JP2016148030A - Antistatic agent for silicone release agent and antistatic silicone release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic agent for a silicone release agent which exhibits little change in peeling force over time and is excellent in antistatic performance.SOLUTION: An antistatic agent composition for a silicone release agent contains a quaternary ammonium salt (A) and a compound (B) having a polyoxyethylene chain. The quaternary ammonium salt (A) is represented by formula (1). [Rand Reach independently represent a 1-22C aliphatic hydrocarbon group; Rrepresents a 1-22C aliphatic hydrocarbon group, a 7-22C arylalkyl group, or a 7-22C arylalkenyl group; Rrepresents an 8-22C aliphatic hydrocarbon group; and Xrepresents an anion being a conjugate base of a superacid having a Hammett acidity function (H) of less than -11.93.]SELECTED DRAWING: None

Description

  The present invention relates to an antistatic agent for silicone release agent, an antistatic silicone release agent containing the antistatic agent for silicone release agent, and a release film formed by applying the antistatic silicone.

A silicone release film is a film in which a silicone release agent is applied on a substrate, for example, a film that is peeled off from the bonding surface of a bonding film such as an adhesive film or an adhesive film, and the release film itself is adhesive or tacky. Such as a release film and a release sheet are included. Specific examples thereof include a single-sided release film having a release agent layer on one side of the substrate and a double-sided release film having release agent layers on both sides of the substrate.

  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.

  When the release film is used, peeling electrification may occur when the release film is peeled off from the adhesive film or the like, and adhesion or entrainment of foreign matter such as dust or dust occurs on the adhesive film and the release film.

However, in the method described in Patent Document 1, since the anionic surfactant bleeds out over time, the pressure-sensitive adhesive is contaminated and the peeling force changes.

JP 2014-233845 A

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an antistatic agent for a silicone release agent that has little change in peel force with time and is excellent in antistatic performance when an antistatic agent is added. There is to do.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention
Antistatic agent composition for silicone release agent containing quaternary ammonium salt (A) and compound (B) having polyoxyethylene chain; Antistatic silicone release containing antistatic agent composition for silicone release agent An antistatic release film having a layer of the antistatic silicone release agent composition on at least a part of at least one side of a substrate.

The antistatic release film using the antistatic agent composition for a silicone release agent of the present invention has little change in peel force over time and is excellent in antistatic performance.

The antistatic agent composition for a silicone release agent of the present invention contains a quaternary ammonium salt (A) and a compound (B) having a polyoxyethylene chain. Preferably, an organic metal compound (C) may be further contained for the reason of coating film adhesion. Further, preferably, an aliphatic compound (D) having an unsaturated bond may be contained for the reason of coating film adhesion.

The quaternary ammonium salt (A) in the present invention includes a quaternary ammonium salt (A1) represented by the following general formula (1); and a quaternary ammonium salt (A2) of a cyclic amine (pyridine, morpholine, etc.). ).

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 is a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, arylalkyl having 7 to 22 carbon atoms, arylalkenyl group having 7 to 22 carbon atoms, or alkyl (10 to 24 carbon atoms) amidoalkyl. A (C2-C6) group and / or a C2-C4 hydroxyalkyl group are represented.
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 a carbon number are preferable from the viewpoint of peeling force. 6 to 14 linear or branched aliphatic hydrocarbon groups.

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.

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

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.
When R ³ is an alkyl (10 to 24 carbon) amidoalkyl (2 to 6 carbon) group and / or a hydroxyalkyl group having 2 to 4 carbon atoms, for example, oleamidoethyldiethylmethylammonium, stearamide Examples thereof include ethyl diethylbenzylammonium and stearamidopropyldimethylhydroxyethylammonium groups.

  Of these, trimethyl hexadecyl ammonium, dimethyl didecyl ammonium, dimethyl dodecyl benzyl ammonium and dimethyl tetradecyl benzyl ammonium are preferable from the viewpoint of peeling force.

