JP2000290535A - Active energy ray-curable coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable coating composition which provides a coating excellent in abrasion resistance and excellent in stain resistance and transparency. SOLUTION: A polymer (A) having an organopolysiloxane unit bonded to a main chain via a (meth) acryloyl group and a nitrogen atom, a compound (B) having an alkoxysilyl group, and a polyfunctional (meth) acrylate compound ( C) wherein the content of the polymer (A) is 1 to 40% by weight and the content of the compound (B) is 1 to 4 in the composition.
An active energy ray-curable coating composition having 0% by weight and a compound (C) content of 40 to 98% by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray curable composition which is cured by irradiating it with an active energy ray to form a film having excellent stain resistance, transparency and abrasion resistance, and also excellent antistatic properties. It relates to a coating composition.

[0002]

2. Description of the Related Art Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, vinyl chloride resin, ABS resin, cellulose acetate, etc.
Because of its excellent workability and impact resistance, it is used for various applications such as containers, instrument panels, packaging materials, and housings. However, these plastic products are easily scratched due to their low surface hardness, and transparent resins such as polycarbonate have the drawback that the original transparency and appearance of the resin are significantly impaired depending on the conditions of use, and therefore abrasion resistance. May be restricted for use in fields that require

Therefore, an active energy ray-curable hard coat material (coating material) for imparting abrasion resistance to the surface of these plastic products has been provided. However,
A cured layer of a commercially available active energy ray-curable hard coat material has a high surface resistivity and is apt to generate static electricity. Therefore, there is a problem that the amount of dust and the like attached to the product is large, and the appearance and transparency of the product are easily impaired. Also,
When such a plastic product is used for household goods or electric appliances, it often becomes stained with sweat, fingerprints, cosmetics, ink, or the like due to contact with people or the surrounding environment.

[0004] In order to prevent such contamination, attempts have been made to impart stain resistance and antistatic properties to the coating material applied to the surface of a plastic product. For example, JP-A-10-279833 describes that a film having good performance is formed by a composition having a specific structural unit. However, there is a problem that it is not easy to remove the contaminants when the above-mentioned contaminants adhere to the coating, and application to household goods and the like has never been easy.

[0005] On the other hand, various methods for improving stain resistance by using a surface treating agent have been proposed, for example, Japanese Patent Application Laid-Open No. 6-184527.
JP-A-6-256756 discloses a treating agent comprising a fluoroalkylsilane compound, a long-chain aliphatic silane compound and a silicon isocyanate compound.
A treating agent comprising a fluoroalkylsilane compound and a methylpolysiloxane compound having a Si-H group is described, respectively. Various surface treatment agents including these,
Depending on the type of dirt, it has a reasonable effect, but it is not sufficient.In addition, if it is wiped strongly to remove the adhered dirt or washed with water or a solvent, the treating agent is gradually removed and the effect is reduced. Sustainability was inadequate.

In order to improve the durability, it has been attempted to use a copolymer obtained by copolymerizing a specific polymerizable fluorine-containing compound or silicon-containing compound with another polymerizable compound as a treating agent. For example, Japanese Patent Application Laid-Open No. 10-219
No. 061 describes that an aqueous resin composition containing a resin using a fluorine-containing unsaturated compound as a main component has high stain resistance and durability.
No. 0-7986 discloses that an active energy ray-curable hard coat agent film is overcoated with a copolymer containing a polydimethylsiloxane having a (meth) acrylic group and a polymerizable silane coupling agent copolymerizable therewith. In this case, it is described that high fingerprint stain resistance (adhesion, wiping) and durability can be realized.

In addition, Japanese Patent Laid-Open Publication No.
No. 0-7940 describes a film based on an aqueous coating agent containing colloidal silica and a tetramethoxysilane oligomer, and various kinds of stain-resistant coating agents containing silica or silicate have been proposed. For organic dirt, for example, Japanese Patent Application Laid-Open No. 9-2
No. 68280, a coating obtained by overcoating a tetraalkoxytitanium solution and converting the surface layer to a titanium oxide layer on an undercoating layer based on silica and a fluororesin, which has antibacterial properties and a cigarette stain. In addition to being described as having excellent decomposability of organic stains, various antifouling coating agents using titanium oxide having a photocatalytic action have been proposed. However, these various stain resistance improvers are difficult to achieve compatibility with surface hardness and antistatic performance, have insufficient sustainability, or have no effect depending on the type of stain. There was a problem.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and maintains high abrasion resistance (high hardness) and transparency (excellent appearance) while maintaining a high level of resistance to a wide variety of stains. It is an object of the present invention to provide an active energy ray-curable coating composition that can impart stain resistance (anti-adhesion property and removability) and provide a film having excellent durability.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a composition having a specific composition containing a specific polymer can solve the above-mentioned problems. Heading, the present invention has been completed. That is, the gist of the present invention is to provide a polymer (A) having an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group”) and an organopolysiloxane unit bonded to the main chain via a nitrogen atom, A compound (B) having a group,
And a polyfunctional acrylate or methacrylate (hereinafter referred to as “(meth) acrylate”) compound (C), wherein the content of the polymer (A) in the composition is 1 to 40% by weight, An active energy ray-curable coating composition wherein the content of (B) is 1 to 40% by weight and the content of compound (C) is 40 to 98% by weight.

Another subject of the present invention is that the polymer (A)
Has a structure in which an organopolysiloxane compound having an amino group is added to a (meth) acryloyl group, the polymer (A) has a quaternary ammonium base, or the polymer (A) is not via a nitrogen atom. In the above composition having an organopolysiloxane unit bonded to the main chain. Another gist of the present invention is that the compound (B) having an alkoxysilyl group contains a tetraalkoxysilane or a silicate oligomer that is a condensate thereof, and a tetraalkoxytitanium or a titanate oligomer that is a condensate thereof. The above-mentioned composition containing a tetraalkoxy zirconium or a zirconate oligomer which is a condensate thereof, and the compound (B) having an alkoxysilyl group, in addition to the tetraalkoxysilane or the silicate oligomer, 0.01 to 10 parts by weight of tetraalkoxytitanium or titanate oligomer per 100 parts by weight of compound
0 parts by weight, and 0 to 50 parts by weight of a tetraalkoxy zirconium or zirconate oligomer, respectively. The oligomer is a fluorine-containing alkoxysilane or a fluorine-containing silicate oligomer, or the tetraalkoxysilane or the silicate oligomer is modified with an alcohol having an alkyl group having 10 or more carbon atoms, the alcohol-modified alkoxysilane or the alcohol-modified silicate oligomer. In the composition.

