JP2010001398A - Antistatic coating agent composition and film obtained by curing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic coating agent composition developing excellent antistatic properties in a small quantity, and provide an antistatic film which is obtained by curing the antistatic coating agent composition and has excellent antistatic properties, transparency, scratch resistance, and adhesion to a base material. <P>SOLUTION: The antistatic coating agent composition comprises 100 pts.wt of a hard coat base containing at least either of a monomer having a plurality of ethylene groups and a prepolymer containing a plurality of ethylene groups, 0.5-50 pts.wt. of a polar polymer compound consisting of a copolymer of a macromonomer having a monomer containing at least one of polar structure selected from an ion pair and betaine or a repeating unit of this monomer, and a macromonomer containing a repeating unit of a monomer containing a fluorocarbon group, 0.05-10 pts.wt. of a polymer compound containing an amino group, and 0.05-10 pts.wt. of a polymer compound containing a hydroxy group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for applying a coating to a plastic substrate and curing it to impart antistatic properties, and a film obtained by curing the composition.

  Plastic base materials are widely used as raw materials for parts of home appliances, automobile parts, optical members, organic glass sheets, and the like. Plastic substrates are easily scratched and easily charged. Therefore, as disclosed in Patent Documents 1 and 2 below, the coating is performed with a coating agent containing metal fine particles of an antistatic agent or a conductive filler.

  However, if the coating layer contains a large amount of a cationic, anionic or nonionic surfactant, an alkali metal salt, an alkaline earth metal salt or an ammonium salt as an antistatic agent, it will cause bleeding. On the contrary, the antistatic property under high humidity is reduced, and the scratch resistance is reduced. In addition, when the coating agent contains a conductive filler, the antistatic property is excellent, but the transparency is impaired.

  In addition, a coating agent having an adhesive property and an excellent antistatic property as a base material to be coated having a polycarbonate resin or a resin containing a polycarbonate resin is desired.

Japanese Patent Laid-Open No. 10-244618 JP 2000-281736 A JP 2007-191508 A

  The present invention is an antistatic coating agent composition that is highly compatible with a hard coat base and that exhibits excellent antistatic properties even in a small amount, and a cured product thereof, which has antistatic properties, transparency, and scratch resistance. It is an object of the present invention to provide an excellent antistatic coating having excellent properties and having adhesion to a resin substrate, particularly a polycarbonate resin or a resin containing a polycarbonate resin.

  The antistatic coating agent composition according to claim 1 made to achieve the above object is selected from a monomer containing a plurality of ethylene groups and a prepolymer containing a plurality of ethylene groups. 100 parts by weight of a hard coat base containing at least one, a monomer containing at least one polar structure selected from an ion pair and betaine, or a macromonomer having a repeating unit of the monomer and a fluorocarbon group 0.5 to 50 parts by weight of a polar polymer compound composed of a copolymer with a macromonomer containing a repeating unit of the monomer to be polymerized, 0.05 to 10 parts by weight of a polymer compound containing an amino group, and a hydroxyl group The polymer compound is contained in an amount of 0.05 to 10 parts by weight.

  Similarly, the antistatic coating agent composition according to claim 2 is the composition according to claim 1, wherein the ion pair includes a quaternary ammonium halide group, an ammonium phosphate ester group, an ammonium sulfate ester group, a carboxylic acid. It is at least one selected from an ester ammonium group, a halogenated quaternary phosphonium group, a basic sulfonic acid group, and a basic carboxylic acid group.

  The antistatic coating agent composition according to claim 3 is the composition according to claim 1, wherein the betaine has a sulfonate ion group or a carboxylate ion group and a quaternary ammonium group or a quaternary phosphonium group. It is characterized by that.

  The antistatic coating agent composition according to claim 4 is the composition according to claim 1, wherein the polar polymer compound is at least one of a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group. A tertiary amine or a tertiary phosphine is reacted with a copolymer of a monomer containing the above group or an unsaturated macromonomer having a monomer repeating unit and the unsaturated macromonomer containing the fluorocarbon group. The ion pair of the halogenated quaternary ammonium group or the halogenated quaternary phosphonium group is formed.

