TW202018022A - Waterbased antistatic releasing coating composition and antistatic releasing film - Google Patents

Abstract

The present invention relates to a novel water-based antistatic releasing coating agent composition, which can form an antistatic release layer having excellent antistatic properties and releasability with single layer coating, has excellent liquid stability, and can form a cured film excellent in solvent resistance. The releasing coating agent composition comprises: a methylated melamine resin (A); a hydroxyl group-containing organic modified silicone (B); an acid catalyst (C); and a conductive polymer (D).

Description

Water-based antistatic release coating composition and antistatic release film

The invention relates to an aqueous antistatic mold release coating agent composition, and an antistatic mold release film formed by coating and curing the coating agent composition.

Release films have been used as engineering films for casting films such as urethane resins, acrylic resins, and vinyl chloride resins; protective films for adhesive layers such as adhesive tapes, adhesive sheets, and adhesive films; ceramics Engineering film for the manufacture of electronic components such as green sheets and printed circuit boards. As the release film, generally, a release film in which a release layer composed of a silicone-based or non-silicone-based release agent is mainly formed on the surface of a base film such as a polyester film.

Generally, the release film is peeled off after the resin sheet is molded, when an adhesive film is used, or after the electronic component is manufactured, but it is easily charged with static electricity when peeled. Therefore, when resin sheets and the like are stacked and stored, due to electrical repulsion or attraction, there is a problem that the resin sheets are repelled or attached to each other. In the case of the adhesive film, foreign substances such as dust adhere to the adhesive layer to become Causes of adhesive layer contamination. In addition, in the case of ceramic green sheets, with the miniaturization and large capacity of ceramic capacitors, the thinning of ceramic green sheets is also advancing. When the thinning is promoted, the conventional release film is peeled off. The charging becomes serious, and the static interference caused by it becomes a serious problem. Due to these problems, the release film has been increasingly required to have an antistatic function in recent years.

As a method of imparting an antistatic function to the release film, for example, Patent Document 1 proposes to provide an antistatic layer made of a cationic antistatic agent on one side of the base film and a release layer on the other side. However, this method cannot sufficiently prevent the release film from being charged with static electricity, and we believe that the preferred solution is to impart antistatic properties to the surface of the release layer.

In addition, Patent Document 2 proposes to provide an antistatic function to the release film by providing an antistatic layer under the release layer. However, in this method, two coating steps are required to form two coating layers on the base film, and there is a problem that the cost required for the steps is high and the production efficiency is also low.

On the other hand, Patent Document 3 proposes to impart antistatic properties and mold release properties to the base film with one coating layer. However, in Patent Document 3, the above-mentioned coating layer is not cross-linked with a curable resin, a cross-linking agent, etc., so it is easily dissolved in a solvent. When a resin film containing a solvent, an adhesive layer, a ceramic slurry, etc. are coated with this When the layers are in contact, there may be cases where sufficient releasability is not obtained. In addition, Patent Document 3 uses a conductive polymer dispersed in a solvent, but there are few types of solvents that can disperse the conductive polymer. Therefore, when preparing a coating agent for forming the coating layer, the coating The solvent of the agent is limited or a dispersant (surfactant) needs to be used, and there is a problem in handling. In addition, when a surfactant is used, there is also a problem that the surfactant migrates (bleeds out) from the coating layer.

As a method of imparting antistatic properties and mold release properties to the base film through only one coating layer having excellent solvent resistance, for example, the following methods have been considered: a conductive material such as a conductive polymer added to a conventional mold release agent is prepared. A coating agent of a sexual substance forms an antistatic and solvent-resistant release layer composed of the coating agent on the base film. However, the present inventors conducted studies and as a result, it was found that the addition of a conductive substance to the mold release agent causes poor dispersion or dissolution of the conductive substance, and the stability as a coating agent (liquid stability) deteriorates, making it difficult When applying to a substrate. It is also known that the above-mentioned conductive substance may hinder the curing of the mold release agent, and the solvent resistance of the resulting mold release layer is deteriorated. [Prior Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 9-277451 Patent Document 2: Japanese Patent Laid-Open No. 2005-153250 Patent Document 3: Japanese Patent Laid-Open No. 2008-049542

[Problems to be solved by the invention] The problem to be solved by the present invention is to provide an antistatic mold release layer having excellent antistatic properties and mold release properties that can be formed by one-layer coating, has excellent liquid stability, and can form a cured product having excellent solvent resistance A novel aqueous antistatic release coating composition for membranes. [Technical means to solve the problem]

The present inventors conducted intensive research and found that the above-mentioned problems can be solved by an aqueous composition containing a prescribed melamine resin, a prescribed organically modified silicone, an acid catalyst, and a conductive polymer, thereby completing the present invention.

In detail, the present inventors found that by combining a predetermined melamine resin, a predetermined organically modified silicone, and an acid catalyst with a conductive polymer, and making a coating agent containing these components into an aqueous composition, There is obtained a coating agent that does not cause poor dispersion even if it contains a conductive polymer, and has good liquid stability. In addition, it was also found that the coating agent does not inhibit curing, and can form an antistatic release layer excellent in solvent resistance. That is, the present invention relates to the following water-based antistatic release coating composition.

1. A water-based antistatic mold release coating agent composition comprising methylated melamine resin (A), hydroxyl-containing organically modified silicone (B), acid catalyst (C), and conductive polymer (D) .