Another gist of the present invention is the above (A) to
In addition to (C), 0 to 35% by weight of another polymerizable monomer (D) and 0 to 30% by weight of another acrylic polymer (E)
(However, the total of (A) to (E) is 100% by weight)
And 0.1 to 10% by weight based on the total amount of (A) to (E) of the photopolymerization initiator (F). The gist lies in a material, a film, a sheet, or a resin plate having a cured coating formed by applying an active energy ray-curable coating composition and irradiating the active energy ray.

[0012]

Embodiments of the present invention will be described below in detail. First, each component constituting the active energy ray-curable coating composition of the present invention will be described, and then preparation and application of the composition will be described. (1) Mainly through a (meth) acryloyl group and a nitrogen atom
Polymerization with organopolysiloxane units attached to the chain
Body (A) The polymer (A) constituting the active energy ray-curable coating composition of the present invention imparts stain resistance and, if necessary, antistatic property to the formed film, and comprises (meth) It has an organopolysiloxane unit bonded to the main chain through an acryloyl group and a nitrogen atom. As long as the polymer (A) used in the present invention has a (meth) acryloyl group and an organopolysiloxane unit bonded to the main chain via a nitrogen atom, particularly the structure, the number and the bonding position of each functional group, The molecular weight, viscosity and the like are not limited. In the present specification, "bonded to the main chain through a nitrogen atom" means that at least one nitrogen atom is present in a molecular chain connecting the organopolysiloxane unit and the polymer main chain. Further, the polymer (A) used in the present invention may have a quaternary ammonium base unit and / or an organopolysiloxane unit bonded to the main chain without through a nitrogen atom,
Further, an organopolysiloxane compound having an amino group may have a structure added to a (meth) acryloyl group.

Although the method for producing the polymer (A) of the present invention is not particularly limited, it is preferable to produce it according to the following (Step 1) to (Step 3). (Step 1) A compound (a1) having one radically polymerizable group and a hydroxyl group in one molecule, and optionally another acrylic acid or methacrylic acid copolymerizable therewith (hereinafter referred to as “(meth) acrylic acid”). An acid) is polymerized with an ester monomer (a2) to synthesize a polymer having a hydroxyl group. (Step 2) A compound (a3) having a (meth) acryloyl group and an isocyanate group is added to the copolymer to synthesize a polymer (a4) having a (meth) acryloyl group. (Step 3) The organopolysiloxane compound (a5) having an amino group is added to the (meth) acryloyl group of the polymer (a4).

When a quaternary ammonium base is introduced into the polymer (A), a tertiary amine compound (a6) having one radical polymerizable group in one molecule is added in (Step 1). (Step 2) to synthesize a polymer having a tertiary amine and a (meth) acryloyl group, and reacting the tertiary amine with a quaternizing agent. 3) may be performed. This quaternization process
It may be performed after (Step 3).

When introducing an organopolysiloxane unit which binds to the main chain without using a nitrogen atom, in step (1), one radical polymerizable group per molecule or two radical polymerizable groups per molecule is used. The above-mentioned organopolysiloxane compound having a mercapto group may be copolymerized, and then (Step 2) and (Step 3) may be performed. Examples of the compound (a1) having one radical polymerizable group and a hydroxyl group in one molecule used in (Step 1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, -Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid and the like can be mentioned.

In the polymerization of the above (a1), a (meth) acrylate monomer (a2) is additionally used,
It is preferable that the polymer (A) is a copolymer.
Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate,
n-butyl (meth) acrylate, isobutyl (meth)
Acrylate, t-butyl (meth) acrylate, phenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylate such as stearyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acryl Polymerizable silanes such as methyl, methyldimethoxysilyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) And acrylates and polymerizable fluoroalkyl esters such as 2- (perfluorooctyl) ethyl (meth) acrylate.

In the polymerization of (Step 1), a compound having one radical polymerizable group and one hydroxyl group in one molecule when copolymerizing with the (meth) acrylate monomer (a2) in combination The amount of (a1) used is preferably 1% by weight or more, and more preferably 5% by weight or more of the total amount of the monomers.
If this amount is less than 1% by weight, the amount of (meth) acryloyl groups and polysiloxane units introduced in the subsequent steps will be small, and the stain resistance tends to be reduced.

The polymerization of (Step 1) is generally carried out in a solvent using a radical polymerization initiator. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; ethyl acetate,
Esters such as propyl acetate and butyl acetate; acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether;
Examples include ether esters such as -methoxyethyl acetate, 2-ethoxyethyl acetate, and 2-butoxyethyl acetate, and these may be used in combination.

Examples of the radical polymerization initiator used in the polymerization reaction include organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide and cumene hydroperoxide; 2,2'-azobisisobutyronitrile;2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,
An azo compound such as 4-dimethylvaleronitrile) is preferably used. The monomer concentration in the polymerization solution is usually 10 to 60% by weight. The polymerization initiator is used usually in an amount of 0.1 to 10% by weight, preferably 0.3 to 2% by weight, based on the monomer mixture.

Next, in (Step 2), a compound (a3) having a (meth) acryloyl group and an isocyanate group is added to the polymer synthesized in (Step 1) to obtain a polymer having a (meth) acryloyl group. (A4) is synthesized. The structure of the compound (a3) used in (Step 2) is not particularly limited as long as it has a (meth) acryloyl group and an isocyanate group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Having a hydroxyl group such as acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate An adduct of (meth) acrylic acid ester and an isocyanate compound such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and the like in a molar ratio of 1: 1 can be mentioned. As the compound (a3), a compound having an acryloyl group is preferable because of high polymerization reactivity.

The polymer synthesized in (Step 1) and the compound (a)
3) is used in a ratio of -OH group / -NCO group ≥1, preferably 1 to 10. The reaction is performed at 60 to 110 ° C for 1 to 20
It is preferable to carry out by stirring for a time. In the reaction of (Step 2), it is preferable to use a polymerization inhibitor such as, for example, hydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butylcatechol, and phenothiazine in order to prevent polymerization of the (meth) acryloyl group. . The polymerization inhibitor is used in an amount of 0.01 to 1% by weight, preferably 0.05 to 0.
5% by weight. In order to accelerate the reaction, a catalyst such as dibutyltin dilaurate or 1,4-diazabicyclo [2.2.2] octane may be used.