  The antistatic coating agent composition according to claim 5 is the composition according to claim 1, wherein the polar polymer compound is a (meth) acrylic acid monoester monomer, an unsaturated carboxylic acid monomer, or (meth) acrylamide. It is copolymerized with at least one other unsaturated monomer selected from a monomer, a styrene monomer, a vinyl ether monomer, and a vinyl ester monomer.

  The antistatic coating agent composition according to claim 6 is the antistatic coating agent composition according to claim 1, wherein the polymer compound containing an amino group is a homopolymer of an unsaturated macromonomer containing an amino group, or Copolymerization of an unsaturated macromonomer containing an amino group with at least one unsaturated monomer selected from a (meth) acrylic acid monoester monomer, a (meth) acrylamide monomer, a styrene monomer, a vinyl ether monomer, and a vinyl ester monomer It is a thing.

  The antistatic coating agent composition according to claim 7 is the antistatic coating agent composition according to claim 1, wherein the polymer compound containing a hydroxyl group contains a homopolymer of an unsaturated monomer containing a hydroxyl group, or a hydroxyl group. Co-polymerized with an unsaturated monomer and at least one unsaturated monomer selected from a (meth) acrylic acid monoester monomer, an unsaturated carboxylic acid monomer, a (meth) acrylamide monomer, a styrene monomer, a vinyl ether monomer, and a vinyl ester monomer. It is a polymerized product.

  The antistatic coating agent composition according to an eighth aspect is the one according to the first aspect, characterized in that a photopolymerization initiator or a thermal polymerization initiator is contained.

  The antistatic coating film according to claim 9, which has been made to achieve the above object, is obtained by curing the antistatic coating agent composition according to claim 1 on a plastic substrate. Is.

  Similarly, the antistatic coating film according to claim 10 is characterized in that the plastic substrate according to claim 9 is a substrate containing polycarbonate.

  The method for forming an antistatic coating film according to claim 11, which was made to achieve the above object, applied the antistatic coating agent composition according to claim 1 to a plastic substrate. Then, by irradiating the active energy rays there, the ethylene group-containing monomer and / or the ethylene group-containing prepolymer is crosslinked and cured.

  The antistatic coating composition of the present invention comprises a polymer compound that exhibits antistatic properties, and since this polymer compound has a high surface modification property, it is excellent in antistatic properties simply by containing a small amount thereof. It is possible to prepare a coating composition that develops properties. In addition, since the polymer compound containing an amino group and the polymer compound containing a hydroxyl group are localized at the interface between the coating agent and the plastic substrate, localization of the polar polymer compound at the same interface is prevented. . As a result, the orientation of the polar polymer compound on the surface of the coating agent becomes more prominent, and an excellent antistatic property is exhibited only by containing a small amount of these polymer compounds. It becomes a coating agent composition for various plastic substrates, particularly polycarbonate substrates. This composition can be easily applied to a plastic substrate and cured to obtain a film having a low surface resistance and excellent antistatic properties, transparency, scratch resistance and adhesion.

Preferred form for carrying out the invention

  A preferred form of the antistatic coating agent composition is prepared as follows.

  Addition of 2- (meth) acryloyloxyethyl isocyanate to the hydroxyl group of a halogenated alkylstyrene block polymer into which 2-mercaptoethanol has been introduced at the terminal end makes it possible to contain a halogenated alkyl group containing an unsaturated group at the terminal end. Saturated macromonomer is synthesized. Next, a fluorocarbon group having an unsaturated group introduced at the end by adding 2- (meth) acryloyloxyethyl isocyanate to the hydroxyl group of the block polymer of the fluorocarbon group-containing (meth) acrylate having 2-mercaptoethanol introduced at the end A containing unsaturated macromonomer is synthesized.

