JP6177834B2 - Antistatic agent for silicone adhesive and antistatic silicone adhesive - Google Patents

Description

  The present invention relates to an antistatic agent for a silicone adhesive and an antistatic silicone adhesive. More specifically, the present invention relates to an antistatic silicone pressure-sensitive adhesive having an excellent balance of antistatic properties, stain resistance, and heat resistance.

  In recent years, heat treatment at a higher temperature than before has been performed in masking and temporary fixing applications for semiconductor parts reflow process and resin sealing process, and the use of silicone adhesives with excellent heat resistance has increased. ing.

  However, since the silicone pressure-sensitive adhesive is excellent in electrical insulation, static electricity called peeling charge is generated when the pressure-sensitive adhesive tape is peeled off after completion of the process. This static electricity attracts surrounding dust and causes electrostatic breakdown of electronic components. Therefore, in order to prevent the generation of static electricity, a method has been proposed in which an ion conductive antistatic agent such as a lithium salt is contained in a silicone adhesive (see, for example, Patent Document 1).

  However, in the method described in Patent Document 1, the antistatic performance is not sufficient, and in order to increase the antistatic performance, if a large amount of ionic conductive antistatic is included, bleeding of the ionic conductive antistatic agent is performed. There were problems such as contamination of the adherend due to out and a decrease in adhesive strength.

JP 2009-30028 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silicone adhesive charging agent that is excellent in antistatic performance, has little contamination to the adherend, and can maintain antistatic performance even when exposed to high temperatures. It is to provide an inhibitor.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention is an antistatic agent for a silicone adhesive containing a compound (B) having a _polysiloxane structure (b2) and a polyoxyethylene chain (b3) _, and a quaternary ammonium salt (A). The antistatic agent for silicone pressure-sensitive adhesives , wherein the quaternary ammonium salt (A) is a quaternary ammonium salt (A1) represented by the general formula (1) ;
[Wherein, R ¹ and R ² each independently represent a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms , and R ³ represents a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms. Group, an arylalkyl group having 7 to 22 carbon atoms or an arylalkenyl group having 7 to 22 carbon atoms , R ⁴ represents a linear or branched aliphatic hydrocarbon group having 8 to 22 carbon atoms, and X ⁻ represents -11. Represents an anion which is a conjugate base of a super strong acid having a Hammett acidity function (H ₀ ) of less than .93 . ]
Antistatic silicone pressure-sensitive adhesive composition containing the antistatic agent for silicone pressure-sensitive adhesive; Antistatic silicone pressure-sensitive adhesive obtained by heating and reacting the antistatic silicone pressure-sensitive adhesive composition; Antistatic silicone pressure-sensitive adhesive Is a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet formed by coating at least a part of at least one side of a substrate; and a pressure-sensitive adhesive film containing the antistatic silicone pressure-sensitive adhesive.

  The antistatic agent of the present invention is excellent in antistatic performance, has little contamination to the adherend, and can maintain the antistatic performance even when exposed to high temperatures.

The antistatic agent for silicone pressure-sensitive adhesives of the present invention contains a compound (B) having a _polysiloxane structure (b2) and a polyoxyethylene chain (b3) _, and a quaternary ammonium salt (A). (A) and (B) may be used individually by 1 type, or may use 2 or more types together.

  The quaternary ammonium salt (A) in the present invention is a quaternary ammonium salt (A1) represented by the following general formula (1); alkyl (C10-24) amidoalkyl (C2-6) A quaternary ammonium salt (A2) having a group and / or a hydroxyalkyl group having 2 to 4 carbon atoms, the anion being a conjugate base of a super strong acid; and a cyclic amine (pyridine and A quaternary ammonium salt (A3) of morpholine and the like.

R ¹ and R ² in the general formula (1) each independently represent a linear or branched aliphatic hydrocarbon group (alkyl group and alkenyl group) having 1 to 22 carbon atoms.
As the linear aliphatic hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, Examples include alkyl groups obtained by removing hydroxyl groups from alcohol derived from coconut oil (hereinafter abbreviated as coconut oil alkyl groups) and oleyl groups. Examples of branched hydrocarbon groups include isopropyl groups and 2-ethylhexyl groups. Among these, from the viewpoint of compatibility with silicone, a linear or branched aliphatic hydrocarbon group having 1 to 14 carbon atoms is preferable, and a linear or branched aliphatic group having 1 to 8 carbon atoms is more preferable. A hydrocarbon group, particularly preferred is an aliphatic hydrocarbon group having 1 or 2 carbon atoms, and most preferred is a methyl group. R ¹ and R ² may be the same or different, but are preferably the same.

R ³ represents a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, an arylalkyl having 7 to 22 carbon atoms, or an arylalkenyl group having 7 to 22 carbon atoms.
Examples of the linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms include those exemplified as R ¹ and R ² , and examples of the arylalkyl group having 7 to 22 carbon atoms include a benzyl group and A phenethyl group etc. are mentioned, A styryl group, a cinnamyl group, etc. are mentioned as a C7-C22 aryl alkenyl group.

Of R ³ , a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, an arylalkyl group and arylalkenyl group having 7 to 15 carbon atoms, and more preferably carbon are preferable from the viewpoint of contamination resistance. It is a linear or branched aliphatic hydrocarbon group of formula 6-14.

R ⁴ represents a linear or branched aliphatic hydrocarbon group (alkyl group, alkenyl group, etc.) having 8 to 22 carbon atoms.
Examples of the linear aliphatic hydrocarbon group include octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, coconut oil alkyl group and oleyl group, and branched aliphatic hydrocarbons. Examples of the group include a 2-ethylhexyl group.

