JP2022152582A - Coating agent composition, article - Google Patents

Abstract

A coating agent composition that provides a coating layer having excellent antifouling properties and antistatic properties; and a film having the coating layer.
A coating composition comprising a (meth)acrylate (A) having tri- or higher functionality, a quaternary ammonium group-containing polymer (B), and a compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure. Article: An article comprising a substrate and a coating layer provided on at least a part of the surface of the substrate, wherein the coating layer is a cured product of the coating agent composition.
[Selection figure] None

Description

TECHNICAL FIELD The present invention relates to coating agent compositions and articles.

In recent years, the demand for image display devices having liquid crystal displays, such as smartphones and tablet terminals, is increasing. In order to protect the screen display portion or image display body of these displays, a protective film obtained by coating a base film is used.

From the viewpoint of optical properties such as transparency, triacetyl cellulose film, cycloolefin film, polyester film, acrylic film, polycarbonate film, transparent polyimide film, etc. are used as protective films for screen display parts such as displays or image display bodies. A plastic film is used. However, since these plastic films exhibit high electrical insulation, they tend to be electrified, and dust tends to adhere to their surfaces.

Accordingly, several coating agent compositions containing a quaternary ammonium group-containing polymer have been proposed in order to form a coating layer having antistatic properties (Patent Documents 1 to 3).
Patent Literature 1 describes a resin composition for forming a hard coat layer. This resin composition for forming a hard coat layer is a (meth)acrylic monomer obtained by copolymerizing a vinyl group-containing monomer having a quaternary ammonium group and a (meth)acrylic monomer copolymerizable therewith. It contains a copolymer; a polyurethane oligomer having a tri- or more functional vinyl group; and an acrylic monomer having a di- to hexa-functional vinyl group.
Patent Document 2 describes an antistatic hard coat resin composition. This antistatic hard coat resin composition comprises a compound having a (meth)acryloyl group; a quaternary ammonium group-containing polymer; acetone; a mixed solvent with one or more alcohols selected from the group consisting of methanol, ethanol and isopropyl alcohol; contains
Patent Document 3 describes a surface-hardened article comprising a base material and a cured coating film formed on the surface thereof. The cured coating film contains a quaternary ammonium base-containing polymer and metal oxide fine particles (C) having an average particle size of 5 to 500 nm.

JP 2008-56872 A JP 2013-91698 A JP 2013-132784 A

However, in the coating layer obtained from the conventional coating agent composition as proposed in Patent Documents 1 to 3, stains and fingerprints adhering to the surface of the coating layer cannot be sufficiently wiped off. Insufficient sexuality.
Therefore, the present inventor thought that the antifouling property of the coating composition could be improved by using an antifouling agent. It has been found that there is a problem that excellent antifouling properties and antistatic properties cannot be achieved at the same time.
The present invention has been made in view of such circumstances, and provides a coating agent composition that provides a coating layer with excellent antifouling and antistatic properties; an article having a coating layer with excellent antifouling and antistatic properties. offer.

The present invention has the following aspects.
[1] A coating agent composition containing a (meth)acrylate (A) having a functionality of 3 or more, a quaternary ammonium group-containing polymer (B), and a compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure. .
[2] The coating composition of [1], wherein the tri- or higher functional (meth)acrylate (A) is a tri- or higher functional urethane (meth)acrylate.
[3] The coating composition of [1] or [2], wherein the quaternary ammonium group-containing polymer (B) is a quaternary ammonium group-containing acrylic polymer.
[4] The coating composition of any one of [1] to [3], wherein the compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure further has a (meth)acryloyl group.
[5] Any one of [1] to [4], wherein the compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure further has a perfluoroalkylene group which may have an oxygen atom between carbon atoms. Coating agent composition.
[6] A substrate and a coating layer provided on at least a part of the surface of the substrate; the coating layer being a cured product of the coating agent composition according to any one of [1] to [5] An article that is.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a coating agent composition that provides a coating layer with excellent antifouling properties and antistatic properties; and an article having a coating layer with excellent antifouling properties and antistatic properties.

The coating agent composition of the present invention contains the compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure as an antifouling agent, and the quaternary ammonium base-containing polymer (B) as an antistatic agent.
When the antifouling agent is used as described above, the antistatic performance of the coating layer deteriorates, and both excellent antifouling and antistatic properties cannot be achieved at the same time. A coating layer which is hard to be damaged, can achieve both excellent antifouling properties and antistatic properties, and is excellent in antifouling properties and antistatic properties can be obtained.
Although the reason why such an effect is obtained is not clear, it is considered as follows.
In the present invention, since the compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure is included as an antifouling agent, the quaternary ammonium base-containing polymer (B) is formed in the matrix of the (meth)acrylate (A) having trifunctional or higher functionality. Moderate phase separation occurs, and the compound (C) tends to be unevenly distributed on the surface of the coating film. Therefore, it is considered that both excellent antifouling property and antistatic property can be achieved.