In (Step 3), an organopolysiloxane compound (a5) having an amino group in the (meth) acryloyl group of the polymer (a4) obtained in (Step 2) is added. The structure of the organopolysiloxane compound having an amino group is not particularly limited as long as the compound has at least one organopolysiloxane unit and at least one amino group. The amino group may be bonded to a terminal or a side chain of the organopolysiloxane structure. The organopolysiloxane unit contained in the compound preferably has a structure represented by the following general formula (1).

[0023]

Embedded image

In the formula, R ¹ and R ² are a methyl group or a phenyl group, which may be the same or different. n represents an integer of 5 or more. Preferred organopolysiloxane compounds include polyalkyl (C ₁ -C ₆ ) aminodialkylsiloxanes having an amine equivalent of 500 to 20,000. In the reaction of Michael addition of the organopolysiloxane compound having an amino group to the (meth) acryloyl group of the polymer (a4), (meth) acryloyl group / amino group> 1, preferably 10 to 1000 are mixed. The reaction is preferably stirred at 60-110 ° C for 1-20 hours. By this reaction, the polymer (a4)
A structure is formed in which an organopolysiloxane compound having an amino group is added to a part of the (meth) acryloyl group.

The presence of a quaternary ammonium base in the polymer (A) is preferred because the surface resistance of the resulting film is reduced and antistatic properties are obtained. As described above, when a quaternary ammonium base is introduced into the polymer (A),
In step (1), a tertiary amine compound (a6) having one radical polymerizable group in one molecule is copolymerized. Examples of the tertiary amine compound having one radical polymerizable group in one molecule which can be used here include the following general formula (2)
Is a compound having a structure represented by

[0026]

Embedded image

(Wherein, R ³ is H or CH ₃ , R ⁴ and R ⁵ are H or C 1 having 1 or more carbon atoms which may have a substituent)
An alkyl group of 1 to 9, k represents an integer of 1 to 6)

As the compound (a6) represented by the above general formula, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) )
Acrylate, N, N-dimethylaminobutyl (meth)
Acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate and the like can be mentioned.

In this case, the amount of the tertiary amine compound (a6) should be 20 to 95% by weight, preferably 45 to 90% by weight in the polymerizable monomer when importance is placed on the antistatic performance. Is good. If the content is less than 20% by weight, the antistatic performance, which is the purpose of introducing this compound, cannot be sufficiently obtained. Examples of the quaternizing agent for quaternizing the polymer containing the tertiary amine include alkyl chlorides such as methyl chloride and butyl chloride; halides such as methyl bromide, methylbenzyl chloride and benzyl chloride; dimethyl sulfate; Alkyl sulfates such as diethyl sulfate and dipropyl sulfate; and sulfonic acid esters such as methyl p-toluenesulfonate and methyl benzenesulfonate.

The reaction for converting the tertiary amine portion of the polymer (a4) into a quaternary ammonium salt with a quaternizing agent is carried out by mixing an equivalent amount of the tertiary amine and the quaternizing agent, at 20 to 80 ° C. for 1 to 20 hours. It is preferable to carry out by stirring. In carrying out the quaternization reaction, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and the like; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and the like in order to increase the hydrophilicity of the solvent. It is preferable to add ethers; water; or a mixture thereof.

An organopolysiloxane having one radically polymerizable group in one molecule, which is used when introducing an organopolysiloxane unit which binds to the main chain without using a nitrogen atom in the polymer (A). The siloxane compound preferably has an organopolysiloxane unit represented by the above general formula (1), and the radical polymerizable group includes acryl, methacryl, styryl, cinnamate, vinyl, allyl and the like. It is preferred to have the group Further, when a compound (a2) having one radical polymerizable group and a hydroxyl group in one molecule is polymerized, two mercapto groups in one molecule which can be introduced into the polymer via a sulfide bond by chain transfer. Organopolysiloxane compounds having a group can also be suitably used.

(2) Compound having an alkoxysilyl group
(B) The compound (B) having an alkoxysilyl group used in the present invention includes a silane compound having an alkoxy group,
Preferably, tetraalkoxysilane and a silicate oligomer which is a condensate thereof are included. Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, dimethoxydiethoxysilane, and modified tetraalkoxy in which these are modified with a monofunctional alcohol to control compatibility and reactivity. Silane can be mentioned. As the silicate oligomer, silicate oligomers obtained by condensing these tetraalkoxysilanes can be suitably used. Further, modified silicate oligomers obtained by modifying these silicate oligomers with a monofunctional alcohol can also be used.

Examples of the monofunctional alcohol include aliphatic alcohols, fluorinated aliphatic alcohols, and fluorinated surfactants containing one hydroxyl group per molecule. Examples of the catalyst to be added at the time of modification include various transesterification catalysts, for example, boric acid derivatives such as boron tributoxide, tin carboxylate such as dibutyltin dilaurate, and metals such as aluminum triacetylacetonate. Examples thereof include complex salts, titanates such as tetraisopropoxytitanium and tetrabutoxytitanium, zirconates such as zirconium tetrabutoxide, and alkoxides such as barium and calcium.

As the aliphatic alcohol, one having 1 carbon atom
Long-chain aliphatic alcohols having an alkyl group such as 0 to 30 (e.g., lauryl alcohol, stearyl alcohol, etc.) are preferred because the initial stain resistance of the finally obtained coating is improved. Further, a fluorinated aliphatic alcohol (eg, trifluoroethanol, perfluorooctylethanol, perfluorodecylethanol, etc.) or a fluorinated surfactant containing one or more hydroxyl groups per molecule (eg, perfluoroalkylcarboxylic acid) Or an alkylene oxide adduct of perfluorosulfonic acid) is preferable because the reactivity is improved and the initial stain resistance of the coating is also improved.

In the case of carrying out the modification, for example, 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight of a monofunctional alkyl alcohol and a catalyst are added per 100 parts by weight of tetraalkoxysilane, and By stirring at 100 ° C. for 1 hour or more, and then aging at room temperature for 1 day or more, a modified product having good performance can be obtained. It is preferable to use a polyfunctional alkoxide having high reaction activity in combination with the compound (B) having an alkoxysilyl group, since the appearance and stain resistance of the coating are further improved.