  The halogenated alkyl group-containing unsaturated macromonomer and the fluorocarbon group-containing unsaturated macromonomer in which an unsaturated group is introduced at this end are substituted with 2-mercaptoethanol, for example, a carboxylic acid in the molecule such as 2-mercaptopropionic acid. A block polymer of alkyl styrene styrene and fluorocarbon group-containing (meth) acrylate is obtained using a chain transfer agent having a carboxylic acid group, and a vinyl compound having a glycidyl group in its molecule, such as glycidyl methacrylate, in its carboxylic acid group. It can also be synthesized by adding.

  The halogenated alkyl group-containing unsaturated macromonomer, the fluorocarbon group-containing unsaturated macromonomer, and the (meth) acrylic acid monoester are copolymerized at a polymerization ratio of 5 to 90: 5 to 90: 0 to 80. A tertiary amine or tertiary phosphine is reacted with a halogenated alkyl group in the copolymer to obtain a polar polymer compound in which a repeating unit of a halogenated quaternary ammonium group or a halogenated quaternary phosphonium group is formed.

  In the synthesis of the halogenated alkyl group-containing unsaturated macromonomer used when synthesizing the polymer compound in which the halogenated quaternary ammonium group or the halogenated quaternary phosphonium group repeating unit is formed, Instead, for example, a vinyl compound having a tertiary amine in the molecule such as dimethylaminoethyl methacrylate is used, and carbon and halogen in the molecule such as benzyl chloride are used instead of the tertiary amine or tertiary phosphine used later. It is also possible to synthesize by using an alkyl halide, an aryl halide, or a halogenated aralkyl having a bond. In addition, by using phosphate esters or sulfate esters such as trimethyl phosphate, dimethyl sulfate or methyl p-toluenesulfonate instead of benzyl chloride, halogen-free ion pairs can be used as polar structural repeating units. A polymer compound having a fluorocarbon group can be obtained.

  On the other hand, an unsaturated group was introduced at the terminal 3 by adding 2- (meth) acryloyloxyethyl isocyanate to the hydroxyl group of a block polymer of a tertiary amine-containing (meth) acrylate having 2-mercaptoethanol introduced at the terminal 3. A secondary amine-containing unsaturated macromonomer is synthesized. The tertiary amine-containing unsaturated macromonomer and (meth) acrylic acid monoester are copolymerized at a weight ratio of 5 to 100: 0 to 95 to obtain a tertiary amine-containing polymer compound. Further, a hydroxyl group-containing (meth) acrylate block polymer into which 2-mercaptoethanol is introduced at the terminal is synthesized to obtain a hydroxyl group-containing polymer compound.

  When this polar polymer compound, a tertiary amine-containing polymer compound, a hydroxyl group-containing polymer compound, an ethylene group-containing monomer and / or an ethylene group-containing prepolymer as a hard coat base, and a polymerization initiator are kneaded. An antistatic coating agent composition is obtained.

  In the antistatic coating agent composition, 0.5 to 10 parts by weight of a polar polymer compound and tertiary amine with respect to 100 parts by weight of a hard coat base containing a monomer containing a plurality of ethylene groups and / or a prepolymer containing a plurality of ethylene groups When 0.25 to 1 part by weight of the containing polymer compound, 0.25 to 1 part by weight of the hydroxyl group-containing polymer compound, and 1 to 10 parts by weight of the polymerization initiator are contained, extremely excellent antistatic properties are exhibited. More preferable.

  The fluorocarbon group in the polar polymer compound is easily compatible with oxygen in the air. Furthermore, the tertiary amine-containing polymer compound and the hydroxyl group-containing polymer compound are likely to be localized at the interface between the plastic substrate and the coating composition. Therefore, the film obtained by curing this composition is easy to orient the polymer containing fluorocarbon groups on the surface. As a result, even if the amount of the polar polymer compound in the composition is small, the surface resistance value of the coating can be effectively reduced.

  Specifically, the raw material of the antistatic coating agent composition is as follows.

  Examples of the halogenated alkyl group, the halogenated aryl group, or the halogenated aralkyl group-containing unsaturated compound include chloromethylstyrene. The tertiary amine and tertiary phosphine are not particularly limited, but amines having a methyl group or an ethyl group are particularly preferable.