The following terms used herein have the following meanings.
(Meth)acrylate is a generic term for methacrylate and acrylate.
(Meth)acryloyl group is a generic term for methacryloyl group and acryloyl group.
(Meth)acryl means a generic term for methacryl and acryl.
"~" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.

<Coating agent composition>
The coating agent composition of the present invention (hereinafter also referred to as “this coating agent composition”) comprises a trifunctional or higher (meth)acrylate (A), a quaternary ammonium base-containing polymer (B), a fluorine atom-containing structure and and a compound (C) having a cyclic siloxane structure.

(Trifunctional or higher (meth)acrylate (A))
The trifunctional or higher (meth)acrylate (A) is not particularly limited as long as it is a compound having three or more (meth)acryloyl groups in one molecule. The tri- or higher functional (meth)acrylate (A) may be a monomer or an oligomer.

Examples of (meth)acrylates (A) having a functionality of three or more monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth) acrylates, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, Isocyanuric acid ethylene oxide-modified poly(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified penta Erythritol tetra(meth)acrylate, succinic acid-modified pentaerythritol poly(meth)acrylate, caprolactone-modified pentaerythritol poly(meth)acrylate and the like.

Examples of the oligomer tri- or higher functional (meth)acrylate (A) include tri- or higher functional urethane (meth)acrylate (A1). The trifunctional or higher urethane (meth)acrylate (A1) is a compound having three or more (meth)acryloyl groups and one or more urethane bonds.
Trifunctional or higher urethane (meth)acrylate (A1) includes, for example,
A reaction product of a hydroxyl group-containing (meth)acrylate compound (a1) containing one or more (meth)acryloyl groups and a polyvalent isocyanate compound (a2);
A reaction product of a hydroxyl group-containing (meth)acrylate compound (a1) containing one or more (meth)acryloyl groups, a polyvalent isocyanate compound (a2) and a polyol compound (a3);
A reaction product of a hydroxyl group-containing (meth)acrylate compound (a4) containing a hydroxyl group and three or more (meth)acryloyl groups and a monoisocyanate compound (a5);
etc.
Among them, trifunctional or higher urethane (meth)acrylate (A1) from the standpoint of antifouling property, scratch resistance, etc. is a reaction of a hydroxyl group-containing (meth)acrylate compound (a1) and a polyvalent isocyanate compound (a2). Products are preferred.

Regarding the hydroxyl group-containing (meth)acrylate compound (a1) containing one or more (meth)acryloyl groups, the hydroxyl group-containing (meth)acrylate compound containing one (meth)acryloyl group includes, for example, 2-hydroxy hydroxyalkyl (meth)acrylates such as ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate; 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate , polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like.
Examples of hydroxyl group-containing (meth)acrylate compounds containing two (meth)acryloyl groups include glycerin di(meth)acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol di(meth)acrylate, and the like. is mentioned.
The hydroxyl group-containing (meth)acrylate compound (a1) containing one or more (meth)acryloyl groups may be used alone or in combination of two or more.

Examples of polyvalent isocyanate compounds (a2) include aromatic compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Polyisocyanates; aliphatic polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc. trimer compounds and polymer compounds of these polyisocyanates; allophanate-type polyisocyanates; biret-type polyisocyanates; water-dispersed polyisocyanates;

Among them, diisocyanate compounds are preferable from the viewpoint of stability during the urethanization reaction, and aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated Alicyclic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane are more preferred.
Isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and norbornene diisocyanate are preferred from the viewpoint of small cure shrinkage, and isophorone diisocyanate is particularly preferred from the viewpoint of excellent reactivity and versatility.
The polyvalent isocyanate compound (a2) may be used alone or in combination of two or more.

The polyol compound (a3) is not particularly limited as long as it contains two or more hydroxyl groups. Examples include aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyisoprene polyols, and (meth)acrylic polyols.

Examples of aliphatic polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2. -ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1,6- Hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,8- Aliphatic alcohols containing two hydroxyl groups such as octanediol; Sugar alcohols such as xylitol and sorbitol; Aliphatic alcohols containing three or more hydroxyl groups such as glycerin, trimethylolpropane and trimethylolethane; is mentioned.

Examples of alicyclic polyols include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol.

Examples of polyether-based polyols include alkylene structure-containing polyether-based polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, and polyhexamethylene glycol; Examples include polymers and block copolymers.