Examples of the polyfunctional alkoxides having high reaction activity that can be used include titanium compounds such as tetraalkoxytitanium or titanate oligomer which is a condensate containing tetraalkoxytitanium as a main component and tetraalkoxyzirconium or a condensation product thereof. And zirconium compounds such as zirconate oligomers. Specific examples of the tetraalkoxytitanium include tetrabutoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, tetramethoxytitanium, and condensates thereof (for example, tetrabutoxytitanium tetramer). The same applies to tetraalkoxy zirconium.

When the above-mentioned titanium compound or zirconium compound is used in addition to the above-mentioned compound having an alkoxysilyl group, tetraalkoxysilane or silicate oligomer, the mixing ratio of the titanium compound or the zirconium compound is 100 parts by weight of the above-mentioned silane compound. From 0.01 to 100
It is preferable to use 0 to 50 parts by weight, preferably 0.1 to 20 parts by weight of the zirconium compound, preferably 0.1 to 50 parts by weight. The amount of these compounds used is
If the amount is less than the above range, an effect such as improvement in activity by using these is hardly obtained, while if the amount exceeds the above range, voids (holes) are formed in the cured film to be formed, or the coating film is not coated. In addition to coating defects due to cissing, the ester bond in the polymer component is liable to be decomposed, resulting in deterioration of abrasion resistance.

It should be noted that 2 to 10 moles of β are used per mole of tetraalkoxytitanium and tetraalkoxyzirconium.
-Addition of diketones (such as acetylacetone) or β-ketoesters (such as ethyl acetoacetate) further increases the reaction activity of tetraalkoxysilane or silicate oligomer, and at the same time decomposes other components (particularly polyfunctional acrylates). Undesired side reactions can be suppressed. Further, 0.1 to 0.1 mol per mole of tetraalkoxytitanium and tetraalkoxyzirconium
When 5 moles of amines (such as secondary amines such as diethanolamine and tertiary amines such as triethanolamine) are added together, excessive reaction of tetraalkoxysilane or silicate oligomer is suppressed, and at the same time, decomposition of other components is prevented. It is also possible to suppress undesired side reactions.

(3) Polyfunctional (meth) acrylate compound
(C) Polyfunctional (meth) acrylate compound (C) that can be used in the active energy ray-curable coating composition of the present invention.
Is a compound having three or more (meth) acryloyl groups in the molecule. Multifunctional (meth) acrylate compound (C) having three or more (meth) acryloyl groups in the molecule
Examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, and caprolactone. Modified tris ((meth) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol It may be mentioned tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Further, urethane (meth) acrylate obtained by reacting a polyisocyanate compound with a hydroxyl group-containing polyfunctional (meth) acrylate having a hydroxyl group and three or more (meth) acryloyl groups in a molecule, or tetracarboxylic dianhydride A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a hydroxyl group-containing polyfunctional (meth) acrylate having a hydroxyl group and three or more (meth) acryloyl groups in a molecule can also be used. These polyfunctional (meth) acrylates may be used in combination of two or more. In the present invention, it is preferable to use an acrylate compound as the (meth) acrylate compound.

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-biphthalic anhydride, 4,4'-oxodiphthalic anhydride,
3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride , 1,2,3,4-butanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-
1,2-dicarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bicyclo [2.2.
2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like.

Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate having a hydroxyl group and three or more (meth) acryloyl groups in the molecule include pentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) acrylate. Examples include acrylate, dipentaerythritol penta (meth) acrylate, and mixtures thereof. Among these multifunctional (meth) acrylates having three or more (meth) acryloyl groups in the molecule, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetracarboxylic dianhydride and the like A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a hydroxyl group-containing polyfunctional (meth) acrylate having a hydroxyl group and three or more (meth) acryloyl groups therein, and a mixture thereof have excellent abrasion resistance. It is particularly desirable in that it provides a coating.

(4) Other polymerizable monomers (D) such as stain resistance, hardness, transparency, and antistatic properties.
Other polymerizable monomers, for example, having one or two (meth) acryloyl groups in one molecule as long as the characteristic properties of the film formed from the composition of the present invention are not impaired. An acrylate or the like may be contained in the composition.
For example, urethane (meth) acrylates and di (meth) acrylates having two (meth) acryloyl groups, epoxy (meth) acrylates and the like, and hydroxyl group-containing (meth) acrylates having one (meth) acryloyl group and the like, It can be used within a range that does not impair the above performance.

(5) Other Acrylic Polymers (E) The composition of the present invention may have a film formed from the composition of the present invention, such as stain resistance, hardness, transparency or antistatic property. Other acrylic polymers can be added as long as the characteristic performance is not impaired. Typical examples thereof include polymethyl methacrylate or a copolymer of an alkyl (meth) acrylate and a (meth) acrylate containing a hydroxyl group, and a silane cup containing an alkyl (meth) acrylate and a radical polymerizable group. Examples thereof include a copolymer with a ring agent, and a (meth) acrylate copolymer having a (meth) acryloyl group in a side chain, but are not limited thereto. Such an acrylic polymer can be used in a range that does not impair the characteristic performance of the present invention.

(6) Photopolymerization Initiator (F) Other In the case where ultraviolet rays are used as active energy rays for curing the active energy ray-curable coating composition of the present invention, a photopolymerization initiator is used in addition to the above components. This is preferred because curing is accelerated. As a photopolymerization initiator that can be used in the present invention, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone,
Benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2 -Morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1
-One, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4
-Diethylthioxanthone, etc., and two or more of these photopolymerization initiators can be used in combination as appropriate.

The active energy ray-curable coating composition of the present invention may contain an ultraviolet absorber (for example, benzotriazole, benzophenone,
Salicylic acid-based, cyanoacrylate-based UV absorbers),
UV stabilizers (e.g., hindered amine-based UV stabilizers), antioxidants (e.g., phenolic, sulfur-based, phosphorus-based antioxidants), antiblocking agents, slip agents,
Various additives, such as leveling agents, to be added to this type of composition can be incorporated in the composition in an amount of 0.01 to 2% by weight.

