JPH07258582A - Coating composition, molding surface-coated therewith, and its production - Google Patents

Abstract

PURPOSE:To obtain a coating composition which can give a coating film improved in abrasion and weathering resistances by mixing a specified cross- linking polymerizable compound with fine silica particles and an actinic radiation polymerization initiator. CONSTITUTION:A coating composition is prepared by mixing 100 pts.wt. mixture comprising 50-100wt.% cross-linking polymerizable compound having at least two (meth)acryloyloxy groups in the molecule and 0-50wt.% compound copolymerizable therewith with fine silica particles surface-coated with a hydrolyzate of a mixture comprising 5-95 parts by mole silane compound of any one of formulas III (wherein R<1> is H or methyl; R<2> is a 1-10C hydrocarbon group; R<3> is H or R<2>; and R4 is a 1-10C bivalent hydrocarbon group; R<5> and R<6> are each R<3>; and m is 0-2) and 95-5 parts by mole silane compound of formula IV (wherein R<7> and R<8> are each R<2>; R<9> is R<3>; and n and p are each 0-3; and n+p=0-3) and 0.01-10 pts.wt. actinic radiation polymerization initiator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coating composition capable of forming a cured coating having excellent abrasion resistance and weather resistance by irradiation with active energy rays, and a cured product of the coating composition. As a molded article whose surface is covered, in particular, head lamp cover, windshield, vehicle window glass, vehicle roofing material, building window glass, building roofing material, road soundproof wall, name plate and display face plate, etc. , A surface-coated molded article having excellent wear resistance and weather resistance.

[0002]

2. Description of the Related Art In recent years, transparent plastic materials having high crush resistance have been widely used as substitutes for transparent glass.

However, the transparent plastic material is
Compared to glass, it has a softer surface, is more likely to be scratched, and lacks abrasion resistance, which is a serious drawback. Therefore,
Many attempts have heretofore been made to improve the wear resistance of transparent plastic materials.

As one of the most general methods, for example, as described in JP-A-53-102936, JP-A-53-104638, JP-A-54-97633 and the like, there are a plurality of molecules in a molecule. A molded product having a coating with excellent scratch resistance, which is obtained by applying a curing liquid containing a compound having an acryloyloxy group or a methacryloyloxy group as a main component to the surface of the molded product and curing it by irradiation with active energy rays such as heat or ultraviolet rays. There is a way to get. The curable liquid used in this method is relatively inexpensive and easily available, but since the cured coating film obtained is an organic material, the present state is that the wear resistance of the molded article having this coating is limited. .

On the other hand, as a method for imparting higher surface hardness, for example, Japanese Patent Laid-Open Nos. 48-26822 and 59-59.
As disclosed in Japanese Patent No. 64671, etc., a method of applying an alkoxysilane compound to the surface of a plastic molded article and curing it by heat to obtain a molded article having a coating, or JP-A-56-106969, Kaihei 2-2
As described in Japanese Patent No. 72041, there is known a method in which a coating composition comprising colloidal silica and a curing liquid is applied to the surface of a plastic molded article and a molded article having a coating cured by heat is obtained.

However, since the coating compositions using these methods use an organic solvent in order to improve the coating properties, cracks may occur in the plastic to be coated during the drying process, Coating defects such as uneven coating are likely to occur, and the appearance of the obtained coated molded product is likely to have a problem. Further, the release of the organic solvent into the air is inevitable in the coating process, which is not preferable from the viewpoint of global environment protection, which has been attracting attention in recent years.

Furthermore, the coating film formed from these curing liquids is industrially disadvantageous because it consumes a large amount of energy because it is cured by heat and it takes a long time to cure.

On the other hand, Japanese Examined Patent Publication No. 62-21815, Japanese Examined Patent Publication No. 1-55307, No. 3-2168, No. 3-6190, Japanese Unexamined Patent Publication No. 59-204669, No. 62-256874. JP-A-2-6413
No. 8, gazette 4-18423 gazette, and gazette 4-21474.
No. 3, gazette No. 4-220411 gazette, and No. 5-9818.
No. 9, gazette 5-306374, gazette 6-2536.
No. 3, No. 6-41468, and No. 6-151.
Japanese Patent No. 694 discloses a coating composition composed of colloidal silica, an alkoxysilane having an acryl group or a methacryl group, and a polyfunctional acrylate.