Polyester-based polyols include, for example, condensation polymers of polyhydric alcohols and polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); polyhydric alcohols, polycarboxylic acids, and cyclic esters. reactant; and the like.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylene. diol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.), and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and trimellitic acid; and the like. These may be used individually by 1 type, and may use 2 or more types together.

Cyclic esters include, for example, propiolactone, β-methyl-δ-valerolactone, ε-caprolactone and the like.

Examples of polycarbonate-based polyols include reaction products of polyhydric alcohols and phosgene, ring-opening polymers of cyclic carbonates (alkylene carbonates and the like), and the like. These may be used individually by 1 type, and may use 2 or more types together.

The polyhydric alcohol in the polycarbonate-based polyol includes the same compounds as the polyhydric alcohol in the polyester-based polyol. Alkylene carbonates include, for example, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate and the like. These may be used individually by 1 type, and may use 2 or more types together.

The polycarbonate-based polyol is not particularly limited as long as it is a compound having a carbonate bond in the molecule and a hydroxyl group at the end of the molecule. The polycarbonate-based polyol may further have an ester bond in addition to the carbonate bond.

Examples of polyolefin-based polyols include those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon skeleton and hydroxyl groups at the molecular terminals thereof.

Examples of polybutadiene-based polyols include those having a butadiene copolymer as a hydrocarbon skeleton and having hydroxyl groups at the molecular terminals thereof.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

Examples of polyisoprene-based polyols include those having a copolymer of isoprene as a hydrocarbon skeleton and hydroxyl groups at the molecular terminals thereof.
The polyisoprene-based polyol may be a hydrogenated polyisoprene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

Examples of (meth)acrylic polyols include (meth)acrylic acid ester polymers or copolymers having at least two hydroxyl groups in the molecule. Examples of such (meth)acrylic acid esters include the above-described hydroxyl group-containing (meth)acrylate compounds containing one ethylenically unsaturated group. If desired, other copolymerizable monomers can be copolymerized. Examples of copolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, Acrylic acid esters such as 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate and other (meth)acrylate alkyl esters, styrene, methylstyrene and the like Examples include styrene compounds.
In addition, a hydroxyl group-containing (meth)acrylic polyol obtained by reacting a (meth)acrylic polymer having a glycidyl group in a side chain with a carboxylic acid such as (meth)acrylic acid may be used, and a (meth)acrylic polyol having a carboxylic acid in a side chain (meth)acrylic acid may be used. ) A hydroxyl group-containing (meth)acrylic polyol obtained by reacting an acrylic polymer with a glycidyl group-containing compound may also be used.

Among them, polyester-based polyols and polyether-based polyols are preferable, and polyether-based polyols are particularly preferable in terms of flexibility of the cured product (adhesive) and compatibility with the photopolymerizable compound (B), and polytetramethylene. Glycols are most preferred.
One of the polyol compounds (a3) may be used alone, or two or more thereof may be used in combination.

The number average molecular weight of the polyol compound (a3) is preferably 200 to 3,000, more preferably 250 to 2,000, even more preferably 300 to 1,000. If the number average molecular weight of the polyol compound (a3) is too small, the crosslink density tends to be too high, resulting in poor adhesion to the substrate. If the number average molecular weight of the polyol-based compound (a3) is too large, the crystallinity tends to be high and the viscosity tends to be high.

A number average molecular weight is a number average molecular weight by standard polystyrene molecular weight conversion. For example, high-performance liquid chromatography ("Waters 2695 (main body)" and "Waters 2414 (detector)" manufactured by Nippon Waters Co., Ltd.), column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range : 100 to 2×10 ⁷ , theoretical plate number: 10,000 plates/line, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) are connected in series. .

Examples of the hydroxyl group-containing (meth)acrylate compound (a4) containing three or more (meth)acryloyl groups include pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, and ethylene oxide-modified pentaerythritol. tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate and the like.
Among them, dipentaerythritol penta(meth)acrylate and pentaerythritol tri(meth)acrylate are preferable.

Urethane (meth)acrylate (A1) can be synthesized according to a known method. For example, for the reaction product of the hydroxyl group-containing (meth)acrylate compound (a1) and the polyvalent isocyanate compound (a2), the method described in paragraphs [0036] to [0042] of JP-A-2020-152786. can be synthesized according to

The weight average molecular weight of the urethane (meth)acrylate (A1) that can be used in the present invention is preferably 1,000 to 60,000, more preferably 1,500 to 50,000, and further 1,800 to 30,000. preferable. If the weight-average molecular weight is too small, curing shrinkage of the cured product tends to increase.