  The fluorocarbon group-containing unsaturated monomer may be a fluorocarbon group-containing (meth) acrylate, such as 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H , 1H, 5H octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluoroisopropylethyl (meth) acrylate, p-perfluorooctyloxybenzyl (meth) acrylate, and the like. Among them, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate and the like having a perfluoroalkyl group at the terminal are preferable. In particular, it is not limited to these. These fluorocarbon group-containing unsaturated monomers can be used alone or in combination of two or more.

  (Meth) acrylic acid monoester, which is another unsaturated monomer constituting polar polymer compound, is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclopentyl (meth) acrylate, benzyl (meth) acrylate, ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylate such as isobornyl (meth) acrylate, monofunctional polyoxyalkylene (meth) acrylate, monofunctional polyester (meth) acrylate, monofunctional polycaprolactone (meth) acrylic It includes over bets, but not limited thereto. In addition, copolymerizable unsaturated monomers other than (meth) acrylic acid monoester monomers include unsaturated carboxylic acid monomers such as (meth) acrylic acid, crotonic acid, maleic acid, and itaconic acid; t-butyl-n -(Meth) acrylic acid amide monomers such as butoxymethylacrylamide; styrene monomers such as styrene and α-methylstyrene; vinyl ether monomers such as lauryl vinyl ether; vinyl ester monomers such as vinyl butyrate However, it is not particularly limited to this. These unsaturated monomers can be used alone or in combination of two or more.

  The polar polymer compound is an ion pair-containing unsaturated monomer exemplified by trialkylammoniomethyl styrene chloride or trialkylphosphoniomethyl styrene chloride or (3-propyl sulfonic acid-1) in the same weight ratio as above. Polarities derived from betaine structure-containing unsaturated monomers exemplified by 2-vinylpyridinium betaine and N, N-dimethyl-N- (2-methacryloyloxyethyl) -N- (3-sulfopropyl) ammonium betaine An unsaturated macromonomer having a repeating unit having a structure, a fluorocarbon group-containing unsaturated macromonomer, and a (meth) acrylic acid monoester may be copolymerized. The macromonomer is prepared in the same manner as described above.

  The tertiary amine-containing unsaturated monomer constituting the polymer compound containing a tertiary amine may be a tertiary amine-containing (meth) acrylate, such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate. . These tertiary amine-containing unsaturated monomers can be used alone or in combination of two or more.

  (Meth) acrylic acid monoester which is one of the other unsaturated monomers constituting the polymer compound is (meth) acrylic acid mentioned in the case of (meth) acrylic acid monoester constituting the polar polymer compound Substances similar to monoesters can be used. Moreover, these unsaturated monomers can be used individually by 1 type, and can use 2 or more types together.

  The hydroxyl group-containing unsaturated monomer constituting the polymer compound containing a hydroxyl group may be a hydroxyl group-containing (meth) acrylate, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( And (meth) acrylate. These hydroxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

  Examples of the ethylene group plural-containing monomer include ethylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, Examples thereof include glycerin monomethacrylate monoacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  The ethylene group-containing prepolymer is obtained by, for example, condensing trimethylolpropane ethylene oxide adduct tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyhydric alcohol and polybasic acid. (Meth) acrylates, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and polyisocyanates such as burettes and uretrates, glycerin monomethacrylate monoacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol A reaction product with (meth) acrylate having a hydroxyl group in the molecule such as penta (meth) acrylate can be mentioned.

  The polymerization initiator is, for example, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2 -Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Examples of the agent include benzoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 2,2-bis (4,4-di-butylperoxycyclohexyl). Propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate T-butyl peroxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2 5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4, 4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, Organic peroxide initiators such as di-t-butyl peroxide, t-butyltrimethylsilyl peroxide, t-butyl hydroperoxide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1- [ (1-Cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane Sun-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) ) -2-Methylpropionamidine] dihydride chloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N- [1,1] -Bis (hydroxymethyl) ethyl] propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropyl) Lopan), dimethyl-2,2-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [2- (hydroxymethyl) propionitrile] And azo-based initiators.

