JP2006008882A - Antistatic pressure-sensitive adhesive agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellently adhesive antistatic pressure-sensitive adhesive agent for mitigating problems about reduction in the antistatic effect and the occurrence of poor appearance due to discoloring or opacification at high temperatures, and about the loss of antistatic performance upon peeling to break or contaminate costly electronic components, and to provide an adhesive tape, sheet, or film using the adhesive agent. <P>SOLUTION: The antistatic pressure-sensitive adhesive agent comprises a hydrocarbyl (meth)acrylate copolymer and a specified onium salt. The adhesive tape, sheet, or film is manufactured by applying the pressure-sensitive adhesive agent to at least one surface of the base material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

Conventionally, as an adhesive tape or sheet for the purpose of antistatic properties when peeling from an adherend, for example, an acrylic copolymer and an antistatic compound (polyether polyol, anionic, cationic, nonionic and Known are those obtained by coating a base material with a pressure-sensitive adhesive to which an amphoteric surfactant is added (for example, see Patent Documents 1 and 2).
Of these antistatic compounds, cationic surfactants are known to exhibit particularly excellent antistatic properties.

JP-A-6-128539 JP 58-191777 A

  However, since the cationic surfactant is thermally decomposed when heated together with other additives, there are drawbacks in that the antistatic effect is reduced and appearance defects such as coloring and opacification occur. Further, since it is easily decomposed at a high temperature, there is a problem that a desired antistatic property is not exhibited at the time of peeling and an expensive electronic member is damaged or contaminated.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to an antistatic pressure-sensitive adhesive comprising the hydrocarbyl (meth) acrylate copolymer (A) and an onium salt (B) represented by the following general formula (1). .
[Wherein, Q is N or P, and R ^{1 to} R ³ are each a saturated or unsaturated hydrocarbon group having 1 to 22 carbon atoms (provided that any two of R ^{1 to} R ³ are O if necessary) Or may be bonded via N to form a heterocyclic ring.), Or a hydrocarbon group separated by a nonionic molecular chain, R ⁴ is an alkyl group having 1 to 8 carbon atoms or an aromatic ring-containing hydrocarbon The group X ⁻ represents a conjugate base of a super strong acid having a Hammett acidity function (−H ₀ ) of 12 to 25. ]

The antistatic pressure-sensitive adhesive of the present invention has the following effects.
(1) Excellent high temperature stability, extremely low antistatic effect and appearance discoloration.
(2) Excellent high-temperature stability and less likely to cause adherend contamination during peeling.

[Hydrocarbyl (meth) acrylate copolymer (A)]
The monomer constituting (A) in the present invention includes hydrocarbyl (meth) acrylate (a1), active hydrogen-containing monomer (a2), and, if necessary, other ethylenically unsaturated monomer (a3).

  The hydrocarbyl group of the hydrocarbyl (meth) acrylate (a1) may be aliphatic [carbon number (hereinafter abbreviated as C) 1 to 25 (preferably 4 to 18), 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 and the like] and alkenyl groups [ethenyl, propenyl, butenyl, hexenyl, decenyl and oleyl groups and the like]], alicyclic [C4-18, such as cyclobutyl, cyclopentyl and cyclohexyl groups] and araliphatic [C7-18, For example, benzyl and phenylethyl groups] carbyl groups, and mixtures of two or more thereof And the like. Of 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 carbyl group is preferable, and n-butyl and 2 are more preferable. -An ethylhexyl group.

  The active hydrogen-containing monomer (a2) is a monomer having a functional group (for example, a carboxyl group, a hydroxyl group, an amino group, a methylol group, and an amide group) containing active hydrogen that reacts with the crosslinking agent (C) described later. (A21) to (a25).

(A21) 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) _n (CO-LO) _m -CO-CH ₂ -CH ₂ -COOH

(In the formula, A represents a C2-4 alkylene group, n represents an integer of 1-30, L represents a C3-19 alkylene group, m represents an integer of 0-5, and R ′ represents H or a methyl group.)
[C8-130, for example 2-hydroxyalkyl (C2-3 of alkyl group) (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, etc. And mixtures of two or more thereof

(A22) Hydroxyl group-containing compound / C5-12 unsaturated carboxylic acid ester (1) Hydroxyalkyl (C2-6) (meth) acrylate [hydroxyethyl, hydroxypropyl and hydroxybutyl (meth) acrylate etc.], and lactone thereof ( C4-20, for example, butyrolactone, valerolactone, caprolactone and laurolactone) 1-5 mol adduct (2) poly (n = 2-30) oxyalkylene (C2-4) (meth) acrylate [poly (n = 10) Oxyethylene mono (meth) acrylate, etc.]
(3) Poly (n = 2-30) oxyalkylene (C2-4) unsaturated carboxylic acid diester [poly (n = 10) oxyethylenemaleic acid diester, etc.], poly (n = 2-30) oxyalkylene (C2 -4) (meth) allyl ether [poly (n = 10) oxyethylene (meth) allyl ether, etc.]
C3-8 unsaturated alcohol [(meth) allyl alcohol, crotyl alcohol, 1-buten-3-ol, 2-butene-1,4-diol, etc.]
-C8-15 styrene compound [hydroxystyrene, etc.]
C5-20 ethers [hydroxyalkyl (C2-6) alkenyl (C3-6) ethers such as 2-hydroxyethylpropenyl ether]
(4) Methylol group-containing compound / C4-10 hydroxyl group-containing (meth) acrylamide [N-methylol (meth) acrylamide etc.]

