The present invention relates to an antistatic pressure-sensitive adhesive. More specifically, the present invention relates to an antistatic pressure-sensitive adhesive having excellent antistatic properties and adhesive properties.

  Conventionally, as an adhesive for the purpose of antistatic properties when peeling from an adherend, for example, an acrylic copolymer and an antistatic agent (polyether polyol, surfactant, metal conductive filler, carbon black) And the like (see, for example, Patent Documents 1, 2, and 3) are known.

JP-A-6-128539 JP 58-191777 A JP 2004-307787 A

  However, these conventional pressure-sensitive adhesives have problems such as contamination of the surface of the adherend due to bleeding out of the antistatic agent and deterioration of the pressure-sensitive adhesive properties over time. In addition, some of these pressure-sensitive adhesives containing antistatic agents contain many impurities that may cause corrosion, malfunction, or malfunction inside electronic equipment. There is also the problem of difficulty.

As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention. That is, the present invention provides a hydrocarbyl (meth) acrylate copolymer (A) having at least one quaternary onium-organic acid group represented by the following general formula (1) at the molecular side chain and / or molecular end. An antistatic pressure-sensitive adhesive characterized by containing
[Wherein Q is N, R ¹ and R ³ are each separated by a linear, branched or ring-containing hydrocarbon group having 1 to 20 carbon atoms which may contain O and / or N or a nonionic molecular chain. The hydrocarbon group having 1 to 20 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms or a ring-containing hydrocarbon group, A ¹ and A ² are alkylene groups having 2 to 4 carbon atoms, and m and n are m + n is a positive integer such that 2 to 20, p is 0 or 1, X ⁻ is hydrogen from an organic acid group selected from the group consisting of a carboxylic acid group, a (phosphite) group, a sulfonic acid group, and a sulfamic acid group. Represents an excluded residue. ]
And a pressure-sensitive adhesive tape, a pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive film obtained by applying the pressure-sensitive adhesive to at least a part of at least one side of the substrate.

The antistatic pressure-sensitive adhesive of the present invention has the following effects.
(1) Excellent antistatic properties.
(2) Excellent transparency.
(3) Less adherend contamination.
(4) Little deterioration of adhesive strength over time.

The pressure-sensitive adhesive of the present invention is a hydrocarbyl (meth) acrylate copolymer having at least one quaternary onium-organic acid group represented by the following general formula (1) at the molecular side chain and / or molecular end ( A) is contained.

In the formula, Q represents N. R ¹ and R ³ are each a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12), preferably 1 to 12 carbon atoms (hereinafter abbreviated as C), which may contain O and / or N. Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms separated by a nonionic molecular chain. When C of R ¹ and / or R ³ exceeds 20, the antistatic property of the adhesive is deteriorated.
Nonionic molecular chains include divalent groups selected from ethers, thioethers, carbonyls, esters, iminos, amides, urethanes, ureas, carbonates, dihydrocarbylsiloxy and heterocyclic groups containing N or O. .
Among the hydrocarbon groups of R ¹ and R ^3, the hydrocarbon group not containing O and / or N includes a methyl group, an ethyl group, a cyclohexyl group, a phenyl group, a benzyl group, etc .; contains O and / or N Examples of the hydrocarbon group include a hydroxymethyl group, a hydroxyethyl group, and an aminoethyl group.
Of the hydrocarbon groups of R ¹ and R ³ , examples of the hydrocarbon group separated by a nonionic molecular chain include a methoxy group, an ethoxy group, a methoxyethyl group, and an ethoxyethyl group.

R ² represents a C1-8 (preferably 1 to 4) alkyl group or a ring (alicyclic ring or aromatic ring) -containing hydrocarbon group. When C of R ² exceeds 8, the antistatic property of the adhesive is deteriorated.
A ¹ and A ² are each a C2-4 alkylene group, m and n are positive integers where m + n is 2 to 20, and p is 0 or 1.
X ^- represents a carboxylic acid group, (sub) phosphate group, residues obtained by removing a hydrogen from an acid group of a polymerizable organic acid selected from the group consisting of sulfonic acid and sulfamic acid group. Examples of the polymerizable organic acid include those described below.

In the production method (A), the organic acid group in the hydrocarbyl (meth) acrylate copolymer (A01) having an organic acid group at the molecular side chain and / or molecular end is represented by the following general formula (3). A method of reacting the quaternary onium salt (z) shown is included.

In the formula (3), Q, R ^{1 to} R ³ , A ¹ , A ² , m, n and p are the same as those in the formula (1).
Z ⁻ represents a counter anion selected from the group consisting of residues of alkylating agents and hydroxyl ions. Examples of the alkylating agent include those described below.

  Hydrocarbyl (meth) acrylate (co) polymer (A01) includes organic acid group-containing monomer (a11), hydrocarbyl (meth) acrylate (a2) excluding (a11), and (a11) if necessary. Active hydrogen-containing monomers (a3) other than (a2), (a11), (a2), and (co) polymers having other polymerizable monomers (a4) other than (a3) as structural units are included.

  The organic acid group-containing monomer (a11) is a monomer having an organic acid group [carboxylic acid group, (phosphite) group, sulfonic acid group, sulfamic acid group, etc.] described below (a111) to (a114) Is included.

(A111) α, β-unsaturated carboxylic acid monobasic acid [C3-10, such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid];
Dibasic acids [C4-8, such as maleic acid, itaconic acid, fumaric acid, citraconic acid and mesaconic acid];
Monoester of dibasic acid [monohydrocarbyl (C1-18) ester of dibasic acid];
Succinic acid monoester of hydroxyl group-containing (meth) acrylate represented by the following general formula

_{CH 2 = C (R ')} - COO (AO) q (CO-L-O) r -CO-CH 2 -CH 2 -COOH

(In the formula, R ′ is H or a methyl group, A is a C2-4 alkylene group, L is a C3-19 alkylene group, q is an integer of 0-5, and r is an integer of 1-30).
[C8-130, for example 2-hydroxyalkyl (alkyl group is C2-3) (meth) acrylate succinic anhydride ring-opening adduct, (poly) (n = 1-30) oxyalkylene (C2-4) mono ( Succinic anhydride ring-opening adduct of meth) acrylate, compound obtained by ring-opening addition of succinic anhydride to caprolactone (1-5 mol) adduct of 2-hydroxyalkyl (alkyl group C2-3) (meth) acrylate] ;
And mixtures of two or more of these

(A112) α, β-unsaturated (sub) phosphate ester monomer (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxy-2-hydroxypropyl acid phosphate, (meth) Acryloyloxy-3-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, allyl alcohol acid phosphate, (meth) acryloyloxyethyl acid phosphate, and mixtures of two or more thereof

(A113) α, β-unsaturated sulfonic acid monomer Vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, isethionic acid (meth) acrylate, and mixtures of two or more thereof

(A114) α, β-unsaturated sulfamic acid monomer N-hydroxyethyl-N- [2- (meth) acryloyloxyethyl] sulfamic acid, N, N-bis [2- (meth) acryloyloxyethyl] sulfamic acid, Adducts of (meth) acryloyl isocyanate and N, N-di (2-hydroxyethyl) sulfamic acid, and mixtures of two or more thereof.

  Of these, (meth) acrylic acid, maleic acid, itaconic acid, (meth) acryloyloxyethyl acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid, isethionic acid (meth) acrylate are preferred from an industrial viewpoint. N-hydroxyethyl-N- [2- (meth) acryloyloxyethyl] sulfamic acid and adducts of (meth) acryloyl isocyanate and N, N-di (2-hydroxyethyl) sulfamic acid, more preferably ( (Meth) acrylic acid, (meth) acryloyloxyethyl acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid and N-hydroxyethyl-N- [2- (meth) acryloyloxyethyl] sulfamic acid, and two of these In a mixture of That.

The hydrocarbyl group in the hydrocarbyl (meth) acrylate (a2) excluding (a11) is aliphatic [C1-25 (preferably 4-18, more preferably 4-8), such as an alkyl group [methyl, Ethyl, n-, i-propyl, n-, i-, sec- and t-butyl, n-, i-, sec- and neopentyl, n-octyl, 2-ethylhexyl, nonyl, decyl, lauryl, tridecyl, myristyl Cetyl and stearyl groups, etc.] and alkenyl groups [ethenyl, propenyl, butenyl, hexenyl, decenyl and oleyl groups]], alicyclic [C4-18, eg cyclobutyl, cyclopentyl and cyclohexyl groups] and araliphatic [C7- 18, eg benzyl and phenylethyl groups] hydrocarbyl groups And the like.
Among these, from the viewpoint of the glass transition point (A) (hereinafter abbreviated as Tg, measurement is based on DSC (scanning differential thermal analysis) method), an aliphatic hydrocarbyl group is preferable, and n-butyl is more preferable. And 2-ethylhexyl group.