  The antistatic coating agent composition contains additives such as silicon-based resins, silica particles, metal particles, metal oxide particles, organic salts, and inorganic salts, and diluents depending on the performance required for the film. Also good.

  Diluents include monoalkyl ethers of alkylene glycols such as propylene glycol monomethyl ether; alkyl alcohols such as isopropyl alcohol; alkyl carboxylic acid esters of alkylene glycol monoalkyl alcohols such as butyl glycol acetate; ketones such as methyl ethyl ketone; Examples include acid esters such as ethyl acetate; aliphatic hydrocarbons such as hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene; and halogenated solvents such as methyl chloride.

  The antistatic coating agent composition is applied to a plastic substrate. When it is irradiated with an active energy ray such as ultraviolet ray, radiation, infrared ray, X-ray, electron beam, visible light or heat, it is cured to form an antistatic coating.

  Hereinafter, examples of the antistatic coating agent composition of the present invention and trial production examples of the antistatic film obtained by curing the composition will be shown, but the scope of the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of Macromonomer of Chloromethylstyrene 100 parts by weight of chloromethylstyrene, 5 parts by weight of 2-mercaptoethanol, 100 parts by weight of methyl ethyl ketone, and dimethyl 2,2′-azobis (2-methyl) were added to a four-necked flask. 5 parts by weight of propionate) was added and reacted at 75-80 ° C. for 13 hours under a nitrogen atmosphere. Thereafter, 9.93 parts by weight of 2-methacryloyloxyethyl isocyanate, 0.04 parts by weight of methoquinone and 0.01 parts by weight of dibutyltin dilaurate were added and reacted at 75-80 ° C. for 6 hours. Ensure that the peak of the isocyanate groups of 2250 cm ^-1 in infrared absorption spectrum had disappeared, to obtain a macromonomer of chloromethylstyrene (CMS macromonomers).

(Synthesis Example 2) Synthesis of trifluoroethyl methacrylate macromonomer Light ester M-3F (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) which is 2,2,2-trifluoroethyl methacrylate in a four-necked flask; M- (3F monomer) 100 parts by weight, 2-mercaptoethanol 5 parts by weight, methyl ethyl ketone 100 parts by weight, and dimethyl 2,2′-azobis (2-methylpropionate) 5 parts by weight. The reaction was carried out at 0 ° C. for 7 hours. Thereafter, 9.93 parts by weight of 2-methacryloyloxyethyl isocyanate, 0.04 parts by weight of methoquinone and 0.01 parts by weight of dibutyltin dilaurate were added and reacted at 75-80 ° C. for 6 hours. In the infrared absorption spectrum, it was confirmed that the peak of the isocyanate group at 2250 cm ⁻¹ disappeared, and a macromonomer (M-3F macromonomer) of trifluoroethyl methacrylate was obtained.

(Synthesis Example 3) Synthesis of dimethylaminoethyl methacrylate macromonomer 100 parts by weight of light ester DM (trade name: DM monomer manufactured by Kyoeisha Chemical Co., Ltd.), which is dimethylaminoethyl methacrylate, in a four-necked flask, 2- 5 parts by weight of mercaptoethanol, 100 parts by weight of methyl ethyl ketone, and 5 parts by weight of dimethyl 2,2′-azobis (2-methylpropionate) were added, and the mixture was reacted at 75-80 ° C. for 13 hours in a nitrogen atmosphere. Then, 9.93 parts by weight of 2-methacryloyloxyethyl isocyanate, 0.04 parts by weight of methoquinone, and 0.01 parts by weight of dibutyltin dilaurate were added and reacted at 75 to 80 ° C. for 3 hours. Ensure that the peak of the isocyanate groups of 2250 cm ^-1 in infrared absorption spectrum had disappeared, to obtain the macromonomer of dimethylaminoethyl methacrylate (DM macromonomers).