(A23) Amino group-containing compound-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.]
C5-10 primary and secondary amino group-containing acrylamide [N-aminoalkyl (C2-6) (meth) acrylamide such as N-aminoethyl (meth) acrylamide; (meth) acrylamide alkyl (C2-6) alkyl ( C1-6) amines such as (meth) acrylamidoethylbutylamine]
Alkenylamine compounds [C3-15, such as mono- and di- (meth) allylamine, crotylamine]

(A24) Etherified product of methylol group-containing compound / alkyl (C1-4) etherified product of C4-10 hydroxyl group-containing (meth) acrylamide [N-butoxymethyl (meth) acrylamide etc.]
(A25) Amide group-containing vinyl compound-C3-30 (meth) acrylamide compound such as (meth) acrylamide, N-alkyl (C1-6) (meth) acrylamide [N-methyl (meth) acrylamide, N-butyl ( Meth) acrylamide, etc.], N, N-dihydrocarbyl [alkyl (C1-6) and / or aralkyl (C7-15)] (meth) acrylamide [N, N-dimethylacrylamide, N, N-dibenzylacrylamide] Etc.], diacetone acrylamide, C4-20 amide group-containing vinyl compounds excluding the above (meth) acrylamide compounds, such as (meth) acrylformamide, N-methyl-N-vinylacetone amide, cyclic amide (N-vinyl pyrrolidone) etc)

  Of these (a2), (a21), (a22) and (a24) are preferable from the viewpoint of the balance between tack and cohesive force of the pressure-sensitive adhesive, and (meth) acrylic acid and poly (n = 2-30) Succinic anhydride ring-opening adduct of oxyalkylene (C2-4) mono (meth) acrylate, 2-hydroxyalkyl (C2-3 of alkyl group) (meth) acrylate caprolactone (1-5 mol) Compounds obtained by ring-opening addition of succinic anhydride to adducts, hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide.

Other ethylenically unsaturated monomers (a3) include the following (a31) to (a35).
(A31) Carbyl (C1-3) (meth) acrylate formed from C1-3 monool and (meth) acrylic acid [methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, etc.]
(A32) Poly (n = 2-30) oxyalkylene alkyl (C1-18) ether (meth) acrylate [methanol ethylene oxide (hereinafter abbreviated as EO) 10-mole adduct (meth) acrylate, methanol propylene oxide ( Hereinafter abbreviated as PO) (Meth) acrylate etc. of 10 mol adduct]

(A33)
(1) C3-20 tertiary or quaternary nitrogen-containing (meth) acrylamide compound / tertiary nitrogen-containing [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, etc.]
・ Quaternary nitrogen-containing vinyl compounds [quaternized products of the above-mentioned tertiary nitrogen-containing vinyl compounds (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.)]

(2) Tertiary or quaternary nitrogen-containing (meth) acrylate / tertiary nitrogen-containing [dialkyl (C1-4) aminoalkyl (C1-4) (meth) acrylate [N, N-dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc.], heterocyclic-containing (meth) acrylate [morpholinoethyl (meth) acrylate, etc.], etc.
-Quaternary nitrogen-containing [(meth) acrylate [the quaternized product of the above-mentioned tertiary amino group-containing (meth) acrylate (which is quaternized 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.

(A34) Unsaturated hydrocarbon (1) Aliphatic unsaturated hydrocarbon C2-18 or more olefin [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.], C4- 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

(A35) 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, such as diallyl phthalate, methyl-4-vinylbenzoate, 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) allyloxyalkane (C2-6) [diallyloxyethane, triaryloxyethane, tetraallyloxybutane, tetrametaallyloxyethane, etc.]
Aromatic vinyl ether (C8-20, such as vinyl phenyl ether, phenoxystyrene)

(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)
(4) Unsaturated dicarboxylic acid diesters C4-34 unsaturated dicarboxylic acid diesters such as dialkyl fumarate (two alkyl groups are C1-22 linear, branched or alicyclic groups), dialkyl Maleate (two alkyl groups are C1-22 linear, branched or alicyclic groups)

  Of those exemplified as (a3) above, from the viewpoint of the cohesive strength of the pressure-sensitive adhesive, (a31), (a33), (a34) and (a35) are preferable, and (a31) and (a33) are more preferable. (1), (2), (a34) (3) and (a35), particularly preferred are methyl (meth) acrylate, ethyl (meth) acrylate, styrene and vinyl acetate.