X ⁻ in the general formula (1) is not particularly limited, and examples thereof include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ and I ^{− and the} like), carboxylate anions {mono- or dicarboxylic acids having 1 to 7 carbon atoms]. Acid (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid and other ions (—COO ⁻ )), sulfonic acid ion {sulfonic acid having 1 to 20 carbon atoms (methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, Ions such as trifluoromethanesulfonic acid and p-toluenesulfonic acid (—SO ₃ ⁻ )}, phosphate ions {ion of phosphoric acid or C 1-10 phosphate group-containing compound (—OPO ₃ ²⁻ )}, Examples include thiocyanate ion, perchlorate ion, sulfate ion and nitrate ion, and inorganic acids.

Particularly preferred, X in the general formula (1) ^- is a conjugate base of a superacid having a Hammett acidity function of less than -11.93 _{(H 0).}

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 having a Hammett acidity function (H ₀ ) of −12.00 or less from the viewpoint of antistatic performance of the quaternary ammonium salt (A1) represented by the general formula (1). Conjugated bases, more preferably trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfone) imide, bis (nonafluorobutanesulfonyl) imide, tetrafluoroboric acid, hexafluoro Conjugated bases of phosphorus fluoride, chlorofluoroboric acid, antimony hexafluoride, arsenic hexafluoride or taurine hexafluoride, particularly preferred are conjugates of trifluoromethanesulfonic acid, boron tetrafluoroboric acid or hexafluorophosphoric acid Base, bis (trifluoromethanesulfone) imide, most preferred is trifluoromethanesulfonic acid, tetrafluoromethane Conjugate base of boron acids, and bis (trifluoromethanesulfonyl) imide.

The quaternary ammonium group constituting (A2) 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 (A2), 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 antistatic performance and peel strength, and more preferably dimethyldidecylammonium tetrafluoroborate and didecyldimethylammonium trifluoromethanesulfone. Acid salts, didecyldimethylammonium bis (trifluoromethanesulfone) imide, trimethylhexadecylammonium tetrafluoroborate, dimethyl coconut oil alkylbenzylammonium tetrafluoroborate and dimethyl coconut oil alkylbenzylammonium trifluoromethanesulfonic acid.

  The production method of the quaternary ammonium salt (A) is not particularly limited, and known methods such as the following methods [I] and [II] can be mentioned, and the method [II] is preferable.

[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 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, examples of the compound (B) having a polyoxyethylene chain include a compound (B1) having an ethylenically unsaturated bond and a polyoxyethylene chain, and a compound (B2) having a polysiloxane structure and a polyoxyethylene chain. Can be mentioned.

  As the compound (B1) having an ethylenically unsaturated bond and a polyoxyethylene chain, for example, an ethylene oxide adduct of (meth) acrylic acid or (meth) allyl alcohol and the terminal hydroxyl group of the adduct are chlorinated (meta ) Bifunctional compounds blocked with acrylic or (meth) allyl chloride.

  As the compound (B2) having a polysiloxane structure and a polyoxyethylene chain, for example, a urethane urea compound obtained by reacting an amino-modified silicone and polyethylene glycol (hereinafter abbreviated as PEG) using a polyisocyanate, an epoxy-modified silicone, Esterified products obtained by reacting PEG with dicarboxylic acid, urethanized products obtained by reacting carbinol-modified silicone and PEG with polyisocyanate, polyether-modified silicone, mercapto-modified silicone and PEG using polyisocyanate. Addition reaction of thiourethanated product, carboxylated silicone or carboxylic anhydride modified silicone and PEG esterified product and methylhydrogen silicone and PEG having an ethylenically unsaturated bond at the terminal or side chain It includes the compounds obtained by.

  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.).

  Since the compound (B) having a polyoxyethylene chain is preferably bonded to the silicone skeleton from the viewpoint of peeling force, the compound (B1) having an ethylenically unsaturated bond and a polyoxyethylene chain is preferable, and further a quaternary A compound having a polyoxyethylene chain having two or more ethylenically unsaturated bonds is preferred in order to suppress bleeding out of the ammonium salt (A) and reduce the peel force change, and two or more ethylenically unsaturated bonds are preferred. Most preferred are terminal compounds.

  From the viewpoint of antistatic performance, the number of repeating units of the oxyethylene group of the polyoxyethylene chain in the compound (B) having a polyoxyethylene chain is preferably 2 to 100, more preferably 5 to 50.