  Next, a polymer compound was synthesized. Ingredients for synthesis are shown in Table 1.

(Synthesis Example 4) Synthesis of tertiary amine-containing polymer compound In a four-necked flask, 20 parts by weight of methyl methacrylate, and 80 parts by weight of the dimethylaminoethyl methacrylate macromonomer obtained in Synthesis Example 3 in terms of resin content And 67 parts by weight of methyl ethyl ketone containing the same, 83 parts by weight of methyl ethyl ketone, and 5 parts by weight of dimethyl 2,2′-azobis (2-methylpropionate) were added, and the mixture was 13 hours at 75-80 ° C. in a nitrogen atmosphere. Reaction was conducted to obtain a tertiary amine-containing polymer compound.

Synthesis Example 5 Synthesis of Hydroxyl-Containing Polymer Compound 100 parts by weight of light ester HOP (trade name: HOP monomer manufactured by Kyoeisha Chemical Co., Ltd.), which is 2-hydroxypropyl methacrylate, in a four-necked flask, 2-mercaptoethanol 5 parts by weight, 100 parts by weight of methyl ethyl ketone, and 5 parts by weight of dimethyl 2,2′-azobis (2-methylpropionate) are added and reacted at 75 to 80 ° C. for 13 hours in a nitrogen atmosphere to obtain a hydroxyl group-containing polymer. A compound was obtained.

(Synthesis Example 6) Synthesis of Polymer Compound 1 In a four-necked flask, 100 parts by weight of the chloromethylstyrene macromonomer obtained in Synthesis Example 1 in terms of resin content and 84 parts by weight of methyl ethyl ketone containing it. Mixture, 20 parts by weight of methyl methacrylate, a mixture of 80 parts by weight of the macromonomer of trifluoroethyl methacrylate obtained in Synthesis Example 2 in terms of resin and 67 parts by weight of methyl ethyl ketone containing the same, dimethyl 2,2′- 10 parts by weight of azobis (2-methylpropionate) was added and allowed to react at 75-80 ° C. for 9 hours under a nitrogen atmosphere. To the reaction mixture, 55.3 parts by weight of triethylamine and 55.6 parts by weight of ethanol were added and reacted at 60 ° C. for 6 hours. The amine value was measured by a titration method, and it was confirmed that all the tertiary amines were quaternized. Thus, polymer compound 1 was obtained.

(Synthesis Example 7) Synthesis of Polymer Compound 2 In a four-necked flask, 100 parts by weight of the dimethylaminoethyl methacrylate macromonomer obtained in Synthesis Example 3 in terms of resin content and 84 parts by weight of methyl ethyl ketone containing the same 20 parts by weight of light acrylate 130A (trade name manufactured by Kyoeisha Chemical Co., Ltd .; 130A monomer), which is methoxy-polyethylene glycol acrylate, and the trifluoroethyl methacrylate macromonomer obtained in Synthesis Example 2 as a resin component A mixture of 80 parts by weight and 67 parts by weight of methyl ethyl ketone containing it, 10 parts by weight of dimethyl 2,2′-azobis (2-methylpropionate) and 59 parts by weight of methyl ethyl ketone were added. It was made to react at 75-80 degreeC for 9 hours. To the reaction mixture, 82.2 parts by weight of diethyl sulfuric acid and 210 parts by weight of ethanol were added and reacted at 60 ° C. for 3 hours. The amine value was measured by a titration method, and it was confirmed that all the tertiary amines were quaternized. Thus, polymer compound 2 was obtained.

以下に、本発明を適用する帯電防止コーティング剤組成物及びそれを硬化させた帯電防止被膜の試作例を実施例１〜４に示す。また本発明を適用外のコーティング剤組成物及びそれを硬化させた被膜の試作例を比較例１〜４に示す。

Examples 1-4 of the antistatic coating agent composition to which the present invention is applied and the antistatic coating film obtained by curing the composition are shown in Examples 1 to 4. Moreover, the comparative example 1-4 shows the prototype of the coating agent composition which does not apply this invention, and the film which hardened it.