2. The water-based antistatic mold release coating composition described in item 1 above, wherein the component (A) is selected from the group consisting of imine-type methylated melamine resin, methylol-type methylated melamine resin, At least one of the group consisting of an imino·methylol type methylated melamine resin and a full ether type methylated melamine resin.

3. The water-based antistatic mold release coating composition according to item 1 or 2 above, wherein the component (B) is a hydroxyl group-containing polyether modified silicone and/or a hydroxyl group-containing silicone modified acrylic acid Resin.

4. The water-based antistatic mold release coating composition according to any one of items 1 to 3 above, wherein the component (C) is an organic sulfonic acid and/or an organic phosphoric acid.

5. The water-based antistatic release coating composition according to any one of items 1 to 4, wherein the component (D) is a poly(thiophene) type and/or a poly(aniline) type.

6. The water-based antistatic mold release coating agent composition according to any one of items 1 to 5 above, which further contains a basic compound (E).

7. An antistatic release film comprising the cured film and plastic film of the water-based antistatic release coating composition described in any one of items 1 to 6 above.

8. The antistatic release film according to item 7 above, wherein the plastic film is a polyethylene terephthalate film. [Effect of the invention]

The water-based antistatic mold release coating composition of the present invention can form a cured film having excellent antistatic properties, light peeling force, and excellent solvent resistance. In addition, the cured film formed from the coating agent composition is also excellent in antifouling properties. In addition, the coating agent composition has excellent liquid stability, and can be easily applied to a substrate film or the like.

Since the water-based antistatic mold release coating composition of the present invention can realize a layer having both antistatic properties and mold release properties by coating with one layer, it is possible to easily produce a mold release having an antistatic function film. In addition, the coating agent composition is suitable as an antistatic release coating agent for an antistatic release film, and the base film of the antistatic release film is a polyester film.

The water-based antistatic mold release coating composition (hereinafter also referred to as water-based coating composition) of the present invention is an organic group containing a methylated melamine resin (A) (hereinafter also referred to as (A) component) and a hydroxyl group Modified silicone (B) (hereinafter also referred to as (B) component), acid catalyst (C) (hereinafter also referred to as (C) component) and conductive polymer (D) (hereinafter also referred to as (D) component )'S water system composition.

The component (A) is a resin containing structural units derived from methylated melamine represented by the following formula. (A) The component must have at least one methoxymethyl group (—CH ₂ OCH ₃ ), and the average degree of polymerization of the (A) component is 1.1 to 10. The component (A) is a component that forms a cross-linked structure in a cured film formed from the aqueous coating agent composition of the present invention, and the cured film is excellent in solvent resistance.

（式（1）中，R¹ ～R⁶ 可以相同或不同，分別表示氫原子、羥甲基（－CH₂ OH）、甲氧基甲基（－CH₂ OCH₃ ）、乙氧基甲基（－CH₂ OCH₂ CH₃ ）、正丁氧基甲基（－CH₂ OCH₂ CH₂ CH₂ CH₃ ）和異丁氧基甲基（－CH₂ OCH（CH₃ ）CH₂ CH₃ ）中的任一者。其中，R¹ ～R⁶ 中的至少一個為甲氧基甲基。）

(In formula (1), R ¹ to R ⁶ may be the same or different, and each represents a hydrogen atom, a hydroxymethyl group (—CH ₂ OH), a methoxymethyl group (—CH ₂ OCH ₃ ), an ethoxymethyl group (-CH ₂ OCH ₂ CH ₃ ), n-butoxymethyl (-CH ₂ OCH ₂ CH ₂ CH ₂ CH ₃ ) and isobutoxymethyl (-CH ₂ OCH (CH ₃ ) CH ₂ CH ₃ ) Any one of them, wherein at least one of R ¹ to R ⁶ is methoxymethyl.)

From the viewpoint of excellent curability at a low temperature in a short time, the component (A) is preferably a resin containing a structural unit derived from a perether methylated melamine in which all of R ¹ to R ⁶ are methoxymethyl ( Hereinafter also referred to as full-ether methylated melamine resin). In addition, regarding component (A), from the viewpoint of excellent liquid stability, it is preferable to include an imino type derived from at least one of R ¹ to R ⁶ that is a methoxymethyl group and the rest are all hydrogen atoms. Resin that constitutes a unit of methylated melamine (hereinafter also referred to as an imino-type methylated melamine resin); from the same viewpoint, it is also preferable that at least one of R ¹ to R ⁶ is methoxy Resin that is a constituent unit of methylol-type methylated melamine in which the methyl group and the rest are all methylol groups (hereinafter also referred to as methylol-type methylated melamine resin); from the same viewpoint, it is also preferable It is a resin containing at least one of R ¹ to R ⁶ which is a methoxymethyl group, and the rest is a constitutional unit of an imino-methylol-type methylated melamine in which a hydrogen atom and a methylol group are mixedly present ( Hereinafter also referred to as imino·methylol type methylated melamine resin). (A) A component can be used individually or in combination of 2 or more types. Examples of the all-ether-type methylated melamine resin include 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine and the like.