  The organometallic compound (C) in the present invention is preferably an organoiron compound (C1), an organoaluminum compound (C2), or an organotitanium compound (C3). Only one kind of these organometallic compounds may be used, or two or more kinds may be appropriately mixed and used.

In the present invention, the organic iron compound (C1) is not particularly limited. Specifically, ferric octylate, ferric acetate, ferric propionate, ferric naphthenate, and iron acetylacetonate are used. Can be mentioned.

Although it does not specifically limit as organoaluminum compound (C2), Specifically, aluminum (III) acetylacetonate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetate Acetate, aluminum-di-iso-propoxide-monomethyl acetoacetate and the like.

Although it does not specifically limit as an organic titanium compound (C3), Specific examples include titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; Examples thereof include titanium chelates such as titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, and titanium ethylacetoacetate.

In the organometallic compound (C), an organometallic compound having a chelate structure is more preferred. It is also described in detail in the “Crosslinking agent handbook” (Yamashita Shinzo, Kaneko East Assistant Editor, Taiseisha, 1990 edition).

Examples of the aliphatic compound (D) having an unsaturated bond in the present invention include acrylic compounds, methacrylic compounds, and olefin compounds, and α-olefin compounds are preferable from the viewpoint of coating film adhesion.

An α-olefin is an alkene having a carbon-carbon double bond at the α-position, that is, at the terminal. A linear or branched α-olefin having 3 to 25 carbon atoms is preferred from the viewpoint of coating film adhesion.

In the antistatic agent composition for a silicone release film, the quaternary ammonium salt (A) is 0.1% based on the total weight of the quaternary ammonium salt (A) and the compound (B) having a polyoxyethylene chain. 30% or less by weight, preferably 1% or more and 25% or less, and the compound (B) having a polyoxyethylene chain is contained by 70% or more and 99.9% or less by weight, preferably 75% or more and 99% or less by weight. The
The content of the organometallic compound (C) is 10% by weight to 100% by weight with respect to the total weight of (A) and (B), and the content of the aliphatic compound (D) having an unsaturated bond is (A ) And (B) is preferably 10% by weight or more and 100% by weight or less.

  The antistatic agent composition for silicone release agent of the present invention comprises (A), (B), (C), and (D) and, if necessary, other components as usual mixing device (mixing tank equipped with a stirrer And a static mixer or the like).

The antistatic release film in the present invention comprises an antistatic silicone release agent layer formed by applying the antistatic silicone release composition of the present invention to at least a part of at least one side of a substrate. Have.
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. The antistatic silicone release agent composition of the present invention contains the antistatic agent composition for a silicone release agent of the present invention and a silicone release agent.

  The antistatic silicone release agent composition of the present invention contains the antistatic agent composition for a silicone release agent of the present invention and a silicone release agent.

Examples of the silicone release agent include silicone compounds that are generally used as silicone release agents, and this is the main component of the antistatic silicone release agent. 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 release agent can be used by applying it to a substrate, etc., and when an organic solvent is used, it can be used by further volatilizing the organic solvent, but it improves the cohesive strength of the applied silicone release agent and is good It is preferable to use after cross-linking since a good releasability is obtained. Examples of the crosslinking method include, but are not limited to, an addition reaction, a method using UV, and the like.

  In the present invention, since the compound (B) having a polyoxyethylene chain is preferably bonded to the silicone skeleton, an addition reaction type silicone release agent is preferably used.

The addition reaction type silicone release agent is generally an organic solvent-soluble copolymer composed of _0.5 unit of R ₃ SiO (where R is a monovalent hydrocarbon group) and SiO ₂ unit, and an alkenyl group-containing polysiloxane of terminal silanol. A condensation reaction product or mixture with an organosiloxane is subjected to an addition reaction with a polyorganohydrogensiloxane. Examples of the platinum addition curing type silicone release agent include commercially available “KS-774” (manufactured by Shin-Etsu Chemical Co., Ltd.) and “KS-3703T” (manufactured by Shin-Etsu Chemical Co., Ltd.).

  The silicone release agent used in the present invention is preferably a platinum addition curable type that can be cured at a relatively low temperature.