Among R ⁴ , a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms is preferable from the viewpoint of contamination resistance, and a linear or branched aliphatic hydrocarbon group having 10 to 16 carbon atoms is more preferable. It is a group.

As a specific example of the quaternary ammonium group constituting (A1), when R ³ is an aliphatic hydrocarbon group, for example, one having one long-chain alkyl group (trimethyldodecyl ammonium, trimethyl tetradecyl ammonium, Trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl coconut oil alkyl ammonium, trimethyl-2-ethylhexyl ammonium, dimethyl ethyl dodecyl ammonium, dimethyl ethyl tetradecyl ammonium, dimethyl ethyl hexadecyl ammonium, dimethyl ethyl octadecyl ammonium, dimethyl ethyl coconut oil alkyl ammonium , Dimethylethyl-2-ethylhexylammonium, methyldiethyldodecylammonium, methyldiethyltetradecylammonium Ni, methyldiethylhexadecylammonium, methyldiethyloctadecylammonium, methyldiethyl coconut oil alkylammonium and methyldiethyl-2-ethylhexylammonium), having two long-chain alkyl groups (6 to 22 carbon atoms) (dimethyldihexylammonium , Dimethyldioctylammonium, dimethyldidecylammonium and dimethyldidodecylammonium) and those having one long-chain alkenyl group (8 to 22 carbon atoms) (trimethyloleylammonium, dimethylethyloleylammonium and methyldiethyloleylammonium). .
When R ³ is an arylalkyl group, for example, dimethyldecylbenzylammonium, dimethyldodecylbenzylammonium, dimethyltetradecylbenzylammonium, dimethylhexadecylbenzylammonium, dimethyl coconut oil alkylbenzylammonium, dimethyloleylbenzylammonium and dimethyl-2 -Ethylhexylbenzylammonium.

  Among these, trimethyl hexadecyl ammonium, dimethyl didecyl ammonium, dimethyl dodecyl benzyl ammonium and dimethyl tetradecyl benzyl ammonium are preferable from the viewpoint of stain resistance.

X ⁻ in the general formula (1) represents an anion which is a conjugate base of a super strong acid having a Hammett acidity function (H ₀ ) of less than −11.93.

X ^- is a superacid which is a conjugate acid, 100% acid having a stronger acid strength than sulfate ( "superacid-superbase" Kozo Tanabe, Ryoji Noyori al, Kodansha Scientific published, p1 reference) and, Hammett The acidity function (H ₀ ) is less than -11.93 of 100% sulfuric acid, and examples include proton acids and acids composed of proton acids and Lewis acids.

Specific examples of the strong acid of the protonic acid include trifluoromethanesulfonic acid (H ₀ = -14.10), pentafluoroethanesulfonic acid (H ₀ = -14.00), and the like.

Examples of the protonic acid used in the combination of the protonic acid and the Lewis acid include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide). Examples of the Lewis acid include boron trifluoride and pentafluoride. Examples thereof include phosphorus, antimony pentafluoride, arsenic pentafluoride, and taurine pentafluoride.
A combination of a protonic acid and a Lewis acid is arbitrary, but specific examples of super strong acids obtained by combining them include boron tetrafluoride acid, hexafluorophosphoric acid, chlorofluoroboronic acid, hexafluoroantimonic acid, hexa Examples thereof include fluorinated arsenic acid and taurine hexafluoride.

X ⁻ is preferably a super strong acid conjugate having a Hammett acidity function (H ₀ ) of −12.00 or less from the viewpoint of heat resistance of the quaternary ammonium salt (A1) represented by the general formula (1). Bases, more preferably trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, boron tetrafluoride, phosphorus hexafluoride, chlorofluoroboronic acid, antimony hexafluoride, arsenic hexafluoride or taurine hexafluoride A base, particularly preferred is a conjugated base of trifluoromethanesulfonic acid, tetrafluoroboric acid or hexafluorophosphoric acid, and most preferred is a conjugated base of trifluoromethanesulfonic acid or tetrafluoroboric acid.

  A quaternary ammonium salt having an alkyl (10 to 24 carbon) amidoalkyl (2 to 6 carbon) group and / or a hydroxyalkyl group having 2 to 4 carbon atoms and an anion is a conjugate base of a super strong acid (A2 Examples of the quaternary ammonium group constituting) include oleamidoethyldiethylmethylammonium, stearamideethyldiethylbenzylammonium, and stearamidopropyldimethylhydroxyethylammonium groups.

Examples of the anion constituting the (A2), wherein (A1) X in ^- the same groups as those exemplified superacid conjugate base as, preferable ones are also same.

  The quaternary ammonium group constituting (A3) includes an alkyloxy (carbon number 8-24) methylpyridinium group (for example, stearyloxymethylpyridinium group), an alkyl (carbon number 8-24) oxymethylpyridinium group (for example, , Hexadecyloxymethylpyridinium group) and alkyl (C10-24) pyridinium group (for example, tetradecylpyridinium group).

Examples of the anion constituting the (A3), wherein (A1) X in ^- the same groups as those exemplified superacid conjugate base as, preferable ones are also same.

  The quaternary ammonium salt (A) is preferably (A1) from the viewpoint of heat resistance, stain resistance, compatibility with silicone and adhesive strength, and more preferably dimethyldidecyl ammonium tetrafluoroboric acid. Salts, didecyldimethylammonium trifluoromethanesulfonate, trimethylhexadecylammonium tetrafluoroborate, dimethyl coconut oil alkylbenzylammonium tetrafluoroborate and dimethyl coconut oil alkylbenzylammonium trifluoromethanesulfonate.

  The production method of (A) is not particularly limited, and known methods such as the following methods [I] and [II] are exemplified, and the method [II] is preferred.