These coating compositions can also be used as solvent-free coating materials, and from these coating materials, plastic molded articles having considerably excellent surface hardness can be obtained. The interface between the colloidal silica and the alkoxysilane undergoes hydrolysis, resulting in a cured film.
There was a drawback that cracks and whitening occurred and the weather resistance was not sufficient.

In order to solve these problems, the present inventors have proposed, as disclosed in JP-A-6-100798, silica fine particles whose surface is modified with a hydrolyzate of an alkoxysilane having a styryl group, and a polyfunctional acrylate. It has been found that the coating composition consisting of, and an active energy ray polymerization initiator has good properties. However, although this coating composition also has better performance than conventional ones, it is still not sufficient, has a high surface hardness, and can form a cured coating excellent in weather resistance, and can be used even without a solvent. The present situation is that no active energy curable coating composition has been obtained yet.

[0011]

The present invention was obtained as a result of extensive studies to solve the above-mentioned problems, and the purpose thereof is to enable coating without using a solvent,
Another object of the present invention is to provide an active energy ray-curable coating composition capable of forming a cured coating having high surface hardness, good appearance and weather resistance, and excellent abrasion resistance and scratch resistance, and a method for producing the same. Another object of the present invention is to provide a molded product whose surface is coated with a cured product of this coating composition.

[0012]

That is, the present invention is
As the component (a), a crosslinkable polymerizable compound (a-1) having at least two acryloyloxy groups and / or methacryloyloxy groups in the molecule, or 50% by weight or more of the crosslinkable polymerizable compound (a-1). A mixture consisting of 50% by weight or less of a compound (a-2) copolymerizable therewith,
As the component (b), the following general formulas (I) to (IV)

[Chemical 3] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
10 hydrocarbon group, R ³ is a hydrogen atom or 1 to 10 carbon atoms
10 hydrocarbon groups, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ and R ⁶ are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and m is 0 Represents an integer of 2. 5 to 95 parts by mole of at least one silane compound (b-1) selected from silane compounds represented by
The following general formula (V)

[Chemical 4] (In the formula, R ⁷ and R ⁸ are the same or different and have 1 to 1 carbon atoms.
A hydrocarbon group of 0, R ⁹ is a hydrogen atom or a carbon number of 1 to 10
Hydrocarbon groups, n and p are integers of 0 to 3, and n + p is 0 to 3. ) A silane compound (b
-2) A coating composition comprising: silica fine particles whose surface is modified with a hydrolyzate of a mixture with 95 to 5 parts by mole, and an active energy ray polymerization initiator as a component (c). is there.

Another aspect of the present invention is a method for producing the coating composition by mixing the components (a), (b) and (c), in a dispersion of silica fine particles. The surface of the silica fine particles is modified with a hydrolyzate of the silane compound (b-2), and then the dispersion medium of the silica fine particles and water are distilled off after adding the component (a). A method for producing a coating composition, which comprises the step of adding the compound (b-1) to further modify the surface of the silica fine particles with a hydrolyzate thereof. Further, a molded product whose surface is coated with a cured product of the coating composition is also an object of the present invention.

[0014]

The inventors of the present invention have previously developed a silica fine particle modified with a hydrolyzate of a silane compound (b-1) and a polyfunctional acrylate and / or methacrylate (hereinafter abbreviated as (meth) acrylate) as main components. In order to improve the weather resistance of the cured coating obtained from the conventional coating composition, the mechanism of developing the surface hardness of this cured coating and the factors affecting the weather resistance were eagerly studied.