  The content of the antistatic agent composition for a silicone release agent of the present invention in the antistatic silicone release agent composition of the present invention is such that the antistatic agent composition in the release agent composition is from the viewpoint of peeling force and antistatic performance. The total weight is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight.

The antistatic release film is formed by providing a release layer on at least a part of at least one side on a substrate.
The release layer is formed by applying a silicone release agent containing the antistatic composition of the present invention. An application layer may be provided in order to improve the coating film adhesion between the release layer and the substrate. Regarding the coating layer, a coating stretching method (in-line coating) may be used, so-called off-line coating that is applied outside the system on a once produced film may be employed, and any method may be employed.

Polyorganosiloxane can be used as the coating layer. Organopolysiloxane has at least 3, preferably 3 to 1000 hydrolyzable groups bonded to silicon atoms in one molecule. Examples of the hydrolyzable group include, but are not limited to, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group and an isopropenoxy group directly bonded to a silicon atom, and an acyloxy group such as an acetoxy group. .

  In the present invention, it is preferable to use a catalyst in the coating layer for the purpose of promoting hydrolysis and condensation reaction. Specific examples of the catalyst include organic acids such as acetic acid, butyric acid, maleic acid and citric acid, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, basic compounds such as triethylamine, tetrabutyl titanate, dibutyltin dilaurate, Organic metal salts such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dibutyltin benzylmalate, etc. it can. The above catalysts may be used alone or in combination of two or more.

  Further, inorganic particles may be contained for the purpose of improving the adhesion and slipperiness of the coating layer, and specific examples include silica, alumina, kaolin, calcium carbonate, titanium oxide, barium salt and the like.

In addition, the antistatic agent composition for a silicone release film of the present invention includes a crosslinking agent, an antifoaming agent, a coating property improving agent, a thickener, an organic lubricant, an organic polymer particle, and an antioxidant as necessary. , UV absorber foaming agents, dyes and the like may be contained.

  The antistatic release film of the present invention is obtained by directly applying the antistatic silicone release agent composition of the present invention to at least a part of at least one side of a substrate using various coating apparatuses, and heating it to form an organic solvent or The dispersion medium can be produced by drying and curing the dispersion medium.

  The antistatic release film of the present invention is obtained by directly applying the antistatic silicone release agent of the present invention to at least a part of at least one surface of a substrate such as a PET film using various coating apparatuses, The solvent or the dispersion medium can be produced by a method of drying and curing.

  Examples of the coating apparatus include a gravure coater, a roll coater, a reverse coater, a doctor blade, a bar coater, a comma coater, a fountain die coater, a lip coater, and a knife coater.

  The thickness of each release layer of the release tape, release sheet and release film of the present invention is usually 0.01 to 10 μm, and preferably 0.1 to 1 μm from the viewpoint of the release force of the release agent.

  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 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. To 250 parts (0.52 mole part) of 83% methanol solution of dimethyldi n-decylammonium methyl carbonate obtained was added 79.5 parts (0.53 mole part) of trifluoromethanesulfonic acid at room temperature 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 (A1-1) solid at room temperature.

Production Example 2
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. To 250 parts (0.52 mole part) of 83% methanol solution of dimethyldi n-decylammonium methyl carbonate obtained, 149 parts (0.53 mole part) of bis (trifluoromethanesulfone) imide was added at room temperature and stirred for 2 hours. did. 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 bis (trifluoromethanesulfone) imide salt (A1-2) which is liquid at room temperature.

Production Example 3
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer and a temperature control device, 300 parts (0.5 mol) of polyethylene glycol (“PEG600” manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 600 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 70-80 ° C. for 4 hours while ventilating nitrogen in the liquid, cooled to 40 ° C., and filtered under nitrogen pressure to obtain 340 parts of PEG600 diallyl ether compound (B1-1). .

Production Example 4
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer and a temperature controller, 500 parts (0.5 mol) of polyethylene glycol (“PEG1000” manufactured by Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 600 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 70-80 ° C. for 4 hours while ventilating nitrogen through the solution, cooled to 40 ° C., and filtered under nitrogen pressure to obtain 510 parts of PEG1000 diallyl ether compound (B1-2). .