[I] An alkali metal salt (sodium salt or potassium salt) of the super strong acid is added to an aqueous solution (20 to 70% by weight) of a quaternary ammonium salt (for example, a salt comprising a chloroanion) (a quaternary ammonium salt). / Equivalent ratio of super-strong acid salt is usually 1/1 to 1 / 1.5, preferably 1 / 1.05 to 1 / 1.3), stirred and mixed at room temperature for about 2 hours, and about 70 to 80 ° C. After stirring for 1 hour, the lower layer (aqueous layer) which has been allowed to stand and separate is removed, and the water in the upper layer is distilled off under reduced pressure to obtain the desired quaternary ammonium salt.

[II] Carbonic acid dialkyl ester (alkyl group having 1 to 5 carbon atoms) of the same equivalent or more (preferably 1.1 to 5.0 equivalents) as the tertiary amine is, for example, 10 based on the weight of the tertiary amine. The reaction is carried out at a reaction temperature of 80 to 200 ° C., preferably 100 to 150 ° C. in the presence or absence of an organic solvent (eg methanol) in an amount of ˜1,000% by weight to form a quaternary ammonium salt. Further, the super strong acid is added (1.0 to 1.2 equivalents based on the equivalent amount of quaternary ammonium), and the mixture is stirred at 10 to 50 ° C. for 1 hour for salt exchange. The organic solvent is distilled off at 80 to 120 ° C. under reduced pressure to obtain the desired quaternary ammonium salt.

  In the present invention, the compound (B) includes an ethylenically unsaturated bond (b11) and / or a hydrosilyl group (b12) and a polyoxyethylene chain (b3) (B1), polysiloxane structures (b2) and (b3). Or (b11) and / or compound (B3) having (b12), (b2) and (b3), and a mixture of two or more of these may be used.

Examples of the compound (B11) having an ethylenically unsaturated bond (b11) and a polyoxyethylene chain (b3) in (B1) include polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, and ethylene oxide of trimethylolpropane diallyl ether. Adduct (hereinafter abbreviated as EO adduct), EO adduct of pentaerythritol triallyl ether, EO adduct of glycerin monoallyl ether, EO adduct of allylamine, EO adduct of (meth) acrylic acid, etc. However, it is not particularly limited to this.

Examples of the compound (B12) having a hydrosilyl group (b12) and a polyoxyethylene chain (b3) in (B1) include etherified products of polyethylene glycol monoallyl ether and chlorodimethylsilane, and etherified products of polyethylene glycol and chlorodimethylsilane. , Etherified product of trimethylolpropane diallyl ether and chlorodimethylsilane, EO adduct of pentaerythritol triallyl ether and chlorodimethylsilane, EO adduct of glycerol monoallyl ether, EO adduct of allylamine and chlorodimethylsilane Although etherified compound etc. are mentioned, it is not specifically limited to this.

As the compound (B2) having a polysiloxane structure (b2) and a polyoxyethylene chain (b3), for example, urethane urea obtained by reacting amino-modified silicone with polyethylene glycol (hereinafter abbreviated as PEG) using polyisocyanate. An esterified product obtained by reacting epoxy-modified silicone and PEG with dicarboxylic acid, a urethanized product obtained by reacting carbinol-modified silicone and PEG with polyisocyanate, polyether-modified silicone, mercapto-modified silicone and PEG. Thiourethanate reacted with polyisocyanate, esterified product of carboxyl-modified silicone or carboxylic anhydride-modified silicone and PEG, and methylhydrogen silicone and P having an ethylenically unsaturated bond at the terminal or side chain Compounds obtained by addition reaction of G, and PEG-modified silicone, and the like, but is not particularly limited thereto.

  As polyisocyanate used for (B2), C4-C22 chain aliphatic polyisocyanate (ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, etc.), C8-C18 alicyclic polyisocyanate (isophorone) Diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, etc., aromatic polyisocyanate having 8 to 26 carbon atoms (1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tri) Range isocyanate and 4,4'- or 2,4'-diphenylmethane diisocyanate) and C10-18 aromatic aliphatic polyisocyanate (m- or p-xylylene diisocyanate, etc.).

Examples of (B3) include urethane ureas obtained by reacting (b11) and (B2) with polyisocyanate, and etherified products of (B2) and allyl chloride, but are not particularly limited thereto. Absent. Examples thereof include ethers of (B2) and chlorodimethylsilane, but are not particularly limited thereto.

  The number of repeating units of the oxyethylene group of the polyoxyethylene chain in the compound (B) having a polyoxyethylene chain is preferably from 2 to 100, more preferably from 3 to 70, more preferably from the viewpoint of antistatic performance. Is 4 to 60, particularly preferably 4 to 50.

  The antistatic agent of the present invention is an organic solvent, a tackifying resin, a plasticizer, a filler, a pigment, an ultraviolet absorber, an antioxidant, and a silane coupling agent as necessary, as long as the effects of the present invention are not impaired. And a crosslinking agent and the like.

  Examples of the organic solvent include esters having 2 to 8 carbon atoms (for example, methyl formate, ethyl acetate and butyl acetate), alcohols having 1 to 8 carbon atoms (for example, isopropanol), hydrocarbons having 4 to 8 carbon atoms (for example, hexane, cyclohexane, Toluene and xylene), ketones having 3 to 9 carbon atoms (for example, acetone, methyl ethyl ketone, and cyclohexanone).

From the viewpoint of easy handling of the antistatic agent, the amount of the organic solvent used is preferably 0.01 to 900% by weight, more preferably 5 to 400, based on the total weight of the constituent components excluding the organic solvent of the antistatic agent. % By weight.
The viscosity (25 ° C.) of the antistatic agent using an organic solvent is preferably 100 to 50,000 mPa · s, more preferably 200 to 30,000 mPa · s from the viewpoint of coating.