(Examples 1-4 and Comparative Examples 1-4)
Polymer compounds obtained in Synthesis Examples 4 to 7, dipentaerythritol hexaacrylate (trade name: Light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.) and pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer (as a hard coat base) Kyoeisha Chemical Co., Ltd. trade name: urethane acrylate UA-306I), solvent as methyl ethyl ketone, and photopolymerization initiator as 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) 2 and blended uniformly to prepare a composition. The obtained composition was applied to a transparent polycarbonate substrate with a thickness of about 10 μm with a bar coater (No. 14) to form a coating film, and dried at 90 ° C. for 5 minutes. It was placed on a conveyor with a speed of 5 m / min, and irradiated with ultraviolet rays with an 80 W / cm high-pressure mercury lamp 10 cm away from it to cure the coating film to obtain a test piece having a coating thickness of 3 μm.

  The physical properties of the obtained test pieces were evaluated by performing appearance observation, surface resistance measurement test, pencil hardness measurement test, scratch resistance evaluation test, and adhesion evaluation test as follows.

(Appearance observation)
The coating state of the cured coating was visually observed. Evaluation was made in two stages, with ○ being transparent and △ being not transparent.

(Surface resistance measurement test)
About the surface resistance value of the film of the test piece under relative humidity 60% at 20 degreeC, it measured using resistivity meter DSM-8103 and SME-8311 (all are the Toa DKK company brand name).

(Pencil hardness measurement test)
According to JIS K 5400, the pencil hardness of the coating film of the test piece was measured using a pencil scratch tester. A load of 1 kg was applied from above while maintaining pencils of various hardnesses at an angle of 45 °, the coating on the test piece was scratched 1 cm, and the presence or absence of scratches was visually observed. Repeated 5 times, the highest hardness among the pencil hardnesses that were not damaged in 5 times was defined as the hardness of the coating.

(Abrasion resistance evaluation test)
The coating of the test piece was rubbed 10 times with a No. 0000 steel wool applied with a load of 200 g / cm ² , and the presence or absence of scratches was visually observed. Evaluated in 4 grades, ◎ for those with little or no scratches, ○ for those with slight scratches, △ for countless scratches, and × for those with whitening. did.

(Adhesion evaluation test)
According to JIS K 5400, 100 grids were made by making 11 vertical and horizontal cuts at 1 mm intervals on the coating surface of the test piece. After the cellophane tape was brought into close contact with the surface, the number of cells remaining without being peeled off was counted.

These results are summarized in Table 2.

表２から明らかなとおり、本発明の帯電防止コーティング剤組成物から得た被膜は、帯電防止性、透明性、耐擦傷性、密着性に優れ、高い硬度を示した。

As is clear from Table 2, the film obtained from the antistatic coating agent composition of the present invention was excellent in antistatic property, transparency, scratch resistance and adhesion, and exhibited high hardness.

  As is clear from the comparison between Comparative Examples 1 and 2 and Comparative Example 3, the surface resistance value is reduced by adding a small amount of the tertiary amine-containing polymer compound or the hydroxyl group-containing polymer compound to the polar polymer compound. As can be seen, Comparative Example 1 had a small decrease in surface resistance, and Comparative Example 2 had a reduced transparency of the coating.

  As apparent from the comparison between Examples 1 to 3 and Comparative Examples 1 to 3, the surface resistance was maintained while maintaining other functions by adding a small amount of each of the tertiary amine-containing polymer compound and the hydroxyl group-containing polymer compound. The value could be further reduced. This is because the polymer compound containing a tertiary amine in the molecule and the polymer compound containing a hydroxyl group in the molecule are localized at the interface between the base material and the coating, thereby bringing the polymer compound to the polar polymer compound interface. This is considered to be because the orientation of the film was suppressed and the orientation to the coating surface was strengthened. As is clear from comparison between Example 4 and Comparative Example 4, it can be said that the same effect can be obtained even when the antistatic coating agent composition of the present invention containing no chlorine is used.