  The active hydrogen-containing monomer (a3) excluding (a11) is a monomer having a functional group (carboxyl group, hydroxyl group, amino group, hydroxymethyl group, etc.) containing active hydrogen that reacts with the crosslinking agent (B) described later. Yes, the following (a31) to (a35) may be mentioned.

(A31) Hydroxyl-containing compound (1) Unsaturated carboxylic acid ester of C5-12 Hydroxyalkyl (C2-6) (meth) acrylate [hydroxyethyl-, hydroxypropyl- and hydroxybutyl (meth) acrylate etc.], and lactone thereof (C4-20, such as butyrolactone, valerolactone, caprolactone and laurolactone) 1-5 mole adducts;
Poly (n = 2-30) oxyalkylene (C2-4) (meth) acrylate [poly (n = 10) oxyethylene mono (meth) acrylate and the like];
Poly (n = 2-30) oxyalkylene (C2-4) unsaturated carboxylic acid diester [poly (n = 10) oxyethylene maleic acid diester, etc.], poly (n = 2-30) oxyalkylene (C2-4) (Meth) allyl ether [poly (n = 10) oxyethylene (meth) allyl ether, etc.]
(2) C3-8 unsaturated alcohol (meth) allyl alcohol, crotyl alcohol, 1-butene-3-ol, 2-butene-1,4-diol, etc. (3) C8-15 styrene compound hydroxystyrene, etc. (4) C5-20 ether hydroxyalkyl (C2-6) alkenyl (C3-6) ether [2-hydroxyethylpropenyl ether etc.]
(5) Methylol group-containing compound C4-10 hydroxyl group-containing (meth) acrylamide [N-methylol (meth) acrylamide etc.]

(A32) Amino group-containing compound (1) C5-15 primary, secondary amino group-containing (meth) acrylate aminoalkyl (C2-6) (meth) acrylate [aminoethyl (meth) acrylate etc.], alkyl (C1 -6) aminoalkyl (C1-6) (meth) acrylate [t-butylaminoethyl methacrylate etc.] etc. (2) C5-10 secondary and secondary amino group-containing acrylamide N-aminoalkyl (C2-6) (meta ) Acrylamide [N-aminoethyl (meth) acrylamide etc.], (Meth) acrylamide alkyl (C2-6) alkyl (C1-6) amine [(Meth) acrylamide ethylbutylamine etc.]
(3) Alkenylamine compounds C3-15, such as mono- and di- (meth) allylamine, crotylamine

  Of these (a3), from the viewpoint of the balance between tackiness of adhesive and cohesive force, (a31) is preferred, and hydroxyethyl (meth) acrylate is more preferred.

Examples of the other polymerizable monomer (a4) excluding (a11), (a2), and (a3) include the following (a41) to (a44).
(A41) Poly (n = 2 to 30) oxyalkylene alkyl (C1-18) ether (meth) acrylate Ethylene oxide of methanol (hereinafter abbreviated as EO) 10 mole adduct (meth) acrylate, propylene oxide of methanol (hereinafter referred to as “a”) , Abbreviated as PO) (meth) acrylate of 10 mole adduct, etc.

(A42)
(1) C3-20 tertiary or quaternary nitrogen-containing (meth) acrylamide compound Tertiary nitrogen-containing (meth) acrylamide compound [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, etc.]; quaternary nitrogen Containing (meth) acrylamide compound [quaternized product of the above-mentioned tertiary nitrogen-containing vinyl compound (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate)]

(2) Tertiary or quaternary nitrogen-containing (meth) acrylate Tertiary nitrogen-containing (meth) acrylate [dialkyl (C1-4) aminoalkyl (C1-4) (meth) acrylate [N, N-dimethylaminoethyl (meta) ) Acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc.], heterocyclic-containing (meth) acrylate [morpholinoethyl (meth) acrylate, etc.]]; quaternary nitrogen-containing (meth) acrylate [ (Meth) acrylate [the quaternized product of the above-mentioned tertiary amino group-containing (meth) acrylate (a quaternized product using the quaternizing agent), etc.], etc.]

(3) Heterocycle-containing vinyl compound Pyridine compound (C7-14, such as 2- and 4-vinylpyridine), imidazole compound (C5-12, such as N-vinylimidazole), pyrrole compound (C6-13, such as N-vinyl) (4) Nitrile group-containing vinyl compound C3-15 nitrile group-containing vinyl compound, for example, (meth) acrylonitrile, cyanostyrene, cyanoalkyl (C1-4) acrylate (5) Other vinyl compounds Nitro group-containing vinyl compounds ( C8-16, such as nitrostyrene) etc.

(A43) Unsaturated hydrocarbon (1) Aliphatic unsaturated hydrocarbon C2-18 or more olefin [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.]; 10 or more dienes [butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.] and the like (2) alicyclic unsaturated hydrocarbon C4-18 or more cyclic unsaturated Saturated hydrocarbons such as cyclohexene, (di) cyclopentadiene, pinene, limonene, indene (3) Aromatic unsaturated hydrocarbons C8-20 or more aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, vinyl Toluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene Emissions, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene

(A44) Vinyl ester, vinyl ether, vinyl ketone, unsaturated dicarboxylic acid diester (1) Vinyl ester Aliphatic vinyl ester (C4-15, such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl adipate, isopropenyl acetate , Vinyl methoxyacetate, vinyl benzoate); aromatic vinyl esters (C9-20, eg diallyl phthalate, methyl-4-vinyl benzoate, acetoxystyrene)

(2) Vinyl ether Aliphatic vinyl ether [C3-15, such as vinyl alkyl (C1-10) ether [vinyl methyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, etc.], vinyl alkoxy (C1-6) alkyl (C1-4) Ether [vinyl-2-methoxyethyl ether, methoxybutadiene, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, etc.], poly ( 2-4) (meth) allyloxyalkanes (C2-6) [diallyloxyethane, triaryloxyethane, tetraallyloxybutane, tetrametaallyloxyethane, etc.]]; aromatic vinyl ethers (C8-20, such as vinyl) Phenyl ether, phenoxystyrene), etc.

(3) Vinyl ketone Aliphatic vinyl ketone (C4-25, such as vinyl methyl ketone, vinyl ethyl ketone); Aromatic vinyl ketone (C9-21, such as vinyl phenyl ketone), etc. (4) Unsaturation of unsaturated dicarboxylic acid diester C4-34 Dicarboxylic acid diesters such as dialkyl fumarate (two alkyl groups are C1-22 linear, branched or alicyclic groups), dialkyl maleates (two alkyl groups are C1-22 Straight chain, branched chain or alicyclic group).

  Of those exemplified as (a4) above, (a42), (a43) and (a44) are preferred from the viewpoint of the cohesive strength of the pressure-sensitive adhesive, and (a42) (1), (2), (a43) are more preferred. ) (3) and (a44), particularly preferred are styrene and vinyl acetate.

The hydrocarbyl (meth) acrylate copolymer (A01) is composed of (a11) and (a2) and, if necessary, (a3) and (a4) monomers.
The content of each monomer based on the total weight of the monomers (a11), (a2), (a3) and (a4) is preferably from the viewpoint of cohesive force and tack of the pressure-sensitive adhesive, and tackiness. 1 to 30%, more preferably 0.5 to 25%, particularly preferably 1 to 20%; (a2) is preferably 40 to 99.8%, more preferably 60 to 99% from the viewpoint of adhesive strength and tack. In particular, 70 to 98%; (a3) is usually 30% or less, from the viewpoint of adhesive strength, preferably 20% or less, more preferably 10% or less; (a4) is usually 30% or less, from the viewpoint of adhesive strength Preferably it is 20% or less, More preferably, it is 10% or less.

  The quaternary onium salt (z) constituting (A) in the present invention includes a quaternized compound (z0) represented by the following general formula (4) using an alkylating agent. .

The tertiary compound (z0) is represented by the following general formula (4), and Q, R ¹ , A ¹ , A ² , m, n, and p are the same as described above.

Examples of (z0) include an alkylene oxide (hereinafter abbreviated as AO) adduct of an amine. Examples of the amine include the following primary and secondary amines.
Primary amines include aliphatic amines (C1-20, such as ethylamine, octylamine, dodecaneamine), aromatic amines (C6-20, such as aniline, naphthylamine), alicyclic amines (C6-20, such as cyclohexylamine). ), Alkanolamines (C2-6, such as monoethanolamine) and mixtures thereof;
Secondary amines include aliphatic amines (C2-20, such as dimethylamine, diethylamine), aromatic amines (C7-20, such as N-methylaniline, diphenylamine, phenylnaphthylamine), alicyclic amines (C7-20, For example, N-methylcyclohexylamine), alkanolamines (C4-10, such as diethanolamine), heterocyclic amines (C5-20, such as N-methyl-2-furylamine), and mixtures thereof.

