TW201331350A - Coating composition for prevention of static charge - Google Patents

Abstract

Provided are: a coating composition for prevention of static charge, which has good basic properties such as antistatic properties, water resistance, transparency and scratch resistance and is capable of easily providing a coating film; a method for producing a coating film using this coating composition for prevention of static charge; and a coating film which is produced by this production method. A coating composition for prevention of static charge, which contains (A) a nonionic polymerizable compound that has four or more active energy ray-curable reactive groups, (B) a nonionic polymerizable compound that has one to three active energy ray-curable reactive groups, and (C) at least one cationic group-containing polymerizable compound that is selected from the group consisting of compounds represented by formula (I) and compounds represented by formula (II).

Description

Antistatic coating composition

The present invention relates to a coating composition for antistatic coating, a method for producing a coating film using the antistatic coating composition, and a coating film produced by the production method.

Since the prior art, in order to improve film properties or surface characteristics, a coating film of a corresponding property has been used in the fields of painting or printing. For example, plastics are widely used because of their excellent workability, quality, cost, etc., but they are easily electrostatically charged due to high volume resistivity, and adhesion of foreign matter such as dust, adhesion of films, and poor printing are caused. The case where the coating film is used to improve surface characteristics. As the method for improving the surface characteristics, there is known a method of applying an antistatic agent to the surface of a film; a method of previously practicing an antistatic agent into a resin and allowing the antistatic agent to exude; coating on a substrate A method of forming a resin film thereon by an antistatic agent; a method of forming a coating film containing an antistatic agent, and the like.

As an antistatic agent used for such use, a composition having a specific structure is proposed in Patent Documents 1 to 4 below. For example, Patent Document 1 discloses an antistatic agent containing an anion portion containing a nitrate ion or an alkylsulfonate ion and a cationic portion containing a specific amine. Further, Patent Document 2 discloses a resin molded article in which surface hardening and antistatic properties are imparted by multi-stage coating. Further, in Patent Documents 3 and 4, an active energy ray-curable antistatic resin composition is disclosed.

Patent Document 5 discloses that a quaternary ammonium salt monomer is included and has two or more A polymer having an antistatic property and a releasability of a polymer of a monomer having an ethylenically unsaturated functional group. Further, Patent Document 6 discloses an antireflection film comprising a leveling agent containing a fluorine or a siloxane compound and having optical properties, scratch resistance and antistatic property.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-123924

Patent Document 2: Japanese Patent Laid-Open No. 61-95035

Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-263627

Patent Document 4: Japanese Patent Laid-Open Publication No. 2009-287010

Patent Document 5: International Publication No. 1997-042637

Patent Document 6: International Publication No. 2011-089787

The present invention relates to a coating composition for antistatic, comprising: a nonionic polymerizable compound (A) having four or more reactive energy ray-curable reactive groups, and having 1 to 3 active energy ray curability Polymerization of at least one cationic group containing a reactive group, a nonionic polymerizable compound (B), and a group selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the formula (II) The compound (C), and the ratio of the compound (C) to the total of the above compounds (A), (B) and (C) is 1% by mass or more and 20% by mass or less.

In recent years, with the popularization of LCD (Liquid Crystal Display) and the like, an antistatic coating group having higher basic performance is required. The antistatic resin composition described in the above Patent Documents 1 to 6 is still insufficient in terms of antistatic effect, water resistance, transparency, scratch resistance, or ease of processing. Room for improvement.

The present invention relates to a coating composition for antistatic which is excellent in basic properties such as antistatic property, water resistance, transparency, and scratch resistance and which can easily obtain a coating film. Moreover, the present invention relates to a method for producing a coating film using the antistatic coating composition, and a coating film produced by the production method.

The inventors of the present invention have found that it is possible to easily obtain not only an antistatic effect but also a specific two kinds of nonionic polymerizable compounds having a reactive energy ray-curable reactive group and a cationic group-containing polymerizable compound. Further, the coating film is excellent in water resistance, transparency, and scratch resistance.

That is, the present invention relates to the following [1] to [3].

[1] A coating composition for antistatic, comprising: a nonionic polymerizable compound (A) having four or more active energy ray-curable reactive groups, and having 1 to 3 active energy ray hardening reactions The polymerizable group containing at least one of the group consisting of the nonionic polymerizable compound (B) and the compound represented by the following formula (I) and the compound represented by the formula (II) The compound (C), and the proportion of the compound (C) in the total of the above compounds (A), (B) and (C) is 1% by mass or more and 20% by mass or less. (In the formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; X ^- represents an inorganic acid ion; m represents an integer of 1 to 4, n represents an integer of 0 to 3, and m + n = 4 ; when n is an integer of 2 or more, R ¹ may be the same or different)

(In the formula (II), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. , Y represents NH; X ^- represents inorganic acid ion).

[2] A method for producing a coating film, which comprises applying the above-mentioned antistatic coating composition of the present invention to a substrate, and then irradiating an active energy ray to form a coating film.

[3] A coating film for antistatic treatment, which is obtained by the above-described production method of the present invention.

According to the present invention, it is possible to provide an antistatic coating composition which is excellent in basic properties such as antistatic property, water resistance, transparency, and scratch resistance, and which can easily obtain a coating film, and a coating film using the antistatic coating composition. A manufacturing method and a coating film produced by the production method.

The antistatic coating composition of the present invention contains a nonionic polymerizable compound (A) having four or more active energy ray-curable reactive groups, and a reactive group having one to three active energy ray-curable groups. The nonionic polymerizable compound (B) and at least one selected from the group consisting of the compound represented by the above formula (I) and the compound represented by the above formula (II) contain a cation The polymerizable compound (C), and the ratio of the compound (C) to the total of the above-mentioned compounds (A), (B), and (C) is 1% by mass or more and 20% by mass or less as a coating composition. It exhibits the unique effects of excellent antistatic properties, water resistance, transparency, and scratch resistance.

The details of the mechanism for exhibiting the effects of the present invention are not clear, but it is presumed to be as follows.

When the coating composition contains a nonionic polymerizable compound having a large number of reactive groups and a nonionic polymerizable compound having a small number of reactive groups, it is first produced to have a phase having a higher crosslinking density and a lower phase. A polymer of mutually phased microphase-separated structures. Then, the polymerizable cationic compound having a polymerization rate slower than that of the nonionic polymerizable compound contained in the coating composition is selectively diffused into the continuous phase having a low crosslinking density to carry out polymerization. Therefore, it is presumed that since a continuous phase of a cationic compound polymer is formed in a polymer such as a coating film, it exhibits good antistatic property. Further, it is presumed that the macroscopic phase separation or bleed out of the cationic compound polymer is suppressed, so that transparency and scratch resistance are improved.

[Antistatic Coating Composition]

The antistatic coating composition of the present invention contains a nonionic polymerizable compound (A) having four or more active energy ray-curable reactive groups, and a reactive group having one to three active energy ray-curable groups. a nonionic polymerizable compound (B) and at least one cationic group-containing polymerizable compound (C) selected from the group consisting of compounds represented by the following formulas (I) and (II), and a compound (C) The ratio of the total amount of the above compounds (A), (B), and (C) is 1% by mass or more and 20% by mass or less.

(In the formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. X ^- represents an inorganic acid ion. m represents an integer of 1 to 4, n represents an integer of 0 to 3, and m + n = 4 In the case where n is an integer of 2 or more, R ¹ may be the same or different).

(In the formula (II), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. , Y represents NH. X ^- represents inorganic acid ion).

<Nonionic polymerizable compound (A)>

The nonionic polymerizable compound (A) (also referred to as the compound (A)) in the present invention means a reactive group having four or more active energy ray curability.