The hydrocarbyl (meth) acrylate copolymer (A) is composed of (a1), (a2) and, if necessary, (a3).
The lower limit of the ratio (a1) based on the weight of (A) is preferably 50%, more preferably 60%, particularly preferably 70% from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive, and aggregation of the pressure-sensitive adhesive. From the viewpoint of force, the upper limit is preferably 99.9%, more preferably 99.5%, particularly preferably 99.0%; the ratio of (a2) is preferably from the viewpoint of the cohesive force of the pressure-sensitive adhesive. 1%, more preferably 0.2%, particularly preferably 0.5%, and the upper limit is preferably 20%, more preferably 10%, particularly preferably 5% from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive; The proportion of a3) is preferably 30% or less, more preferably 20% or less, and particularly preferably 0.1 to 10% from the viewpoint of the cohesive strength of the pressure-sensitive adhesive.

  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 the cohesive strength of the pressure-sensitive adhesive, and 2,000,000 from the viewpoint of the viscosity of the coating liquid. More preferably 1,800,000, particularly preferably 1,200,000.

  The active hydrogen equivalent of (A) is preferably 300 to 80,000 (more preferably 700 to 40,000, particularly preferably 1,000 to 20,000) from the viewpoint of adhesive strength. Here, the active hydrogen equivalent is the number average molecular weight of (A) determined by titration method (terminal group quantification method) (hereinafter abbreviated as Mn, except for Mn representing manganese element) Mn is (A). It is the value divided by the number of active hydrogen in it.

The Tg of (A) is preferably -100 ° C., more preferably −90 ° C., particularly preferably −80 ° C. from the viewpoint of the adhesive strength of the pressure-sensitive adhesive, and from the viewpoint of tackiness of the pressure-sensitive adhesive. The upper limit is 30 ° C, more preferably 0 ° C, particularly preferably -10 ° C.
Furthermore, (A) may be used as a mixture of two or more kinds from the viewpoint of the adhesion of the pressure-sensitive adhesive.

(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.), etc.] vinyl polymerizable emulsifiers [anion compounds (sulfoethyl sodium methacrylate, etc.), cationic compounds ( Dimethylaminomethyl methacrylate and the like)] 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 with a gas chromatography or the like that the monomer residual ratio (% by weight) is usually 5% or less, preferably 1% or less.

[Onium salt (B)]
The onium salt (B) in the present invention is represented by the following general formula (1).
[Wherein, Q is N or P, and R ^{1 to} R ³ are each a linear or branched hydrocarbon group having 1 to 22 carbon atoms (however, any two of R ^{1 to} R ³ are optionally May be bonded via O or N to form a heterocyclic ring.), Or a hydrocarbon group separated by a nonionic molecular chain, R ⁴ is an alkyl group having 1 to 8 carbon atoms or an aromatic ring-containing carbon A hydrogen group, X ⁻ represents a conjugate base of a super strong acid having a Hammett acidity function (−H ₀ ) of 12 to 25. ]

  The cation constituting (B) is quaternary onium (ammonium or phosphonium) in which N or P is bonded to a hydrocarbon group or a hydrocarbon group separated by a nonionic molecular chain. The nonionic molecular chain includes a divalent organic group selected from ether, thioether, carbonyl, ester, imino, amide, urethane, urea, carbonate, siloxy and a group having a heterocyclic structure containing N or O.

(B) can be obtained by quaternizing amine or phosphine with an alkylating agent.
Amines include 1, 2 and tertiary amines, and mixtures thereof.
Primary amines include aliphatic amines (C1-20, such as ethylamine, octylamine, dodecaneamine), aromatic amines (C6-30, such as aniline, naphthylamine), alicyclic amines (C6-30, such as cyclohexylamine). )etc;
Secondary amines include aliphatic amines (C2-30, such as dimethylamine, diethylamine), aromatic amines (C7-30, such as N-methylaniline, diphenylamine, phenylnaphthylamine), alicyclic amines (C7-30, For example, N-methylcyclohexylamine), heterocyclic amine (C5-30, such as N-methyl-2-furylamine) and the like;

  Tertiary amines include aliphatic amines (C3-29 such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, diethyl-1-propylamine), aromatic Amines (C6-30, such as triphenylamine, N-ethyl-N-propylaniline), alicyclic amines (C8-29, such as N, N-dimethylcyclohexylamine), heterocyclic amines [C5-30, For example, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N, N′-dimethylpiperazine, 1, 5-Diazabicyclo [4,3,0] nonene-5,1,8-diazabisch [5,4,0] undecene-7, pyridine, 1-methylimidazole, 1,2-dimethylimidazole, 1,2, -dimethylimidazoline, 1,4-dimethyl-2-ethylimidazoline, and the like. .

Examples of phosphines include 1, 2 and tertiary phosphines, and mixtures thereof.
Primary phosphine includes aliphatic phosphine (C1-20, such as methylphosphine, ethylphosphine), aromatic phosphine (C6-14, such as phenylphosphine, naphthylphosphine), alicyclic phosphine (C6-14, such as cyclohexylphosphine). )etc;
Secondary phosphines include aliphatic phosphines (C2-40, eg dimethylphosphine, diethylphosphine), aromatic phosphines (C7-20, eg methylphenylphosphine), alicyclic phosphines (C7-14, eg methylcyclohexylphosphine). The tertiary phosphine includes aliphatic phosphine (C3-60, such as trimethylphosphine, triethylphosphine), aromatic phosphine (C8-60, such as triphenylphosphine), and alicyclic phosphine (C8-60, such as triphenylphosphine). Cyclohexylphosphine) and the like.