  AO includes C2-4, such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide and tetrahydrofuran (hereinafter abbreviated as EO, PO, BO and THF, respectively). As well as combinations of two or more of these (random addition and / or block addition).

Of (z0), compatibility with (A) and industrial viewpoints are preferred. R ¹ is an alkyl group having a C1 to 12 group, and more preferably N-alkyl (C1-12) diethanolamine.

  Examples of alkylating agents include halogenated hydrocarbons [halogenated alkyls (C1-8, such as methyl chloride, ethyl chloride, butyl bromide, methyl iodide), aromatic ring-containing halides (C6-8, such as phenyl bromide, benzyl chloride). Etc.], carbonic acid dialkyl ester (alkyl group is C3-8, such as dimethyl carbonate, diethyl carbonate), dialkyl sulfate ester (C2-8, such as dimethyl sulfate, diethyl sulfate), organic lithium compound (C4-8, such as butyllithium, Phenyl lithium), Grignard reagents (such as those obtained by reacting the above halogenated hydrocarbons with magnesium), and the like. Of these, dialkyl carbonate is preferred from the viewpoint of adherend contamination.

Among the quaternary onium salts (z), a quaternary onium / carbonate salt (z1) represented by the following general formula (2) is preferable from the viewpoint of less adherend adherend contamination.

In the formula, Q and R ^{1 to} R ³ are the same as described above, and R ⁴ represents a C1 to 8 (preferably 1 to 4) alkyl group or a ring-containing hydrocarbon group.

  (Z1) is obtained by quaternizing the tertiary compound (z0) with the carbonic acid dialkyl ester, and the cation constituting (z1) is the same as the cation in the general formula (1).

  The following are mentioned as a manufacturing method of the hydrocarbyl (meth) acrylate copolymer (A) in this invention.

(1) A method of reacting the quaternary onium salt (z) with an organic acid group in the hydrocarbyl (meth) acrylate copolymer (A01).
The reaction is carried out in the presence or absence of a solvent, and an anion exchange reaction or a neutralization reaction is carried out, whereby a hydrocarbyl (meth) acrylate copolymer (A) having a quaternary onium / organic acid group. Is obtained.
When the quaternary onium salt (z) is a quaternary onium / carbonate ester salt (z1), the reaction with the organic acid group in (A01) is similarly performed in the presence or absence of a solvent. Then, the hydrocarbyl (meth) acrylate copolymer (A) is obtained by appropriately removing carbon dioxide generated as a by-product in the anion exchange reaction from the reaction system.

  In the production of (A), the equivalent ratio of (z) to the organic acid group in (A01) is usually 0.001 / 1-1 / 1, preferably from the viewpoint of antistatic properties, 0.01 / 1 1/1, more preferably 0.05 / 1 to 1/1.

(2) In advance, at least one organic acid group of the polymerizable monomer (a11) containing an organic acid group is reacted with the quaternary onium salt (z) in the same manner as described above. A method of producing a monomer (a12) having a quaternary onium / organic acid base and copolymerizing it with the above (a2) and, if necessary, (a3) and (a4).

  In the present invention, the content of the quaternary onium / organic acid base represented by the general formula (1) in (A) is based on the weight of (A). From the viewpoint of force, it is preferably 0.1 to 30%, more preferably 0.2 to 20%, particularly preferably 0.5 to 10%.

  Weight average molecular weight of (A) [Hereinafter abbreviated as Mw, measurement is based on gel permeation chromatography (GPC) method (polystyrene conversion). ] Is preferably 50,000, more preferably 100,000, particularly preferably 200,000 from the viewpoint of cohesive strength of the pressure-sensitive adhesive, and 2,000,000, preferably upper limit from the viewpoint of the viscosity of the coating liquid. It is preferably 1,800,000, particularly preferably 1,200,000.

The lower limit of Tg of (A) is preferably −100 ° C., more preferably −90 ° C., particularly preferably −80 ° C. from the viewpoint of the adhesive strength of the adhesive, and the upper limit preferable from the viewpoint of tack of the adhesive is 30 ° C. More preferably, it is 0 ° C., particularly preferably −10 ° C.
Furthermore, (A) is preferably used as a mixture of two or more types from the viewpoint of the adhesive strength of the adhesive to the adherend.

(A) can be produced by various polymerization methods (bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
Solvents used in solution polymerization include esters (C2-8, such as ethyl acetate, butyl acetate), alcohols (C1-8, such as methanol, ethanol, octanol), hydrocarbons (C4-8, such as n-butane, cyclohexane). , Toluene), ketone (C3-9, such as methyl ethyl ketone), and the like.
The amount of the solvent used is usually 5 to 900%, preferably 10 to 400% based on the total weight of the monomers, and the monomer concentration (% by weight) is usually 10 to 95%, preferably 20 to 90%. is there.

Examples of the dispersion medium in emulsion polymerization and suspension polymerization include water, alcohol (C1-12, such as ethanol, butanol, 2-ethylhexanol), ester (C4-10, such as ethyl acetate, ethyl propionate), and light naphtha. Can be mentioned.
As an emulsifier in emulsion polymerization, an anionic surfactant [metal soap (sodium oleate, sodium stearate, etc.), sulfate ester (sodium lauryl sulfate, etc.)], nonionic surfactant [polyethylene glycol type surfactant (nonylphenol ethylene) Oxide 40 mol adducts, etc.), polyhydric alcohol type surfactants (ethoxylated tetramethyldecynediol, lauric acid monoglyceride, etc.), vinyl polymerizable emulsifiers [anion compounds (sulfoethyl sodium methacrylate, etc.), cationic compounds (Such as dimethylaminomethyl methacrylate) and the like].

  As a dispersion stabilizer in suspension polymerization, water-soluble polymers [for example, polyvinyl alcohol (polymerization degree 200 to 5,000), polyvinyl pyrrolidone (Mw 2,000 to 1,000,000), etc.]] and water-insoluble are hardly used. Inorganic compounds (for example, hydroxyapatite, magnesium phosphate, barium sulfate, etc.) can be mentioned.

The amount of the dispersion medium used in the emulsion polymerization and suspension polymerization is usually 0.01 to 15%, preferably 0.1 to 10%, based on the total weight of the monomers, and the monomer concentration (% by weight) is usually It is 10 to 90%, preferably 30 to 70%.
The usage-amount of an emulsifier is 0.01 to 15% normally based on the total weight of a monomer, Preferably it is 0.5 to 10%.
Moreover, the usage-amount of a dispersion stabilizer is 0.01-15% normally based on the total weight of a monomer, Preferably it is 0.1-10%.

The above polymerization may be carried out by using various polymerization initiators [azo compounds [2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile, etc.]], peroxides (benzoyl peroxide). Oxide, di-t-butyl peroxide, lauryl peroxide, etc.).
Further, the system temperature in the polymerization reaction is usually −5 to 150 ° C., preferably 30 to 120 ° C. from the viewpoint of easy temperature control, and the reaction time is usually 0.1 to 50 hours, preferably from the viewpoint of easy production. Is 2 to 24 hours. The end point of the reaction can be confirmed by measuring by gas chromatography or the like that the monomer residual ratio (% by weight based on the total monomer weight) is usually 5% or less, preferably 1% or less.

  For the purpose of further improving the cohesive strength of (A) in the present invention, when (A) has an active hydrogen atom, the functional group (carboxyl group, hydroxyl group, amino group, An organic compound having 2 to 5 reactive functional groups (at least one functional group selected from the group consisting of isocyanate, epoxy, hydrazide, oxazolinyl, and aziridinyl groups) in one molecule that can react with a hydroxymethyl group and the like ( B1) and at least one crosslinking agent (B) selected from the group consisting of polyvalent (2-4 valent) metal compounds (B2) may be further added.

The molecular weight per functional group of (B1) is preferably a molecular weight of 40, more preferably 60 from the viewpoints of cohesive force and adhesive force and tack of the pressure-sensitive adhesive, and a preferable upper limit from the viewpoint of cohesive force and adhesive force is Mw 20,000. More preferably, it is 10,000, and particularly preferably 5,000.
The molecular weight per valence of the polyvalent metal (B2) is preferably a lower limit of 40, more preferably 50 from the viewpoint of cohesive force and adhesive force of the pressure-sensitive adhesive, and tack, and an upper limit of 140 preferable from the viewpoint of cohesive force and adhesive force. More preferably, 130, particularly preferably 110.

  (B1) includes poly (2-5) isocyanate (B11), poly (2-5) epoxide (B12), hydrazide (B13), oxazoline compound (B14) and aziridine compound (B15).