In the present specification, the reactive group which can be hardened by irradiation with an active energy ray means that the polymerization is directly carried out by irradiation with an active energy ray such as ultraviolet rays or an electron beam, or the photopolymerization initiator is used. A functional group which undergoes polymerization to cause a hardening reaction.

Examples of the reactive group which can be reacted by irradiation with an active energy ray include a functional group having an ethylenic double bond, and specific examples thereof include an acrylonitrile group, a methacryl fluorenyl group, a vinyl group, and an allyl group. Among these, mention From the viewpoint of high reactivity, antistatic property, water resistance, transparency, and scratch resistance, an acryl fluorenyl group and a methacryl fluorenyl group are preferred, and an acryl fluorenyl group is more preferred.

The compound having four or more such reactive groups can be easily obtained, for example, by an esterification (dehydration) reaction of a compound having four or more hydroxyl groups with (meth)acrylic acid. The compound having four or more hydroxyl groups is preferably di-trimethylolpropane, pentaerythritol, and dipentaerythritol, more preferably di-trishydroxyl, from the viewpoint of improving antistatic property, water resistance, and scratch resistance. Methylpropane and dipentaerythritol are further preferably dipentaerythritol.

In the present specification, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid", and the same applies to the same description.

Examples of the compound having four reactive groups include di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and the like. The alkylene oxide modified product, the lactone modified product, the (poly)ester modified product, and the like.

Examples of the compound having five reactive groups include dipentaerythritol penta (meth) acrylate, an alkylene oxide-modified product thereof, a lactone-modified product, and a (poly)ester-modified product.

Examples of the compound having six reactive groups include dipentaerythritol hexa(meth)acrylate, an alkylene oxide-modified product thereof, a lactone-modified product, and a (poly)ester-modified product.

Further, (meth)acrylic acid urethane having at least four reactive groups, polyester (meth) acrylate or the like can also be used.

As the alkylene oxide-modified product, an alkylene oxide adduct of a polyhydric alcohol such as di-trimethylolpropane or dipentaerythritol is preferably esterified with (meth)acrylic acid. In this case, as the alkylene oxide, ethylene oxide and propylene oxide are preferable. The average addition mole number of the alkylene oxide is preferably from 1 to 20.

As the lactone-modified product, an adduct of a lactone such as di-trimethylolpropane or dipentaerythritol and a lactone such as caprolactone (preferably ε-caprolactone) can be preferably used ( Methyl) acrylic acid is esterified.

Further, as the (poly)ester-modified product, a condensate of a polyol such as di-trimethylolpropane or dipentaerythritol and a polyester may be preferably esterified with (meth)acrylic acid. In this case, the (poly)ester is preferably a (poly)ester of a divalent aliphatic dicarboxylic acid such as maleic acid or a divalent aliphatic diol such as diethylene glycol. Further, the term "poly" ester means a monoester or a polyester.

The reactive group of the nonionic polymerizable compound (A) is preferably 4 or more, preferably 5 or more, more preferably from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance. It is 6 or more. Further, from the viewpoint of industrial availability, the reactivity group is preferably 10 or less, more preferably 9 or less, still more preferably 8 or less.

In addition, the reactive group of the nonionic polymerizable compound (A) is preferably 4 to 10, more preferably 5 to 9, and still more preferably 6 to 8.

<Nonionic polymerizable compound (B)>

The nonionic polymerizable compound (B) (also referred to as the compound (B)) in the present invention means a reactive group having 1 to 3 active energy ray curability. By.

The reactive group which can be reacted by the irradiation of the active energy ray can be, for example, a functional group having an ethylenic double bond, as in the case of the reactive group in the nonionic polymerizable compound (A), and specific examples thereof include propylene. Mercapto group, methacryl oxime group, vinyl group, allyl group and the like. Among these, from the viewpoint of improving reactivity, antistatic property, water resistance, transparency, and scratch resistance, an acryl oxime group and a methacryl oxime group are preferred, and an acryl oxime group is more preferred.

The nonionic polymerizable compound (B) having 1 to 3 such reactive groups can be easily, for example, by esterification (dehydration) reaction of a compound having 1 to 3 hydroxyl groups with (meth)acrylic acid or the like. obtain. As a compound having 1 to 3 hydroxyl groups, from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance, trimethylolpropane, glycerin, ethylene glycol, propylene glycol, and polyethylene are preferable. An alcohol, a polypropylene glycol, an aliphatic diol, an aromatic diol, and the like, such as an alkylene oxide adduct.

Examples of the compound having three reactive groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and glycerol tris(methyl). An acrylate, tris((meth) propylene methoxyethyl) isocyanurate, and an alkylene oxide modified product, a lactone modified product, a (poly) ester modified product, and the like. Among these, a triacrylate of trimethylolpropane and an alkylene oxide adduct thereof is preferred from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance.

The alkylene oxide is preferably ethylene oxide from the viewpoint of improving transparency and scratch resistance, and is preferably propylene oxide from the viewpoint of improving antistatic properties and water resistance. Improve antistatic, water resistance and transparency The addition molar number of the above alkylene oxide is preferably from 1 to 5, more preferably from 2 to 4, still more preferably 3, from the viewpoint of scratch resistance.

Examples of the compound having two reactive groups include trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and glycerol di(methyl). a diol or the like, a trihydric or higher polyhydric alcohol and a (meth)acrylic acid diester, and the alkylene oxide modified product, a lactone modified product, a (poly)ester modified product; Methyl) acrylate, propylene glycol di(meth) acrylate, hexane diol di(meth) acrylate, decanediol di(meth) acrylate, decanediol di(meth) acrylate, neopentyl a diol compound such as diol di(meth)acrylate or tricyclodecane dimethanol di(meth)acrylate, and a diester of (meth)acrylic acid, and a lactone modified product thereof (poly) Ester modification; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol polypropylene glycol di(meth)acrylate, polyhexylene glycol di(methyl) a polyglycol compound such as acrylate and a diester of (meth)acrylic acid, and a lactone modified product, a (poly)ester modified product; a bisphenol A di(meth)acrylate, and a ring thereof Alkoxy modified, lactone modified, (poly) ester modified; urethane diacrylate and the like.

Among these, from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance, a diester of a diol compound and acrylic acid is preferable, and among them, a 1,6-hexanediol is more preferable. Diacrylate, 1,10-decanediol diacrylate and tripropylene glycol diacrylate, further preferably 1,6-hexanediol diacrylate and 1,10-decanediol diacrylate .

Examples of the compound having one reactive group include alkyl (meth)acrylate and its alkylene oxide modified product, lactone modified product, (poly)ester modified product, and (meth)acrylic acid hydroxyl group. Alkyl esters and the like.

As the alkylene oxide modified product, the lactone modified product, and the (poly)ester modified product, the above may preferably be mentioned.

Further, a (meth)acrylic acid urethane or a polyester (meth) acrylate having a reactive group of 3 or less may also be used.

The reactive base of the nonionic polymerizable compound (B) is preferably two or three from the viewpoint of improving the antistatic property, water resistance and scratch resistance, and is resistant to scratching and antistatic properties. The viewpoint of the balance of water resistance and the viewpoint of improving the antistatic property are preferably two.

The solubility parameter (SP (Solubility Parameter value, unit [MPa ^1/2 ])) of the compound (A) is preferably 18.0 or more, and more preferably 18.5, from the viewpoint of improving antistatic property, water resistance, and scratch resistance. The above is further preferably 19.0 or more. Further, from the same viewpoint, it is preferably 21.0 or less, more preferably 20.5 or less, still more preferably 20.0 or less.