Examples of tackifying resins include terpene resins, terpene phenol resins, phenol resins, aromatic hydrocarbon modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (aliphatic, aromatic or alicyclic synthetic petroleum resins, etc. ), Coumarone-indene resin, xylene resin, styrene resin, dicyclopentadiene resin, and hydrogenated products of these having hydrogenated unsaturated double bonds. The tackifier resin may be used alone or in combination of two or more.
The amount of tackifying resin used is usually 100% by weight or less based on the total weight of (A) and (B), and preferably 0.01 to 50% by weight from the viewpoint of the adhesive strength of the adhesive.

Examples of the plasticizer include hydrocarbon plasticizers [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, paraffin wax, copolymerization of ethylene and α-olefin (3 to 20 carbon atoms) (weight ratio). 99.9 / 0.1 to 0.1 / 99.9) Copolymerization of oligomer (Mw 5,000 to 100,000) and propylene with α-olefin (4 to 20 carbon atoms) excluding ethylene (weight ratio 99) .9 / 0.1-0.1 / 99.9) oligomers (Mw 5,000-100,000) etc.]; chlorinated paraffins; ester plasticizers such as phthalates (diethyl phthalate, dibutyl phthalate, dioctyl phthalate) , Didecyl phthalate, dilauryl phthalate, distearyl phthalate and diisononyl phthalate Etc.), adipic acid esters (dioctyl adipate, etc.), sebacic acid esters (dioctyl sebacate, etc.) and animal and vegetable fats and oils (eg linoleic acid and linolenic acid); and hydrogenated unsaturated double bonds among them And hydrogenated substances. A plasticizer may be used individually by 1 type, or may use 2 or more types together.
The amount of the plasticizer used is usually 50% by weight or less based on the total weight of (A) and (B), and preferably 0.01 to 30% by weight from the viewpoint of the adhesive strength and cohesive strength of the adhesive.

Examples of the filler include magnesium carbonate, calcium carbonate, aluminum sulfate, calcium sulfate, barium sulfate, calcium sulfite, molybdenum disulfide, aluminum silicate, calcium silicate, diatomaceous earth, quartzite powder, talc, silica and zeolite.
The filler is a fine particle having a volume average particle diameter of preferably about 0.01 to 5 μm, and may be used alone or in combination of two or more.
The amount of the filler used is usually 50% by weight or less based on the total weight of (A) and (B), and preferably 0.01 to 30% by weight from the viewpoint of the adhesive strength and cohesive strength of the adhesive.

Examples of pigments include inorganic pigments (alumina white, graphite, titanium oxide (ultrafine titanium oxide, etc.), zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, resurge, lithopone, Barite, Cadmium red, Cadmium mercury red, Bengala, Molybdenum red, Red lead, Yellow lead, Cadmium yellow, Barium yellow, Strontium yellow, Titanium yellow, Titanium black, Chrome oxide green, Cobalt oxide, Cobalt green, Cobalt / Chromium green, Ultramarine blue, bituminous blue, cobalt blue, cerulean blue, manganese purple and cobalt purple) and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyed lakes and the like).
The pigment is a fine particle having a volume average particle diameter of preferably about 0.01 to 5 μm, and may be used alone or in combination of two or more.
The amount of the pigment used is usually 20% by weight or less based on the total weight of (A) and (B), and preferably 0.01 to 10% by weight from the viewpoint of the adhesive strength and cohesive strength of the adhesive.

Examples of ultraviolet absorbers include salicylic acid derivatives (such as phenyl salicylate, salicylic acid-p-octylphenyl and salicylic acid-p-tert-butylphenyl), benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 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 and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) Methane and the like], benzotriazole compounds {2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl) Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) ben Triazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- [2 '-Hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole and 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 and ethyl-2-cyano-3 , 3′-diphenyl acrylate, etc.). These ultraviolet absorbers may be used alone or in combination of two or more.
The usage-amount of a ultraviolet absorber is normally 5 weight% or less based on the total weight of (A) and (B), Preferably it is 0.01 to 1 weight% from a viewpoint of the adhesive force of an adhesive.

Antioxidants include phenolic (hindered phenol) such as 2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol) and Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate]; sulfur-based such as dilauryl 3,3′-thiodipropionate (DLTDP) and distearyl 3,3′-thiodipropionate (DSTDP); phosphorus-based (organic phosphite optionally containing halogen) ), For example, triphenyl phosphite (TPP), triisodecyl phosphite (TDP), tris (2,4- -T-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and their halo substituents; amine-based (hindered aromatic amines) such as octyl diphenylamine, N -N-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine and the like. These antioxidants may be used alone or in combination of two or more.
The amount of the antioxidant used is usually 5% by weight or less based on the total weight of (A) and (B), preferably 0.01 to 1% by weight from the viewpoint of the adhesive strength and stain resistance of the adhesive. is there.

  Examples of silane coupling agents include vinyl group-containing alkoxysilane compounds [vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, etc.], (meth) acryloyloxy group-containing alkoxysilane compounds (3-methacryloyloxypropyltri). Methoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-acryloyloxypropyltrimethoxysilane), epoxy group-containing alkoxysilane compounds [3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.], isocyanate group-containing alkoxysilane compounds (3-isocyanatopropyltriethoxysilane, etc.), amino Group-containing alkoxysilane compounds [3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.], Ureido group-containing alkoxysilane compounds (3-ureidopropyltriethoxysilane, etc.), mercapto group-containing alkoxysilane compounds (3-mercaptopropylmethyldimethoxysilane, etc.), sulfide group-containing alkoxysilane compounds [bis (triethoxysilylpropyl) tetrasulfide Etc.]. Among these, an epoxy group-containing alkoxysilane compound is preferable from the viewpoint of curability of the pressure-sensitive adhesive. A silane coupling agent may be used individually by 1 type, or may use 2 or more types together.