  As polyisocyanate (B11), C (excluding carbon in NCO group, the same shall apply hereinafter) 2-18 aliphatic polyisocyanate, C4-15 alicyclic polyisocyanate, C6-20 aromatic polyisocyanate, C8 -15 aliphatic aliphatic polyisocyanates and one or more compounds selected from the group consisting of modified products of these polyisocyanates.

As the aliphatic polyisocyanate (hereinafter abbreviated as PI), diisocyanate (hereinafter abbreviated as DI) [ethylene DI, tetramethylene DI, hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexamethylene DI, Lysine DI, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Etc.], triisocyanate (hereinafter abbreviated as TI) [1,6,11-undecane TI, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene TI and lysine ester TI (lysine and alkanol) Phosgenates of reaction products with amines), 2- Socynatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanatohexanoate, etc.], and modified products of DI described above, etc. .
Of these, tetramethylene DI and HDI are preferred from the viewpoint of availability and industrial viewpoint.

As the alicyclic PI, DI [isophorone DI (IPDI), dicyclohexylmethane DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene -1,2-dicarboxylate, norbornane DI, etc.], TI [bicycloheptane TI, etc.], and modified products of DI described later.
Among these, IPDI, hydrogenated MDI, and hydrogenated TDI are preferable from the viewpoint of availability and industrial viewpoint.

Aromatic PIs include DI [tolylene DI (TDI) [2,4- and 2,6-TDI and mixtures thereof], diphenylmethane DI (MDI) [4,4′- and 2,4′-MDI and these A mixture of a bifunctional and trifunctional or higher functional PI [crude TDI, crude MDI (polymethylene polyphenyl polyisocyanate), etc.], and a modified product of the above-mentioned DI described later. Can be mentioned.
Among these, TDI, MDI and NDI are preferable from the viewpoint of availability and industrial viewpoint.

Examples of the araliphatic PI include DI [xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene DI (TMXDI), diisocyanatoethylbenzene, etc.], modified products of the above-mentioned DI, and the like. Can be mentioned.
Among these, XDI and TMXDI are preferable from the viewpoint of availability and industrial viewpoint.

  Examples of the modified product of PI include compounds in which a part of the NCO group of PI exemplified above is modified to carbodiimide, uretdione, uretoimine, urea, burette, isocyanurate and / or urethane group.

Among the modified PIs, the urethane group-modified product includes an NCO-terminated urethane prepolymer (a pseudo prepolymer containing free PI) obtained by reacting an excess amount of the above-exemplified PI with an active hydrogen compound. Are included).
Examples of the active hydrogen compound include low-molecular polyvalent (divalent to tetravalent or higher) alcohol, and divalent poly (n = 2 to 30) oxyalkylene (C2 to 4).

Examples of the low molecular weight polyvalent (divalent to tetravalent or higher) alcohol include 2- to 3-valent alcohol [aliphatic alcohol [divalent [C2-20, such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1 , 4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentyl glycol (hereinafter abbreviated as EG, DEG, PG, BD, HG, MPD, NPG), 1,9-nonanediol, , 4-bis (hydroxymethyl) cyclohexane], trivalent [C3-8, such as glycerin, trimethylolpropane (hereinafter abbreviated as GR, TMP, etc.)]; alicyclic alcohol [C4-20, for example, 1,4 -Dihydroxycyclohexane, 2,2-bis (4,4'-hydroxycyclohexyl) propa An aromatic ring-containing alcohol [C8-15, such as m- and p-xylylene glycol, 1,4-bis (hydroxyethyl) benzene], etc.] and a tetrahydric or higher polyhydric alcohol [C5-10 or Further, for example, pentaerythritol, α-methyl glucoside, sorbitol, xylit, mannitol, glucose, fructose, sucrose, dipentaerythritol, polyglycerin (degree of polymerization 2-20) and the like.
Examples of the divalent to trivalent poly (n = 2 to 30) oxyalkylene (C2 to 4) include the above low molecular polyhydric alcohol and / or polyhydric phenol (C6 to 20, for example, catechol, resorcinol, bisphenol A, -S, and And polyether polyols obtained by adding alkylene oxide (C2-4, hereinafter abbreviated as AO) to -F).

  The PI exemplified above may be blocked with a blocking agent. Examples of the blocking agent include phenol compounds (C6-24, such as phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, chlorophenol, nitrophenol, thymol, mono-, di- and tri-α-phenylethylphenol. Active methylene compounds [C4-20, such as acetoacetate (ethyl acetoacetate, butyl acetoacetate, etc.), malonic acid diesters (diethyl malonate, ethylbutyl malonate, ethylbenzyl malonate, etc.), acetylacetone, Benzimidazole and 1-phenyl-3-methyl-5-pyrazolone]; lactams (C4-12, eg ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolacta Oxime (C3-12 such as acetooxime, methyl ethyl ketone oxime, cyclohexanone oxime, maldooxime, acetoaldoxime, benzophenone oxime and diethylglyoxime); alcohol (C1-24 such as methanol, ethanol, n-butanol, t- Butyl alcohol, t-amyl alcohol, dimethylethynyl carbinol, dimethyl phenyl carbinol, methyl diphenyl carbinol, triphenyl carbinol, 1-nitro-t-butyl carbinol, 1-chloro-t-butyl carbinol and triphenyl Secondary aromatic amines (C6-20, such as diphenylamine, o-, m-, p-ditoluylamine, N-naphthyltoluidine, N-naphthylxylidine, phenol) Α-naphthylamine, phenyl β-naphthylamine, carbazole, 2,2′-dinitrodiphenylamine and 2,2′-dichlorophenylamine); mercapto compounds (C1-18, such as 2-mercaptobenzothiazole, 2-mercaptothiazoline, dodecyl mercaptan) , Ethyl 2-mercaptothiazole, 2-mercapto5-chlorobenzothiazole, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, phenyl mercaptan, toluyl mercaptan, ethylphenyl mercaptan and ethynyldimethylthiocarbinol); imidazole compound (C3- 10, eg imidazole and 2-ethylimidazole); acid amides (C3-50, eg acetanilide, acrylamide and Fine dimer acid amides); imide (C4～10, e.g. succinimide, phthalimide, and glutaric acid imide) and bisulfite salts.

  In the NCO-terminated urethane prepolymer, the equivalent ratio of NCO group to active hydrogen in PI (NCO / active hydrogen equivalent ratio) is usually 1.1 / 1 to 100/1, preferably 2/1 to 80/1. More preferably, it is 3/1 to 60/1. The NCO content (% by weight) in the urethane prepolymer is usually 3 to 35%.

Examples of the polyepoxide (B12) include glycidyl type polyepoxide (B121) (epoxy equivalent 80 to 2,500) and non-glycidyl type polyepoxide (B122) (epoxy equivalent 43 to 10,000).
Examples of (B121) include glycidyl ether [polyglycol (above) glycidyl ether (bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, pyrogallol triglycidyl ether, etc.), glycidyl ether of low molecular weight polyhydric alcohol (above) ( EG-, PG- and NPG diglycidyl ether, TMP- and GR triglycidyl ether, etc.), glycidyl ether of polyether polyol (described above) [polyethylene glycol (hereinafter abbreviated as PEG) (Mw 200-2,000), polypropylene glycol ( (Hereinafter abbreviated as PPG) (Mw 200 to 2,000) and diglycidyl ether of bisphenol A AO 1 to 20 mol addition product]]; glycidyl ester [polycarboxylic acid (n = 2 to 4 Glycidyl ester (diglycidyl ester of adipic acid, phthalic acid and dimer acid, trimellitic acid triglycidyl ester, etc.); glycidyl amine [primary amine (C2-10, such as hexamethylenediamine, aniline, toluidine, Xylylenediamine) or poly (n = 2 to 4 or more) amine glycidylates [N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiamino] Diphenylmethane, N, N, N ′, N′-tetraglycidylxylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidylhexamethylenediamine ] Etc. are mentioned.

  (B122) include aliphatic polyepoxides [C4-20, such as epoxidized (poly) alkadiene [epoxidized butadiene, epoxidized poly (n = 2 to 4 or more) butadiene, epoxidized oils and fats (epoxidized soybean oil, etc.] And the like] and alicyclic polyepoxides (such as limonene dioxide and dicyclopentadiene dioxide).

  As the hydrazide (B13), polycarboxylic acids [C2-15, such as aliphatic (oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, maleic acid), aromatic (phthalic acid, terephthalic acid, isophthalic acid, Naphthalenedicarboxylic acid etc.)] and the like, and alkylene (C2-6) dihydrazide (ethylene-1,2- and propylene-1,3-dihydrazide etc.).

  Examples of the oxazoline compound (B14) include C3-10, such as 2-oxazoline, and 2-alkyl (C1-4) substituted products thereof, such as 2-methyl-, 2-ethyl-2-, 2-isopropyl-2- and 2-n-propyl-2-oxazoline is mentioned.