  Further, as is clear from the comparison between Example 1 and Examples 2 and 3, the effect is further improved by adjusting the addition amount of the tertiary amine-containing polymer compound and the hydroxyl group-containing polymer compound to the polar polymer compound. In particular, the surface resistance value could be reduced.

  The antistatic coating composition of the present invention is used to form an antistatic coating on building materials such as liquid crystal screens, home appliances, production lines thereof, and soundproof polycarbonate plates that should avoid charging and dust adsorption. .

Claims (11)

100 parts by weight of a hard coat base containing at least one selected from a monomer containing a plurality of ethylene groups and a prepolymer containing a plurality of ethylene groups,
A monomer containing at least one polar structure selected from an ion pair and betaine, or a macromonomer having a repeating unit of the monomer and a macromonomer containing a repeating unit of a monomer containing a fluorocarbon group; 0.5 to 50 parts by weight of a polar polymer compound comprising a copolymer of
An antistatic coating agent composition comprising 0.05 to 10 parts by weight of a polymer compound containing an amino group and 0.05 to 10 parts by weight of a polymer compound containing a hydroxyl group.   The ion pair is selected from a halogenated quaternary ammonium group, a phosphoric acid ester ammonium group, a sulfuric acid ester ammonium group, a carboxylic acid ester ammonium group, a halogenated quaternary phosphonium group, a basic sulfonic acid group, and a basic carboxylic acid group. The antistatic coating agent composition according to claim 1, wherein the antistatic coating agent composition is at least one kind.   The antistatic coating agent composition according to claim 1, wherein the betaine has a sulfonate ion group or a carboxylate ion group and a quaternary ammonium group or a quaternary phosphonium group.   The polar polymer compound is a monomer containing at least one kind of a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group, or an unsaturated macromonomer having a repeating unit of a monomer; A copolymer with the unsaturated macromonomer containing the fluorocarbon group was reacted with a tertiary amine or tertiary phosphine to form the ion pair of the halogenated quaternary ammonium group or the halogenated quaternary phosphonium group. The antistatic coating agent composition according to claim 1, wherein   The polar polymer compound is at least one other unsaturated monomer selected from a (meth) acrylic acid monoester monomer, an unsaturated carboxylic acid monomer, a (meth) acrylamide monomer, a styrene monomer, a vinyl ether monomer, and a vinyl ester monomer. The antistatic coating agent composition according to claim 1, which is copolymerized with the antistatic coating agent.   The polymer compound containing an amino group is a homopolymer of an unsaturated macromonomer containing an amino group, or an unsaturated macromonomer containing an amino group, a (meth) acrylic acid monoester monomer, (meth) acrylamide 2. The antistatic coating agent composition according to claim 1, wherein the antistatic coating agent composition is a copolymer of at least one unsaturated monomer selected from a monomer, a styrene monomer, a vinyl ether monomer, and a vinyl ester monomer.   The polymer compound containing a hydroxyl group is a homopolymer of an unsaturated monomer containing a hydroxyl group, an unsaturated monomer containing a hydroxyl group, a (meth) acrylic acid monoester monomer, an unsaturated carboxylic acid monomer, (meth) 2. The antistatic coating agent composition according to claim 1, which is a copolymer of at least one unsaturated monomer selected from an acrylamide monomer, a styrene monomer, a vinyl ether monomer, and a vinyl ester monomer.   2. The antistatic coating agent composition according to claim 1, further comprising a photopolymerization initiator or a thermal polymerization initiator.   The antistatic film which hardened the antistatic coating agent composition in any one of Claims 1-8 on the plastic base material.   10. The antistatic coating film according to claim 9, wherein the plastic substrate is a substrate containing polycarbonate.   The antistatic coating agent composition according to any one of claims 1 to 8 is applied to a plastic substrate and irradiated with an active energy ray, whereby the ethylene group plural-containing monomer and / or the ethylene group plural A method for forming an antistatic coating, comprising: cross-linking and curing a prepolymer containing content.