The weight-average molecular weight is the weight-average molecular weight in terms of standard polystyrene molecular weight. -806L (exclusion limit molecular weight: 2×10 ⁷ , separation range: 100 to 2×10 ⁷ , number of theoretical plates: 10,000 plates/line, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm ) can be measured by connecting three in series.

The viscosity of the urethane (meth)acrylate (A1) at 60° C. is preferably from 500 to 100,000 mPa·s, more preferably from 800 to 50,000 mPa·s, even more preferably from 1,000 to 35,000 mPa·s. If the viscosity is too high, workability tends to decrease. Viscosity is a value measured by an E-type viscometer.

The coating agent composition of the present invention may contain a (meth)acrylate compound in addition to the tri- or higher functional (meth)acrylate (A).
Examples of such (meth)acrylate compounds include monofunctional (meth)acrylates and derivatives thereof, and bifunctional (meth)acrylates and derivatives thereof.
In addition to these trifunctional or higher (meth)acrylates (A), the (meth)acrylate compound is usually 20 parts by weight or less per 100 parts by weight of the trifunctional or higher (meth)acrylate (A), It is preferably 10 parts by weight or less.

Monofunctional (meth)acrylates and derivatives thereof include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl ( meth)acrylate, n-tridecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethyl (meth)acrylate , ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and its cationizing agents modified, diethylaminoethyl (meth) acrylate and its cationizing agents modified, cyanoethyl (meth) ) Alkoxy polyalkylene glycol (meth) acrylate such as acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, (meth)acrylic acid, 2 -(meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyl propyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, etc. be done.

Bifunctional (meth)acrylates and derivatives thereof include, for example, ethylene glycol di(meth)acrylate, diethylene glycol (meth)diacrylate, butanediol (meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth) acrylates, ethoxylated di(meth)acrylates, propoxylated hexanediol di(meth)acrylates, triethylene glycol di(meth)acrylates, polyethylene glycol di(meth)acrylates, tripropylene glycol di(meth)acrylates, polypropylene glycol di( Bifunctional (meth)acrylate such as meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentylglycol di(meth)acrylate, bifunctional urethane (meth)acrylate, bifunctional epoxy acrylate, bifunctional polyester acrylate and the like.

(Quaternary ammonium base-containing polymer (B))
The quaternary ammonium base-containing polymer (B) is a polymer having one or more quaternary ammonium bases (excluding tri- or higher functional (meth)acrylates (A)).
Examples of the main skeleton polymer constituting the quaternary ammonium group-containing polymer (B) include, for example, a quaternary ammonium group-containing acrylic polymer, a quaternary ammonium group-containing olefin polymer, a quaternary ammonium group-containing ester polymer, a quaternary Cellulose-based polymers containing ammonium bases, styrene-based polymers containing quaternary ammonium bases, copolymers thereof, and the like are included. Among them, a quaternary ammonium base-containing acrylic polymer is preferable.
The quaternary ammonium base-containing polymer (B) may be used alone or in combination of two or more.

The quaternary ammonium group-containing polymer (B) can be obtained, for example, by copolymerizing a monomer having a quaternary ammonium group and an unsaturated group with another compound having an unsaturated group (e.g., monomer, oligomer). .

Monomers having a quaternary ammonium base and an unsaturated group include, for example, (meth)acryloyloxyethyltrimethylammonium chloride, 2-hydroxy-3-(meth)acryloxypropyltrimethylammonium chloride, 2-hydroxy-3-(meth) ) acryloxypropyltriethylammonium bromide, 2-hydroxy-3-(meth)acryloxypropyltributylammonium chloride, 2-hydroxy-3-(meth)acryloxypropylmethylethylbutylammonium chloride, 2-hydroxy-3-(meth) ) acryloxypropyldimethylphenylammonium chloride, 2-hydroxy-3-(meth)acryloxypropyldimethylcyclohexylammonium chloride and the like.

Compounds having other unsaturated groups include cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as hexyl, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate; 2- (meth)acryloyloxyethyl succinic acid; 2-(meth)acryloyloxyethyl hexahydrophthalic acid;

The number average molecular weight of the quaternary ammonium group-containing polymer (B) is determined, for example, by polystyrene standards using gel permeation chromatography (GPC). The number average molecular weight of the quaternary ammonium group-containing polymer (B) is generally in the range of 5,000 to 500,000, preferably 7,000 to 300,000. If the number average molecular weight of the quaternary ammonium group-containing polymer (B) is below the lower limit of the numerical range, bleeding to the surface of the coating layer is likely to occur. If the number average molecular weight of the quaternary ammonium group-containing polymer (B) exceeds the upper limit of the numerical range, the compatibility in the present coating agent composition may decrease.