  Examples of the aziridine compound (B15) include C10-50, for example, poly (n = 2-4 or more) amine derivatives [1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridinyl urea. 1,1 ′-(hexamethylene) bis-3,3-aziridinylurea, etc.], poly (2-aziridinylpropionate) of low molecular weight polyhydric alcohol (described above) [ethylenebis- (2-aziridinini Lupropionate), trimethylolpropane-tris- (2-aziridinylpropionate), 2,4,6-triaziridinyl-1,3,5-triazine and the like.

  The polyvalent metal compound (B2) includes polyvalent (2-4 valent) metals [IIA group (Mg, Ca, etc.), IIB group (Zn, etc.), IIIA group (Al, etc.), IVA group (Sn, Pb, etc.) ), Transition metals (Ti, Zr, manganese, Fe, Co, Ni, Cu, etc.)] chelate compounds (chelates with chelators such as β diketones, acetylacetone, acetoacetates, etc.) {eg aluminum chelate compounds [aluminum acetyl Acetonate [Kawaken Fine Chemical Co., Ltd. “Aluminum Chelate A (W)” etc.] etc.]}; Rosin metal salt (hardened rosin such as Ca, Zn); and Carboxylic acid metal salt [Carboxylic acid (C2-20, For example, a polyvalent metal (same as above) salt of acetic acid or stearic acid].

  The amount of the crosslinking agent (B) used is expressed in terms of the equivalent ratio of the active hydrogen in the copolymer (A) and the functional group (B1) that reacts with the active hydrogen or the valence of (B2). From the viewpoint of adhesive residue on the adherend and adhesion to the adherend, the amount is preferably 1 / 0.01 to 1/2, and more preferably 1 / 0.02 to 1/1.

  In the antistatic pressure-sensitive adhesive of the present invention, a tackifying resin (C1), a plasticizer (C2), a filler (C3), a pigment (C4), a pigment, and the like, as long as the effects of the present invention are not impaired. At least one additive (C) selected from the group consisting of an ultraviolet absorber (C5), an antioxidant (C6) and a silane coupling agent (C7) can be further added.

Examples of the tackifying resin (C1) include terpene, terpene phenol, phenol, aromatic hydrocarbon modified terpene, rosin, modified rosin, synthetic petroleum (aliphatic, aromatic and alicyclic synthetic petroleum resin, etc.), coumarone- Examples include indene, xylene, styrenic and dicyclopentadiene resins, and hydrogenates of these having unsaturated double bonds, and mixtures thereof.
The amount of (C1) used is usually 100% or less based on the weight of (A), and preferably 5 to 50% from the viewpoint of the adhesive strength and tack of the adhesive.

Plasticizers (C2) include hydrocarbons [C6-Mw 100,000, such as process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, paraffin wax, ethylene and α-olefin (C3-20). Polymerization (weight ratio 99.9 / 0.1 to 0.1 / 99.9) oligomer (Mw 5,000 to 100,000), copolymer of α-olefin (C4-20) excluding ethylene and propylene (weight ratio) 99.9 / 0.1-0.1 / 99.9) oligomer (Mw 5,000-100,000) etc.]; chlorinated paraffin [chlorinated normal paraffin (C8-22), chlorinated branched paraffin (C20- 32) etc.]; esters [C8-30, such as phthalic acid esters (diethyl phthalate, dibutyl phthalate, dioctyl) Phthalate, didecyl phthalate, dilauryl phthalate, distearyl phthalate, diisononyl phthalate, etc.), adipic acid ester (dioctyl adipate, etc.), sebacic acid ester (dioctyl sebacate, etc.)], etc .; Among these, a hydrogenated product having an unsaturated double bond; and a mixture thereof.
The amount of (C2) used is usually 50% or less based on the weight of (A), and preferably 2 to 30% from the viewpoints of adhesive coating properties, adhesive adhesive strength, and cohesive strength.

Fillers (C3) include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfites (calcium sulfite, etc.), metal sulfides (molybdenum disulfide, etc.) Silicates (aluminum silicate, calcium silicate, etc.), diatomaceous earth, quartzite powder, talc, silica, zeolite, and mixtures thereof. (C3) is preferably fine particles having a volume average particle diameter of 0.01 to 5 μm from the viewpoint of the adhesive strength of the adhesive.
The amount of (C3) used is usually 50% or less based on the weight of (A), and preferably 5 to 30% from the viewpoint of tackiness and cohesive strength of the pressure-sensitive adhesive.

As the pigment (C4), inorganic pigments [earth-based pigments (yellow ocher, tail belt, gypsum, etc.), calcined earth (burnt schenner, etc.), mineral pigments (lapis lazuli, azurite, etc.), oxide pigments (cobalt blue, Titanium white, zinc white, etc.), hydroxide pigments (bilijan, alumina white, etc.), sulfide pigments (cadmium yellow, cadmium red, etc.), silicate pigments (talc, clay, etc.), phosphate pigments (mineral violet, etc.) , Carbonate pigments (calcium carbonate, silver white, etc.), metal powder pigments (aluminum powder, gold powder, etc.), carbon pigments (carbon black, ivory black, etc.), organic pigments (vegetable pigments (madder lake, etc.), animal nature Pigments (cochineal, sepia, etc.), lake pigments (alizarin lake, quinoline yellow Azo pigments (first yellow, disazo yellow, naphthol red, etc.), azo complex pigments (nickel azo yellow, benzimidazolone yellow, etc.), phthalocyanine pigments (phthalocyanine blue, etc.), condensed polycyclic pigments (thioindigo, perylene red) And the like, and mixtures thereof.
(C4) is preferably fine particles having a volume average particle diameter of 0.01 to 5 μm from the viewpoint of the adhesive strength of the adhesive. The amount of (C4) used is usually 20% or less based on the weight of (A), and preferably 1 to 10% from the viewpoint of tackiness and cohesive strength of the pressure-sensitive adhesive.

Examples of the ultraviolet absorber (C5) include salicylic acid derivatives (phenyl salicylate, salicylic acid-p-octylphenyl, salicylic acid-p-tert-butylphenyl, etc.); benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy Benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2- Hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2, 2 ', 4 4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane Etc.]; benzotriazole compounds {2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert- Butyl-phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, -(2'-hydroxy-5'-n-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- [2' -Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like}; cyanoacrylate compounds (2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-cyano-3, 3'-diphenyl acrylate, etc.); and mixtures thereof.
The amount of (C5) used is usually 5% or less based on the weight of (A), and preferably 0.1 to 1% from the viewpoint of the ultraviolet absorption effect and the adhesive strength of the adhesive.

Antioxidants (C6) include hindered phenols [2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), Ethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] etc.]; Sulfur [Dilauryl 3,3′-thiodipropionate (DLTDP), Distearyl 3,3′-thiodipropionate (DSTDP), etc.]]; Phosphorus [may have a halogen Organic phosphites such as triphenyl phosphite (TPP), triisodecyl phosphite (TDP), tris (2,4-di-t-butyl Benzyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and their halo-substituted products]; hindered amine system [octyldiphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine etc.]; and mixtures thereof.
The amount of (C6) used is usually 5% or less based on the weight of (A), preferably from 0.05 to 1% from the viewpoint of the antioxidant effect and the adhesive strength of the adhesive.

Examples of the silane coupling agent (C7) include polymerizable unsaturated group-containing silicon compounds (vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, etc.), epoxy group-containing silicon compounds [3-glycidoxypropyl Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.], amino group-containing silicon compound [3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and the like], 3-chloropropyltrimethoxysilane and the like, and mixtures thereof.
The amount of (C7) used is usually 15% or less based on the weight of (A), preferably from 0.001 to 10%, more preferably from the viewpoint of adhesiveness to the adherend and transparency. 0.005 to 5%.

  The total amount of (C) used based on the weight of (A) is usually 230% or less, preferably 0.001 to 150%, more preferably 10 to 120%.

The antistatic pressure-sensitive adhesive of the present invention is produced by uniformly mixing (A) and, if necessary, (B) and (C) with an ordinary mixing device (mixing tank equipped with a stirrer, static mixer, etc.). it can. (C) may be added at the stage of production of (A) (raw material before production, reaction product during production or product after production).
The content of (A) based on the total weight of the solid content of the pressure-sensitive adhesive of the present invention is preferably 20 to 100%, more preferably 30 to 100%, particularly preferably 40 to 100 from the viewpoint of pressure-sensitive adhesive strength and tack. %.