  Examples of alkylating agents include halogenated hydrocarbons [halogenated alkyls (C1-20, such as methyl chloride, ethyl chloride, butyl bromide, methyl iodide, etc.), aromatic ring-containing halides (C6-20, such as phenyl bromide, benzyl chloride). Etc.], dialkyl carbonates (C3-9, such as dimethyl carbonate, diethyl carbonate, etc.), dialkyl sulfates (C2-8, such as dimethyl sulfate, diethyl sulfate, etc.), organic lithium compounds (C4-12, such as butyllithium, Phenyl lithium, etc.), Grignard reagents (such as those obtained by reacting the above halogenated hydrocarbons with magnesium), and the like.

The counter anion X ⁻ constituting (B) is a conjugate base of a super strong acid having a Hammett acidity function (−H ₀ ) of 12 to 25 (preferably 12.5 to 20, more preferably 13 to 15). When (−H ₀ ) is less than 12, the heat resistance of (B) is insufficient, the antistatic property of the pressure-sensitive adhesive is decreased, appearance discoloration or adherend contamination is likely to occur. If it exceeds, handling becomes difficult.
Super strong acids include proton acids and combinations of proton acids / Lewis acids. Specific examples of the protonic acid include perchloric acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid and the like.
Examples of the protonic acid used in the protonic acid / Lewis acid combination include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), and examples of the Lewis acid include boron trifluoride and pentafluoride. Phosphorus fluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and the like. Protonic acid / Lewis acid combinations are arbitrary, but specific examples include boron tetrafluoride, hexafluorophosphate, chlorofluoroboric acid, antimony hexafluoride, arsenic hexafluoride and tantalum hexafluoride. And at least one super strong acid selected from the group consisting of:
Among the above super strong acids, from the viewpoint of heat resistance, preferred are perchloric acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, and more preferred is a super strong acid composed of a combination of a protonic acid and a Lewis acid, particularly preferred. Is at least one super strong acid selected from the group consisting of boron tetrafluoride, hexafluorophosphoric acid, chlorofluoroboric acid, antimony hexafluoride, arsenic hexafluoride and tantalum hexafluoride.

The following method is mentioned as a manufacturing method of (B) in this invention.
(1) When Q is N (1-1) A tertiary amine is converted to a quaternary ammonium salt by reaction with an alkylating agent, and then an alkali metal (sodium, potassium, etc.) salt of a conjugate base of a super strong acid in the present invention A salt exchange reaction by the method. This salt exchange reaction is performed at around room temperature (10 to 40 ° C.), and salt such as sodium chloride produced is removed if necessary. The reaction is preferably carried out in water or an organic solvent [lower alcohol (C1-8, such as methanol, ethanol, propanol, butanol), etc.] from the viewpoint of salt solubility and ease of removal after the reaction.
(1-2) A method in which an aqueous solution of a super strong acid is added to a quaternary ammonium carbonate obtained from a tertiary amine and a dialkyl (alkyl group is C1-8) carbonic acid (such as dimethyl carbonate) to cause a salt exchange reaction.
In addition, when manufacturing from a primary and secondary amine, after making into a tertiary amine using the said alkylating agent, it can manufacture by the method similar to the manufacturing method from the said tertiary amine.

(2) When Q is P, it can be produced according to the case of (1) above, and the reaction of phosphine with an alkylating agent can be carried out using a hydrocarbon solvent (C6-C20, such as hexane, heptane) or ether (C2- (For example, dimethyl ether), and the quaternized product can be produced by a salt exchange method as in (1).

  In the antistatic pressure-sensitive adhesive of the present invention, the lower limit of the content of (B) based on the weight of (A) is preferably 0.1%, more preferably 0, from the viewpoint of antistatic properties of the pressure-sensitive adhesive. 0.5%, particularly preferably 1%, and the upper limit is preferably 30%, more preferably 10%, and particularly preferably 5% from the viewpoint of adhesiveness.

  In order to further improve the cohesive force of the pressure-sensitive adhesive, the pressure-sensitive adhesive comprising (A) and (B) has a functional group (carboxyl group, hydroxyl group, amino group) having active hydrogen in (A). 2 to 5 reactive functional groups (at least one functional group selected from the group consisting of isocyanates, epoxies, hydrazides, aziridinyl groups, and oxazolinyl groups) that react with methyl groups and amide groups) in one molecule You may further add the at least 1 sort (s) of crosslinking agent (C) chosen from the group which consists of an organic compound (C1) and a polyvalent (2-4 valence) metal compound (C2).

The molecular weight per functional group of (C1) is preferably a lower limit of 40, more preferably 60 from the viewpoint 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 a number average. Molecular weight [hereinafter abbreviated as Mn, measurement is based on titration method (end group determination method). ] 20,000, more preferably 10,000, and particularly preferably Mn5,000.
The molecular weight per coordination of the polyvalent metal (C2) is preferably 40, more preferably 50 from the viewpoint of cohesive force and adhesive force and tack of the pressure-sensitive adhesive, and from the viewpoint of cohesive force and adhesive force. The upper limit is 140, more preferably 130, particularly preferably 110.