As a result, (1) the weather resistance of the cured coating is
It is affected by the degree of surface modification of silica fine particles, and if surface modification is not appropriate, it will lead to deterioration of weather resistance. (2) In order to express the surface hardness of the cured film to a high degree, silica fine particles and polyfunctional ) Some kind of bond must be formed between the acrylate and the polymerized cured product, and the silane compound (b-1) plays that role. (3) Silica fine particles and polyfunctional ( If there are too many bonding points of the cured product of the (meth) acrylate, it will be a factor to impede the flexibility of the cured film, and also during the high temperature / low temperature heat cycle test and the water absorption / dry water absorption cycle test in the weather resistance evaluation. It was found that the cured film was inferior to the expansion and contraction behavior of the molded product, and defects such as cracks appeared in the cured film.

Therefore, based on this finding, as a result of further studies to obtain a coating composition in which the surface hardness and the weather resistance of the cured film are exhibited at the same time, a silane compound used for modifying the surface of the silica fine particles is obtained. As the silane compound (b-1) that causes a bond between the silica fine particles and the polymerized and cured product of the polyfunctional (meth) acrylate, and the silane compound (b-2) that does not cause a bond between them are used together. Therefore, it was revealed that the above performance can be exhibited.

That is, the silane compound (b-1) mainly serves to improve the surface hardness of the coating film, and the silane compound (b-).
2) acts on the surface modification of the silica fine particles and imparts flexibility to the cured film. Therefore, by using a coating composition containing the silica particles modified by both, high surface hardness and good weather resistance are exhibited. It was found that a cured coating that could be obtained was obtained.

The present invention will be described in detail below. The component (a) in the coating composition of the present invention is a crosslinkable polymerizable compound (a) having at least two acryloyloxy groups and / or methacryloyloxy groups (hereinafter abbreviated as (meth) acryloyloxy group) in the molecule. -1). The crosslinkable polymerizable compound (a-1) used in the present invention is
The residue that is a moiety other than the (meth) acryloyloxy group is a hydrocarbon or a derivative thereof, and the molecule may contain an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, or the like.

Examples of the crosslinkable compound (a-1) include an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid or a derivative thereof, or a polyhydric alcohol and a polycarboxylic acid (meta). ) Ester compounds and the like obtained from acrylic acid or derivatives thereof.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a number average molecular weight of about 300 to about 1000, propylene glycol, dipropylene glycol, 1,3.
-Propanediol, 1,3-butanediol, 2,3
-Butanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,9
-Nonanediol, neopentyl glycol (ie 2,
2-Dimethyl-1,3-propanediol), 2-ethylhexyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedimethanol, and other divalent alcohols; trimethylolpropane (ie, 1,1,1-trimethylolpropane), pentaglycerol (ie 1,1,1-trimethylolethane),
Glycerol, 1,2,4-butanetriol, 1,
Trivalent alcohols such as 2,6-hexanetriol; and pentaerythritol (that is, 2,2-bis (hydroxymethyl) -1,3-propanediol), diglycerol, dipentaerythritol and the like.

Specific examples of the crosslinkable compound (a-1) obtained as a poly (meth) acrylate of a polyhydric alcohol include the following general formula (VI).

[Chemical 5] (In the formula, q is an integer of 0 to 4, two or more of X ¹ present in the molecule are two or more (meth) acryloyloxy groups, and the remaining X ¹ are each independently a hydrogen atom, A compound represented by a hydroxyl group, an amino group, an alkyl group or a substituted alkyl group.).

Specific examples of the compound represented by the general formula (VI) include trimethylolpropane tri (meth).
Acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate ) Acrylate, tripentaerythritol penta (meth) acrylate,
Examples include tripentaerythritol hexa (meth) acrylate and tripentaerythritol hepta (meth) acrylate.

Examples of poly (meth) acrylates of polyhydric alcohols other than the compound of the general formula (VI) include diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4
Examples include butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and glycerin tri (meth) acrylate.

When an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid or a derivative thereof is used as the crosslinkable compound (a-1), particularly preferable ester compounds are diethylene glycol di (meth) acrylate and triethylene. Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaglycerol acrylate, dipentaglycerol pentaacrylate and the like.