The quaternary ammonium group-containing polymer (B) can be produced, for example, by polymerizing a monomer component containing a quaternary ammonium group and a monomer having an unsaturated group. The monomer component may further contain a compound having another unsaturated group, a polymerization initiator, and the like, if necessary.

(Compound (C))
Compound (C) has a fluorine atom-containing structure and a cyclic siloxane structure. A fluorine atom-containing structure is a chemical structure (group) having at least one fluorine atom. A cyclic siloxane structure is a cyclic structure having a siloxane bond as a main skeleton.
The structure of compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure is not particularly limited. Examples thereof include compounds represented by the following formula (1).
(R ^f RSiO) ( ^RA R ¹ SiO) _n Formula (1)

In formula (1), R ^f is an organic group containing a fluorine atom; R ¹ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group; R ^A contains a (meth)acryl group is an organic group; n is an integer of 2 or more.

R ^f is an organic group containing a fluorine atom. R ^f is preferably a perfluoroalkylene group optionally having oxygen atoms between carbon atoms, and C _x F _2x+1 (CH ₂ ) _p — (x is an integer of 1 to 8, p is an integer of 2 to 10 and perfluoropolyether-substituted alkyl groups are more preferred.

Examples of R ^f include the following groups.
CF ₃ C ₂ H ₄ -
_{C4F9C2H4- _ _ _
C4F9C3H6- _ _ _
C8F17C2H4- _ _ _
C8F17C3H6- _ _ _
C3F7C ( CF3 ) 2C3H6- _
C3F7OC ( CF3 ) FCF2OCF2CF2C3H6- _ _ _
C3F7OC} ( _CF3 ) _{FCF2OC ( CF3 ) FC3H6-}
CF ₃ CF ₂ CF ₂ OC(CF ₃ )FCF ₂ OC(CF ₃ )FCONHC ₃ H ₆ —

^RA is an organic group containing a (meth)acrylic group. Examples include the following groups.
_CH2 =CHCOO-
_CH2 =C( _CH3 )COO-
_{CH2 = CHCOOC3H6-
CH2 =} C( _CH3 ) _{COOC3H6-
CH2 = CHCOOC2H4O-
CH2} =C _{( CH3} ) _COOC2H4O-

As R 2 ^A , the bond to the Si atom is more preferably a Si—O—C bond for ease of industrial synthesis.

Compounds (C) having a fluorine atom-containing structure and a cyclic siloxane structure also include compounds represented by the following formula (2).

In formula (2), R ² and R ³ are each independently an optionally substituted organic group having 1 to 12 carbon atoms; m is an integer of 3 to 10;

In formula (2), m is preferably an integer of 3 to 6, particularly preferably 3 or 4.

Examples of organic groups for R ² and R ³ include chain alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and t-butyl group; Alkoxy groups such as ethoxy group; Cyclic alkyl groups such as cyclohexyl group and norbornanyl group; Alkenyl groups such as vinyl group, 1-propenyl group, allyl group, butenyl group and 1,3-butadienyl group; Ethynyl group, propynyl group, butynyl group alkynyl group such as group; halogenated alkyl group such as trifluoromethyl group; alkyl group having saturated heterocyclic group such as 3-pyrrolidinopropyl group; aryl group such as phenyl group optionally having alkyl substituent an aralkyl group such as a phenylmethyl group and a phenylethyl group; and the like.

The organic group for R ² and R ³ may have an oxygen atom between carbon atoms, or may have an amide bond between carbon atoms. Also, the organic groups for R ² and R ³ may be perfluoro organic groups in which all hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms.
When imparting water repellency to the coating layer, at least part of R ² and R ³ is preferably a perfluoro organic group which may have an oxygen atom between carbon atoms, and has an oxygen atom between carbon atoms. perfluoroalkylene group is more preferred.

Examples of substituents that the organic group in R ² and R ³ may have include a hydroxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a (meth)acryloyl group, and the like. Among them, a hydroxy group, a halogen atom, and a (meth)acryloyl group are preferred.

Compound (C) may be a reactive siloxane compound or a non-reactive siloxane compound.
A reactive siloxane compound is a compound having a reactive functional group and a siloxane bond. Examples of reactive functional groups include amino groups, epoxy groups, carboxyl groups, carbinol groups, (meth)acryl groups, mercapto groups, and phenol groups.
A non-reactive siloxane compound is a compound that does not have a reactive functional group and has a siloxane bond. For example, polyether-modified siloxane compounds, methylstyryl-modified siloxane compounds, alkyl-modified siloxane compounds, higher fatty acid ester-modified siloxane compounds, hydrophilic special modified siloxane compounds, higher alkoxy-modified siloxane compounds, and fluorine-modified siloxane compounds. etc.