  (C1) includes poly (2-8) isocyanate (C11), poly (2-8) epoxide (C12), hydrazide (C13), oxazoline compound (C14) and aziridine compound (C15).

  As the polyisocyanate (C11), C (excluding carbon in the NCO group, the same shall apply hereinafter) 2 to 18 aliphatic polyisocyanate, C4 to 15 alicyclic polyisocyanate, C6 to 20 aromatic polyisocyanate, C8 -15 aliphatic aliphatic polyisocyanates and one or more compounds selected from the group consisting of modified products of these polyisocyanates.

Aliphatic polyisocyanates include diisocyanates [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcapro. Acid, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.], triisocyanate [1,6,11- Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate Phosgenates of reaction products of alkanolamine and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanatohexa Noate, etc.], and modified products of the diisocyanate described later.
Among these, tetramethylene diisocyanate and HDI are preferable from the viewpoint of availability and industrial viewpoint.

Examples of alicyclic polyisocyanates include diisocyanates [isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4- Cyclohexene-1,2-dicarboxylate, norbornane diisocyanate and the like], triisocyanate [bicycloheptane triisocyanate and the like], and modified products of the diisocyanate described later.
Among these, IPDI, hydrogenated MDI, and hydrogenated TDI are preferable from the viewpoint of availability and industrial viewpoint.

Aromatic polyisocyanates include diisocyanates [tolylene diisocyanate (TDI) [2,4- and 2,6-TDI and mixtures thereof], diphenylmethane diisocyanate (MDI) [4,4′- and 2,4′-MDI. And mixtures thereof], naphthylene diisocyanate (NDI), etc.] mixtures of bifunctional and trifunctional or higher polyisocyanates [crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate), etc.], and modifications of diisocyanates described later. Thing etc. are mentioned.
Among these, TDI, MDI and NDI are preferable from the viewpoint of availability and industrial viewpoint.

Examples of the araliphatic polyisocyanate include diisocyanates [xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), diisocyanatoethylbenzene, etc.], and modified products of the diisocyanate described later. Etc.
Among these, XDI and TMXDI are preferable from the viewpoint of availability and industrial viewpoint.

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

Among the modified polyisocyanates, the urethane group-modified products include NCO-terminated urethane prepolymers (including free polyisocyanates) obtained by reacting an excess amount of the polyisocyanates exemplified above with active hydrogen compounds. A pseudo-prepolymer).
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).

The low molecular weight polyhydric (divalent to tetravalent or higher) alcohol includes a divalent to trivalent alcohol [aliphatic alcohol [divalent (C2 to 20, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol]. 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentyl glycol, 1,9-nonanediol, 1,4-bis (hydroxymethyl) cyclohexane), trivalent (C3-8) Alicyclic alcohol [C4-20, such as 1,4-dihydroxycyclohexane, 2,2-bis (4,4′-hydroxycyclohexyl) propane]; aromatic ring-containing alcohol [ C8-15, such as m- and p-xylylene glycol, 1,4 -Bis (hydroxyethyl) benzene] and the like] and tetrahydric or higher polyhydric alcohols [C5-10 or higher, such as pentaerythritol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, sucrose , Dipentaerythritol, polyglycerin (degree of polymerization of 2 to 20) and the like].
As the bivalent to trivalent poly (n = 2 to 30) oxyalkylene (C2 to 4), the above low molecular polyhydric alcohol and / or polyhydric phenol (C6 to 20, for example, catechol, resorcinol, bisphenol A, -S, And polyether polyol obtained by adding alkylene oxide (C2-4) to -F,).

  The polyisocyanate 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, eg acetooxime, methyl ethyl ketone oxime, cyclohexanone oxime, maldooxime, acetoaldoxime, benzophenone oxime and diethylglyoxime); alcohol (C1-24, eg 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, phenoxyl); 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 groups to active hydrogen in the polyisocyanate (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 in the urethane prepolymer is usually 3 to 35% by weight.

Examples of the polyepoxide (C12) include glycidyl type polyepoxide (C121) (epoxy equivalent of 80 to 2,500) and non-glycidyl type polyepoxide (C122) (epoxy equivalent of 43 to 10,000).
(C121) includes glycidyl ether [polyglycol (above) glycidyl ether (bisphenol A di-, bisphenol F di- and pyrogallol triglycidyl ether, etc.), low molecular polyhydric alcohol (above) glycidyl ether (ethylene glycol) , Propylene glycol and neopentyl glycol diglycidyl ether, trimethylolpropane and glycerin triglycidyl ether, etc.), glycidyl ether of polyether polyol (described above) [polyethylene glycol (Mw 200 to 2,000), polypropylene glycol (Mw 200 to 2,000) ) And diglycidyl ethers of 1-20 mol adducts of alkylene oxide of bisphenol A]]; glycidyl ester [polycarboxylic acid (n = 2 to 2) Or more) glycidyl ester (adipic acid, phthalic acid and dimer acid diglycidyl ester, trimellitic acid triglycidyl ester, etc.); glycidyl amine [primary amine (above) or poly (n = 2 to 4 or more)] Glycidylated amine [N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidylxylylene diene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidylhexamethylenediamine] and the like.