The solubility parameter (SP value, unit [MPa ^1/2 ]) of the compound (B) is preferably 17.0 or more, more preferably 17.5 or more, and still more preferably 18.0 or more from the viewpoint of improving the scratch resistance. Moreover, from the viewpoint of improving the antistatic property, it is preferably 20.0 or less, more preferably 19.0 or less, still more preferably 18.5 or less.

Here, the solubility parameter of the compounds (A) and (B) is the SP value of Hansen, by Hansen, Charles (2007). Hansen Solubility Parameters: A user's handbook, second Edition. Boca Raton, Fla: CRC Press calculates.

The absolute value of the difference between the SP values of the compound (A) and the compound (B) is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, from the viewpoint of improving the antistatic property and the water resistance. More preferably, it is 1.2 or more, further preferably 1.5 or more, and still more preferably 1.8 or more. Moreover, from the viewpoint of improving transparency and scratch resistance, it is preferably 2.0 or less, more preferably 1.7 or less, further preferably 1.4 or less, and still more preferably 1.2 or less.

The molecular weight of the compound (B) is preferably 190 or more, more preferably 200 or more, still more preferably 220 or more, and still more preferably 260 or more from the viewpoint of improving the antistatic property and the water resistance. Moreover, from the viewpoint of improving transparency and scratch resistance, it is preferably 900 or less, more preferably 500 or less, further preferably 320 or less, and still more preferably 240 or less.

<Polymerizable compound (C) containing a cationic group>

The antistatic coating composition of the present invention contains at least one selected from the group consisting of a compound represented by the following formula (I) (compound (I)) and a compound represented by formula (II) (compound (II)). One type of polymerizable compound (C) having a cationic group (compound (C)). The compound (I) and the compound (II) are antistatic components and can lower the surface resistivity value of the coating film.

. a compound represented by the formula (I) (compound (I))

(In the formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. X ^- represents an inorganic acid ion. m represents an integer of 1 to 4, n represents an integer of 0 to 3, and m + n = 4 In the case where n is an integer of 2 or more, R ¹ may be the same or different).

R ¹ in the above formula (I) represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ^{1 is} preferably a hydrocarbon group from the viewpoint of improving antistatic properties and industrial availability. Further, from the same viewpoint, the carbon number of the hydrocarbon group is preferably from 1 to 6, more preferably from 1 to 3, still more preferably from 1 to 2, still more preferably 1.

In the present invention, m of the compound represented by the above formula (I) is preferably from 1 to 2, n is preferably from 2 to 3, more preferably m = 2, and n = 2.

Specific examples of R ¹ include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups (including 2-ethylhexyl group). Furthermore, the term "various" means including various isomers of positive, second, third, and different.

The total carbon number of the compound (I) is preferably from 6 to 18, more preferably from 6 to 15, more preferably from 6 to 12, from the viewpoint of improving the antistatic property and the industrial availability.

X ^- represents a mineral acid ion, specifically, a halide ion such as a chloride ion; a nitrate ion, a sulfate ion, a phosphate ion, or the like. From the viewpoint of the performance of the antistatic property, X ^{- is} preferably a monovalent inorganic acid ion, more preferably a chloride ion and a nitrate ion. Further, from the viewpoints of improving transparency, water resistance, and antistatic performance, and suppressing corrosion of metal parts and the like, X ^{− is} further preferably a nitrate ion.

Specific examples of the compound represented by the above formula (I) include diallyldimethylammonium chloride, diallyldimethylammonium bromide, and diallyldimethylammonium iodide. Diallyldimethylammonium nitrate, diallylethylmethylammonium chloride, diallyloctylmethylammonium chloride, diallyldiethylammonium chloride, dialkyl chloride Propyldioctylammonium, allyltrimethylammonium chloride, alkene Propyltrimethylammonium nitrate, allylethyldimethylammonium chloride, allylpropyldimethylammonium chloride, allyloctyldimethylammonium chloride, allyl chloride Methyl benzyldimethylammonium chloride, allyldiethylmethylammonium chloride, allyldioctyl chloride, diallylmethylamine hydrochloride, diallylmethylamine nitrate, allylic Methyl dimethylamine hydrochloride, allyl dimethylamine nitrate, and the like. These may be used alone or in combination of two or more. Among these compounds, from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance, it is preferably a nitrate and a chloride of diallyldimethylammonium, more preferably a diene propylene. Dimethylammonium nitrate.

. a compound represented by formula (II) (compound (II))

(In the formula (II), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. , Y represents NH. X ^- represents inorganic acid ion).

In the above formula (II), R ² represents a hydrogen atom or a methyl group, and from the viewpoint of improving the antistatic property, a hydrogen atom is preferred.

R ³ represents an alkylene group having 2 to 5 carbon atoms, and from the viewpoint of improving antistatic property and industrial availability, it is preferably an ethyl group and a stretching group, and more preferably a stretching group.

R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ , R ⁵ and R ^{6 are} preferably a hydrocarbon group from the viewpoint of improving antistatic properties and industrial availability. Further, from the same viewpoint, the carbon number of the hydrocarbon group is preferably from 1 to 8, more preferably from 1 and 2, still more preferably 1.

Specific examples of the substituents of R ⁴ , R ⁵ and R ⁶ include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, and allyl groups. Wait.

The total number of carbon atoms of R ⁴ , R ⁵ and R ⁶ is preferably from 2 to 12, more preferably from 3 to 9, more preferably from 3 to 6, and furthermore, from the viewpoints of antistatic property and industrial availability. Good for 3.

From the viewpoint of improving the antistatic property, Y is NH.

X ^- represents a mineral acid ion, and the above may be mentioned. Further, a preferred compound of X ^- is the same as above.

Specific examples of the compound (II) include chlorinated (meth) acrylamide ethyltrimethylammonium chloride, (meth) acrylamidopropyltrimethylammonium chloride, and bromination (methyl). Acrylamide propyltrimethylammonium iodide, iodized (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidopropyltrimethylammonium nitrate, chlorinated (meth) propylene Indole trimethyl amyl ammonium, chlorinated (meth) acrylamide ethyl dimethyl ethyl ammonium, chlorinated (meth) propylene decyl dimethyl dimethyl ammonium, chlorinated (methyl Ethylene decylamine diethylmethylammonium chloride, (meth)acrylamide amine dioctylmethylammonium chloride, (meth) acrylamide ethyl dimethylamine hydrochloride, (meth) acrylamide Propyl dimethylamine nitrate and the like. These compounds may be used alone or in combination of two or more.

Among these compounds, from the viewpoints of improving antistatic property, water resistance, transparency, and scratch resistance, nitrates and chlorides of acrylamide ethyltrimethylammonium, and acrylamide are preferred. The trimethylammonium nitrate nitrate and the chloride are more preferably acrylamidopropyltrimethylammonium nitrate.

In the antistatic coating composition of the present invention, at least one selected from the group consisting of the compounds represented by the above compound (I) and the compound (II) may be used, but the antistatic property and transparency are improved. From the viewpoint of the nature, it is preferred to contain the compound (I).

The antistatic coating composition of the present invention may contain other antistatic components other than the above compound (I) and compound (II). In the above, the total amount of the above compound (I) and the compound (II) is 100 parts by mass based on 100 parts by mass of the total of the compound (I) and the compound (II) and the other antistatic component, from the viewpoint of improving the water resistance and the transparency. It is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, further preferably 90 parts by mass or more, and still more preferably 98 parts by mass or more. Further, as the other antistatic component, a general one may be used, and examples thereof include an anionic surfactant such as an alkyl sulfate salt, a polyoxyethylene alkyl sulfate salt, an alkyl sulfonate or an alkyl phosphate. a cationic surfactant such as a tetraalkylammonium salt; a nonionic surfactant such as a polyoxyethylene alkyl ether, a glycerin mono-fatty acid ester or an alkylamine; an amphoteric interfacial activity such as an alkylcarboxybetaine or an alkylamine oxide; a polymer; a polymer containing a quaternary ammonium salt group; a polymer type antistatic agent such as a polymer containing a polyether; and a conductive polymer such as polythiophene or polyaniline.