The pressure-sensitive adhesive of the present invention is preferably used as a solution to which a solvent is added, an emulsion or a dispersion from the viewpoint of coating.
Solvents include esters (C2-8, such as methyl formate, ethyl acetate, butyl acetate), alcohols (C1-8, such as isopropanol), hydrocarbons (C4-8, such as hexane, cyclohexane, toluene, xylene), ketones ( C3-9, such as acetone, methyl ethyl ketone, and cyclohexanone).
The amount of the solvent used is preferably 5 to 900%, more preferably 10 to 400% based on the total solid content of the pressure-sensitive adhesive from the viewpoint of coating properties, and the solid content concentration of the solution is preferably It is 10 to 95%, more preferably 20 to 90%.
The viscosity (25 ° C.) of the solution is preferably 100 to 50,000 mPa · s, more preferably 200 to 30,000 mPa · s from the viewpoint of coating.

Examples of the dispersion medium in the emulsion and dispersion, the emulsifier in the emulsion, and the dispersion stabilizer in the dispersion include those exemplified in the emulsion polymerization and suspension polymerization of (A). The amount of the dispersion medium used is preferably 10 to 900%, more preferably 50 to 500%, based on the total solid content of the pressure-sensitive adhesive, from the viewpoint of coating properties.
The use amount of the emulsifier is preferably 0.1 to 10%, more preferably 0.5 to 8% based on the total solid content of the pressure-sensitive adhesive from the viewpoint of adhesive strength and water resistance, and the use amount of the dispersion stabilizer. Is preferably 0.1 to 10%, more preferably 0.5 to 8%, based on the total solid content of the pressure-sensitive adhesive, from the viewpoint of adhesive strength.
The viscosity (25 ° C.) of the emulsion and dispersion is preferably 10 to 20,000 mPa · s, more preferably 50 to 10,000 mPa · s from the viewpoint of coating.

Among the pressure-sensitive adhesive tape, sheet and film of the present invention, the pressure-sensitive adhesive tape and pressure-sensitive adhesive sheet are directly applied to at least a part of at least one side of the substrate using various coating apparatuses, and heated. A method of drying the solvent or dispersion medium and advancing the reaction, further curing and curing, or a pressure-sensitive adhesive obtained by applying a pressure-sensitive adhesive to a release film in the same manner, and then drying and curing Can be produced by a method of transferring to at least one side of the substrate.
In addition, the adhesive film is obtained by directly applying the adhesive of the present invention to at least a part of at least one side of a substrate having releasability, such as a release film, using various coating apparatuses, and heating to apply a solvent or dispersion. It can be produced by a method of drying the medium, advancing the reaction, and further curing and curing.
Examples of the coating apparatus include a gravure coater, a roll coater, a reverse coater, a doctor blade, a bar coater, a comma coater, a fountain die coater, a lip coater, and a knife coater.
Base materials include films, sheets, foams and flat yarns of various plastics [polyolefin (polyethylene, polypropylene, etc.), polyurethane, polyethylene terephthalate, polyvinyl chloride, rayon, polyamide resin, etc.], paper (Japanese paper, crepe paper, etc.) , Metal plate or metal foil, woven fabric, non-woven fabric, wood and the like.
Among these base materials, those that are easily charged are desirably provided with antistatic properties by adding or coating various antistatic agents.

Examples of the heating means for curing the pressure-sensitive adhesive of the present invention include hot air (60 to 150 ° C.), (near) infrared light, and high frequency.
Moreover, as said curing conditions, about 3 to 7 days at room temperature or about 12 to 72 hours at 45 degreeC is mentioned, for example.
The coating thickness after drying / curing of the pressure-sensitive adhesive is usually from 1 to 250 μm, and preferably from 10 to 100 μm from the viewpoint of adhesive strength, drying and curability.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents% by weight.
.

[Production of quaternary onium carbonate ester salt (z1)]
Production Example 1
In a stirred autoclave, 295 parts of EO4 molar adduct of methyldiethanolamine, 90 parts of dimethyl carbonate and 64 parts of methanol as a solvent were added and reacted at a reaction temperature of 110 ° C. for 12 hours, and then methanol was distilled off at 50 ° C. under reduced pressure. As a result, 385 parts of quaternary ammonium monomethyl carbonate (z1-1) was obtained.

Production Example 2
In Production Example 1, in place of 295 parts of EO 4 mol adduct of methyldiethanolamine, 911 parts of EO 18 mol adduct of methyldiethanolamine was used in the same manner as in Production Example 1, and quaternary ammonium monomethyl carbonate ( z1-2) 1,001 parts were obtained.

Production Example 3
In Production Example 1, the same procedure as in Production Example 1 except that 295 parts of EO 4 mol adduct of methyldiethanolamine and 391 parts of butylamine 4 mol adduct of cyclohexylamine and 286 parts of dioctyl carbonate were used instead of 90 parts of dimethyl carbonate. To 677 parts of quaternary ammonium monooctyl carbonate (z1-3).

Production Example 4
In Production Example 1, instead of 295 parts of EO4 molar adduct of methyldiethanolamine and 90 parts of dimethyl carbonate, 217 parts of EO2 molar adduct of 2-ethylhexylamine and 242 parts of dibenzyl carbonate were used. In the same manner, 459 parts of quaternary ammonium monobenzyl carbonate (z1-4) was obtained.

Production Example 5
In Production Example 1, quaternary ammonium monomethyl carbonate was prepared in the same manner as in Production Example 1 except that 609 parts of EO2 molar adduct of distearylamine was used instead of 295 parts of EO4 molar adduct of methyldiethanolamine. 699 parts of salt (z1-5) were obtained.

Comparative production example 1
The same procedure as in Production Example 1 was carried out except that 311 parts of didecylmethylamine was used in place of 295 parts of EO4 molar adduct of methyldiethanolamine in Production Example 1, and comparative didecyldimethylammonium monomethyl carbonate (ratio) z1-1) 401 parts were obtained.

[Production of Monomer (a12) Having Quaternary Onium / Organic Acid Base]
Production Example 5
In Production Example 1, quaternary ammonium acrylate is prepared by adding 72 parts of acrylic acid to a 75% methanol solution of (z1-1) before distilling off methanol and removing by-product carbon dioxide and methanol. (A12-1) 531 parts were obtained.

[Production of pressure-sensitive adhesive comprising a hydrocarbyl (meth) acrylate copolymer (A) having a quaternary onium / organic acid group]
Example 1
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube was charged with 184 parts of ethyl acetate and 120 parts of cyclohexane and heated to 75 ° C. Next, 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and a monomer obtained by ring-opening addition of succinic anhydride to a polycaprolactone adduct of 2-hydroxyethyl methacrylate [Product name “FM-1A”, manufactured by Daicel Chemical Industries, Ltd., and so on. 20 parts and 0.3 part of 2,2′-azobisisobutyronitrile (AIBN) were charged to obtain a homogeneous mixed solution. The dropping funnel was attached to the reaction vessel, and was continuously dropped into the reaction vessel over 4 hours while passing nitrogen gas, and radical polymerization was performed. After completion of the dropping, the mixture was aged for 2 hours, and then 81.5 parts of an AIBN / ethyl acetate (1.5 parts / 80 parts) solution was continuously dropped using a dropping funnel over 4 hours for radical polymerization.
Furthermore, after continuing the polymerization at the boiling point (about 90 ° C.) for 4 hours, 216 parts of toluene was added as a diluent solvent, and a solution of the hydrocarbyl (meth) acrylate copolymer (A01-1) having a carboxylic acid group Got.
By adding 4.3 parts of (z1-1) to 100 parts of the solution of (A01-1), the reaction is carried out at a reaction temperature of 80 ° C. for 8 hours, and by-produced carbon dioxide gas is removed to remove quaternary ammonium carboxyls. An antistatic pressure-sensitive adhesive (X-1) comprising a solution of a hydrocarbyl (meth) acrylate copolymer (A-1) having an acid base was obtained. The viscosity of (X-1) (B-type viscometer: 25 ° C., the same shall apply hereinafter) is 6,200 mPa · s, the solid content concentration is 42%, and Mw by GPC method of (A-1) (polystyrene conversion, the same shall apply hereinafter). ) Was 470,000.

Example 2
In Example 1, instead of using 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, and 48 parts of vinyl acetate, 142 parts of n-butyl acrylate, 182 parts of 2-ethylhexyl acrylate, and 40 parts of vinyl acetate were used. Was carried out in the same manner as in Example 1 to obtain a solution of a hydrocarbyl (meth) acrylate copolymer (A01-2) having a carboxylic acid group.
Next, 11.1 parts of (z1-2) is added to 100 parts of the solution of (A01-2), and the same procedure as in Example 1 is followed. Hydrocarbyl having a quaternary ammonium carboxylate group (meta ) An antistatic pressure-sensitive adhesive (X-2) comprising a solution of the acrylate copolymer (A-2) was obtained. The viscosity of (X-2) was 7,800 mPa · s, the solid content concentration was 45.6%, and the Mw of (A-2) was 450,000.