The ester compound obtained from the polyhydric alcohol, polycarboxylic acid and (meth) acrylic acid or their derivatives which can be used as the crosslinkable compound (a-1) is generally a polyhydric compound. It is obtained by reacting a mixture in which the hydroxyl groups of the alcohol and the carboxyl groups of both the polyvalent carboxylic acid and the (meth) acrylic acid or its derivative are finally equivalent.

Of these ester compounds, preferred are polyhydric alcohols such as dihydric alcohols and 3
An esterified product obtained by using a divalent carboxylic acid as a polyvalent carboxylic acid using a divalent alcohol or a mixture of a divalent alcohol and a trivalent alcohol can be mentioned. When a mixture of trihydric alcohol and dihydric alcohol is used, the molar ratio of trihydric alcohol and dihydric alcohol can be arbitrarily selected.

When the divalent carboxylic acid is used in combination with (meth) acrylic acid or its derivative, the molar ratio is 1 mol of the carboxyl group of (meth) acrylic acid or its derivative to the carboxyl of the divalent carboxylic acid. The number of groups is preferably within the range of 2 mol or less. When the divalent carboxylic acid is in excess of the above range, the viscosity of the ester compound produced may be too high, and it may be difficult to form a coating film.

Examples of the divalent carboxylic acid or its derivative used in the synthesis of the above ester compound include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; tetrahydrophthalic acid and 3,6-endomethylenetetrahydrophthalic acid. Alicyclic dicarboxylic acids such as; phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids; other thioglycols, thiodivaleric acid, diglycolic acid, maleic acid, fumaric acid, itaconic acid, and their chlorides, An anhydride, ester, etc. can be mentioned.

Specific examples of the above-mentioned ester compound used as the crosslinkable polymerizable compound (a-1) include malonic acid / trimethylolethane / (meth) acrylic acid and malonic acid /
Trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid /
Trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, adipic acid /
Trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, glutaric acid / tri Methylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylol Ethane / (meta)
Acrylic acid, sebacic acid / trimethylolpropane /
(Meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol /
(Meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, phthalic acid / glycerin /
(Meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / pentaerythritol / Mention may be made of saturated or unsaturated polyester poly (meth) acrylates with a combination of (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, or maleic anhydride / glycerin / (meth) acrylic acid.

Further, as the crosslinkable polymerizable compound (a-1), for example, tolylenetriisocyanate represented by the following general formula (VII) is used.

[Chemical 6] (In the formula, R ¹⁰ represents an alkylene group having ₁ to ₁₀ carbon atoms.), Hexamethylene diisocyanate, tolylene diisocyanate, diphenylethane diisocyanate,
Polyisocyanates such as xylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, or trimethylhexamethylene diisocyanate, and acrylic monomers having active hydrogen, such as 2-hydroxyethyl (meth) acrylate, 2- Hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide and the like are reacted by a conventional method with 1 mol or more of an acrylic monomer per 1 mol of an isocyanate group. Urethane (meth) acrylate obtained; poly [(meth) acryloyloxyethyl] isocyanurate such as tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid.

The component (a) in the coating composition of the present invention contains the above-mentioned crosslinkable polymerizable compound (a-1) as a main component (50% by weight or more) and can be copolymerized therewith. It may be a mixture containing the compound (a-2).

As the copolymerizable compound (a-2), for example, a compound having one (meth) acryloyl group in the molecule is used.

Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl ( (Meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5-dimethyl-1-
Adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth)
Acrylate, 1,4-butylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate,
(Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2 3,3-Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, N-hydroxybutyl (meth) acrylamide, hydroxymethyldiacetone (meth) acrylamide, N-hydroxyethyl-
N-methyl (meth) acrylamide etc. are mentioned.

Further, the following general formula (VIII) or (IX)

[Chemical 7] (Wherein, r is indicates 1 to 10, X ² represents a (meth) acryloyloxy group, R ^{1 1} is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, a benzyl group or substituted benzyl group .) And other mono (meth) acrylates.

Examples of the mono (meth) acrylate represented by the general formula (VIII) and the general formula (IX) include methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate. , Butoxyethylene glycol (meth) acrylate and the like.