Examples of commercially available products of component (A) include CYMEL300, CYMEL301, CYMEL303LF, CYMEL350, CYMEL370N, CYMEL771, CYMEL325, CYMEL327, CYMEL703, CYMEL712, CYMEL701, CYMEL266, CYMEL267, CYMEL285, CYMEL232, CYMEL235, CYMEL235, CYMEL235, CYMEL235 CYMEL272, CYMEL212, CYMEL253, CYMEL254, CYMEL202, CYMEL207 (above manufactured by ALLNEX JAPAN Co., Ltd.); NIKALAC MW-30M, NIKALAC MW-30, NIKALAC MW-30HM, NIKALAC MW-390, NIKALAC MW-100LM, NIKALAC MX- 750LM, NIKALAC MW-22, NIKALAC MS-21, NIKALAC MS-11, NIKALAC MW-12LF, NIKALAC MW-24X, NIKALAC MS-001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX-750, NIKALAC MX- 708, NIKALAC MX-706, NIKALAC MX-042, NIKALAC MX-035, NIKALAC MX-45, NIKALAC MX-43, NIKALAC MX-417, NIKALAC MX-410 (made by Sanwa Chemical Co., Ltd.), etc. Separately or in combination of two or more.

(B) The component means, for example, a hydroxyl group-containing silicone modified with an organic group. Generally, silicone (unmodified silicone) has poor compatibility with the component (A), so it tends to migrate (bleed out) from the cured film of the coating composition. In addition, since the solubility of silicone in aqueous coating agents is poor, most aqueous coating agents containing silicone have poor liquid stability. In addition, in order to improve the liquid stability in the water-based coating agent, the silicone may be used in the form of a silicone emulsion dispersed by an emulsifier (surfactant), and sometimes the emulsion contains The emulsifier will seep from the cured film and contaminate the adherend.

(B) The component has a part modified with an organic group, so it is well compatible with the (A) component, and because it also has a hydroxyl group, it reacts with the (A) component during curing and is fixed in the cured film, making it possible Suppression of this into the layer in contact with the cured film is suppressed. In addition, component (B) is a component that imparts mold releasability, and bleeding from the cured film is suppressed, so that the mold releasability of the cured film can be sustained for a long period of time. In addition, the component (B) tends to have good solubility in the water-based solvent described later, so the liquid stability of the water-based coating agent composition of the present invention is good.

(B) The component is not particularly limited as long as it is a hydroxy-containing organically modified silicone. The modified site may be, for example, at least one selected from the group consisting of a polyester site, a polyether site, an acrylic resin site, and a methanol site. In addition, the modified site only needs to be introduced into one of the one end, both ends, and the side chain of the silicone chain. In addition, it is preferable that the polyester part, the polyether part, the acrylic resin part, and the methanol part as the modified part have hydroxyl groups. Examples of the component (B) include hydroxyl-containing polyester-modified silicone, hydroxyl-containing polyether-modified silicone, hydroxyl-containing silicone-modified acrylic resin, and methanol-modified silicone. (B) One component may be used alone or in combination of two or more.

The commercially available products of the above-mentioned polyether-modified silicone containing hydroxyl groups or polyester-modified silicone containing hydroxyl groups can be exemplified: BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (manufactured by BYK Japan Co., Ltd.) ; X-22-4952, KF-6123 (manufactured by Shin-Etsu Chemical Co., Ltd.); Silsurf A004, Silsurf A008, Silsurf A004, Silsurf C208, Silsurf B608, Silsurf CR1115, Silsurf Di-1010 (manufactured by Siltech), etc.

The commercially available products of the above-mentioned hydroxyl group-containing silicone-modified acrylic resin can be exemplified: ZX-028-G (manufactured by T&K TOKA Co., Ltd.); BYK-SILCLEAN3700 (manufactured by BYK Japan Co., Ltd.); SYMAC US-270, SYMAC US-450, SYMAC US-480 (manufactured by East Asia Synthetic Co., Ltd.), etc. In addition, in this specification, an acrylic resin contains a polymer of acrylate and/or methacrylate.

The above-mentioned commercially available products of methanol-modified silicone can be exemplified: X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22-170DX, KF -6000, KF-6001, KF-6002, KF-6003, KF-6123, X-22-176F (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); Silaplane FM-4441, Silaplane FM-4421, Silaplane FM-4425, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA26 (manufactured by JNC Co., Ltd.), etc.

From the viewpoint of excellent mold releasability, liquid stability, and antifouling properties, the component (B) is preferably a hydroxyl group-containing polyether-modified silicone and/or a hydroxyl group-containing silicone-modified acrylic resin.

(C) The component is an acid catalyst. The acid catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; oxalic acid, acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, and hexane Alkanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid , Nonylnaphthalenesulfonic acid, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, acid phosphate Octyl ester, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleic acid phosphate, behenic acid phosphate, phenyl acid phosphate , Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate Ester, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, Organic acids such as dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bis(nonylphenyl) acid phosphate; osmium salt, benzothiazolium salt, ammonium salt, phosphonium salt Wait for thermal acid generator. (C) One component may be used alone, or two or more components may be used in combination. From the viewpoint of compatibility with the component (A), it is preferable to use organic acids for the component (C). As a more preferable example, organic sulfonic acid and/or organic phosphoric acid may be mentioned.

Regarding the component (C), from the viewpoint of excellent curability, it is preferable to use a strong acid (for example, an organic sulfonic acid) as a catalyst for the "full-ether methylated melamine resin" and the "hydroxymethyl methylated melamine resin" For "imino-type methylated melamine resin" and "imino-methylol-type methylated melamine resin" use weak acid (such as organic phosphoric acid) as a catalyst.