. Method for producing compound (I) and compound (II)

In the compound (the I), and the compound (II) the X ^- is the case when the halide ions, for example, by four of the corresponding amine with the reaction of haloalkyl, or of the corresponding amine with an inorganic acid such as hydrochloric acid in the Obtained by reaction, etc. Further, in the X, Compound (I) (II) ^- A is not a halide ion when four salts ^{(R 1, R 4, R} 5, R 6 are a hydrocarbon group) of the case, it can correspond by four halide salt [X, compound (I) (II) ^- A compound of halide ion] and an inorganic salt of an alkali metal salt exchange, or four of the corresponding hydroxide salt [compound (I) and the compound ( II) the X ^-] being manufactured with inorganic acids and hydroxides as the compound.

In the case of using a raw material containing water, the case of using water in the synthesis, and the case where water is contained in the product, the compound can be obtained by removing water and dissolving in an organic solvent, or removing water after adding an organic solvent. (I) or an organic solution of the compound (II).

The organic solvent used in the production of the compound (I) and the compound (II) is preferably a solubility parameter from the viewpoint of improving the solubility of the above compound (I) and the compound (II) (POLYMER HANDBOOK THIRD EDITION 1989) The SP value described by John Wiley & Sons, Inc. is an organic solvent of 15.0 to 30.0 (MPa) ^1/2 , more preferably 20.0 to 30.0 (MPa) ^1/2 of an organic solvent.

Specific examples thereof include aliphatic hydrocarbons such as hexane; methanol and ethanol (SP value: 26.0), isopropyl alcohol (SP value: 23.5), methoxyethanol, ethoxyethanol, methoxy carbitol, and benzyl chloride. Alcohols such as alcohol (SP value: 24.8); ketones such as acetone (SP value: 20.3), methyl ethyl ketone (SP value: 19.0), methyl isobutyl ketone (SP value: 17.2); dichloromethane Halogen solvents such as chloroform; ethers such as diethyl ether; aromatics such as toluene (SP value: 18.3) and xylene; esters such as n-butyl acetate (SP value: 17.4) and n-ethyl acetate (SP value: 18.6) Or a polar solvent such as an alcohol, a ketone or an ester, from the viewpoint of improving the solubility of the compound (I) and the compound (II). More preferably, it is an alcohol, and further preferably isopropanol.

<Organic solvent used in antistatic coating composition>

The antistatic coating composition of the present invention may also contain an organic solvent. The organic solvent is preferably the same as the organic solvent which can be used in the production of the above-mentioned compound (I) and the compound (II), and the solubility parameter is preferably 15.0 to 30.0 (MPa) ^{1 /} as described above. ² , more preferably 20.0~30.0(MPa) ^1/2 .

The organic solvent is preferably a polar solvent from the viewpoint of improving the solubility of the compounds (A), (B) and (C) in the antistatic coating composition of the present invention, and among them, it is preferably used for the compound. Alcohols, ketones, and esters in the manufacture of (I) and (II). However, in the case where the antistatic coating composition of the present invention is liquid in the absence of a solvent at room temperature and the components in the composition are mutually miscible, the operability is improved and the steps are simplified. Preferably, the antistatic coating composition of the present invention contains no solvent.

The organic solvent in the case where the antistatic coating composition of the present invention contains an organic solvent improves the uniformity and coatability of the antistatic coating composition of the present invention and improves the smoothness of the coating film. Preferably, it is preferably an alcohol, a ketone or a mixture thereof, more preferably isopropanol (IPA), methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and mixtures thereof. It is a mixture of IPA and MEK. Moreover, the content of the organic solvent in the antistatic coating composition of the present invention is preferably from 10 to 70% by mass, more preferably from 20 to 60% by mass, even more preferably 20, from the viewpoint of handling properties such as coating. ~55 mass%.

Further, the content of the above organic solvent is also included in the organic solvent used for producing the cationic group-containing polymerizable compound (C).

<Photopolymerization initiator>

The antistatic coating composition of the present invention preferably contains a photopolymerization initiator which generates radicals or cations by irradiation with an active energy ray such as ultraviolet rays or electron beams. Examples of the photopolymerization initiator include acetophenones, benzophenones, ketals, anthraquinones, and 9-oxosulfuric acid. Examples, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, and the like. More specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, benzyl methyl ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylbenzene 2-hydroxy-2-methylpropan-1-one, benzophenone, and the like. Among these, 1-hydroxy-cyclohexyl-phenyl-ketone is preferred from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance.

The content of the photopolymerization initiator in the antistatic coating composition of the present invention is preferably from 1 to 10% by mass, more preferably from the viewpoint of improving the antistatic property, the water resistance, the transparency, and the scratch resistance. 1 to 5 mass%, more preferably 2 to 3 mass%.

The photopolymerization initiator is relative to the compounds (A), (B), and (C) in the antistatic coating composition of the present invention from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance. The ratio of the total is preferably 2% by mass or more, and more preferably 4% by mass or more. Further, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less.

The photopolymerization initiator is solidified in the antistatic coating composition of the present invention from the viewpoint of improving antistatic property, water resistance, transparency, and scratch resistance. The proportion of the total amount of the component components is preferably 2% by mass or more, and more preferably 4% by mass or more. Further, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less.

<Composition of Antistatic Coating Composition>

In the antistatic coating composition of the present invention, the nonionic polymerizable compound (A) is in the nonionic polymerizable compound (A) and (in view of improving the transparency, the scratch resistance, and the antistatic property). The ratio of B) and the cationic group-containing polymerizable compound (C) is preferably from 25 to 85% by mass, more preferably from 35 to 80% by mass, even more preferably from 45 to 75% by mass.

The ratio of the compound (A) to the total of the compounds (A), (B) and (C) is preferably 15% by mass or more, more preferably 20%, from the viewpoint of improving transparency and scratch resistance. % or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and still more preferably 45% by mass or more. Moreover, from the viewpoint of improving the antistatic property and the water resistance, it is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, and further more preferably It is preferably 55 mass% or less, and more preferably 50 mass% or less.

The nonionic polymerizable compound (B) is in the total of the nonionic polymerizable compounds (A) and (B) and the cationic group-containing polymerizable compound (C) from the viewpoint of antistatic property and water resistance. The proportion is preferably from 5 to 55% by mass, more preferably from 5 to 50% by mass, even more preferably from 10 to 45% by mass.

The ratio of the compound (B) to the total of the compounds (A), (B) and (C) is preferably 5% by mass or more, more preferably 10%, from the viewpoint of improving the antistatic property and the water resistance. More than %, more preferably 20% by mass or more, and thus It is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. Moreover, from the viewpoint of improving transparency and scratch resistance, it is preferably 75% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and still more preferably 55% by mass or less.

The cationic group-containing polymerizable compound (C) is a nonionic polymerizable compound (A) and (B), and a cationic group-containing polymerizable compound (C) from the viewpoints of antistatic property and scratch resistance. The proportion in the total is preferably from 1 to 20% by mass, more preferably from 2 to 18% by mass, still more preferably from 3 to 15% by mass.