As a method for synthesizing the compound (C), for example, a method of addition reaction of allyl (meth)acrylate or the like to a siloxane compound having an organic group containing 3 or more fluorine atoms and 3 or more Si—H groups; A method of dehydrogenating a siloxane compound having an organic group containing 3 or more atoms, a siloxane compound having 3 or more Si—H groups, and a (meth)acrylic compound having an OH group such as hydroxyethyl acrylate.
Among these methods, the addition reaction is preferred. (Meth)acryl groups may also undergo addition reactions, but by using a catalyst such as an amine in the dehydrogenation reaction, the reaction proceeds while retaining the (meth)acryl groups, making it easier to obtain the desired compound. Because it can be obtained.

(composition)
The content of (meth)acrylate (A) is preferably 50 to 99% by weight, more preferably 60 to 97% by weight, based on 100 parts by weight of the solid content of the coating agent composition. If the content of (meth)acrylate (A) is too small, the scratch resistance of the coating layer may deteriorate. If the content of (meth)acrylate (A) is too high, the concentration of the quaternary ammonium base-containing polymer (B) will decrease, making it difficult to improve antistatic properties.

The content of the quaternary ammonium group-containing polymer (B) is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on 100 parts by weight of (meth)acrylate (A). If the content of the quaternary ammonium base-containing polymer (B) is too small, it is difficult to obtain the antistatic effect of the quaternary ammonium base-containing polymer. If the content of the quaternary ammonium base-containing polymer (B) is too high, the transparency of the coating layer may deteriorate.

The content of compound (C) is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on 100 parts by weight of (meth)acrylate (A). If the content of the compound (C) is too small, it is difficult to obtain the antifouling effect of the compound (C). If the content of the compound (C) is too high, the transparency of the coating layer may be lowered, or the antistatic property may not be exhibited.

(Photoinitiator (D))
The present coating agent composition can usually be cured by gamma rays, electron beams, active energy rays such as ultraviolet rays, and heat. When cured with UV light, the coating composition preferably further contains a photopolymerization initiator.
The photopolymerization initiator (D) is not particularly limited, and various photopolymerization initiators can be used. Examples thereof include benzophenone-based initiators, diketone-based initiators, acetophenone-based initiators, benzoin-based initiators, thioxanthone-based initiators, and quinone-based initiators.
The amount (D) of the photopolymerization initiator used is usually in the range of 0.1 to 20% by weight with respect to 100 parts by weight of the solid content of the coating agent composition, but is not particularly limited.

(Solvent (E))
The present coating agent composition may further contain a solvent as required at the time of use. For example, it is possible to appropriately contain a solvent so that the coating layer obtained after curing has a desired thickness.

Examples of solvents include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene; aliphatic hydrocarbons such as n-hexane and n-heptane; dibutyl ether, dimethoxymethane, dimethoxyethane and diethoxyethane. Ethers such as , propylene oxide, dioxane, dioxolane, trioxane, tetrahydrofuran, anisole, and phenetole; , methylcyclohexanone and other ketones; ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, γ-butyrolactone and other esters; methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate, glycol ethers such as propylene glycol monomethyl ether; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and ethylene glycol; and acetonitrile. These solvents may be used individually by 1 type, and may use 2 or more types together.

The content of the solvent is not particularly limited. For example, it can be in the range of 1 to 10,000 parts by weight, preferably 20 to 5,000 parts by weight, and more preferably 40 to 1,000 parts by weight, per 100 parts by weight of the solid content of the coating agent composition.

If necessary, the coating agent composition may contain silicone-based, fluorine-based, or acrylic-based leveling agents, polymerizable monomers having an amide bond such as N-vinylformamide, and the like, within the scope of the present invention. may be added. In addition to these examples, other additives such as antioxidants, organic pigments, organic particles, inorganic particles, flame retardants, dispersants, thixotropic agents (thickeners), antifoaming agents, etc. You may let

For example, an organic peroxide may be added to the present coating composition when curing with heat. Examples of organic peroxides include ketone peroxides, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates and peroxyesters.
The amount of the organic peroxide to be used is usually in the range of 0.1 to 20% by weight per 100 parts by weight of the solid content of the coating agent composition.

The coating agent composition can be used, for example, to prevent scratching (scratches) and contamination of plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials used as building interior materials, wall materials, artificial marble, etc. It can also be used as a protective coating.

<Goods>
The article of the present invention has a base material and a coating layer provided on at least a part of the surface of the base material, and the coating layer is a cured product of the coating agent composition. Therefore, excellent antifouling properties and antistatic properties are exhibited on the surface of the substrate.
The base material is not particularly limited. Examples thereof include resin films and resin substrates such as polycarbonate-based resins, polyester-based resins, acrylic-based resins, triacetylcellulose resins, polyolefin-based resins, polyimide-based resins, polyurethane-based resins, and norbornene-based resins. In addition, metal, wood, paper, glass, slate, etc. may be used as the base material.