(D) The component is a conductive polymer and is a substance that imparts antistatic properties to the cured film.

(D) The component is not particularly limited as long as it is a conductive polymer. From the viewpoint of improving compatibility with (A) to (C) components and liquid stability, component (D) is preferably used in the form of an aqueous solution or dispersion, or a solution or dispersion of an aqueous solvent described later . In this case, the solid content concentration of the component (D) is preferably about 0.1 to 10% by weight.

The component (D) is preferably various well-known heteroatom-containing π-conjugated conductive polymers. "Hetero atom" refers to atoms other than hydrogen and carbon (for example, nitrogen atom, sulfur atom, etc.), "π-conjugated conductive polymer containing hetero atom" refers to having the hetero atom in the molecule and the main chain of the molecule is formed Π conjugated organic polymer compounds. Furthermore, in the present invention, the component (D) is in a state of being doped with various dopants. (D) One component may be used alone, or two or more components may be used in combination.

Examples of the heteroatom-containing π-conjugated conductive polymer include poly(thiophene) and poly(thiophene vinylidene) as the π-conjugated conductive polymer having a heterocyclic ring containing a heteroatom. , Poly (pyrrole), etc. In addition, poly(aniline), which is a π-conjugated conductive polymer having an aromatic ring, can be cited.

The alkyl group, alkoxy group, and alkylene dioxy group may be bonded to the above heterocyclic ring or aromatic ring in a branched or cyclic manner. Examples of alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups. Examples of the alkoxy group include methoxy, ethoxy, butoxy, hexyloxy, decyloxy, and octadecyloxy. Examples of the alkylene dioxy group include ethyl dioxy group, propyl dioxy group, and butyl dioxy group.

The above poly(thiophenes) are not particularly limited. Examples of the poly(thiophenes) include poly(thiophenes), poly(alkylthiophenes), poly(monoalkoxythiophenes), poly(dialkoxythiophenes), and poly(alkylenedioxy) Thiophene) etc.

Examples of the aforementioned poly(alkylthiophenes) include poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), and poly( 3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-18) Alkylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), etc. In addition, examples of the poly(monoalkoxythiophene) include poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), and poly(3 -Hexyloxythiophene), poly(3-heptoxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly (3-octadecyloxythiophene), etc. In addition, examples of the poly(dialkoxythiophenes) include poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), and poly(3,4-dithiophene). Propoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptoxythiophene), poly(3,4 －Dioctyloxythiophene), poly(3,4-didecoxythiophene), poly(3,4-bis(dodecyloxy)thiophene), etc. In addition, examples of the poly(alkylene dioxythiophene) include poly(3,4-ethylidene dioxythiophene), poly(3,4-propylene dioxythiophene), and poly (3,4-butylene dioxythiophene), etc.

Examples of the poly(thiophene vinylidene groups) include poly(thiophene vinylidene groups), poly(alkylthiophene vinylidene groups), poly(monoalkoxythiophene vinylidene groups), and poly(dialkoxy groups). Thiophene vinylidene groups), poly(alkylenedioxythiophene vinylidene groups), etc.

Examples of the poly(alkylthiophene vinylidene groups) include poly(3-methylthiophene vinylidene groups), poly(3-ethylthiophene vinylidene groups), and poly(3-propylthiophene vinylidene groups). , Poly(3-butylthiophene vinylidene), poly(3-hexylthiophene vinylidene), poly(3-heptylthiophene vinylidene), poly(3-octylthiophene vinylidene), poly( 3-decylthiophene vinylidene), poly(3-dodecylthiophene vinylidene), poly(3-octadecylthiophene vinylidene), poly(3,4-dimethylthiophene vinylidene) Group), poly(3,4-dibutylthiophene vinylidene), etc. In addition, examples of the poly(monoalkoxythiophene vinylidene groups) include poly(3-methoxythiophene vinylidene groups), poly(3-ethoxythiophene vinylidene groups), and poly(3- Butoxythiophene vinylidene), poly(3-hexyloxythiophene vinylidene), poly(3-heptoxythiophene vinylidene), poly(3-octyloxythiophene vinylidene), poly( 3-decyloxythiophene vinylidene), poly(3-dodecyloxythiophene vinylidene), poly(3-octadecyloxythiophene vinylidene), etc. In addition, examples of the poly(dialkoxythiophene vinylidene groups) include poly(3,4-dimethoxythiophene vinylidene groups) and poly(3,4-diethoxythiophene vinylidene groups). ), poly(3,4-dipropoxythiophene vinylidene), poly(3,4-dibutoxythiophene vinylidene), poly(3,4-dihexyloxythiophene vinylidene), Poly(3,4-diheptoxythiophene vinylidene), poly(3,4-dioctoxythiophene vinylidene), poly(3,4-didecoxythiophene vinylidene), poly( 3,4-bis(dodecyloxy)thiophene vinyl) etc. In addition, examples of the poly(alkylene dioxythiophene vinylidene groups) include poly(3,4-ethylidene dioxythiophene vinylidene groups) and poly(3,4-propylene divinylidene groups). Oxythiophene vinylidene), poly(3,4-butylene dioxythiophene vinylidene), etc.

Examples of the poly(pyrrole)s include poly(pyrroles), poly(alkylpyrroles), poly(monoalkoxypyrroles), poly(dialkoxypyrroles), and poly(alkylene dipyrroles). Oxypyrrole) etc.