The ratio of the compound (C) to the total of the compounds (A), (B) and (C) is preferably 3% by mass or more, and more preferably 5 mass, from the viewpoint of improving the antistatic property and the water resistance. % or more, further preferably 7% by mass or more, and still more preferably 10% by mass or more. Moreover, from the viewpoint of improving transparency and scratch resistance, it is preferably 20% by mass or less, more preferably 19% by mass or less, still more preferably 16% by mass or less, and still more preferably 13% by mass or less.

In the antistatic coating composition of the present invention, the mass ratio of the nonionic polymerizable compound (A) to (B) is improved from the viewpoint of improving transparency, scratch resistance, antistatic property and water resistance [( A)/(B)] is preferably 95/5~30/70, more preferably 93/7~40/60, further preferably 90/10~45/55, and even more preferably 85/15~45. /5, and even better, 75/25~50/50.

In addition, the ratio of the compound (A) to the total of the compounds (A) and (B) is preferably 15% by mass or more, and more preferably 20% by mass or more, from the viewpoint of improving the transparency and the scratch resistance. Further, it is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. also, From the viewpoint of improving the antistatic property and the water resistance, it is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably more. It is 55 mass% or less.

Further, in the antistatic coating composition of the present invention, the nonionic polymerizable compound (A) + (B) and the cation are contained in view of improving transparency, scratch resistance, antistatic property and water resistance. The mass ratio [(C) / (A) + (B)] of the polymerizable compound (C) is preferably 2/98 to 30/70, more preferably 3/97 to 20/80, and further preferably 4/96~18/82, and more preferably 5/95~15/85.

In addition, the ratio of the compound (C) to the total of the compounds (A) and (B) is preferably 3% by mass or more, more preferably 5% by mass or more, from the viewpoint of improving the antistatic property and the water resistance. It is preferably 7% by mass or more, and more preferably 11% by mass or more. Moreover, from the viewpoint of improving transparency and scratch resistance, it is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

In addition, the antistatic coating composition of the present invention may contain water, and the water content of the antistatic coating composition is suppressed from the viewpoint of suppressing the physical properties of the coating film such as the strength and transparency of the obtained coating film. It is preferably less than 5% by mass, more preferably less than 1% by mass, and further preferably substantially free of water.

The antistatic coating composition of the present invention may contain a polymerizable compound other than the ionic polymerizable compound (A) and (B), a cationic group-containing polymerizable compound (C), a curing agent such as a diisocyanate compound, a pigment, or the like. Dyes, glass beads, polymer beads, beads such as inorganic beads, or inorganic fillers such as calcium carbonate and talc, surface conditioners such as leveling agents, stable Additives such as agents, ultraviolet absorbers, and dispersants.

<Method for Producing Antistatic Coating Composition>

The antistatic coating composition of the present invention is prepared by mixing the nonionic polymerizable compounds (A) and (B), the cationic group-containing polymerizable compound (C), and optionally a photopolymerization initiator, a solvent, and the like. It can be made by stirring. The order of mixing the components is not limited. From the viewpoints of the solubility of the compounds represented by the above formulas (I) and (II), it is preferred to firstly apply the formula (I) and formula (II) of the present invention. The compound and the organic solvent are mixed and mixed with the nonionic polymerizable compounds (A) and (B) and other components. The temperature at the time of mixing is preferably from 0 to 50 ° C, more preferably from 5 to 40 ° C, from the viewpoint of improving solubility and suppressing volatilization of the solvent.

[Method for Producing Antistatic Coating Film and Coating Film]

The antistatic coating film of the present invention can be easily obtained by the method for producing a coating film of the present invention, wherein the antistatic coating composition is applied onto a substrate, and the coating film is irradiated with an active energy ray. Further, after the coating composition is applied onto a substrate, it may be dried as needed.

Examples of the substrate to which the antistatic coating composition is applied include glass, cellulose acetate such as triacetate cellulose (TAC), diacetyl cellulose, and cellulose acetate butyrate; Polyester resin such as polyethylene terephthalate (PET); acrylic resin, polyurethane resin, polycarbonate resin, polyfluorene resin, polyether resin, polyolefin resin, nitrile resin, poly An ether ketone resin, a polyamide resin, or the like.

Examples of the method of applying the antistatic coating composition include a bar coating method, a roll coating method, a screen method, a soft plate method, a spin coating method, a dipping method, a spray method, and a slide coat. Law and so on. Further, the drying conditions after the application can be carried out, for example, at a drying temperature of 50 to 150 ° C and a drying time of 0.5 to 5 minutes.

The active energy ray to be irradiated is preferably ultraviolet ray from the viewpoint of irradiation with a simple device. The amount of the irradiation line varies depending on the active energy ray to be used. For example, in the case of irradiating ultraviolet rays, it is preferable from the viewpoint of efficiently producing a coating film and suppressing damage of the substrate to be coated. In order to set the cumulative irradiation amount to 10 to 500 mJ/cm ² .

The surface resistivity value of the coating film of the present invention is preferably 5 × 10 ¹² Ω or less, and more preferably 1 × 10 ¹² Ω or less, from the viewpoint of maintaining the antistatic property. Further, the surface resistivity value can be measured in accordance with the method described in the examples. Further, from the viewpoint of the durability of the water resistance, it is preferred that the surface resistivity value of the antistatic coating film of the present invention after washing with water is not more than 1 × 10 ¹ Ω or more than the surface resistivity value before water washing.

The haze value of the antistatic coating film is preferably 1% or less from the viewpoint of transparency. Further, the haze value can be measured in accordance with the method described in the examples.

The antistatic coating film of the present invention can be used for various image devices such as an LCD (Liquid Crystal Display), a touch panel, a PDP (Plasma Display Panel), an EL (Electroluminescence), and a compact disc. Surface protection, coating of various lenses, and the like.

According to the above embodiment, the present invention further discloses the following composition, production method (or use).

[1] A coating composition for antistatic, comprising: a nonionic polymerizable compound (A) having four or more active energy ray-curable reactive groups, and having 1 to 3 active energy ray hardening reactions The polymerizable group containing at least one of the group consisting of the nonionic polymerizable compound (B) and the compound represented by the following formula (I) and the compound represented by the formula (II) The compound (C) and the proportion of the compound (C) in the total of the above compounds (A), (B) and (C) are 1% by mass or more and 20% by mass or less.

(In the formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. X ^- represents an inorganic acid ion. m represents an integer of 1 to 4, n represents an integer of 0 to 3, and m + n = 4 In the case where n is an integer of 2 or more, R ¹ may be the same or different)

(In the formula (II), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. , Y represents NH. X ^- represents inorganic acid ion).

Further, in the present invention, the following aspects are preferred.

[2] The antistatic coating composition according to the above [1], wherein the active energy ray-curable reactive group is preferably an acrylonitrile group or a methacryl fluorenyl group.

[3] The antistatic coating composition according to the above [1] or [2], wherein the mass ratio [(A)/(B)] of the nonionic polymerizable compound (A) to (B) is preferably 95. /5~30/70, more preferably 93/7~40/60, more preferably 90/10~45/55, more preferably 85/15~45/55, and even better 75/25~50/ 5.

[4] The antistatic coating composition according to any one of [1] to [3] wherein the nonionic polymerizable compound (A) is in the nonionic polymerizable compounds (A) and (B), and The proportion of the total of the cationic group-containing polymerizable compound (C) is preferably from 25 to 85% by mass, more preferably from 35 to 80% by mass, even more preferably from 45 to 75% by mass.

[5] The antistatic coating composition according to any one of the above [1] to [4] wherein the ratio of the compound (A) to the total of the compounds (A), (B) and (C) is higher. It is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 45% by mass or more, and more preferably 85% by mass or less. More preferably, it is 80 mass% or less, more preferably 70 mass% or less, further preferably 60 mass% or less, further preferably 55 mass% or less, and still more preferably 50 mass% or less.