(7) Coating Composition The active energy ray-curable coating composition of the present invention comprises a polymer (A) having a (meth) acryloyl group and an organopolysiloxane unit bonded to a main chain via a nitrogen atom,
The compound (B) having an alkoxysilyl group and the polyfunctional (meth) acrylate compound (C) are essential components, and if necessary, another polymerizable monomer (D), another acrylic polymer (E) and It can be prepared by mixing a photopolymerization initiator (F) and the like. The content ratio of these components in the composition is as follows. (All weight ratios) When the total amount of the above (A), (B), (C), (D) and (E) (hereinafter referred to as “total resin component amount”) is 100% by weight, 1) weight Combined (A): 1 to 40% by weight, preferably 5 to 2
5% by weight. Below this range, the releasability tends to be insufficient, while above this range the wear resistance of the resulting coating decreases. 2) Compound (B) having an alkoxysilyl group: 1-4
0% by weight, preferably 3 to 30% by weight. If it is less than this range, the stain resistance is inferior, and if it exceeds this range, the resulting coating becomes brittle and cracks easily. 3) Polyfunctional (meth) acrylate compound (C): 40-
98% by weight, preferably 50-95% by weight. If the amount is less than this range, the abrasion resistance of the coating is poor. If the amount exceeds this range, the stain resistance becomes insufficient. 4) Other polymerizable monomer (D): 0 to 35% by weight, preferably 0 to 15% by weight. It is added for adjusting the viscosity of the composition, imparting flexibility to the coating, and improving the appearance, but if it exceeds this range, the stain resistance tends to be insufficient. 5) Other acrylic polymer (E): 0 to 30% by weight, preferably 0 to 20% by weight. It is added for the purpose of improving the appearance, abrasion resistance and stain resistance of the coating. However, if it exceeds this range, the flexibility of the coating is insufficient and cracks are easily caused. 6) Photopolymerization initiator (F): 0.1 to 1 based on the total amount of resin components
0% by weight is preferably added. If it is less than this range, the effect of promoting the reaction is insufficient, and if it exceeds this range, the strength of the formed film tends to be insufficient.

The coating composition of the present invention may be, for example, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyamide, vinyl chloride resin and AB
Solvent drying on plastic substrate such as S resin by dipping method, flow coating method, spraying method, bar coating method, and coating method using coating equipment such as gravure coat, roll coat, blade coat and air knife coat, After irradiation with the active energy ray, coating is performed on the surface of the plastic substrate so as to obtain a film having a thickness of 1 to 50 μm, preferably 1 to 20 μm.

Next, in order to cross-link and cure the applied coating composition layer, ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like, An active energy ray such as an electron beam, α-ray, β-ray, or γ-ray taken out from a particle accelerator of 20 to 2000 kV is irradiated and cured to form a film. Coatings cured by irradiation with active energy rays based on the composition of the present invention can be formed on various materials, and especially when formed on films, sheets and resin plates, the effect is large. ,preferable.

[0049]

The present invention will be more specifically described below with reference to Synthesis Examples and Examples. Components, ratios, procedures, and the like described in the following synthesis examples and examples can be appropriately changed without departing from the spirit of the present invention. Therefore,
The scope of the present invention is not limited by the specific examples described below. Parts and% described in Synthesis Examples and Examples mean parts by weight and% by weight, respectively.

<Synthesis of Sample> (Synthesis Example 1) An acryloyl group was attached to the main chain via a nitrogen atom.
Via a bonding organopolysiloxane unit and a nitrogen atom
Have an organopolysiloxane unit bonded to the main chain
Polymers synthesized 2-ethylhexyl methacrylate 60 parts of (A-1), an organopolysiloxane having a methacryloyl group at one terminal (Chisso Co., Ltd.: FM0725) to 30 parts, 10 parts of 2-hydroxyethyl acrylate and methyl ethyl ketone 200
Part of the mixture was heated to 65 ° C., and 65 ° C.
2 hours after the reaction reached, 0.6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further reacted at 65 ° C. for 5 hours and at 80 ° C. for 2 hours.
A copolymer (P-1) having a solid content of 33% was obtained.

The copolymer solution was mixed with 22.2 parts of isophorone diisocyanate and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscoat 30).
0, hydroxyl value 131 mg KOH / g)
C. for 3 hours, 50.degree. C. for 2 hours, and 80.degree. C. for 3 hours.
The mixture was reacted for a time (infrared absorption spectrum confirmed disappearance of isocyanate group absorption at 2250 cm ^-1 ) to obtain a copolymer (P-2) having an acryloyl group and having an organopolysiloxane side chain.

Next, the obtained copolymer solution was diluted with methyl ethyl ketone to a solid concentration of 20%, and then an organopolysiloxane compound having an amino group (TSF4700, manufactured by Toshiba Silicon Corp., amine equivalent 3000) Is added to 10 parts per 100 parts of solids,
After reacting at 80 ° C. for 1.5 hours, a polymer having an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, and an organopolysiloxane unit bonded to the main chain without a nitrogen atom (A -1) (solid content 27)
%).

(Synthesis Example 2) An acryloyl group and a nitrogen atom
An organopolysiloxane unit bonded to the main chain through
Organopolysiloxane that bonds to the main chain without the interposition of elementary atoms
(A-
Synthesis of 2) The use amounts of 2-ethylhexyl methacrylate and an organopolysiloxane having a methacryloyl group at one end (manufactured by Chisso Corporation: FM0725) were 30 parts and 10 parts, respectively, and N, N-dimethylaminoethyl methacrylate 50 Except for the addition of (P-
1) A copolymer having a solid content of 33% (P-
3) was obtained. About this (P-3), (P
-2) Copolymer having acryloyl group and organopolysiloxane side chain (P-4) in exactly the same manner as in preparation
(Solid content: 45%) was obtained. After diluting the copolymer solution with isopropanol to a solid content of 20%,
Synthesis was performed except that methyl chloride was introduced into the reaction system, the reaction was carried out at 50 ° C. for 6 hours, and then an organopolysiloxane compound having an amino group (TSF4700, manufactured by Toshiba Silicon Corp .; amine equivalent 3000) was added. A polymer having an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, an organopolysiloxane unit bonded to the main chain without a nitrogen atom and a quaternary ammonium base in the same manner as in Example 1 ( A-2) (solid concentration 27%) was obtained.

(Synthesis Example 3) Polymer similar to (A-2)
Synthesis of (A-3) Copolymer (P) was prepared in the same manner as in Synthesis Example 2 except that 2-ethylhexyl methacrylate was not used and the amount of N, N-dimethylaminoethyl methacrylate used was 80 parts. -5) (solid content: 33%), and
In exactly the same manner as in Synthesis Example 2, an organopolysiloxane unit bonded to the main chain via an acryloyl group and a nitrogen atom via a copolymer (P-6) (solid concentration: 45%), without a nitrogen atom A polymer having an organopolysiloxane unit and a quaternary ammonium base bonded to the main chain (A-
3) (solid concentration 28%) was obtained.