Example 3
In Example 1, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 190 parts of n-butyl acrylate, 190 parts of 2-ethylhexyl acrylate, 2 parts -It carried out similarly to Example 1 except having used 4 parts of hydroxyethyl acrylate, and obtained the solution of the hydrocarbyl (meth) acrylate copolymer (A01-3) which has a carboxylic acid group.
Next, 7.5 parts of (z1-3) is added to 100 parts of the solution of (A01-3), and the same procedure as in Example 1 is followed. Hydrocarbyl having a quaternary ammonium carboxylate group (meta ) An antistatic pressure-sensitive adhesive (X-3) comprising a solution of the acrylate copolymer (A-3) was obtained. The viscosity of (X-3) was 5,700 mPa · s, the solid content concentration was 43.2%, and the Mw of (A-3) was 510,000.

Example 4
In Example 1, 184 parts of ethyl acetate, 120 parts of cyclohexane, 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, 20 parts of “FM-1A”, AIBN 0.3 Part, a solution of 1.5 parts of AIBN in 80 parts of ethyl acetate, instead of 216 parts of toluene, 88 parts of ethyl acetate, 88 parts of cyclohexane, 24 parts of quaternary ammonium acrylate (a12-1), n -Toluene 336: 140 parts of butyl acrylate, 188 parts of 2-ethylhexyl acrylate, 8 parts of acrylic acid, 20 parts of methyl methacrylate, 20 parts of styrene, 0.4 parts of AIBN, and 88 parts of ethyl acetate. The quaternary ammonium carboxylic acid was prepared in the same manner as in Example 1, except that An antistatic pressure-sensitive adhesive (X-4) comprising a solution of a hydrocarbyl (meth) acrylate copolymer (A-4) having a base was obtained. The viscosity of (X-4) was 3,900 mPa · s, the solid content concentration was 40.1%, and the Mw of (A-4) was 410,000.

Example 5
In Example 1, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, and 20 parts of “FM-1A”, 166 parts of n-butyl acrylate, 166 parts of 2-ethylhexyl acrylate, 2 parts -Using 20 parts of methacryloyloxyethyl acid phosphate [trade name "JPA-514", manufactured by Johoku Chemical Co., Ltd.], replacing 216 parts of toluene added as a diluent solvent with 184 parts of ethyl acetate and 120 parts of cyclohexane, A solution of hydrocarbyl (meth) acrylate copolymer (A01-5) having a phosphate group was obtained in the same manner as in Example 1 except that the solvent was previously charged in the reaction vessel and the temperature was raised. It was.
Next, 7.8 parts of (z1-5) are added to 100 parts of the solution of (A01-5), and the same procedure as in Example 1 is followed, followed by hydrocarbyl (quaternary ammonium phosphate group) ) An antistatic pressure-sensitive adhesive (X-5) comprising a solution of the acrylate copolymer (A-5) was obtained. The viscosity of (X-5) was 1,100 mPa · s, the solid content concentration was 42.1%, and the Mw of (A-5) was 100,000.

Example 6
In Example 1, 120 parts of cyclohexane was replaced with 120 parts of methanol, and 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, and 20 parts of “FM-1A” were replaced with n-butyl acrylate. 166 parts, 2-ethylhexyl acrylate 166 parts, 2-acrylamido-2-methylpropanesulfonic acid [trade name “TBAS-Q”, manufactured by Nitto Chemical Co., Ltd.] 20 parts were used in the same manner as in Example 1. Then, a hydrocarbyl (meth) acrylate copolymer solution (A01-6) having a sulfonic acid group was obtained.
Next, 4.3 parts of (z1-1) is added to 100 parts of the solution of (A01-6), and the same procedure as in Example 1 is followed, and the hydrocarbyl having a quaternary ammonium sulfonate group (meta ) An antistatic pressure-sensitive adhesive (X-6) comprising a solution of the acrylate copolymer (A-6) was obtained. The viscosity of (X-6) was 7,200 mPa · s, the solid content concentration was 41.9%, and the Mw of (A-6) was 400,000.

Example 7
A reaction vessel was charged with 185 parts of N, N-di (2-hydroxyethyl) sulfamic acid and 593 parts of toluene. At a reaction temperature of 30 ° C., methacryloyl isocyanate [trade name “MAI”, manufactured by Nippon Paint Co., Ltd. ] After adding 222 parts dropwise over 1 hour, the mixture was further reacted for 1 hour, and toluene was distilled off at 50 ° C. under reduced pressure to add methacryloyl isocyanate and N, N-di (2-hydroxyethyl) sulfamic acid. The body (B-1) was obtained.
In Example 1, 120 parts of cyclohexane was replaced with 120 parts of methanol, and 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, and 20 parts of “FM-1A” were replaced with n-butyl acrylate. Using 166 parts, 166 parts of 2-ethylhexyl acrylate, and 20 parts of (B-1), 216 parts of toluene added as a diluting solvent is replaced with 184 parts of ethyl acetate and 120 parts of methanol, and these solvents are charged in a reaction vessel in advance. Except having been heated up, it carried out similarly to Example 1 and obtained the solution of the hydrocarbyl (meth) acrylate copolymer (A01-7) which has a quaternary ammonium sulfamate group.
Next, 4.3 parts of (z1-1) is added to 100 parts of the solution of (A01-7), and the same procedure as in Example 1 is followed, and hydrocarbyl having a quaternary ammonium sulfamate group (meta ) An antistatic pressure-sensitive adhesive (X-7) comprising a solution of the acrylate copolymer (A-7) was obtained. The viscosity of (X-7) was 3,100 mPa · s, the solid content concentration was 42.3%, and the Mw of (A-7) was 150,000.

Comparative Example 1
In Example 1, instead of 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 150 parts of 2-ethylhexyl acrylate and 12 parts of acrylic acid were used. It carried out like Example 1 and obtained the solution of the hydrocarbyl (meth) acrylate copolymer (ratio A01-1) which has a carboxylic acid group.
The viscosity of the solution was 2,900 mPa · s, the solid content concentration was 40.3%, and the Mw of (ratio A01-1) was 410,000. 250 parts of this solution was mixed with 1.5 parts of lithium perchlorate and 30 parts of polyether diol [trade name “Sanix PP-400”, manufactured by Sanyo Chemical Industries, Ltd.], and a comparative antistatic adhesive ( A ratio X-1) was obtained.

Comparative Example 2
In Example 1, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 260 parts of n-butyl acrylate and 2-ethylhexyl Except having used 128 parts of acrylates and 12 parts of acrylic acid, it carried out like Example 1 and the solution of the hydrocarbyl (meth) acrylate copolymer (ratio A01-2) was obtained.
The viscosity of the solution was 4,100 mPa · s, the solid content concentration was 40.4%, and the Mw of (ratio A01-2) was 460,000. 750 parts of this solution was mixed with 7.5 parts of lithium perchlorate and 90 parts of polyether triol [trade name “Sanix GP-4000”, manufactured by Sanyo Chemical Industries, Ltd.], and a comparative antistatic pressure-sensitive adhesive ( A ratio X-2) was obtained.

Comparative Example 3
In Example 1, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 40 parts of n-butyl acrylate, 2-ethylhexyl Except having used 320 parts of acrylates, 20 parts of acrylic acid, and 20 parts of 2-hydroxyethyl acrylate, it carries out similarly to Example 1 and the solution of a hydrocarbyl (meth) acrylate copolymer (ratio A01-3) is obtained. It was.
The viscosity of the solution was 2,100 mPa · s, the solid content concentration was 40.3%, and the Mw of (ratio A01-3) was 400,000. 20 parts of carbon black was dispersed in 980 parts of the solution to obtain a comparative antistatic pressure-sensitive adhesive (ratio X-3).

Comparative Example 4
In Example 1, it replaced with 4.3 parts of (z1-1), and carried out similarly to Example 1 except having used 4.5 parts of (ratio z1-1), and the quaternary ammonium carboxylate group. An antistatic pressure-sensitive adhesive (ratio X-4) comprising a solution of hydrocarbyl (meth) acrylate copolymer (ratio A-1) having The viscosity of (Ratio X-4) was 6,350 mPa · s, the solid content concentration was 42.2%, and the Mw of (Ratio A-1) was 470,000.