[6] The antistatic coating composition according to any one of [1] to [5] wherein the nonionic polymerizable compound (B) is in the nonionic polymerizable compounds (A) and (B), and The proportion of the total of the cationic group-containing polymerizable compound (C) is preferably from 5 to 55% by mass, more preferably from 5 to 50% by mass, even more preferably from 10 to 45% by mass.

[7] The antistatic coating composition according to any one of the above [1] to [6] wherein The proportion of the compound (B) in the total of the compounds (A), (B) and (C) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and further It is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and more preferably 75% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less. Further, it is more preferably 55 mass% or less.

[8] The antistatic coating composition according to any one of the above [1], wherein the cationic group-containing polymerizable compound (C) is used in the nonionic polymerizable compounds (A) and (B), The proportion of the total of the cationic group-containing polymerizable compound (C) is preferably from 1 to 20% by mass, more preferably from 2 to 18% by mass, even more preferably from 3 to 15% by mass.

[9] The antistatic coating composition according to any one of the above [1] to [8] wherein the ratio of the compound (C) to the total of the compounds (A), (B) and (C) is higher. It is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, further preferably 10% by mass or more, and more preferably 20% by mass or less, and still more preferably 19% by mass or less. It is more preferably 16% by mass or less, and still more preferably 13% by mass or less.

[10] The antistatic coating composition according to any one of the above [1] to [9], which further preferably contains a photopolymerization initiator.

[11] The antistatic coating composition according to the above [10], wherein the content of the photopolymerization initiator is preferably from 1 to 10% by mass, more preferably from 1 to 5% by mass, even more preferably from 2 to 3 by mass. %.

[12] The antistatic coating composition according to any one of [1] to [11], wherein the nonionic polymerizable compound (A) preferably has a reactivity group of 5 More preferably, it is 6 or more, and is preferably 10 or less, more preferably 9 or less, still more preferably 8 or less.

[13] The antistatic coating composition according to any one of the above [1] to [12] wherein the nonionic polymerizable compound (B) preferably has a reactivity group of 2 or 3, more preferably 2

[14] The antistatic coating composition according to any one of the above [1] to [13] wherein the compound having four or more active energy ray-curable reactive groups preferably has four or more hydroxyl groups. The compound is obtained by an esterification reaction with (meth)acrylic acid.

[15] The antistatic coating composition according to [14] above, wherein the compound having four or more hydroxyl groups is preferably at least one selected from the group consisting of di-trimethylolpropane, pentaerythritol, and dipentaerythritol. Kind.

[16] The antistatic coating composition according to any one of [1] to [15] wherein the absolute value of the difference between the SP values of the compound (A) and the compound (B) is preferably 0.1 or more, more preferably It is 0.5 or more, more preferably 1.0 or more, still more preferably 1.2 or more, still more preferably 1.5 or more, still more preferably 1.8 or more, and more preferably 2.0 or less, still more preferably 1.7 or less, still more preferably 1.4. Hereinafter, it is more preferably 1.2 or less.

[17] The antistatic coating composition according to any one of [1] to [16] wherein the molecular weight of the compound (B) is preferably 190 or more, more preferably 200 or more, still more preferably 220 or more. More preferably, it is 260 or more, and is preferably 900 or less, more preferably 500 or less, further preferably 320 or less, and still more preferably 240 or less.

[18] As the above-mentioned [1] to [17] of any of an antistatic coating composition, wherein the above formula (I) and (II) the X ^- is preferably selected from the group consisting of nitrate ions and chloride ions One or more kinds of ions in the group.

[19] The antistatic coating composition according to any one of the above [1] to [18], wherein the non-ionic polymerizable compound (A) has a reactivity group of preferably 4 or more and 10 or less.

[20] The antistatic coating composition according to any one of the above [1], wherein the nonionic polymerizable compound (B) has a reactivity of 2 or 3.

[21] The antistatic coating composition according to any one of the above [1] to [20] wherein the cationic group-containing polymerizable compound (C) is preferably a compound represented by the above formula (I).

[22] The antistatic coating composition according to any one of the above [1] to [21] wherein m of the above formula (I) is preferably 2.

[23] The antistatic coating composition according to any one of the above [1] to [22] wherein R ^{1 of the} above formula (I) is preferably a methyl group or an ethyl group.

[24] The antistatic coating composition according to any one of the above [1] to [23] wherein R ⁴ , R ⁵ and R ^{6 in the} above formula (II) are preferably a methyl group.

[25] The antistatic coating composition according to any one of the above [1] to [24] wherein R ^{3 of the} above formula (II) is preferably an exoethyl or a propyl group.

[26] The antistatic coating composition according to any one of [1] to [25] wherein R ^{2 of the} above formula (II) is preferably a hydrogen atom.

[27] The antistatic coating composition according to any one of [1] to [26] wherein the compound having 1 to 3 active energy ray-curable reactive groups is preferably 1~ Esterification reaction of three hydroxyl compounds with acrylic acid Winner.

[28] The antistatic coating composition according to the above [27], wherein the compound having 1 to 3 hydroxyl groups is preferably selected from the group consisting of trimethylolpropane, glycerin, ethylene glycol, propylene glycol, and polyethylene glycol. At least one selected from the group consisting of propylene glycol, polyethylene glycol, polypropylene glycol, aliphatic diol, and aromatic diol.

[29] A method for producing a coating film, which comprises applying the antistatic coating composition according to any one of the above [1] to [28] onto a substrate, and irradiating the active energy ray to form a coating film.

[30] The method for producing a coating film according to [29] above, wherein the substrate is a cellulose resin.

[31] A coating film for antistatic, which is obtained by the production method of [29] or [30] above.

[32] A method for preventing charging of a substrate, which comprises a coating composition comprising: a nonionic polymerizable compound (A) having four or more active energy ray-curable reactive groups, having 1 a nonionic polymerizable compound (B) having three reactive energy ray-hardening reactive groups, and a group selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the formula (II) At least one cationic group-containing polymerizable compound (C).

(In the formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. X ^- represents an inorganic acid ion. m represents an integer of 1 to 4, n represents an integer of 0 to 3, and m + n = 4 In the case where n is an integer of 2 or more, R ¹ may be the same or different)

(In the formula (II), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. , Y represents NH. X ^- represents inorganic acid ion).

[33] The method for preventing charging of a substrate according to [32] above, wherein the substrate is a cellulose resin.

Example

In the present examples and comparative examples, the compound (the cationic group-containing polymerizable compound (C)) represented by the above formula (I) and formula (II) is first prepared, and the nonionic polymerizable compound (A) is prepared. (B), a photopolymerization initiator (UV (Ultraviolet) polymerization initiator), and an organic solvent were mixed to prepare coating compositions of Examples 1 to 34 and Comparative Examples 1 to 9.

[Preparation of a cationic group-containing polymerizable compound (C) and a compound containing a cationic group] (Polymer-containing polymerizable compound (C-I-1))

25.0 g of sodium nitrate (reagent manufactured by Wako Pure Chemical Industries Co., Ltd.) and 75.0 g of ion-exchanged water were placed in a 200 ml beaker, and stirred and dissolved by hand with a glass rod to obtain an aqueous solution of sodium nitrate (effective ingredient 25 mass) %). 40.0 g of the obtained aqueous solution of sodium nitrate and diallyldimethylammonium chloride (Reagents manufactured by Wako Pure Chemical Industries Co., Ltd., active ingredients) 65 mass%) 29.2 g was placed in an eggplant flask and mounted on a rotary evaporator (N-1000 manufactured by Tokyo Science and Technology Co., Ltd.) at room temperature (25 ° C) and atmospheric pressure (1013 hPa). Rotate for 5 minutes (speed: SPEED 4). Thereafter, the air was introduced into the gas atmosphere of the sample at 40 ° C and 300 hPa for 2 hours, and then the water was removed at 40 ° C and 1 hPa for 2 hours. Then, 23 g of isopropyl alcohol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the above-mentioned eggplant type flask, and the mixture was rotated at normal pressure and room temperature for 30 minutes using a rotary evaporator. The obtained suspension was filtered with a membrane filter having a pore size of 0.2 μm to remove salts, thereby obtaining an isopropanol solution containing 50% by mass of a cationic group-containing polymerizable compound (CI-1) (in isopropyl alcohol). In the alcohol solution, the solid content was 50% by mass). Further, the solid content was determined by drying under reduced pressure at 100 ° C and 300 hPa for 12 hours under a nitrogen stream.