  The amount of the silane coupling agent used is usually 5% by weight or less based on the total weight of (A) and (B), preferably 0.01 to 1% by weight from the viewpoint of the adhesive strength and stain resistance of the adhesive. It is.

Examples of the crosslinking agent include methyl hydrogen siloxane.

  The amount of the crosslinking agent used is usually 5% by weight or less based on the total weight of (A) and (B), and preferably 0.01 to 1% by weight from the viewpoint of the adhesive strength and stain resistance of the adhesive. .

  The total content of various additives based on the total weight of (A) and (B) is usually 230% by weight or less, preferably 150% by weight or less, more preferably 0.1 to 120% by weight from the viewpoint of the adhesive strength of the adhesive. %.

  The content of the quaternary ammonium salt (A) in the antistatic agent is preferably 0.1 to 50% by weight based on the total weight of (A) and (B) from the viewpoint of antistatic performance and stain resistance. More preferably, it is 1 to 45% by weight, and particularly preferably 5 to 40% by weight.

  The antistatic agent for silicone pressure-sensitive adhesives of the present invention is obtained by uniformly mixing (A), (B) and other components as necessary with a normal mixing device (such as a mixing tank and a static mixer equipped with a stirrer). Can be manufactured.

Antistatic agent (D) for silicone adhesive of the present invention is
(1) Antistatic agent for silicone adhesive (D), polysiloxane (C1) having an ethylenically unsaturated bond and / or hydrosilyl group (b1) and not having a polyoxyethylene chain (b3), and a platinum group Antistatic silicone pressure-sensitive adhesive composition (F1) containing metal catalyst (E) or (2) Antistatic agent for silicone pressure-sensitive adhesive (D), having ethylenically unsaturated bond and / or hydrosilyl group (b1) It is preferably used as an antistatic silicone pressure-sensitive adhesive composition (F2) containing polysiloxane (C2) having no polyoxyethylene chain (b3) and an organic peroxide (H). Of these, it is more preferable to use (1) an antistatic silicone pressure-sensitive adhesive composition (F1) containing a platinum group metal catalyst (E).
When (C1) and (C2) are expressed as (C), the content of the antistatic agent (D) for silicone pressure-sensitive adhesive is preferably 0.01 to 50 based on the total weight of (C) and (D). % By weight, more preferably 0.1 to 30% by weight, particularly preferably 1 to 10% by weight.
The content of (E) with respect to the total weight of (D) and (C) is preferably 0.1 to 10,000 ppm as a metal. The content of (H) is preferably 0.1 to 10% by weight with respect to the total weight of (D) and (C).
(F1) is heated (50 to 150 ° C.), (F2) is heated (80 to 200 ° C.) and reacted to form an antistatic silicone pressure-sensitive adhesive (G). (G) is applied to at least a part of at least one side of the substrate and used as an adhesive tape or an adhesive sheet, and is preferably used as an adhesive film.

Examples of the polysiloxane (C) having an ethylenically unsaturated bond and / or a hydrosilyl group (b1) in the antistatic silicone adhesive of the present invention include silicone compounds generally used as silicone adhesives. This is the main component of the antistatic silicone adhesive. As the silicone-based compound, for example, a compound mainly composed of a mixture or a reaction product of a copolymer of SiO ₂ unit and (CH ₃ ) ₃ SiO _0.5 unit and silanol group-containing polydimethylsiloxane is used. Thus, those in which the substituent of these siloxane units is substituted with a group other than a methyl group, such as a phenyl group or a vinyl group, are used.

  Silicone pressure-sensitive adhesive can be used by applying it to a substrate, etc. If an organic solvent is used, it can be used by further volatilizing the organic solvent. It is preferable to use it after crosslinking, since a good tackiness can be obtained. The polysiloxane (C) is classified into an addition curing type (C1) and a peroxide curing type (C2) by this crosslinking method.

Peroxide-curing polysiloxane (C2) is an organic solvent-soluble copolymer consisting of _0.5 units of R ₃ SiO (where R is a monovalent hydrocarbon group) and ₂ units of Si ₂ O ₂ and terminal silanols. A condensation reaction product or mixture with polyorganosiloxane is crosslinked with an organic peroxide such as benzoyl peroxide. Examples of the peroxide curable silicone pressure-sensitive adhesive include commercially available “KR-100” [manufactured by Shin-Etsu Chemical Co., Ltd.] and “KR-130” [manufactured by Shin-Etsu Chemical Co., Ltd.].
In the case of peroxide-curing type, it is generated by the reaction between the radical generated by the extraction of the hydrogen atom of the alkyl group in polysiloxane (C2) and the radical that decomposes the peroxide and the unsaturated bond of (B). When the radical to be reacted with the compound (B), a covalent bond is formed and the effect of improving the stain resistance and heat resistance is achieved.

Addition-curable polysiloxane (C1) is generally composed of an R ₃ SiO _0.5 unit (wherein R is a monovalent hydrocarbon group) and an SiO ₂ unit, an organic solvent-soluble copolymer, and an alkenyl group of a terminal silanol. The condensation reaction product or mixture with the polyorganosiloxane is added to the polyorganohydrogensiloxane. Examples of the platinum addition curing type silicone pressure-sensitive adhesive include commercially available “KR-3700” [manufactured by Shin-Etsu Chemical Co., Ltd.] and “KR-3704” [manufactured by Shin-Etsu Chemical Co., Ltd.]. In the case of the addition-curing type, the compound (B) forms a covalent bond with the polysiloxane (C1) and has an effect of improving the stain resistance and heat resistance.