Further, as the copolymerizable compound (a-2), for example, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxypropyl hydrogenogen. Succinate, various known epoxy (meth) acrylates, urethane (meth) acrylates, and the like are also included.

The compound (a-2) is selected according to the intended use of the cured film obtained in the present invention, but when a film having high surface hardness is desired, glass as a homopolymer of the compound (a-2). Those having a high transition temperature are preferably used. Specifically, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,
Examples thereof include 5-dimethyl-1-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate.

When using these compounds (a-2), it is necessary that the content of the compound (a) in the component (a) is 50% by weight or less, and preferably 30% by weight or less. At a ratio outside this range, the compound (a-
When 2) is included, the surface hardness of the cured film obtained by the present invention will be reduced.

The component (b) in the coating composition of the present invention is at least one silane compound (b-1) selected from the silane compounds represented by the general formulas (I) to (IV).
And silica fine particles whose surface is modified with a hydrolyzate of a mixture of at least one silane compound (b-2) selected from the silane compounds represented by the general formula (V).

The phrase "the surface is modified with a hydrolyzate" as used herein means that the hydrolyzate of the silane compound is retained on a part or all of the surface of the silica fine particles, and the surface characteristics of the silica fine particles are Means modified. It should be noted that this also includes silica fine particles that simultaneously retain those that have undergone the condensation reaction of the hydrolyzate of the silane compound.

This surface modification in the present invention can typically be easily carried out by causing hydrolysis of the silane compound or the hydrolysis and condensation reaction in the presence of silica fine particles.

The fine silica particles are not particularly limited, but the average particle diameter of the fine silica particles is 1 nm to 1 μm.
The average particle diameter is more preferably in the range of 5 to 200 nm. When transparency is required for a film formed from a coating material containing silica fine particles, it is preferable to use silica fine particles having an average particle diameter of 5 to 100 nm.

As the silica fine particles, for example, colloidal silica can be used. When using colloidal silica,
The dispersion medium is not particularly limited, but usually water; alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol; cellosolves; dimethylacetamide, toluene, xylene and the like are used. Particularly preferred dispersion media are alcohols, cellosolves, toluene, and water.

The silane compounds (b-1) represented by the general formulas (I) to (IV) used in the present invention cause a bond between the silica fine particles and the component (a) by irradiation with active energy rays. , Is a component that contributes to the development of the surface hardness of the cured coating formed by silica fine particles.

The silane compound (b) represented by the general formula (I)
Examples of -1) include p-vinylphenyltrimethoxysilane, (that is, p-trimethoxysilylstyrene), p-vinylphenyltriethoxysilane, p-vinylphenyltriisopropoxysilane, p-vinylphenylmethyldimethoxysilane. , P-vinylphenylmethyldiethoxysilane, p-vinylphenylethyldimethoxysilane, p-vinylphenylpropyldimethoxysilane, p-vinylphenylphenyldimethoxysilane, p-vinylphenyldimethylmethoxysilane, o-
Vinylphenyltrimethoxysilane, o-vinylphenylmethyldimethoxysilane, m-vinylphenyltrimethoxysilane, p-isopropenylphenyltrimethoxysilane, p-isopropenylphenylmethyldimethoxysilane, m-isopropenylphenyltrimethoxysilane, m -Isopropenylphenylmethyldimethoxysilane and the like.

A silane compound (b) represented by the general formula (II)
-1) include, for example, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-acryloyloxypropylmethyl. Diethoxysilane, γ-acryloyloxypropylethyldimethoxysilane, β-acryloyloxyethyltrimethoxysilane, β-acryloyloxyethylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ -Methacryloyloxypropylmethyldimethoxysilane, γ
-Methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylethyldimethoxysilane, γ-methacryloyloxypropyldimethylmethoxysilane, β-methacryloyloxyethyltrimethoxysilane and β-methacryloyloxyethylmethyldimethoxysilane.

Examples of the silane compound (b-1) represented by the general formula (III) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrin-butoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane and vinyl. Examples thereof include ethyltrimethoxysilane, vinyldimethylmethoxysilane, isopropenyltrimethoxysilane, and isopropenylmethyldimethoxysilane.