Examples of the poly(alkylpyrrole) include poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-propylpyrrole), poly(3-butylpyrrole), and poly( 3-hexylpyrrole), poly(3-heptylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3-18) Alkylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), etc. In addition, examples of the poly(monoalkoxypyrrole) include poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), and poly(3 -Hexyloxypyrrole), poly(3-heptoxypyrrole), poly(3-octyloxypyrrole), poly(3-decyloxypyrrole), poly(3-dodecyloxypyrrole), poly (3-octadecyloxypyrrole), etc. In addition, examples of the poly(dialkoxypyrrole) include poly(3,4-dimethoxypyrrole), poly(3,4-diethoxypyrrole), and poly(3,4-diazole). Propoxypyrrole), poly(3,4-dibutoxypyrrole), poly(3,4-dihexyloxypyrrole), poly(3,4-diheptyloxypyrrole), poly(3,4 －Dioctyloxypyrrole), poly(3,4-didecyloxypyrrole), poly(3,4-bis(dodecyloxy)pyrrole), etc. In addition, examples of the poly(alkylene dioxypyrrole) include poly(3,4-ethylidene dioxypyrrole), poly(3,4-propylene dioxypyrrole), and poly (3,4-Butyldioxypyrrole), etc.

Examples of the poly(aniline) include poly(aniline), poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid). )Wait.

Examples of the above dopants include Lewis acid (PF ₅ , AsF ₅ , SbF _5, etc.), protonic acid (HF, HCl, H ₂ SO ₄ , p-toluenesulfonic acid, etc.), electrolyte anions (Cl ⁻ , Br ^－ , sulfo anions, etc.), anionic polymers, etc.

Examples of the anionic polymer are selected from polystyrenesulfonic acid (hereinafter referred to as PSS), polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butylsulfonic acid, Poly-2-acrylamide-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polypropylene carboxylic acid, At least 1 of the group consisting of polymethacryl carboxylic acid, poly-2-acrylamide-2-methyl propane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, and their salts Species.

From the viewpoint of excellent antistatic properties, the component (D) is preferably poly(thiophene)s and/or poly(aniline)s, and more preferably poly(thiophenes). As the poly(thiophene)s, in view of the ease of obtaining, etc., particularly preferred is poly(alkylene dioxythiophene) doped with PSS (especially poly(3,4-ethylidene dioxy) Thiophene) (hereinafter referred to as PEDOT)). As poly(aniline)s, poly(2-aniline sulfonic acid) and poly(3-aniline sulfonic acid) are particularly preferred in view of availability and the like.

Furthermore, PEDOT doped with PSS can be obtained, for example, as follows: 3,4-ethylidene dioxythiophene (EDOT) as a monomer is present in the aqueous phase in the presence of PSS as a dopant The polymerization is carried out with an oxidizing agent under the following conditions, thus obtained in the form of an aqueous dispersion of the complex compound (PEDOT/PSS) of poly(3,4-ethylidene dioxythiophene) and polystyrene sulfonic acid.

A commercially available product can be used as the aqueous solution of PEDOT/PSS, and examples include Baytron P (manufactured by Starck), Clevios P (manufactured by Heraeus), Orgacon ICP1010 (manufactured by Japan Agfa-Gevaert Co., Ltd.), and the like.

In addition, as long as the effects of the present invention are not impaired, non-heteroatom-based conductive polymer polymers such as poly(acetylene)s, poly(phenylene)s, and poly(phenylene vinylene) can also be used in combination Class, poly (acene) (poly (acene)), etc.

The water-based coating agent composition of the present invention preferably contains (B) component 0.1 to 150 parts by weight, (C) component 1 to 30 parts by weight, and (D) relative to 100 parts by weight of (A) component in terms of solid content. Ingredients 1-40 parts by weight. This makes it possible to achieve a balance between the curability, release properties, and solvent resistance of the cured film formed from the aqueous coating agent composition and the liquid stability with the aqueous coating agent composition. It is more preferable to contain 0.5 to 100 parts by weight of (B) component, 2 to 25 parts by weight of (C) component and 2 to 30 parts by weight of (D) component based on 100 parts by weight of component (A). It is more preferable to contain 1 to 50 parts by weight of (B) component, 3 to 20 parts by weight of (C) component and 5 to 30 parts by weight of (D) component based on 100 parts by weight of (A) component in terms of solid content.

The aqueous coating agent composition of the present invention contains an aqueous solvent. The water-based solvent means only water, or a mixture of a hydrophilic organic solvent and water.

The above water is not particularly limited, and examples thereof include distilled water, ion exchanged water, and ion exchanged distilled water. In addition, the water also includes moisture contained in the component (D) and other components. The water content in the aqueous solvent is not particularly limited, and from the viewpoint of excellent liquid stability, it is preferably about 10 to 100% by weight, more preferably about 15 to 90% by weight, more preferably about 100% by weight with respect to the aqueous solvent. About 20 to 85% by weight, particularly preferably about 30 to 70% by weight.

The hydrophilic organic solvent is not particularly limited as long as it is a water-soluble organic solvent. Examples of the hydrophilic organic solvent include organic solvents that can uniformly dissolve or disperse the components (A) to (C). Specifically, for example, alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, etc. Glycols such as propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol mono Glycol ethers such as methyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; ethylene glycol monoethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol mono Glycol ether acetates such as ether acetate; tetrahydrofuran, acetone, acetonitrile, and mixtures of these.