(Synthesis Example 4) An acryloyl group and a nitrogen atom
An organopolysiloxane unit bonded to the main chain through
Synthesis of polymer having quaternary ammonium base (A-4) Except that an organopolysiloxane having a methacryloyl group at one end was not used and the amount of N, N-dimethylaminoethyl methacrylate used was 60 parts. In the same manner as in Synthesis Example 2 above, copolymer (P-7) (solid content concentration 33%), copolymer (P-8) (solid content concentration 45%)
(A-4) having an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, and a quaternary ammonium group (solid concentration 27%)
I got

(Synthesis Example 5) Polymer similar to (A-4)
Synthesis of (A-5) Copolymer (P-9) (solid content 33%), copolymer in the same manner as in Synthesis Example 4 except that lauryl methacrylate was used instead of 2-ethylhexyl methacrylate. After (P-10) (solid content concentration 45%), a polymer (A-5) having an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, and a quaternary ammonium base (solid content concentration) 26%).

(Synthesis Example 6) Polymer similar to (A-4)
Synthesis of (A-6) Copolymer (P-11) (solid content: 33%), copolymer (C) in the same manner as in Synthesis Example 4 except that stearyl methacrylate was used instead of 2-ethylhexyl methacrylate. P-12) (solid content concentration 45%), a polymer (A-6) having an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, and a quaternary ammonium base (solid content concentration 27%) %).

(Synthesis Example 7) Polymer similar to (A-4)
Synthesis of (A-7) Instead of 2-ethylhexyl methacrylate, 2,2,2
-Copolymer (P-13) (solid content 33%), copolymer (P-14) (solid content 4) in the same manner as in Synthesis Example 4 except that trifluoroethyl methacrylate was used.
5%), a polymer (A-7) having an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, and a quaternary ammonium base (solid content: 28%).
%).

(Synthesis Example 8) Polymer similar to (A-2)
Synthesis of (A-8) 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate and an organopolysiloxane having a methacryloyl group at one end (manufactured by Chisso Corporation: FM0
725) was 20 parts, 5 parts and 15 parts, respectively, and trimethoxysilylpropyl methacrylate 1
Copolymer (P-15) (solids concentration 33%), copolymer (P-1) in the same manner as in Synthesis Example 2 except that 0 part was added.
6) (solid content concentration: 40%), an acryloyl group, an organopolysiloxane unit bonded to the main chain via a nitrogen atom, an organopolysiloxane unit bonded to the main chain without a nitrogen atom, and a quaternary ammonium base (A-8) having a solid content of 27% was obtained.

(Synthesis Example 9) Two kinds of polysiloxane side chains
Synthesis of polymer (A-9) having (A-3) obtained in Synthesis Example 3 and a polysiloxane having an amino group (BY16-8, manufactured by Toray Silicone)
49, amine equivalent 600) and 10 parts of
Reaction at 1 ° C. for 1 hour, having an acryloyl group, two types of polysiloxane units bonded to the main chain via a nitrogen atom, an organopolysiloxane unit bonded to the main chain without a nitrogen atom, and a quaternary ammonium base Polymer (A-9)
(Solid content: 30%).

(Comparative Synthesis Example 1) In the main chain via a nitrogen atom
Heavy without organopolysiloxane units to bind
Synthesis of Compound (X-1) The copolymer (P-8) obtained in Synthesis Example 4 was quaternized in the same manner as in Synthesis Example 4 except that the organopolysiloxane having an amino group was not added. And a polymer (X-1) having an acryloyl group and a quaternary ammonium base
(Solid content 25%).

(Comparative Synthesis Example 2) Organopolysiloxane
An organo that bonds to the main chain without a nitrogen atom as a unit
Synthesis of polymer (X-2) having only polysiloxane unit
In Synthesis Example 4, 60 parts of methyl methacrylate and 10 parts of trimethoxysilylpropyl methacrylate were used in place of 2-ethylhexyl methacrylate and 2-hydroxyethyl methacrylate, and an organopolysiloxane having a methacryloyl group at one end (Chisso Corporation) ): FM0725) Except for adding 30 parts,
In the same manner as in the synthesis of the copolymer (P-7) of Synthesis Example 4, a polymer having only an acryloyl group and an organopolysiloxane unit which is bonded to the main chain without a nitrogen atom as an organopolysiloxane unit (X- 2) (Solid concentration 33
%).

(Comparative Synthesis Example 3) Acryloyl group, quaternary
As ammonium base and organopolysiloxane units
Organopolysiloxy bonded to main chain without nitrogen atom
Synthesis of polymer (X-3) having only a sun unit Except for using the copolymer (P-6) obtained in Synthesis Example 3, an acryloyl group,
As a result, a polymer (X-3) (solid content concentration: 25%) having only an organopolysiloxane unit bonded to the main chain without a nitrogen atom as a quaternary ammonium base and an organopolysiloxane unit was obtained.

(Reference Synthesis Example) Other Acrylic Polymer
(E) A mixture of 90 parts of methyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, and 200 parts of methyl ethyl ketone was heated to reach 65 ° C., and 2 hours after reaching 65 ° C., 2,2, respectively. '-Azobis (2,
4-dimethylvaleronitrile) was added in 0.6 parts each,
Further, the reaction was carried out at 65 ° C. for 5 hours and at 80 ° C. for 2 hours to obtain a solid content of 3.
3% of a copolymer (E-1) was obtained.

(Synthesis Example 10) Having an alkoxysilyl group
Preparation of Compound (B-1) A mixture of 91 parts of tetraethoxysilane and 9 parts of tetraisopropoxytitanium was stirred at 25 ° C. for 1 hour, and allowed to stand for 24 hours to obtain a compound having an alkoxysilyl group (B-
1) was obtained.

(Synthesis Example 11) Having an alkoxysilyl group
Preparation of Compound (B-2) Tributyl borate and aluminum acetylacetonate were added as catalysts to 91 parts of tetraethoxysilane, and after stirring for 1 hour, the mixture was allowed to stand for 24 hours, and 9 parts of tetraisopropoxytitanium was added. , Further stirred for 1 hour and then allowed to stand for 24 hours to obtain a compound having an alkoxysilyl group (B-2)
I got

(Synthesis Example 12) Having an alkoxysilyl group
Preparation of Compound (B-3) A compound (B-3) having an alkoxysilyl group was obtained in the same manner as in Synthesis Example 1 except that tetrabutoxytitanium was used instead of tetraisopropoxytitanium.