  (C122) includes aliphatic polyepoxide [C4-20, such as epoxidized (poly) alkadiene [epoxidized butadiene, epoxidized poly (n = 2 to 4 or more) butadiene, epoxidized oil (epoxidized soybean oil, etc.] And the like] and alicyclic polyepoxides (such as limonene dioxide and dicyclopentadiene dioxide).

  As hydrazide (C13), polycarboxylic acid [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 (C14) 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 (C15) 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 (C2) 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, Mn, 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 and stearic acid]

  The amount of the crosslinking agent (C) used is expressed in terms of the equivalent ratio of the active hydrogen in the copolymer (A) and the functional group of (C1) or (C2) coordination with the active hydrogen. From the viewpoint of the cohesive force of the pressure adhesive, the amount is preferably 1 / 0.01 to 1/2, more preferably 1 / 0.02 to 1/1.

  The pressure-sensitive adhesive of the present invention includes a tackifying resin (D1), a plasticizer (D2), a filler (D3), a pigment (D4), an oxidation as long as the effects of the present invention are not impaired. One or more additives (D) selected from the group consisting of the inhibitor (D5) and the ultraviolet absorber (D6) can be further added.

Examples of the tackifying resin (D1) 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 (D1) used is usually 100% or less based on the total weight of (A) and (B), and preferably 5 to 50% from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive.

As the plasticizer (D2), hydrocarbons [C6 to Mw 100,000, such as process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, paraffin wax, ethylene and α-olefin (C3 to 20) are used. 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.)]; animal and vegetable oils (epoxidized oil, etc.); Among these, a hydrogenated product having an unsaturated double bond; and a mixture thereof.
The amount of (D2) used is usually 50% or less based on the total weight of (A) and (B), and preferably 2 to 30% from the viewpoint of the adhesive strength and cohesive strength of the pressure-sensitive adhesive.

Fillers (D3) 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. (D3) 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 pressure-sensitive adhesive.
The amount of (D3) used is usually 50% or less based on the total weight of (A) and (B), and preferably 5 to 30% from the viewpoint of tack and cohesive strength of the pressure-sensitive adhesive.

Examples of the pigment (D4) include 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.
(D4) 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 pressure-sensitive adhesive. The amount of (D4) used is usually 20% or less based on the total weight of (A) and (B), and preferably 1 to 10% from the viewpoint of tack and cohesive strength of the pressure-sensitive adhesive.

Antioxidants (D5) include hindered phenols [2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), tri 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 (D5) used is usually 5% or less based on the total weight of (A) and (B), and preferably 0.05 to 1% from the viewpoint of the adhesive strength of the pressure-sensitive adhesive.

Examples of the ultraviolet absorber (D6) 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 (D6) used is usually 5% or less based on the total weight of (A) and (B), and preferably 0.1 to 1% from the viewpoint of the adhesive strength of the pressure-sensitive adhesive.

  The total amount of (D) based on the total weight of (A) and (B) is usually 230% or less, preferably 150% or less, more preferably 10 to 120 from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive. %.

The pressure-sensitive adhesive of the present invention comprises (A) and (B) produced separately, and (C) and / or (D), if necessary, a normal mixing device (mixing tank with a stirrer, static mixer) Etc.) can be produced by mixing uniformly. (D) may be added at the stage of production of (A) and / or (B) (raw material before production, reaction product during production, or product after production).
The total content of (A) and (B) in the total solid weight of the pressure-sensitive adhesive of the present invention is preferably 20% or more, more preferably 30 to 100%, from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive. Especially preferably, it is 40 to 100%.

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, cyclohexanone) and the like. From the viewpoint of coatability, the amount used is preferably 5 to 900%, more preferably 10 based on the total solid content of the pressure-sensitive adhesive. The solid concentration of the solution is preferably 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 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. The amount used 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.

The pressure-sensitive adhesive tape, sheet and film of the present invention are applied directly to at least one side of the substrate using the pressure-sensitive adhesive of the present invention using various coating apparatuses, and heated to dry the solvent or dispersion medium, A method in which the reaction is allowed to proceed and curing is further performed, or a pressure-sensitive adhesive obtained by applying a pressure-sensitive adhesive to a release film or the like in the same manner, and then drying and curing is applied to at least the substrate. It can be manufactured by a method of transferring to one side.
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 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 and curing of the pressure sensitive adhesive is usually 5 to 250 μm, and preferably 10 to 100 μm from the viewpoint of the adhesive strength of the pressure sensitive adhesive.

  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 Example 1 [Production of copolymer solution (A1)]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube was charged with 108 parts of ethyl acetate and 22 parts of methanol and heated to 68 ° C. Next, a monomer compounding solution containing 515 parts of 2-ethylhexyl acrylate, 5.2 parts of acrylic acid, 173 parts of ethyl acetate and 35 parts of methanol, and 0.26 part of 2,2′-azobis (2,4-dimethylvaleronitrile) And an initiator solution in which 37 parts of ethyl acetate was dissolved in 15 parts of methanol were continuously dropped with a dropping funnel over 4 hours while nitrogen was blown into a four-necked flask to effect radical polymerization. After the completion of dropping, an initiator solution prepared by dissolving 0.58 part of 2,2′-azobis (2,4-dimethylvaleronitrile) in 26 parts of ethyl acetate was continuously added using a dropping funnel over 2 hours. Further, polymerization was continued at the boiling point for 4 hours, and then 64 parts of ethyl acetate was added and mixed uniformly to obtain a copolymer solution (A1). The viscosity of (A1) was 2,700 mPa · s at 25 ° C., the solid content concentration was 50.5%, and the Mw of the copolymer was about 380,000.