Moreover, you may have an easy-adhesion layer on the surface of a base material. The easy-adhesion layer is preferably provided on one surface of the substrate on which the above-described coating layer is provided, and the above-described coating layer is preferably formed on the surface of the easy-adhesion layer. By providing the easy-adhesion layer, it becomes easier to adhere the coating layer to the substrate. The easy-adhesion layer is formed from an easy-adhesion layer composition containing a binder resin and a cross-linking agent.

The coating layer should just be provided in at least one part of the base material. That is, the coating layer may be provided on a part of the surface of the substrate, or may be provided on the entire surface of the substrate.

The present coating agent composition is usually applied to the surface of a substrate using a known coating apparatus to form a coating film, then dried by removing the solvent, and cured by irradiation with an active energy ray. Therefore, it is used for the purpose of forming an antistatic hard coat layer.
A coating device is not particularly limited. For example, micro gravure coater, gravure coater, Meyer bar coater, die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, curtain coater, calendar coater, extrusion Conventionally known coating devices such as coaters and spray coating can be used.
The drying conditions are not particularly limited, and may be performed at around room temperature or by heating, for example, about 25 to 120°C, preferably 50 to 100°C, more preferably 60 to 90°C. The drying time is not particularly limited as long as the solvent can be sufficiently volatilized, and is, for example, about 10 seconds to 30 minutes, preferably about 15 seconds to 10 minutes.

(thickness)
The thickness of the coating layer is, for example, 1 to 20 μm, preferably 1 to 15 μm, more preferably 2 to 10 μm, particularly preferably 3 to 8 μm. When the thickness of the cured resin layer is at least these lower limit values, the substrate can be appropriately protected by the cured resin layer, and antistatic properties and the like are likely to be satisfactorily exhibited. Further, when the thickness of the cured resin layer is set to the upper limit value or less, it is possible to prevent curling and heat wrinkles in a laminate structure having a cured resin layer, such as a laminated film, and to ensure good flatness.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following description, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

<Raw materials used>
((A) component)
A-1: "Shikou UV-1700B" manufactured by Mitsubishi Chemical Corporation (weight average molecular weight 2000, number of functional groups 10)

A-2: "Shikou UV-7610B" manufactured by Mitsubishi Chemical Corporation (weight average molecular weight 11000, number of functional groups 9)

A-3: "Aronix M403" (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. was used.

A-4: "Viscoat #300" (mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate) manufactured by Osaka Organic Industry Co., Ltd. was used.

((B) component)
B-1: A quaternary ammonium base-containing polymer solution (B-1) synthesized as follows was used.
First, 83.2 parts of polycaprolactone monool (weight average molecular weight: 2,000), m-isopropenyl-α, α were added to a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet. 16.7 parts of ′-dimethylbenzyl isocyanate and 0.03 parts of dioctyltin laurate were charged and reacted at 80°C. b-1) was obtained.
Thermometer, stirrer, water-cooled condenser, a four-necked flask equipped with a nitrogen gas inlet, 10 parts of polyester macromonomer (b-1), 15 parts of methacryloyloxyethyltrimethylammonium chloride, 5 parts of cyclohexyl methacrylate, azobisiso 0.2 parts of butyronitrile, 20 parts of methyl ethyl ketone and 50 parts of isopropyl alcohol were charged and polymerized at 70° C. for 8 hours under a nitrogen stream to obtain a quaternary ammonium group-containing polymer solution (B-1).

B-2: A quaternary ammonium base-containing polymer solution (B-2) synthesized as follows was used.
First, 9 parts of SLMA (mixture of dodecyl methacrylate and tridecyl methacrylate), 18 parts of methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl were added to a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet. 3 parts of methacrylate, 0.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile), 20 parts of methyl ethyl ketone and 50 parts of isopropyl alcohol were charged, polymerized at 65° C. for 3 hours under a stream of nitrogen, and after 3 hours 0.2 part of 2,2′-azobis(2,4-dimethylvaleronitrile) was added and polymerized for 3 hours to obtain a quaternary ammonium group-containing polymer solution (B-2).

((C) component)
C-1: Synthesis of compound (C-1)

69.4 parts by mass (0.1 mol) of the compound represented by the above formula (3), 36.5 parts by mass (0.315 mol) of 2-hydroxyethyl acrylate, and 111.9 parts by mass of toluene were mixed in a reactor. When the mixture became uniform, 1.12 parts by mass (0.0126 mol) of N,N-diethylhydroxylamine was added as a catalyst. After that, the mixture was reacted at 70° C. for 8 hours. After washing with water, toluene and the like were distilled off to obtain the following compound (C-1) having a fluorine atom-containing structure and a cyclic siloxane structure.