The content of the above-mentioned water-based solvent is not particularly limited, but it is usually preferably contained so that the solid content concentration of the water-based coating agent composition of the present invention is in the range of about 0.1 to 50% by weight, more preferably 0.5 to 30% by weight It is included in the left and right range. With the above numerical range, the liquid stability and the like become good.

The water-based coating agent composition of the present invention may further contain a basic compound (E) (hereinafter also referred to as (E) component) as long as the effect of the present invention is not impaired. The component (E) further improves the liquid stability of the coating composition. (E) The component is not particularly limited as long as it is a basic compound. (E) A component can be exemplified by ammonia, primary to tertiary amines, alkali metal compounds, alkaline earth metal compounds, and the like. (E) One component may be used alone or in combination of two or more. From the viewpoint of obtaining a cured film having good solvent resistance, the component (E) is preferably ammonia, primary to tertiary amines, and more preferably tertiary amines such as amine, trimethylamine, triethylamine, and tributylamine.

The content of the component (E) in the aqueous coating agent composition of the present invention is not particularly limited. The content of the component (E) is preferably from 10 to 500 parts by weight relative to 100 parts by weight of the component (D) in terms of solid content in terms of compatibility between liquid stability and solvent resistance.

In the water-based coating agent composition of the present invention, in addition to the above-mentioned components, as long as the effects of the present invention are not impaired, various well-known additives such as a binder, a defoamer, a preservative, a rust inhibitor, and a curing agent can be blended as needed. Agents, pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, pigments, dyes, lubricants, leveling agents, anti-caking agents, conductivity enhancers, etc.

The above-mentioned adhesive is not particularly limited. From the viewpoint of being able to react with the component (A), the binder is preferably a polyhydric alcohol having two or more hydroxyl groups in one molecule. Examples of the binder include polymer polyols such as polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, urethane polyols, and polyolefin polyols; and low molecular weights such as trimethylolpropane. Polyol. The binder may be used alone or in combination of two or more. From the viewpoint of liquid stability, the binder is preferably a polyether polyol, a polyester polyol, an acrylic polyol, or an urethane polyol. Furthermore, the binder is different from the component (B).

In the water-based coating agent composition of the present invention, the content ratio of the component (A) to the above-mentioned binder is not particularly limited, and the component (A) is relative to the binding point from the viewpoint of achieving both rapid curing properties and solvent resistance of the cured film. The weight ratio of the agent [(A)/adhesive agent] is preferably about 99/1 to 50/50 in terms of solid content, and more preferably about 95/5 to 60/40.

The above-mentioned conductivity improving agent is not particularly limited. This conductivity improver improves the antistatic function of the cured film formed of the aqueous coating agent composition. Examples of the conductivity improver include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and cyclohexane. Hexanediol, cyclohexanedimethanol, glycerin, dimethyl sulfoxide, N-methylpyrrolidone, N-methylformamide, N-dimethylformamide, 2-pyrrolidone, etc. Use more than one combination. From the viewpoint of improving the antistatic function, the conductivity improving agent is preferably N-methylpyrrolidone, 2-pyrrolidone, or dimethyl sulfoxide. In addition, the conductivity improving agent and the above-mentioned hydrophilic organic solvent can use the same thing.

The content of the conductivity improver is not particularly limited, but it is preferably about 0.1 to 20% by weight in the coating agent.

The method for producing the water-based coating agent composition of the present invention is not particularly limited, and a method of mixing the above-mentioned components may be mentioned. The order of mixing the components is not particularly limited, and mixing may be started from any components. In addition, the mixing method is not particularly limited, and various well-known methods such as stirring can be used.

The antistatic release film of the present invention is an article containing a cured film of the aqueous coating agent composition of the present invention and a plastic film. The antistatic release film of the present invention can be obtained by applying the coating agent composition to various well-known plastic films, and heating or drying to cure it.

Examples of the plastic film include polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate, and polyacrylic acid. Amine, polyolefin, nylon, epoxy resin, melamine resin, triethyl acetyl cellulose resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, norbornene series A film made of resin and other plastics. The plastic film may be a surface-treated (corona discharge, etc.) plastic film. Among these, polyethylene terephthalate is preferred from the viewpoint of properties such as transparency, dimensional stability, mechanical properties, chemical resistance, and the like. These plastic films may be provided with a layer formed with a coating agent other than the coating agent composition of the present invention on one side or both sides.

The above-mentioned cured film (antistatic release layer) is coated on various substrates in such a manner that the weight after curing is about 0.01 to 10 g/m ² , preferably about 0.05 to 5 g/m ² . The composition is made by heating and drying.

The coating method is not particularly limited, and is carried out by various well-known means. Specific examples include a roll coater, a reverse roll coater, a gravure coater, a blade coater, and a bar coater.

The above heating and drying conditions are not particularly limited, and the aqueous coating agent composition of the present invention is usually cured at about 100°C to 160°C for about 30 seconds to 2 minutes.

Examples of applications of the antistatic release film of the present invention include: antistatic release films for manufacturing processes such as ceramic green sheets, synthetic leather, carbon fiber prepregs, and printed boards; and products related to transfer printing Antistatic release film used; antistatic release film used to protect the adhesive layer of the adhesive film such as polarizing plate or phase difference plate. [Example]

Hereinafter, the present invention will be described in further detail with examples and comparative examples, but the present invention is not limited to these examples. In addition, in each Example and the comparative example, a part or% is a basis of weight.