(Synthesis Example 13) Having an alkoxysilyl group
Preparation of Compound (B-4) The same procedures as in Synthesis Example 1 were carried out except that the amounts of tetraethoxysilane and tetraisopropoxytitanium were 90.9 parts and 0.1 parts, respectively, and 9 parts of tetrabutoxyzirconium were further added. Compound having an alkoxysilyl group (B
-4) was prepared.

(Synthesis Example 14) Having an alkoxysilyl group
Preparation of Compound (B-5) to 99 parts of tetraethoxysilane in the presence of tributyl borate and aluminum acetylacetonate as catalysts
9.9 parts of trifluoroethanol was added for denaturation, then 1 part of tetraisopropoxytitanium was added, and the mixture was stirred for 1 hour and allowed to stand for 24 hours to give the compound (B-5) having an alkoxysilyl group. Prepared.

(Synthesis Example 15) Having an alkoxysilyl group
Preparation of Compound (B-6) Synthesis Example 1 except that a condensed oligomer of tetramethoxysilane was used instead of tetraethoxysilane and lauryl alcohol was used instead of trifluoroethanol.
In the same manner as in 4, a compound (B-6) having an alkoxysilyl group was prepared.

(Synthesis Example 16) Having an alkoxysilyl group
Preparation of Compound (B-7) A compound (B-7) having an alkoxysilyl group was prepared in the same manner as in Synthesis Example 15 except that ethanol was used instead of lauryl alcohol.

(Synthesis Example 17) Having an alkoxysilyl group
Preparation of Compound (B-8) In the same manner as in Synthesis Example 10 except that the amount of tetraethoxysilane was 75 parts and the amount of tetraisopropoxytitanium was 25 parts, a compound having an alkoxysilyl group (B-
8) was prepared.

<Evaluation Method> The coating films prepared in the following Examples and Comparative Examples were evaluated by the following methods. Transparency (haze value (%)) Measured according to JIS K 7105. Using wear -resistant wheels made of wear-resistant Caliberase CS-10F,
A taper wear test was performed under the condition of 100 rotations with a load of 500 g, and the difference (ΔH%) between the haze values before and after the wear test was evaluated.

Contact angle Using a P-type contact angle measuring device manufactured by Kyowa Kagaku Co., Ltd., using a sample conditioned at 23 ° C. and a relative humidity of 65% for 24 hours or more, 0.002 ml of water or squalene was applied to the measurement surface. It was dropped and measured at 23 ° C. (unit: degree).

Ink Stain Resistance (Evaluation of Stain Resistance- 1) The ink stain resistance was evaluated in terms of wiping properties and repeated erasability. In each of the evaluations, 2% was measured at 23 ° C and 65% relative humidity.
A line was drawn on the sample conditioned for 4 hours or longer with an oil-based marker pen ("Magic Ink" (trade name) black / red) and a water-based marker pen (black), and left still for 24 hours under the above conditions. Use things. The wiping property was determined by using a grained paper (JK Wiper 150-
S, manufactured by Jujo Paper Co., Ltd.), and the test was performed by manually wiping three times. The evaluation was performed in three stages. After three wipings, the one that was completely wiped out was evaluated as "O", the one with a slight trace of the line as "△", and the one with some or all of the ink attached. “×” was assigned.

When repeated erasing was performed within five times using a lens coating hardness tester (MIL-C-675 method, load 0.4 kg weight), condition adjustment and drawing were performed using the same sample. This test was repeated, and the number of times the test was repeated until it could not be wiped off was taken as the value of the repeated erasability. In the above two evaluations, when the wiping property is “○” for all the inks and the repetitive erasability is 10 or more times for the oil-based ink and 5 or more times for the aqueous ink, it can be said that the ink stain resistance is excellent. .

Fingerprint Resistance (Evaluation of Contamination Resistance-2) Fingerprint resistance was evaluated based on fingerprint adhesion and fingerprint wiping. Fingerprint adhesion was measured by putting the thumb that had been wiped immediately before (preferably using a crimped paper for wiping) perpendicular to the sample surface.
After pressing for 2 seconds, the fingerprint adhesion after that was evaluated visually by relative evaluation. As a standard sample for evaluation, the polymer (X-2) prepared in Comparative Synthesis Example 2 was used as a 0.3% methyl ethyl ketone solution on a polyethylene terephthalate film (T600E, manufactured by Diafoil Hoechst Co., Ltd.).
After applying to a thickness of 3 μm and curing by heating at 80 ° C. for 2 hours,
A sample left at 23 ° C. and a relative humidity of 65% for 24 hours or more was used. A sample having the same grade as the STD was evaluated as “Δ”, a sample better than this was evaluated as “○”, and a sample inferior was evaluated as “X”.

The fingerprint wiping property was determined by leaving a sample for which the above-mentioned fingerprint adhesion was evaluated for 1 hour, and then manually using a rubbing paper (JK Wiper 150-S, manufactured by Jujo Paper Co., Ltd.) for wiping. The number of times of wiping and wiping until the fingerprint disappeared was determined. The evaluation was performed in three stages, and was evaluated as “○” when the wiping was performed three times, “△” when the wiping was performed four to five times, and “X” when the erasing was not possible after six wiping.

The same evaluation as the ink stain resistance (wiping property) was performed by using carbon powder, coffee, tobacco ash and sauce instead of the life stain resistant marker pen, and the appearance after wiping was also evaluated. . The same applies to the evaluation method.

After immersing the water- resistant coating film sample in water at room temperature for 30 minutes, the contact angle and the ink stain resistance were evaluated, and the samples before and after immersion were compared. A sample with little difference was evaluated as "O", and a sample with reduced performance was evaluated as "X". The ethanol-resistant coating film sample was wiped with a cloth impregnated with ethanol, and then evaluated in the same manner as the above-mentioned water resistance. Using a grained paper (JK Wiper 150-S, manufactured by Jujo Paper Co., Ltd.) for wiping the coating surface of the durable sample
After wiping 0 times, conditioning the condition at 23 ° C. and a relative humidity of 65% for 24 hours or more, the contact angle was measured and the ink stain resistance test was performed to evaluate the durability of the coating film.