By using (B) and the quaternary ammonium salt (A) in combination, the effect of exhibiting excellent antistatic performance and stain resistance is exhibited.

  The silicone pressure-sensitive adhesive used in the present invention is preferably a platinum addition curable type that can be cured at a relatively low temperature.

  The antistatic silicone pressure-sensitive adhesive of the present invention is an organic solvent similar to that exemplified in the description of the anti-static agent for silicone pressure-sensitive adhesives of the present invention, as long as it does not impair the effects of the present invention. Resins, plasticizers, fillers, pigments, ultraviolet absorbers, antioxidants, silane coupling agents and the like can be further contained.

  The pressure-sensitive adhesive tape and pressure-sensitive adhesive sheet of the present invention are prepared by directly applying the antistatic silicone pressure-sensitive adhesive of the present invention to at least a part of at least one side of a substrate using various coating apparatuses, and heating the organic solvent or dispersion medium. It is manufactured by a method of drying and curing, or a method of transferring a pressure-sensitive adhesive obtained by drying and curing after applying a pressure-sensitive adhesive to a release film or the like on at least one side of a substrate, etc. can do.

Base materials include films of various plastics [polyolefin (polyethylene, polypropylene, etc.), polyurethane, polyethylene terephthalate, polyvinyl chloride, rayon, polyamide, etc.], sheets, foam, flat yarn, paper (Japanese paper, crepe paper, etc.), metal Examples include plates, metal foils, woven fabrics, nonwoven fabrics, and wood.
Among these base materials, those that are easily charged are desirably provided with antistatic properties by adding or coating various antistatic agents.

  The pressure-sensitive adhesive film of the present invention is obtained by directly applying the antistatic silicone pressure-sensitive 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 Then, the organic solvent or the dispersion medium can be dried and manufactured by a method of curing.

  The platinum group metal catalyst (E) is added for hydrosilylation addition and curing of (C1).

The platinum group metal catalyst (E) is a platinum group metal catalyst, and examples of the central metal include platinum, palladium, iridium, rhodium, osmium, ruthenium, etc. Among them, platinum is preferable. Platinum catalysts include chloroplatinic acid, chloroplatinic acid alcohol solution, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane, etc. Is mentioned.

The organic peroxide (H) is a component that is blended to form the composition into a desired shape and then apply a heat treatment to cure it by a crosslinking reaction.

As the organic peroxide (H), all known ones used for radical polymerization reactions and the like can be used, and specifically, diacyl peroxide, dialkyl peroxide, peroxydicarbonate, peroxyester, peroxyester, and the like. One or more selected from the group consisting of oxyketals, hydroperoxides and silyl peroxides are used.

  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.

  The thickness of each pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, pressure-sensitive adhesive sheet and pressure-sensitive adhesive film of the present invention is usually 1 to 250 μm, and preferably 10 to 100 μm from the viewpoints of adhesive strength, drying and curability.

  Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. Below, a part shows a weight part.

[Production Example of Quaternary Ammonium Salt (A)]
Production Example 1
A glass reaction vessel equipped with a heating / cooling device, a stirrer and a dropping funnel was charged with 56 parts of methanol, 163 parts (0.88 mole part) of methyldi-n-decylamine and 144 parts (1.6 mole part) of dimethyl carbonate, After reacting at 120 ° C. for 20 hours, a part of methanol and dimethyl carbonate was distilled off to obtain 250 parts (0.52 mole part) of 83% methanol solution of dimethyldi-n-decylammonium methyl carbonate. Further, after the temperature was raised to 30 to 60 ° C., 114 parts (0.55 mole part) of 42% aqueous solution of boron tetrafluoride was gradually added over 2 hours while maintaining the temperature. Thereafter, the mixture was further stirred at the same temperature for 1 hour, and then the upper layer that had been allowed to stand and separated was collected and transferred to another glass reaction vessel, and methanol and water were distilled off at 80 to 100 ° C. under reduced pressure to be crude. Product-1 was obtained. Further, 9 parts (0.50 mole part) of water was added, and stripping was performed under reduced pressure (degree of vacuum -0.09 MPaG, 105 ° C. × 3 hours). Thereafter, the molten salt was melted at 80 ° C., and the deposited salt was removed by filtration through a 200 mesh wire mesh to obtain 206 parts of dimethyldi-n-decylammonium tetrafluoroborate (A1-1) solid at room temperature.

Production Example 2
To 95 parts of a 83% methanol solution of dimethyldi n-decylammonium methyl carbonate obtained in the same manner as in Production Example 1 (0.52 mole part), 79.5 parts (0.53 mole part) of trifluoromethanesulfonic acid at room temperature. Was added and stirred for 2 hours. Granular caustic potash was added to the reaction solution to neutralize it (pH: 6-8), and the precipitated salt was filtered, and then methanol in the filtrate was distilled off. Further, 9 parts (0.50 mole part) of water was added, Stripped under reduced pressure (same conditions as above) and taken out in a molten state at 120 ° C. to obtain 250 parts of dimethyldi n-decylammonium trifluoromethanesulfonate (A1-2) solid at room temperature.