Example 1 NIKALAC MX-035 (imino·methylol type methylated melamine resin solid content concentration 70% manufactured by Sanwa Chemical Co., Ltd.) (hereinafter, referred to as (A1) component) as component (A) 11.4 weight Parts, BYK-SILCLEAN 3720 (component of polyether-modified silicone containing hydroxy groups at 25% solids concentration made by BYK Japan Co., Ltd.) as component (B) (hereinafter, referred to as component (B1)) 8 parts by weight, as ( C) Component AP-8 (octyl acid phosphate solid content concentration: 100% manufactured by Taiba Chemical Industry Co., Ltd.) (hereinafter, referred to as (C1) component) 1 part by weight, (D) component aquaPASS-01x (Water dispersion of polyaniline sulfonic acid with 5% solid content concentration manufactured by Mitsubishi Chemical Co., Ltd.) (hereinafter referred to as (D1) component) is prepared by mixing 40 parts by weight, and it is diluted with 550 parts by weight of water and 550 parts by weight of isopropyl alcohol It was prepared until the solid content concentration was 1% to obtain a water-based antistatic release coating agent composition (hereinafter also referred to as coating agent).

Example 2 (A1) component 13.6 parts by weight, (B1) component 2 parts by weight, (C1) component 1 part by weight, as (D) component ORGACON ICP1010 (poly(3,4-ethylidene dioxythiophene) and poly Aqueous dispersion of styrenesulfonic acid composite with a solid content concentration of 1.2% manufactured by AGFA Materials Co., Ltd. (hereinafter, referred to as (D2) component) 83.3 parts by weight, and (E) component triethylamine 0.7 parts by weight It was prepared by diluting it with 550 parts by weight of water and 550 parts by weight of isopropyl alcohol to a solid content concentration of 1% to prepare a coating agent.

Example 3 In Example 2, the component (A1) was changed to 13.9 parts by weight and the component (B1) was changed to 4 parts by weight to obtain a coating agent.

Example 4 In Example 2, the component (A1) was changed to 11.4 parts by weight and the component (B1) was changed to 8 parts by weight to obtain a coating agent.

Example 5 In Example 2, the component (A1) was changed to 10 parts by weight and the component (B1) was changed to 12 parts by weight to obtain a coating agent.

Example 6 In Example 2, the component (A1) was changed to 7.1 parts by weight and the component (B1) was changed to 20 parts by weight to obtain a coating agent.

Example 7 In Example 2, the component (A1) was changed to 11.4 parts by weight, and the component (B) was changed to BYK377 (polyether-modified silicone solid content concentration containing hydroxyl groups 100% manufactured by BYK Japan Co., Ltd.) (hereinafter, Denoted as (B2) component) 2 parts by weight to obtain a coating agent.

Example 8 In Example 2, the component (A1) was changed to 10 parts by weight, and the component (B) was changed to SYMAC US-480 (silicone-modified acrylic resin solid content concentration containing hydroxyl group 25%, manufactured by East Asia Synthetic Co., Ltd. ) (Hereinafter referred to as (B3) component) 12 parts by weight to obtain a coating agent.

Example 9 In Example 2, the component (A) was changed to 8 parts by weight of CYMEL 303LF (full-ether methylated melamine resin solid content concentration 100% manufactured by ALLNEX JAPAN Co., Ltd.) (hereinafter referred to as (A2) component), Change (B1) component to 8 parts by weight, (C) component to p-toluenesulfonic acid (hereinafter, referred to as (C2) component) 0.5 part by weight, and (E) component to 0.5 part by weight to obtain a coating Covering agent.

Example 10 In Example 4, the (A) component was changed to NIKALAC MX-730 (imino-type methylated melamine resin solid content concentration 80% manufactured by Sanwa Chemical Co., Ltd.) (hereinafter, referred to as (A3) component) 10 parts by weight to obtain a coating agent.

Example 11 (A1) component 11.4 parts by weight, (B1) component 8 parts by weight, (C1) component 1 part by weight, (D2) component 83.3 parts by weight, (E) component triethylamine 0.7 parts by weight, as conductivity is improved 8 parts by weight of N-methylpyrrolidone was prepared, and it was prepared by diluting 550 parts by weight of water and 550 parts by weight of isopropyl alcohol to a solid content concentration of 1% to obtain a coating agent.

Example 12 In Example 11, the component (D2) was changed to 41.7 parts by weight to obtain a coating agent.

Example 13 (A1) component 10.7 parts by weight, (B1) component 4 parts by weight, (C1) component 1 part by weight, (D2) component 83.3 parts by weight, (E) component triethylamine 0.7 parts by weight, as a binder ADEKA POLYETHER GM-30 (polyether polyol solid content concentration 100% manufactured by ADEKA Co., Ltd.) 2.5 parts by weight is prepared, and it is prepared by diluting it with 550 parts by weight of water and 550 parts by weight of isopropyl alcohol to a solid content concentration of 1% To get the coating agent.

Example 14 In Example 9, the (A) component was changed to CYMEL 370N (hydroxymethyl methylated melamine resin solid content concentration 88% manufactured by Sanwa Chemical Co., Ltd.) (hereinafter, referred to as (A4) component) 9 weight Parts to obtain a coating agent.