Production Example 2 [Production of ammonium salt solution (B1)]
An autoclave equipped with a stirrer and a thermometer was charged with 87 parts of diethylmethylamine and 100 parts of methanol and heated to 50 ° C. Next, 60 parts of methyl chloride was gradually dropped over 2 hours using a dropping funnel, and then aged at the same temperature for 4 hours. After distilling off methanol under reduced pressure, 300 parts of water and 110 parts of sodium tetrafluoroborate were added and stirred at room temperature for 1 hour. After the precipitated salt was filtered off, the salt was washed with water and dried under reduced pressure, and then dissolved by adding 190 parts of methanol to obtain an ammonium salt solution (B1). The solid content concentration of (B1) was 48.2%.

Production Example 3
In an autoclave equipped with a stirrer and a thermometer, 297 parts of stearyldimethylamine, 300 parts of methanol and 290 parts of dimethyl carbonate were charged, heated to 120 ° C., and aged at the same temperature for 9 hours. Subsequently, 209 parts of borohydrofluoric acid (mixture of hydrogen fluoride and boron trifluoride) 42% aqueous solution was gradually added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. Methanol and water were distilled off under reduced pressure, and then 400 parts of methanol was added and dissolved to obtain an ammonium salt solution (B2). The solid content concentration of (B2) was 49.6%.

Comparative production example 1
In Production Example 2, after completion of the quaternization reaction, methanol was not distilled off, and the obtained ammonium salt solution was used as a comparative ammonium salt solution (ratio B1). The solid content concentration of this product was 57.2%.

Comparative production example 2
In Production Example 2, instead of 87 parts of diethylmethylamine and 100 parts of methanol, 297 parts of stearyldimethylamine and 350 parts of methanol were used, and after completion of the quaternization reaction, methanol was not distilled off and the ammonium salt solution obtained as it was Was used as a comparative ammonium salt solution (ratio B2). The solid content concentration of the obtained ammonium salt solution was 49.4%.

Example 1
(A1) 100 parts, (B1) 10 parts and an aluminum chelate compound [trade name: aluminum chelate A (W), manufactured by Kawaken Fine Chemicals Co., Ltd., and so on. 10 parts of a 5% ethyl acetate solution (C1) was added to obtain a pressure sensitive adhesive (K1).
(K1) is coated on a single side of a polyester film [trade name: “Lumirror” type T, manufactured by Toray Industries, Inc.] using a bar coater so that the dry film thickness is 25 μm, and at 60 ° C. for 1 minute. Further, each was dried with hot air at 100 ° C. for 1 minute, and further cured at 45 ° C. for 3 days to prepare an adhesive tape test piece. The test piece was evaluated according to the following performance evaluation method. The results are shown in Table 1.
In the above, “Lumirror” was replaced with a release polyester film [“Super Tech SP-PET38” manufactured by Lintec Corporation], and the same composition was applied onto the film. The pressure sensitive adhesive film was obtained. The film was evaluated according to the following performance evaluation method. The results are shown in Table 1.

Example 2
In Example 1, instead of 10 parts of (B1) and 10 parts of (C1), 10 parts of (B2) and 0.6 parts of a polyglycidyl compound [“TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Ltd.] were used. A pressure sensitive adhesive (K2) was obtained in the same manner as in Example 1 except that. A pressure-sensitive adhesive tape test piece and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1 using (K2), and performance evaluation was performed. The results are shown in Table 1.

Comparative Example 1
In Example 1, a pressure-sensitive adhesive (ratio K1) was obtained in the same manner as in Example 1 except that (Ratio B1) was used instead of (B1). A pressure-sensitive adhesive tape test piece and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1 using (Ratio K1), and performance evaluation was performed. The results are shown in Table 1.

Comparative Example 2
In Example 2, a pressure-sensitive adhesive (Ratio K2) was obtained in the same manner as in Example 1 except that (Ratio B2) was used instead of (B2). A pressure-sensitive adhesive tape test piece and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1 using (Ratio K2), and performance evaluation was performed. The results are shown in Table 1.

[Performance evaluation method]
(1) Adhesive force The adhesive-coated surface of the adhesive tape test piece was attached to a stainless steel plate (SUS304, the same shall apply hereinafter) so that the application area would be 25 mm wide x 100 mm long [one round trip with a 2 kg load roll. ] Adhesive strength at room temperature (23 ° C.) according to JIS-Z-0237 for 30 minutes after pasting and heat treated at 60 ° C. for 1 month after 30 minutes pasting (unit: N / 25 mm) Measure.