A silane compound (b) represented by the general formula (IV)
Examples of -1) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ.
-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ- Aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyl Methyldiethoxysilane, N, N-dimethyl-
γ-aminopropyltrimethoxysilane, N, N-diethyl-γ-aminopropyltrimethoxysilane and the like can be mentioned.

In the present invention, the silane compound (b-
As 1), a silane compound represented by the general formula (IV), for example, γ-aminopropyltrimethoxysilane or γ
A coating composition using aminopropyltriethoxysilane or the like is particularly preferable from the viewpoint of improving the weather resistance of the cured coating. The silane compounds (b-1) represented by the general formulas (I) to (IV) are used alone or in combination of two or more kinds.

A silane compound (b) represented by the general formula (V)
-2) contributes to the surface modification of the silica fine particles, but since it does not have the binding ability between the silica fine particles and the polymerized cured product of the component (a), it improves the flexibility of the cured film and It is a component that exhibits good weather resistance.

A silane compound (b) represented by the general formula (V)
As specific examples of -2), tetramethoxysilane, tetraethoxysilane, tetra n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane,
Examples include phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and the like, and mixtures thereof.

The molar ratio of the silane compound (b-1) and the silane compound (b-2) used in the present invention is 5: 95-.
It is in the range of 95: 5, preferably in the range of 10:90 to 90:10, and particularly preferably in the range of 10:90 to 60:40.

When the coating composition containing silica fine particles modified with the silane compound (b-1) and the silane compound (b-2) used in a molar ratio outside the above range is used, The surface hardness is lowered and the weather resistance is deteriorated.

When colloidal silica is used as the silica fine particles, the silane compound is mixed in a dispersion of colloidal silica and hydrolyzed by water in this system or newly added water, so that the surface of the hydrolyzed product is obtained. The modified silica fine particles (b) can be obtained.

When carrying out the hydrolysis reaction of the silane compound, an inorganic acid or an organic acid can be used as a catalyst.
Examples of the inorganic acid include hydrohalic acid such as hydrochloric acid, hydrofluoric acid and hydrobromic acid, and sulfuric acid, nitric acid, phosphoric acid and the like. Examples of the organic acid include formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid and the like.

It is preferable to use a solvent in order to carry out the reaction mildly and uniformly. As this solvent, those capable of compatibilizing the reaction product silane alkoxide with water and the catalyst are preferable.

Specific examples include water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl isobutyl ketone; and ethers such as tetrahydrofuran and dioxane.

As the solvent, the above-mentioned colloidal silica dispersion medium may be used as it is, or a necessary amount may be newly added. When newly added, the above-mentioned solvent can be used.

The amount of the solvent used is not particularly limited as long as it can dissolve the reactant uniformly, but if the concentration of the reactant is too dilute, the reaction rate may be significantly slowed down.
The hydrolysis and condensation reaction of the silane compound is from room temperature to 120 ° C.
The temperature is preferably about 30 minutes to 24 hours, more preferably about room temperature to the boiling point of the solvent for about 1 to 10 hours.

The compounding ratio of the silica fine particles as the component (b) and the silane compound is not particularly limited, but the silane compound (b-1) is added to 100 parts by weight of the silica fine particles (solid content in the case of colloidal silica). And a silane compound (b-
The mixture of 2) is preferably used in an amount of 5 to 200 parts by weight, more preferably 10 to 100 parts by weight. Further, the compounding ratio of the component (a) and the component (b) is not limited, but the component (b) is preferably 1 to 20 with respect to 100 parts by weight of the component (a).
0 parts by weight, particularly preferably 5 to 60 parts by weight are used.

In the coating composition of the present invention, the active energy ray used for curing is, for example, β ray,
Radiation such as γ-rays, X-rays, and accelerated electron beams, and ultraviolet rays are included. Since a polymerization reaction can occur in the coating composition of the present invention, it is necessary to add an active energy ray polymerization initiator (c). is there.