[Production Example of (B11)]
Production Example 3
A stainless steel pressure-resistant reaction vessel equipped with a stirrer and a temperature controller was charged with 80 parts (1.4 mol) of allyl alcohol and 1.2 parts of potassium hydroxide, sealed, and then purged with nitrogen at room temperature under stirring. went. The temperature was raised to 95 ° C., and 700 parts (15.9 mol) of ethylene oxide was added dropwise in the range of 90 to 100 ° C. After the reaction, the mixture was cooled to 70 ° C., 0.5% water was added, and then 1 part by weight of Kiyoward (KW) -600 (manufactured by Kyowa Chemical Co., Ltd.) was added to the reaction product and mixed. The alkali catalyst was subjected to an adsorption treatment at 70 to 80 ° C. in a nitrogen atmosphere, followed by nitrogen pressure filtration, and the filtrate was dehydrated in an oxygen concentration range of 0.1% or less and 95 to 105 ° C. When the moisture reached 0.05%, the mixture was immediately cooled to obtain 687 parts of allyl alcohol ethylene oxide adduct (10 mol adduct) (B11-1).

Production Example 4
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer and a temperature controller, 200 parts (0.5 mol) of polyethylene glycol having a number average molecular weight of 400 (“PEG400” manufactured by Sanyo Chemical Industries Ltd.) and 0.1 part of sodium borohydride And 78.8 parts (1.0 mol) of allyl chloride are charged, and the temperature in the reaction vessel is adjusted to 20 ° C. or lower in a nitrogen atmosphere. After adjusting the temperature, 60.0 parts of sodium hydroxide was added over 2 hours while controlling the temperature in the kettle to be kept at 60 ° C. or lower, and then aged at 85 ° C. for 4 hours. Next, after adjusting the crude product to 70 ° C., 331.4 parts of ion-exchanged water was added and stirred for 30 minutes to dissolve the remaining alkali and product salt in the crude product. After dissolving the salt, the reaction vessel was kept at a temperature of 70 ° C. for 30 minutes, and the separated lower layer water was extracted. Next, 3 parts of KW-600 (manufactured by Kyowa Chemical Industry) and 2 parts of KW-700 (manufactured by Kyowa Chemical Industry) were added to the upper layer and mixed. After mixing, the mixture was dehydrated under reduced pressure at 70 to 80 ° C. for 4 hours while passing nitrogen through the liquid, cooled to 40 ° C., and filtered under nitrogen pressure to obtain 240 parts of PEG400 diallyl ether compound (B11-2). .

Production Example 5
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer and a temperature control device, 500 parts (0.5 mol) of polyethylene glycol (“PEG1000” manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 1000 and 0.1 part of sodium borohydride And 78.8 parts (1.0 mol) of allyl chloride are charged, and the temperature in the reaction vessel is adjusted to 40 ° C. in a nitrogen atmosphere. After adjusting the temperature, 60.0 parts of sodium hydroxide was added over 2 hours while controlling the temperature in the kettle to be kept at 60 ° C. or lower, and then aged at 85 ° C. for 4 hours. Next, after adjusting the crude product to 70 ° C., 331.4 parts of ion-exchanged water was added and stirred for 30 minutes to dissolve the remaining alkali and product salt in the crude product. After dissolving the salt, the reaction vessel was kept at a temperature of 70 ° C. for 30 minutes, and the separated lower layer water was extracted. Next, 3 parts of KW-600 (manufactured by Kyowa Chemical Industry) and 2 parts of KW-700 (manufactured by Kyowa Chemical Industry) were added to the upper layer and mixed. After mixing, the mixture was dehydrated under reduced pressure at 70-80 ° C. for 4 hours while ventilating nitrogen through the solution, cooled to 40 ° C., and filtered under nitrogen pressure to obtain 540 parts of PEG1000 diallyl ether compound (B11-3). .

Production Example 5
[Production Example of (B12)]
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer and a temperature control device, 500 parts (0.5 mol) of polyethylene glycol (“PEG1000” manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 1000 and 0.1 part of sodium borohydride And 94 parts (1.0 mol) of chlorodimethylsilane are prepared, and the temperature in the reaction vessel is adjusted to 40 ° C. in a nitrogen atmosphere. After temperature adjustment, 60.0 parts of sodium hydroxide was added over 2 hours while controlling the temperature in the kettle to be kept at 30 ° C. or lower, and then aged at 85 ° C. for 4 hours. Next, after adjusting the crude product to 70 ° C., 331.4 parts of ion-exchanged water was added and stirred for 30 minutes to dissolve the remaining alkali and product salt in the crude product. After dissolving the salt, the reaction vessel was kept at a temperature of 70 ° C. for 30 minutes, and the separated lower layer water was extracted. Next, 3 parts of KW-600 (manufactured by Kyowa Chemical Industry) and 2 parts of KW-700 (manufactured by Kyowa Chemical Industry) were added to the upper layer and mixed. After mixing, dehydrated under reduced pressure at 70 to 80 ° C. for 4 hours while bubbling nitrogen through the liquid, cooled to 40 ° C., filtered with nitrogen pressure, and 540 parts of etherified product of PEG1000 and chlorodimethylsilane (B12-1) Got.

[Production example of (B2)]
Production Example 6
In a flask equipped with a stirrer, a condenser and a thermometer, 82 parts (2 mol) of carboxyl-modified silicone oil (“X-22-162C” manufactured by Shin-Etsu Chemical Co., Ltd.), polyethylene glycol (“PEG2000” manufactured by Sanyo Chemical Industries, Ltd.) 18 Part (1 mol) and 0.3 part of an esterification catalyst (“p-toluenesulfonic acid monohydrate” manufactured by Nacalai Tesque) are added all at once, and the water is generated at a temperature of 180 ± 5 ° C. under a nitrogen stream. The mixture was reacted for 24 hours while distilling off to obtain PEG-modified silicone (B2-1).