(2) Re-peelability As in (1), the adhesive tape test piece was affixed and heat treated at 60 ° C for 1 month after 2 hours of pasting and the stainless steel plate after 2 hours of pasting, and at room temperature (23 ° C). About what was left still for 2 hours, a test piece is peeled off at normal temperature (23 degreeC), respectively, and it determines with the naked eye according to the following reference | standard.
○: No fogging, no corrosion and no adhesive residue on the substrate surface.
X: Cloudiness, corrosion, or adhesive residue is observed on the substrate surface.

(3) Retention force As in (1), a stainless steel plate 30 minutes after application of the adhesive tape test piece, and one that was heat-treated at 60 ° C. for 1 month after 30 minutes application, in accordance with JIS-Z-0237 After standing at 40 ° C. for 30 minutes, the measurement is started at a load of 1 kg at the same temperature, and the deviation after 24 hours is measured to measure the holding force (unit: mm).

(4) Ball tack For a pressure-sensitive adhesive tape test piece and a sample obtained by heat-treating the test piece at 60 ° C. for 1 month, ball tack (represented by a ball number) at normal temperature (23 ° C.) is measured according to JIS-Z-0237. .
(5) Antistatic property The pressure-sensitive adhesive film was allowed to stand for 24 hours in an atmosphere of 23 ° C. and 50% RH, and the film was heat-treated at 160 ° C. for 1 hour, and then 24 hours in an atmosphere of 23 ° C. and 50% RH. The volume resistivity value (unit: Ω · cm) is measured using the super insulation meter [DSM-8103, manufactured by Toa Denpa Kogyo Co., Ltd.] under the same atmosphere for the sample that has been allowed to stand for a period of time.
(6) Appearance discoloration About the pressure-sensitive adhesive tape test piece and the test piece heat-treated at 160 ° C. for 1 hour, using a colorimetric color difference meter [ND-300A, manufactured by Nippon Denshoku Industries Co., Ltd.] , Abbreviated as YI).

  From the above results, the antistatic pressure-sensitive adhesive of the present invention (Examples 1 and 2) exhibited superior antistatic properties compared to the comparative pressure-sensitive adhesive (Comparative Examples 1 and 2), and the pressure-sensitive adhesive of the present invention. The adhesive tape obtained from the adhesive (Examples 1 and 2) exhibits superior adhesive strength, removability, holding power and ball tack as compared with the comparative adhesive tape (Comparative Examples 1 and 2), and has a small appearance discoloration. I understand.

  Applications of the antistatic pressure-sensitive adhesive of the present invention include pressure-sensitive adhesive tapes, sheets and films, stickers (labels), boards, and other laminates. In addition, the adhesive tape, sheet and adhesive film of the present invention are for electric / electronic component processing (dicing tape, carrier tape, etc.), for surface protection (image display device, stainless steel plate, plastic plate and painted surface protection, etc.) It can be suitably used for various applications such as packaging (packaging of plastic cases, packaging, etc.), masking (glass sealing, building curing, etc.), medical (adhesive plaster etc.), and office use.

Claims (7)

An antistatic pressure-sensitive adhesive comprising a hydrocarbyl (meth) acrylate copolymer (A) and an onium salt (B) represented by the following general formula (1).
[Wherein, Q is N or P, and R ^{1 to} R ³ are each a linear or branched hydrocarbon group having 1 to 22 carbon atoms (however, any two of R ^{1 to} R ³ are optionally May be bonded via O or N to form a heterocyclic ring.), Or a hydrocarbon group separated by a nonionic molecular chain, R ⁴ is an alkyl group having 1 to 8 carbon atoms or an aromatic ring-containing carbon A hydrogen group, X ⁻ represents a conjugate base of a super strong acid having a Hammett acidity function (−H ₀ ) of 12 to 25. ] (A) is a hydrocarbyl (meth) acrylate having 4 to 18 carbon atoms in the hydrocarbyl group (a1) 50 to 99.9% by weight, active hydrogen-containing monomer (a2) 0.1 to 20% by weight, 2. The pressure-sensitive adhesive according to claim 1, wherein the pressure-sensitive adhesive is a copolymer having 0 to 30% by weight of another ethylenically unsaturated monomer (a3) as necessary. The pressure-sensitive adhesive according to claim 1 or 2, wherein the anion constituting (B) is a conjugate base of a super strong acid comprising a combination of a protonic acid and a Lewis acid. The pressure sensitive adhesive according to any one of claims 1 to 3, wherein the content of (B) is 0.1 to 30% based on the weight of (A). Furthermore, at least one kind of bridge | crosslinking chosen from the group which consists of the organic compound (C1) which has 2-5 reactive functional groups which react with the active hydrogen in (A) in 1 molecule, and a polyvalent metal compound (C2). The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein an agent (C) is added. Furthermore, 1 type, or 2 or more types of additives (D) chosen from the group which consists of tackifying resin, a plasticizer, a filler, a pigment, antioxidant, and an ultraviolet absorber are added. Any one of the pressure-sensitive adhesives. A pressure-sensitive adhesive tape, sheet and film obtained by applying the pressure-sensitive adhesive according to any one of claims 1 to 6 to at least one surface of a substrate.