Example 8
To 100 parts of the above (X-1), 10% toluene of N, N, N ′, N′-tetraglycidylxylylenediamine [manufactured by Mitsubishi Gas Chemical Industries, Ltd., trade name “TETRAD-X”] as a crosslinking agent 1 part of the solution was added and mixed uniformly to prepare a blended solution. This compounded liquid was applied to a release polyester film [Lintec Co., Ltd., trade name “Super Tech SP-PET38”] base material so that the film thickness after drying was 100 μm, and further 100 minutes at 60 ° C. for 100 minutes. Each was dried with hot air at 1 ° C. for 1 minute, further cured at 45 ° C. for 3 days, and then peeled off from the release polyester film to obtain a pressure-sensitive adhesive film (a film made of only a pressure-sensitive adhesive without a base material).
In the above, “Super Tech” was replaced with a polyester film [trade name “Lumirror” type T, manufactured by Toray Industries, Inc.], and the above mixture was dried on the film so that the film thickness was 25 μm after drying. In the same manner as described above, a pressure-sensitive adhesive film (a film composed of a base material and a pressure-sensitive adhesive; the same applies hereinafter) was obtained. The pressure-sensitive adhesive film or pressure-sensitive adhesive film was evaluated according to the following performance evaluation method. The results are shown in Table 1.

Examples 9-13
The same operation as in Example 8 was performed using (X-2) to (X-6) to prepare an adhesive film or an adhesive film, and each performance was evaluated. The evaluation results are shown in Table 1.

Example 14
In Example 8, instead of 100 parts of (X-1) and 1 part of a 10% toluene solution of N, N, N ′, N′-tetraglycidylxylylenediamine, (X-7) 100 parts, acetylacetone aluminum [ The same operation as in Example 8 was carried out except that 0.15 part of Nippon Kagaku Sangyo Co., Ltd., trade name “Nursem Aluminum”] was used, and an adhesive film or an adhesive film was prepared to evaluate each performance. did. The evaluation results are shown in Table 1.

Comparative Examples 5-8
The same operation as in Example 8 was performed using (Ratio X-1) to (Ratio X-4) to prepare an adhesive film or an adhesive film, and each performance was evaluated. The evaluation results are shown in Table 1.

[Performance test method]
(1) Adhesive strength Adhesive film test piece was affixed to a stainless steel plate (SUS304, the same shall apply hereinafter) so that the affixed area would be 25 mm wide × 100 mm long [one reciprocation with a 2 kg load roller, and so on. ] Adhesive strength at normal temperature (23 ° C.) according to JIS-Z-0237 for 30 minutes after pasting (initial) and after 30 minutes after pasting, heat treated at 60 ° C. for 1 week (after heating promotion) (Unit: N / 25 mm) was evaluated.
(2) Antistatic properties (surface resistivity, volume resistivity)
After the pressure-sensitive adhesive film test piece was allowed to stand for 12 hours under the condition of 23 ° C. × 65% RH, the surface specific resistance and volume specific resistance were evaluated by the method described in JIS-K6911.
(3) Transparency The pressure-sensitive adhesive film test piece was visually observed and the presence or absence of cloudiness of the pressure-sensitive adhesive film was evaluated according to the following criteria.
○: No cloudiness ×: Cloudiness is present (4) Peelability Here, peelability is the pressure-sensitive adhesive due to cloudiness of the pressure-sensitive adhesive application surface of the pressure-sensitive adhesive film after peeling off from the adherend, residual adhesive paste on the adherend, etc. It means the presence or absence of roughness (irregularity) on the coated surface.
After sticking an adhesive film test piece on a stainless steel plate so that the pasting area is 25 mm wide × 100 mm long, condition (1) [normal temperature (23 ° C.) × after 2 hours to 60 ° C. × 6 hours after heat treatment , Normal temperature (23 ° C. × 2 hours later) or condition (2) [normal temperature (23 ° C.) × 2 hours later, 60 ° C. × 1 month after heat treatment, normal temperature (23 ° C.) × 2 hours later] Is evaluated with the naked eye according to the following criteria.
○: No roughening such as cloudiness or adhesive residue marks on the adhesive application surface ×: Roughness such as fogging or adhesive residue marks is observed on the adhesive application surface

(5) Dissolution test (dissolution test of alkali metals and halogen ions)
20 ml of ultrapure water was put into a 100 ml Erlenmeyer flask, 1 g of a pressure-sensitive adhesive film test piece was immersed therein, and allowed to stand in an autoclave at 121 ° C. for 24 hours. The immersion liquid after taking out the test piece was concentrated to 1/10, and the concentration of metal ions was measured with an atomic absorption photometer. The halogen ion was measured by a colorimetric method.
(6) Contamination to adherend surface Adhesive film test piece of 50 x 100 mm area is attached to a stainless steel plate and left to stand for 1 week under the condition of 60 ° C x 90% RH. The presence or absence of contamination such as cloudiness and adhesive residue on the surface was observed with the naked eye and evaluated according to the following criteria.

○: Neither cloudy or adhesive residue △: Slightly cloudy or adhesive residue ×: Remarkably cloudy or adhesive residue

(7) Holding power (cohesive force)
Measured according to JIS-Z-0237. That is, the adhesive application surface of the adhesive film test piece was pasted on a stainless steel plate so that the area was 25 mm × 25 mm, and it was pressure-bonded by reciprocating a 2 kg load roller for 1 hour under the condition of 23 ° C. × 65% RH. After leaving still, it left still for 30 minutes in 40 degreeC and 65% RH atmosphere, applied 1 kg load, and measured the shift | offset | difference distance (unit: mm) after 24 hours.

  From the results shown in Table 1, the antistatic pressure-sensitive adhesive of the present invention is superior in antistatic property, transparency, peelability, adherend non-contaminating property and holding power as compared with the comparative example, and the adhesive force and its aging. It turns out that it is excellent also in stability.

  An adhesive tape formed by applying the antistatic adhesive of the present invention to at least a part of at least one side of a substrate, an adhesive sheet, and an adhesive film comprising the adhesive are a polarizing plate, a retardation plate, a light diffusing plate, etc. Various optical members, surface protection films such as stainless steel and plastic, tapes for processing electronic parts such as dicing tapes and carrier tapes, various optical members such as polarizing plates, retardation plates and light diffusion plates, liquid crystal displays, organic EL displays, plasmas It can be used for a wide range of image display devices such as displays and field emission displays, and is extremely useful.

Claims (7)

It contains a hydrocarbyl (meth) acrylate copolymer (A) having at least one quaternary onium-organic acid group represented by the following general formula (1) at the molecular side chain and / or molecular end. An antistatic adhesive characterized by.
[Wherein, Q is N, R ¹ and R ³ are each a straight-chain, branched or ring-containing hydrocarbon group or nonionic molecular chain having 1 to 20 carbon atoms which may contain O and / or N. A hydrocarbon group having 1 to 20 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms or a ring-containing hydrocarbon group, A ¹ and A ² are alkylene groups having 2 to 4 carbon atoms, and m and n are , M + n is a positive integer from 2 to 20, p is 0 or 1, X ⁻ is hydrogen from an organic acid group selected from the group consisting of a carboxylic acid group, a (phosphite) group, a sulfonic acid group and a sulfamic acid group Represents residues without. ] The copolymer represented by the following general formula (2) is a copolymer having (A) an organic acid group-containing monomer (a11) and a hydrocarbyl (meth) acrylate (a2) excluding (a11) as essential constituent units. A copolymer obtained by reacting a quaternary onium-carbonate ester salt (z1), or a quaternary onium-organic acid group-containing monomer (a12) obtained by reacting the (z1) with the (a11); The pressure-sensitive adhesive according to claim 1, which is a copolymer having (a2) as an essential structural unit.
[Wherein Q is N, R ¹ and R ³ are each separated by a linear, branched or ring-containing hydrocarbon group having 1 to 20 carbon atoms which may contain O and / or N or a nonionic molecular chain. The hydrocarbon group having 1 to 20 carbon atoms, R ² and R ⁴ are an alkyl group having 1 to 8 carbon atoms or a ring-containing hydrocarbon group, A ¹ and A ² are alkylene groups having 2 to 4 carbon atoms, m and n represents a positive integer such that m + n is 2 to 20, and p represents 0 or 1. ] The pressure-sensitive adhesive according to claim 2, further comprising an active hydrogen-containing monomer (a3) excluding (a11) and (a2) and another polymerizable monomer (a4) added to the structural unit. The content of each monomer based on the total weight of the monomers is 0.1 to 30% for (a11) or (a12), 40 to 99.8% for (a2), 30% or less for (a3), (a4) The pressure-sensitive adhesive according to claim 3, wherein is 30% or less .
Furthermore, at least one selected from the group consisting of an organic compound (B1) and a polyvalent metal compound (B2) having 2 to 5 reactive functional groups in one molecule capable of reacting with the active hydrogen atom in (A). The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the crosslinking agent (B) is added. Further, at least one additive (C) selected from the group consisting of a tackifier, a plasticizer, a filler, a pigment, an ultraviolet absorber, an antioxidant and a silane coupling agent is added. The pressure-sensitive adhesive according to any one of 5. A pressure-sensitive adhesive tape formed by applying the pressure-sensitive adhesive according to any one of claims 1 to 6 to at least a part of at least one side of a substrate, a pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive film comprising the pressure-sensitive adhesive.