C'-2: A commercially available product "DAC-HP" from Daikin Industries, Ltd. was used.

C'-3: DIC's commercial product "RS76E" was used.

((D) component: photopolymerization initiator)
D-1: "Omnirad-127" (trade name) manufactured by IGM Resin
D-2: "Omnirad-2959" (trade name) manufactured by IGM Resin
D-3: "Omnirad-184" (trade name) manufactured by IGM Resin

((E) component: solvent)
MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone PGM: propylene glycol monomethyl ether IPA: isopropyl alcohol

<Examples 1 to 9, Comparative Examples 1 to 4>
Each component was blended according to the composition shown in Table 1 to prepare a coating agent composition for each example. In Table 1, the parts of (D): photopolymerization initiator and (E): solvent are based on 100 parts by weight of (meth)acrylate (A).

Then, using a bar coater, the coating composition of each example was applied to a polyester film (manufactured by Mitsubishi Chemical Corporation, "Diafoil", thickness 125 μm) that had been treated for easy adhesion, and then dried in a dryer at 80° C. for 1 minute. Heat was applied to dry the coating. Thereafter, using a high-pressure mercury lamp, ultraviolet rays were irradiated at an illuminance of 150 mW/cm ² and an integrated light amount of 500 mJ/cm ² to form a coating layer on the surface of the polyester film.

<Evaluation method>
(Antistatic property)
After adjusting the state by leaving the polyester film provided with the coating layer in a constant temperature and humidity room at 23 ° C. and a humidity of 50% RH for 24 hours, in the constant temperature and humidity room under the same conditions, a high resistance resistivity meter (Mitsubishi Chemical A voltage of 100 V was applied using Analyticc's "Hiresta-UP MCP-HT450"), and the surface resistance value (Ω/□) was measured.

(Anti-fouling)
On the surface of the coating layer, draw a line with an oil-based ink marker ("Mackey Care Extra Fine (black)" manufactured by Zebra), and after 10 seconds, wipe the surface with tissue paper (manufactured by Crecia). evaluated.
◯: The ink can be wiped off without remaining on the coating layer.
Δ: The ink can be partially wiped off, but a portion remains on the coating layer.
x: The ink cannot be wiped off and remains on the coating layer.

(water contact angle)
After adjusting the state by leaving the laminate with the coating layer formed on the PET film in a constant temperature room at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours, a contact angle meter ("DropMaster DM500" manufactured by Kyowa Interface Science Co., Ltd. ), 0.002 mL of pure water is dropped on the coating layer, and after 2 seconds, a contact angle meter (“DropMaster 500” manufactured by Kyowa Interface Science Co., Ltd.) is used to measure the contact angle (°) against water. measured respectively. Generally, a water contact angle of 90° or more is considered to be water repellent, but a water contact angle of 100° or more is sometimes required for display applications.

As shown in Table 2, the coating layers obtained in Examples 1 to 9 exhibited excellent antistatic properties and excellent antifouling properties.
On the other hand, the coating layers obtained in Comparative Examples 1 to 3 exhibited antifouling properties, but the surface resistance values were above the upper limit of measurement and the antistatic properties were lowered.
The coating layer obtained in Comparative Example 4 exhibited antistatic properties, but was insufficient in antifouling properties.

According to the coating agent composition of the present invention, a coating layer having excellent antifouling properties and antistatic properties can be obtained.
The article of the present invention has a coating layer with excellent antifouling and antistatic properties.

Claims (6)

A coating composition comprising a (meth)acrylate (A) having a functionality of 3 or more, a quaternary ammonium group-containing polymer (B), and a compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure. 2. The coating composition according to claim 1, wherein the tri- or higher functional (meth)acrylate (A) is a tri- or higher functional urethane (meth)acrylate. The coating agent composition according to claim 1 or 2, wherein the quaternary ammonium group-containing polymer (B) is a quaternary ammonium group-containing acrylic polymer. The coating agent composition according to any one of claims 1 to 3, wherein the compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure further has a (meth)acryloyl group. The coating according to any one of claims 1 to 4, wherein the compound (C) having a fluorine atom-containing structure and a cyclic siloxane structure further has a perfluoroalkylene group which may have an oxygen atom between carbon atoms. agent composition. Having a base material and a coating layer provided on at least a part of the surface of the base material,
An article, wherein the coating layer is a cured product of the coating agent composition according to any one of claims 1 to 5.