(Polymer-containing polymerizable compound (C-II-1))

The diallyldimethylammonium chloride was used as the acrylamide acrylamidopropyltrimethylammonium (reagent manufactured by Tokyo Chemical Industry Co., Ltd., the active ingredient was 75 mass%), and the blending amount was 32.4 g. In addition, an isopropanol solution containing 50% by mass of the cationic group-containing polymerizable compound (C-II-1) was obtained by the same method as the above (CI-1) (in an isopropanol solution, solid matter) The composition is 50% by mass).

(Polymer-containing polymerizable compound (C-I-2))

A package was obtained by the same method as the above (C-I-1) except that sodium nitrate was not used and the amount of diallyldimethylammonium chloride was 50 g. An isopropanol solution containing 50% by mass of a cationic group-containing polymerizable compound (C-I-2). (In the isopropyl alcohol solution, the solid content was 50% by mass).

(Polymer-containing polymerizable compound (C-III))

25.0 g of sodium nitrate was changed to 5.0 g, 75.0 g of ion-exchanged water was changed to 16.3 g, and diallyldimethylammonium chloride was changed to propylene oxyethylidene trimethylammonium chloride (a reagent manufactured by Aldrich Co., Ltd.) In the same manner as the above (CI-1), except that the active ingredient (80% by mass) of 14.2 g and the isopropyl alcohol 23 g were changed to methanol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) of 12.9 g. A methanol solution containing 50% by mass of a cationic group-containing polymerizable compound (C-III) (solid content: 50% by mass in a methanol solution).

(The compound containing a cationic group (C-IV))

The diallyldimethylammonium chloride was changed to polyallyl diallyldimethylammonium (a reagent manufactured by Aldrich Co., Ltd., active ingredient: 35 mass%), 135.7 g, and 23 g of isopropyl alcohol was changed to ion-exchanged water. a mixed solvent (ion exchange water/methanol = 1/2 (mass ratio)) of 75 g with methanol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), except for the above (CI-1) The method obtained a water/methanol solution containing 27% by mass of a compound (C-IV) having a cationic group (in a water/methanol solution, a solid content of 27% by mass).

(Polymer-containing polymerizable compound (C-V))

Sodium nitrate was changed to 30.5 g of acrylamide sodium 2-methylpropane sulfonate (50% by mass of active ingredient manufactured by Aldrich Co., Ltd.), and diallyldimethylammonium chloride was changed to ethylmethylimidazolium chloride. (Reagents manufactured by Tokyo Chemical Industry Co., Ltd.) 9.7 g, 23 g of isopropanol changed to methanol (Wako Pure Chemical Industries) A methanol solution containing 50% by mass of a cationic group-containing polymerizable compound (CV) (in a methanol solution) was obtained by the same method as the above (CI-1) except for the above (CI-1). The solid content was 50% by mass).

(The compound containing a cationic group (C-VI))

No sodium nitrate was used, and diallyldimethylammonium chloride was changed to triethanolamine lauryl sulfate (Emal 20T manufactured by Kao Corporation, 40% by mass of active ingredient) 38.3 g, in addition to the above (CI-1) In the same manner, an isopropanol solution (50% by mass of the solid content in an isopropanol solution) containing 50% by mass of the cationic group-containing compound (C-VI) was obtained.

[Preparation of antistatic coating composition]

The materials of Examples 1 to 34 and Comparative Examples 1 to 9 were prepared by mixing the materials according to the blending amounts (parts by mass) shown in Tables 1 to 3. Further, in Examples 1 to 34 and Comparative Examples 4 to 9, a mixed solution of isopropyl alcohol (IPA) and methyl ethyl ketone (MEK) (mass ratio of IPA/MEK = 1/2) was used as a solvent. In Comparative Examples 1 and 3, methanol was used as a solvent, and in Comparative Example 2, a mixed solvent of ion-exchanged water and methanol (ion-exchanged water/methanol = 1/2 (mass ratio)) was used as a solvent, and the composition was solid-formed. The preparation was carried out in such a manner that the composition of the material became 50% by mass.

The values (parts by mass) in Tables 1 to 3 are the relative mass ratios of the solid components. Further, "mass ratio A" means "A/(A+B+C) x 100", "mass ratio B" means "B/(A+B+C) x 100", and "mass ratio C1" means "C" /(A+B)×100", "mass ratio C2" means "C/(A+B+C)×100".

The physical properties of the compounds (A) and (B) are shown in Table 4.

[Production of coated film]

Each of the obtained antistatic coating compositions was applied to a cellulose triacetate (TAC) film by using a bar coater (gap: 9 to 13 μm) so that the thickness of the coating film after UV irradiation was 4 μm. On the rough side (width: 10 cm × length 12 cm × thickness 80 μm), it was dried at 70 ° C for 1 minute using a hot air dryer ("PH-202" manufactured by ESPEC). The dried film was subjected to UV irradiation (200 mJ/cm ² ) under a nitrogen stream (using an inert gas bottle) by a UV irradiation apparatus ("LH10-10" manufactured by Fusion UV Systems Japan Co., Ltd.) to obtain a coating film ( Thickness 4 μm). Further, the coating thickness was measured at three points on the upper, the center, and the lower portion of the center line of the width of the coated surface, and the average value was used.

[Surface resistivity value of coating film (evaluation of antistatic property)]

The film was measured for each of the coating films of the examples and the comparative examples by a high-resistance meter (manufactured by Yokogawa YHP) in a room having a temperature of 23 ° C and a relative humidity of 40%. The surface resistivity value (Ω) of the central part. Further, the smaller the value of the surface resistivity value, the more excellent the antistatic property. The results are shown in Tables 1 to 3 in such a manner that the base is set to a logarithm (log value) of 10.

[Surface resistivity value after water washing of coated film (evaluation of water resistance)]

With respect to each of the coating films of the examples and the comparative examples, after washing with water and drying, the surface resistivity value (Ω) was measured by the same method as the evaluation of the above-mentioned antistatic property. The water is drained from the faucet with an inner diameter of 14 mm at a flow rate of 10 L/min, and the coating film is placed 10 cm directly below the faucet in a vertical contact with the tap water, and water is evenly poured on the coated surface. The way to move one side is to wash for 30 seconds. Thereafter, using NIPPON The super dry paper towel manufactured by PAPER CRECIA Co., Ltd. removes moisture from the coated surface, and is ventilated and dried at a temperature of 23 ° C and a relative humidity of 40% until no water droplets are present. Further, the smaller the value of the surface resistivity value, the more excellent the water resistance. The results are shown in Tables 1 to 3 in such a manner that the base is set to a logarithm (log value) of 10.