Production Example 7
[Production Example of (B3)]
In a flask equipped with a stirrer, a condenser and a thermometer, 11.2 parts (2 mol) of allyl alcohol ethylene oxide adduct (B11-1) and carboxyl-modified silicone oil (“X-22-162C” manufactured by Shin-Etsu Chemical Co., Ltd.) 41 parts (1 mol) and 0.3 part of an esterification catalyst ("p-toluenesulfonic acid monohydrate" manufactured by Nacalai Tesque) are added all at once, and the temperature is generated at 180 ± 5 ° C under a nitrogen stream. The reaction was carried out for 24 hours while distilling off water to obtain an allyl group-containing PEG-modified silicone (B3-1).

Reference example 1
100 parts of polysiloxane (C-1) ("KR-3700", manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3 part of dimethyldi-n-decylammonium tetrafluoroborate (A-1), allyl alcohol ethylene oxide adduct (B1-1) 5 parts, platinum group metal catalyst (“CAT-PL-50T”, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part, antioxidant [“ADK STAB AO-60G” (produced by ADEKA)] 3 parts and 110 parts of toluene were mixed, applied onto a polyimide film (25 μm) so that the film thickness after drying was 30 μm, and dried and cured at 130 ° C. for 10 minutes to prepare an adhesive film.

Examples 6, 7, and 10, Reference Examples 2 to 5, Reference Examples 8, 9, and 11 and Comparative Examples 1 to 5
An adhesive film was prepared in the same procedure as in Example 1 after mixing each component with the formulation shown in Table 1 (unit: “parts”). Table 2 shows the results of measuring or evaluating the surface specific resistance value, the contamination on the adherend surface, and the adhesive strength by the following test method using the obtained adhesive film.
In addition, the composition and trade name of each component in Table 1 are as follows.
-(A'-1): Lithium bistrifluoromethanesulfonylimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B′-1): PEG-1000 (manufactured by Sanyo Chemical Industries): polyethylene glycol having a molecular weight of 1000 (C-1): silicone adhesive: “KR-3700” (manufactured by Shin-Etsu Chemical Co., Ltd.)
(C-2): Silicone adhesive: “KR-100” (manufactured by Shin-Etsu Chemical Co., Ltd.)
(E-1) Platinum group metal catalyst: “CAT-PL-50T” (manufactured by Shin-Etsu Chemical Co., Ltd.)
(H-1) Organic peroxide: “NIPPER BMT-K40” (manufactured by NOF Corporation)
・ Polyorganohydrogensiloxane: “KF-9901” (manufactured by Shin-Etsu Chemical Co., Ltd.)
Antioxidant: “ADK STAB AO-60G” (manufactured by ADEKA)

[Performance test method]
(1) Antistatic properties (surface resistivity)
After the adhesive film test piece at the initial stage and after the heat test (200 ° C. × 10 minutes) was allowed to stand for 12 hours under the condition of 23 ° C. × 65% RH, the surface specific resistance value was measured by the method described in JIS-K6911. .

(2) Contamination to the surface of the adherend An adhesive film test piece having an area of 50 × 100 mm is attached to a stainless steel plate, and an initial sample and a sample after a heat test (200 ° C. × 10 minutes) are obtained at 60 ° C. × 90 After standing for 1 week under the condition of% RH, the test piece was peeled off, and the presence or absence of contamination such as cloudiness and adhesive residue on the surface of the stainless steel plate was observed with the naked eye and evaluated according to the following criteria.
○: Neither fogging nor adhesive residue △: Slightly cloudy or adhesive residue ×: Significant cloudiness or adhesive residue

(3) 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 2 kg load roller, and so on. The adhesive strength (unit: N / 25 mm) at normal temperature (23 ° C.) was evaluated in accordance with JIS-Z-0237 for the paste after 30 minutes.

An adhesive tape formed by applying an antistatic silicone adhesive containing the antistatic agent 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 semiconductor component reflow process. And masking in resin sealing processes, electronic materials for temporary fixing of parts, antireflection film, protective film, polarizer film, retardation film, optical compensation film, brightness enhancement film, light guide plate, prism sheet, electromagnetic wave shield It can be used for optical applications such as films and near-infrared absorbing films, and is extremely useful.

Claims (6)

_An antistatic agent for a silicone pressure-sensitive adhesive comprising a compound (B) having a polysiloxane structure (b2) and a polyoxyethylene chain (b3) _, and a quaternary ammonium salt (A), The antistatic agent for silicone adhesives whose ammonium salt (A) is a quaternary ammonium salt (A1) represented by General formula (1) .
[Wherein, R ¹ and R ² each independently represent a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms , and R ³ represents a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms. Group, an arylalkyl group having 7 to 22 carbon atoms or an arylalkenyl group having 7 to 22 carbon atoms , R ⁴ represents a linear or branched aliphatic hydrocarbon group having 8 to 22 carbon atoms, and X ⁻ represents -11. Represents an anion which is a conjugate base of a super strong acid having a Hammett acidity function (H ₀ ) of less than .93 . ]   Antistatic agent for silicone adhesive according to claim 1_, polysiloxane (C1) having an ethylenically unsaturated bond and / or a hydrosilyl group (b1) and no polyoxyethylene chain (b3), and a platinum group metal Antistatic silicone pressure-sensitive adhesive composition containing a catalyst.   An antistatic agent for a silicone adhesive according to claim 1; a polysiloxane (C2) having an ethylenically unsaturated bond and / or a hydrosilyl group (b1) and not having a polyoxyethylene chain (b3); An antistatic silicone pressure-sensitive adhesive composition containing an oxide. Antistatic silicone adhesive obtained by reacting the antistatic silicone pressure-sensitive adhesive composition according to claim 2 or 3. The adhesive tape or adhesive sheet formed by apply | coating the adhesive of Claim 4 to at least one part of at least one side of a base material. An adhesive film containing the adhesive according to claim 4 .