Comparative example 1 9 parts by weight of (A2) component, 1 part by weight of (B2) component, and 0.5 part by weight of (C2) component are prepared, and prepared by diluting 550 parts by weight of water and 550 parts by weight of isopropyl alcohol to a solid content concentration of 1% To get the coating agent.

Comparative example 2 In Example 4, the component (C) was not used, and a coating agent was obtained.

Comparative Example 3 In Example 7, it was changed from BYK377 to BYK-378 (solid content concentration of polyether-modified silicone not containing hydroxyl group 100% manufactured by BYK Japan Co., Ltd.) (hereinafter referred to as (B'1) component) 2 weight Parts to obtain a coating agent.

Comparative Example 4 In Example 9, the solvent for dilution was changed from water and isopropyl alcohol to 1100 parts by weight of methyl ethyl ketone to obtain a coating agent.

(Liquid stability) The coating agent of Example 1 was stored in an environment with a temperature of 23° C. and a humidity of 50%, and the state change of the liquid with time was observed to evaluate the liquid stability of the coating agent. The coating agents of other examples and comparative examples were evaluated for liquid stability in the same manner. ○: There was no change after 1 day immediately after mixing, and no aggregates were generated. ×: From immediately after mixing to one day later, aggregates were generated due to poor dispersion or poor dissolution.

<Manufacture of antistatic release film> The coating agent of Example 1 was coated on a polyethylene terephthalate film (film thickness 50 μm “Lumirror T60” manufactured by Toray Industries, Ltd.) and the cured film was 0.1 μm, and dried at 150° C. 1 Minutes to obtain an antistatic release film. Antistatic release films were also obtained for the coating agents of other examples and comparative examples.

(Solvent resistance) The cured film of the antistatic release film of Example 1 was wiped with a cotton swab immersed in methyl ethyl ketone, and the number of reciprocations until the substrate was exposed was measured to evaluate the solvent resistance of the cured film. The antistatic release films of other examples and comparative examples were also evaluated for solvent resistance. ○: The surface of the base film (polyethylene terephthalate film) was not exposed even after wiping 50 times or more. △: The surface of the base film was exposed when wiped 10 to 49 times. ×: The surface of the base film is exposed when wiped 1 to 9 times.

(Peel force) On the cured film of the antistatic release film of Example 1, a polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd.: 25 mm width) was pressure-bonded while being pressed at 2° C. using a 2 kg pressure roller. Store for 1 hour. Then, the tape was pulled at an angle of 180° at a demolding speed of 0.3 m/min, and the force required for peeling (N/25 mm) was measured. For the antistatic release films of other examples and comparative examples, the peel force was also measured in the same manner.

(Surface resistivity) The surface resistivity (Ω/□) of the coated surface of the antistatic release film of Example 1 was measured based on JIS K6911 using a resistivity meter (“Hiresta UP MCP-HT450” manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Surface resistivity (Ω/□) in an environment with a voltage of 100V, a temperature of 23°C, and a humidity of 50%. The surface resistivity was also measured for the antistatic release films of other examples and comparative examples.

(Antifouling) The cured film of the antistatic release film of Example 1 was drawn with an oil-based marker (made by ZEBRA Corporation, "Mckie (red)") and dried, and then dried with a non-woven fabric (made by Asahi Kasei Corporation, "BEMCOT M-3II") wiped to evaluate the antifouling property of the cured film. The evaluation criteria are as follows. The antistatic release films of other examples and comparative examples were also evaluated for antifouling properties. ○: No trace of wiping ×: Can't erase

[Table 1]

[Table 2]

The notes and abbreviations in Tables 1 and 2 are as follows. (1) The solvent resistance is poor, so the peeling force and surface resistivity were not evaluated. (2) The coating agent becomes poorly dispersed, the liquid stability becomes poor, and the base film cannot be coated. (Abbreviations and specifics of compounds) TEA: Triethylamine NMP: N-methylpyrrolidone GM-30: ADEKA POLYETHER GM-30 (made by polyether polyol ADEKA Co., Ltd.)

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Claims (8)

An aqueous antistatic mold release coating agent composition, which includes methylated melamine resin (A), hydroxyl-containing organically modified silicone (B), acid catalyst (C), and conductive polymer (D). The water-based antistatic mold release coating composition according to claim 1, wherein the component (A) is selected from the group consisting of imine-type methylated melamine resin, methylol-type methylated melamine resin, At least one of the group consisting of amino-methylol-type methylated melamine resin and full-ether-type methylated melamine resin. The water-based antistatic release coating composition according to claim 1 or 2, wherein the component (B) is a hydroxyl group-containing polyether modified silicone and/or a hydroxyl group-containing silicone modified acrylic Resin. The water-based antistatic release coating agent composition according to any one of claims 1 to 3, wherein the component (C) is an organic sulfonic acid and/or an organic phosphoric acid. The water-based antistatic release coating composition according to any one of claims 1 to 4, wherein the (D) component is a poly(thiophene) type and/or a poly(aniline) type. The aqueous antistatic mold release coating composition according to any one of claims 1 to 5, which further contains a basic compound (E). An antistatic release film comprising the cured film and the plastic film of the water-based antistatic release coating composition according to any one of claims 1 to 6. The antistatic release film according to claim 7, wherein the plastic film is a polyethylene terephthalate film.