The wet heat durability sample was allowed to stand at 60 ° C. and a relative humidity of 95% for one week, and then conditioned at 23 ° C. and a relative humidity of 65% for 24 hours. This sample was tested for contact angle and ink stain resistance by the methods described above, and the durability of the coating film was evaluated. Surface resistivity Using a sample conditioned under the same conditions as above, using a surface resistance meter (manufactured by Takedariken: TR-8601 type)
The measurement was performed with an applied voltage of 100 V and a value of 1 minute.

<Examples 1 to 11, Comparative Examples 1 to 4> The active energy ray-curable coating composition was prepared by blending the respective components at the ratios shown in Table 1, and this was applied to a 100 μm thick biaxial coating composition. A stretched polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd .: T600E) was applied using a bar coater so that the film thickness after drying was 5 μm, and was heated and dried at 80 ° C. for 2 minutes. Output density 115w /
This film was fixed at a position of 10 cm under a light source of a high-pressure mercury lamp of 10 cm and irradiated with ultraviolet rays at 700 mJ / cm ² to form a coating film. This coating was evaluated as described above.
The results are shown in Tables 2 and 3. The surface resistivity of the biaxially stretched polyethylene terephthalate film as the substrate is 10
Exceeds ¹⁶ Ω, wear resistance 28.5%, haze 1.5%
Met.

[0083]

[Table 1]

Note: The amount of component (A) is based on solid content.
Adjusted to a final solids concentration of 35%. DPHA: dipentaerythritol hexaacrylate C-1: dipentaerythritol hexaacrylate /
Pentaerythritol triacrylate = 3/2 C-2: dipentaerythritol hexaacrylate /
Pentaerythritol triacrylate = 5/2 HOA-MPE: 2-acryloyloxyethyl-2-
Hydroxyethylphthalic acid 907 (Irgacure 907): 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone TPT: Tetraisopropoxytitanium Comparative Example 3: Corresponding to JP-A No. 10-7986 TR: Commercially available fluorine-based antifouling agent (Dainippon Ink Co., Ltd.)
Made: Defensa TR-220)

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

<Examples 12 to 24> Each component was blended at the ratios shown in Table 4 and evaluated in the same manner as in Examples 1 to 11. The results are shown in Table 5.

[0090]

The active energy ray-curable coating composition of the present invention provides a coating having excellent stain resistance, transparency and abrasion resistance, and having a high level of antistatic property by adjusting the composition. It is also possible. This coating is further excellent in solvent resistance, water resistance and durability. Further, a film having excellent stain resistance to various stains can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 183/04 C09D 183/04 // C08F 290/06 C08F 290/06 (72) Inventor Kazuhide Hayama Yokkaichi, Mie Prefecture No. 1 Tohocho Mitsubishi Chemical Corporation Yokkaichi Office F-term (reference) 4F006 AA35 AA36 AB24 AB32 AB37 AB39 AB52 BA02 BA07 BA11 BA15 CA04 CA07 CA08 DA03 DA04 4F071 AA12 AA12X AA22 AA22X AA24 AA33 AA34 AA50 BC BG05W BG06W BG07W BG073 CG04W CK05W CP02X CP08X CP16W CP17W CQ03X EC076 EE039 EH078 EH107 EH108 EL037 EL038 EL057 EN069 ET008 EU239 EV319 EW149 EX036 FD149 4J027 AB10 BA02 AC01 AF08 BA02 CD08 4J038 CG142 DL022 DL032 DL081 DL101 DM022 FA012 FA241 GA08 GA09 JA23 JC32 KA03 KA04 NA01 NA05 NA11 NA20 PA17 PC08

Claims (12)

[Claims] 1. A polymer (A) having an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group”) and an organopolysiloxane unit bonded to a main chain via a nitrogen atom, having an alkoxysilyl group A composition containing the compound (B) and a polyfunctional acrylate or methacrylate (hereinafter, referred to as “(meth) acrylate”) compound (C), wherein the content of the polymer (A) in the composition is 1 to 40% by weight, the content of compound (B) is 1 to 40% by weight, and the content of compound (C) is 40
An active energy ray-curable coating composition which is ９８98% by weight. 2. The active energy ray-curable coating composition according to claim 1, wherein the polymer (A) has a structure in which an organopolysiloxane compound having an amino group is added to a (meth) acryloyl group. 3. The active energy ray-curable coating composition according to claim 1, wherein the polymer (A) has a quaternary ammonium salt group. 4. The active energy ray-curable coating composition according to claim 1, wherein the polymer (A) has an organopolysiloxane unit bonded to the main chain without through a nitrogen atom. 5. The compound according to claim 1, wherein the compound (B) having an alkoxysilyl group contains tetraalkoxysilane or a silicate oligomer that is a condensate thereof, and tetraalkoxytitanium or a titanate oligomer that is a condensate thereof. The active energy ray-curable coating composition according to claim 1. 6. The active energy ray-curable coating composition according to claim 5, wherein the compound (B) having an alkoxysilyl group contains tetraalkoxyzirconium or a zirconate oligomer which is a condensate thereof. 7. The compound (B) having an alkoxysilyl group may contain, in addition to the tetraalkoxysilane or the silicate oligomer, 0.01 to 100 parts by weight of the tetraalkoxytitanium or titanate oligomer per 100 parts by weight of the silane compound; Tetraalkoxy zirconium or zirconate oligomer
The active energy ray-curable coating composition according to claim 5 or 6, which is a mixture containing 50 parts by weight of each. 8. The active energy ray-curable coating composition according to claim 5, wherein the tetraalkoxysilane or silicate oligomer is a fluorinated alkoxysilane or fluorinated silicate oligomer. 9. The alcohol-modified alkoxysilane or alcohol-modified silicate oligomer according to claim 5, wherein the tetraalkoxysilane or the silicate oligomer is modified with an alcohol having an alkyl group having 10 or more carbon atoms. Active energy ray-curable coating composition. 10. In addition to the above (A) to (C), 0 to 35% by weight of another polymerizable monomer (D) and 0 to 30% by weight of another acrylic polymer (E) ( Provided that the total of (A) to (E) is 100% by weight) and that the photopolymerization initiator (F) is 0.1 to 10% by weight based on the total amount of (A) to (E). Item 10. The active energy ray-curable coating composition according to any one of Items 1 to 9. 11. A material having a cured film formed by applying the active energy ray-curable coating composition according to claim 1 and irradiating it with an active energy ray. 12. A film or sheet having on its surface a cured film formed by applying the active energy ray-curable coating composition according to any one of claims 1 to 10 and irradiating it with an active energy ray. Or a resin plate.