[Haze value of coated film (evaluation of transparency)]

The haze value (%) of the coating films of the examples and the comparative examples was determined by a haze meter HM-150 manufactured by Murakami Color Research Laboratory in accordance with JIS K 7105 Optical Properties Test Method (5.5 and 6.4). Specifically, the diffuse transmittance and the total light transmittance were measured using an integrating sphere type light transmittance measuring device, and the ratio was expressed. Furthermore, the smaller the value of the haze value, the higher the transparency. The results are shown in Tables 1 to 3.

[Evaluation of scratch resistance]

Using the "AB301" manufactured by Tester Co., Ltd., the coated surface was abraded by steel wool #0000 (4 cm × 4 cm) at 60 g/cm ² and 30 round trips per minute for 20 round trips. test. Then, the haze value (%) of the center portion of the range in which the steel wool of the coated surface was reciprocated was measured by the same method as the evaluation of the transparency described above, and the haze value difference before and after the scratch test was determined by the following formula (%). ). The results are shown in Tables 1 to 3. The smaller the difference in haze value, the more excellent the scratch resistance.

Haze value difference (%) = haze value after scratch test (%) - haze value before scratch test (%)

In addition, the physical properties and the like of the materials used in the examples and comparative examples shown in Tables 1 to 3 are as follows.

(Compound (A))

A-1: dipentaerythritol hexaacrylate

(Japan Chemicals Co., Ltd. manufactures "KAYARAD DPHA")

A-2: dipentaerythritol pentaacrylate mono-fatty acid ester

(Manufactured by Nippon Kayaku Co., Ltd. [KAYARAD D-310])

A-3: dipentaerythritol hexaacrylate caprolactone modification

(Acrylic acid (6 mol) ester of a compound obtained by reacting dipentaerythritol (1 mol) with caprolactone (2 mol)

(Manufactured by Nippon Kayaku Co., Ltd. [KAYARAD DPCA20])

A-4: di-trimethylolpropane tetraacrylate

(Manufactured by Nippon Kayaku Co., Ltd. [KAYARAD T-1420(T)])

(Compound (B))

B-1: Trimethylolpropane triacrylate

(Manufactured by Nippon Kayaku Co., Ltd. [KAYARAD TMTPA])

B-2: Trimethylolpropane Ethylene oxide modified triacrylate

(Triacrylate of ethylene oxide 3 molar addition of trimethylolpropane)

(Manufactured by Nippon Kayaku Co., Ltd. [KAYARAD THE-330])

B-3: Trimethylolpropane propylene oxide modified triacrylate

(trimethylolpropane propylene oxide 3 molar addition of triacrylate)

(Manufactured by Nippon Kayaku Co., Ltd. [KAYARAD TPA-330])

B-4: 1,6-hexanediol diacrylate

(Manufactured by Osaka Organic Chemical Industry Co., Ltd. [Viscoat #230])

B-5: 1,10-nonanediol diacrylate

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. [NK Ester A-DOD-N])

B-6: tripropylene glycol diacrylate

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. [NK Ester APG-200])

B-7: urethane bisacrylate

(Manufactured by Daicel-Cytec Co., Ltd. [EBECRYL 8402])

B-8: Tetraethylene glycol diacrylate

(Manufactured by Osaka Organic Chemical Industry Co., Ltd. [Viscoat #335HP])

B-9: 1,4-butanediol diacrylate

(Manufactured by Osaka Organic Chemical Industry Co., Ltd. [Viscoat #195])

B-10: Dipropylene glycol (average heptamer) diacrylate

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. [NK Ester APG-400])

B-11: Dipropylene glycol (average dodepolymer) diacrylate

(Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. [NK Ester APG-700])

D-1:1-hydroxy-cyclohexyl-phenyl-one

(made by Wako Pure Chemical Industries Co., Ltd.)

As is clear from Tables 1 to 3, the coating composition of the present invention has excellent basic properties such as antistatic property, water resistance, transparency, and scratch resistance, and a coating film can be easily obtained.

Claims (20)

A coating composition for antistatic, comprising: a nonionic polymerizable compound (A) having four or more reactive energy ray-curable reactive groups, and a reactive group having one to three active energy ray-curable groups At least one cationic group-containing polymerizable compound (C) selected from the group consisting of a compound represented by the following formula (I) and a compound represented by formula (II); and a nonionic polymerizable compound (B) And the ratio of the compound (C) in the total of the above compounds (A), (B), and (C) is 1% by mass or more and 20% by mass or less. (In the formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; X ^- represents an inorganic acid ion; m represents an integer of 1 to 4, n represents an integer of 0 to 3, and m + n = 4 ; when n is an integer of 2 or more, R ¹ may be the same or different) (In the formula (II), R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group having 2 to 5 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. , Y represents NH; X ^- represents inorganic acid ion). The antistatic coating composition of claim 1, wherein the active energy ray is hard The reactive group is a propylene fluorenyl group or a methacryl fluorenyl group. The antistatic coating composition according to claim 1 or 2, wherein the cationic group-containing polymerizable compound (C) is a nonionic polymerizable compound (A) and (B), and a cationic group-containing polymerizable compound (C) The ratio of the total amount is 5% by mass or more and 20% by mass or less. The antistatic coating composition according to any one of claims 1 to 3, wherein a ratio of the nonionic polymerizable compound (A) to the total of the nonionic polymerizable compounds (A) and (B) is 20% by mass or more and 95% by mass or less. The antistatic coating composition according to any one of claims 1 to 4, wherein the nonionic polymerizable compound (A) is polymerizable with the nonionic polymerizable compound (A) and (B), and a cationic group. The proportion of the total of the compound (C) is 15% by mass or more and 85% by mass or less. The antistatic coating composition according to any one of claims 1 to 5, wherein the nonionic polymerizable compound (B) is polymerizable in the nonionic polymerizable compounds (A) and (B), and a cationic group. The proportion of the total of the compound (C) is 5% by mass or more and 75% by mass or less. The antistatic coating composition according to any one of claims 1 to 6, wherein the absolute value of the difference between the SP values of the nonionic polymerizable compound (A) and (B) is 0.1 or more and 2.0 or less. The antistatic coating composition according to any one of claims 1 to 7, wherein the nonionic polymerizable compound (B) has a molecular weight of 190 or more and 900 or less. The antistatic coating composition according to any one of claims 1 to 8, wherein the X ^-form of the above formulae (I) and (II) is selected from the group consisting of nitrate ions and chloride ions. Ions. The antistatic coating composition according to any one of claims 1 to 9, wherein the nonionic polymerizable compound (A) has a reactivity group of 4 or more and 10 or less. The antistatic coating composition according to any one of claims 1 to 10, wherein the nonionic polymerizable compound (B) has the above reactive group of 2 or 3. The antistatic coating composition according to any one of claims 1 to 11, wherein the cationic group-containing polymerizable compound (C) is a compound represented by the above formula (I). The antistatic coating composition according to any one of claims 1 to 12, wherein m of the above formula (I) is 2. The antistatic coating composition according to any one of claims 1 to 13, wherein R ¹ of the above formula (I) is a methyl group or an ethyl group. The antistatic coating composition according to any one of claims 1 to 11, wherein R ⁴ , R ⁵ and R ^{6 in the} above formula (II) are a methyl group. The antistatic coating composition according to any one of claims 1 to 11, wherein the R ³ of the above formula (II) is an exoethyl or a propyl group. The antistatic coating composition according to any one of claims 1 to 11, 15 or 16, wherein R ² of the above formula (II) is a hydrogen atom. The antistatic coating composition according to any one of claims 1 to 17, which further contains a photopolymerization initiator. A method for producing a coating film, which is characterized in that after applying the antistatic coating composition according to any one of claims 1 to 18 to a substrate, irradiation activity A coating film is formed by the energy rays. A coating film for antistatic, which is obtained by the production method of claim 19.