Example 1
100 parts of a silicone release agent (“KS-3703T”, manufactured by Shin-Etsu Chemical Co., Ltd.), 2 parts of dimethyldi-n-decylammonium trifluoromethanesulfonate (A1-1), 10 parts of PEG600 diallyl ether compound (B1-1), Tris (2,4-pentanedionato) aluminum (III) (manufactured by Tokyo Chemical Industry Co., Ltd.) (C1-1) 2 parts, 1-decene (manufactured by Kanto Chemical Co., Ltd.) (D1-1) 2 parts, platinum catalyst (" CAT-PL-50T "(manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part, 460 parts of toluene, and 460 parts of MEK (methyl ethyl ketone) are mixed, and a PET film (Toray Mirror L-38T60) is applied so that the coating amount is 0.1 m ^2. ), And dried and cured at 120 ° C. for 30 seconds to produce a release film.

Examples 2-9 and Comparative Examples 1-4
A release 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 1 shows the results of measuring and evaluating the surface resistivity, peel force, peel force change rate over time, and coating film adhesion by the following test methods using the peelable film obtained in Table 1.

・ Allyl alcohol EO 12 mol addition product (B1-3) (SANYOCOL H-1200, manufactured by Sanyo Chemical Industries)

[Performance test method]
(1) Antistatic properties (surface resistivity)
After allowing the sample film 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) Release force of release film (α)
A single-sided adhesive tape (Nitto 31B tape (25 mm width, 25 μm thickness)) was reciprocated once on the surface of the release layer of the sample film, and the release force after standing for 1 hour at room temperature (N / 25 mm). The peeling force was determined as peeling force (α) by performing 180 ° peeling under a tensile speed of 300 mm / min using a tensile tester.

(3) Rate of change in peel force over time After affixing a single-sided adhesive tape (Nitto 31B tape (25 mm width, 25 μm thickness)) with a 2 kg roller on the surface of the release layer of the sample film, high temperature and high humidity The peeling force (N / 25 mm) after standing at 60 ° C., 90 RH% for 1 week and then at room temperature for 1 hour was measured. Peeling force was determined by using a tensile tester and peeling at 180 ° under the condition of a tensile speed of 300 mm / min.
Change rate of peel force with time (%) = [{(β) − (α)} / (α)] × 100 The rate of change in peel force over time is preferably less than 100%.

(4) Coating film adhesion After leaving the sample film in a high-temperature and high-humidity tank at 60 ° C. in a 90% RH atmosphere for 4 weeks, the sample film was taken out. After drying at room temperature for 5 hours, the release surface of the sample film was rubbed 5 times with a finger, and the state of the release layer was visually observed.
<Criteria>
○: The coating film does not fall off. Δ: The coating film becomes cloudy but does not fall off. ×: The coating film has fallen off.

From the evaluation results in Table 1, in the antistatic release film using the antistatic agent composition containing the quaternary ammonium salt (A) and the compound (B) having a polyoxyethylene chain, the peel force change with time There are few, and it is excellent in antistatic performance.

The antistatic release film of the present invention can be very suitably used as a release film (carrier film and separator) for pressure-sensitive adhesive sheets, and is extremely useful.

Claims (7)

  An antistatic agent composition for a silicone release agent comprising a quaternary ammonium salt (A) and a compound (B) having a polyoxyethylene chain. The antistatic agent composition according to claim 1, 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 − 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. ]   The antistatic agent composition according to claim 1 or 2, wherein the compound (B) having a polyoxyethylene chain is a compound (B1) having an ethylenically unsaturated bond and a polyoxyethylene chain.   Furthermore, the antistatic agent composition of any one of Claims 1-3 formed by containing an organometallic compound (C).   Furthermore, the antistatic agent composition of any one of Claims 1-4 formed by containing the aliphatic compound (D) which has an unsaturated bond.   The antistatic silicone release agent composition containing the antistatic agent composition for silicone release agents of any one of Claims 1-5, and a silicone release agent. An antistatic release film having a layer of the antistatic silicone release agent composition according to claim 6 on at least a part of at least one side of a substrate.