As a specific example of the component (c),
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin,
Toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-
1-one, 4- (2-hydroxyethoxy) phenyl-
(2-hydroxy-2-methylpropyl) ketone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone , 2, 4
Carbonyl compounds such as dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and methylphenylglyoxylate; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobis Azo compounds such as isobutyronitrile and azobis-2,4-dimethylvaleronitrile; peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzoyldiethoxyphosphine Oxide, bis (2,
Examples include phosphine oxide compounds such as 6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide.

Of these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and methylphenylglyoxylate are preferable. These active energy ray polymerization initiators may be used alone or in combination of two or more kinds. The blending amount of the active energy ray polymerization initiator (c) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (a).

The coating composition of the present invention basically contains no organic solvent, but an organic solvent may be added if desired. As the organic solvent, a solvent that can be uniformly mixed with the components (a) and (c) can be used, and a solvent that can uniformly disperse the component (b) can be used.

In particular, the boiling point at atmospheric pressure is 50 ° C. or higher and 200 ° C.
The following is suitable and the viscosity at room temperature (25 ° C.) is 10 centiboise or less. If the boiling point of the organic solvent is out of the above range, the coating solution may dry up, or inconvenience may occur such that it cannot be dried after coating.
Further, when the viscosity is out of the above range, the coating property tends to deteriorate.

As the organic solvent, for example, ethanol,
Alcohols such as isopropyl alcohol, normal propyl alcohol, normal butyl alcohol, and isobutyl alcohol; aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and methyl ethyl ketone;
Ethers such as dioxane; esters such as ethyl acetate and butyl acetate: N, N-dimethylformamides and the like. These organic solvents may be used alone or in admixture of two or more.

Further, the coating composition of the present invention preferably contains an ultraviolet absorber (d) for the purpose of preventing deterioration of the cured coating and protecting the substrate. Examples of the ultraviolet absorber (d) include benzophenone-based, benzotriazole-based, oxalic anilide-based, cyanoacrylate-based, and triazine-based UV absorbers. In the coating composition of the present invention, the benzotriazole-based Those are preferably used.

Specific compounds include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-
5'-t-octylphenyl) benzotriazole, 2
-[2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl ) Benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5′-octoxycarbonylethylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-polyethyleneglycoxycarbonylethylphenyl) benzotriazole and the like can be mentioned. These ultraviolet absorbers (d) may be used alone or in combination of two or more kinds.

In the coating material composition of the present invention,
Further, a light stabilizer (e) can be contained, and among them, a hindered amine light stabilizer is preferably used.

Specific compounds include bis (2,2,2
6,6-tetramethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2
6,6-Tetramethylpiperidine, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionyloxy} -2,2
6,6-Tetramethylpiperidine, 8-acetyl-3-
Dodecyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4,5] decane-2,4-dione,
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine and the like can be mentioned.

Of these, the most preferably used is
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, bis (1-octoxy-2,2,6,6-tetramethyl-4
-Piperidyl) sebacate.

As is generally known, depending on the kind of these light stabilizers (e), precipitation may occur in the coating composition or gelation of the system may occur, making it impossible to apply. However, this can be avoided by selecting the composition of the component (a), the component (b-1) and the component (b-2) and adding a solvent.

Specifically, among the coating compositions of the present invention, in the solventless type, the silane compounds represented by the general formulas (I) to (III) described above as the component (b-1) are used. When bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate or bis (1,2,2,2) is used
6,6-pentamethyl-4-piperidyl) sebacate and the like, the general formula (X)

[Chemical 8] (However, in the formula, R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹³ is a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁴ is a divalent hydrocarbon group having 4 to 12 carbon atoms. When a hindered amine light stabilizer represented by the formula (4) is used, gelling of the coating composition occurs, so 4-benzoyloxy-2,2,2
6,6-Tetramethylpiperidine and bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)
The following general formula (XI) or (XII) such as sebacate

[Chemical 9] (However, in the formula, R ¹⁵ may be a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁶ may be a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁷ may contain a carbon-carbon double bond. A hydrocarbon group having 1 to 12 carbon atoms, R ¹⁸ represents a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁹
Represents a divalent hydrocarbon group having 4 to 12 carbon atoms. By using the hindered amine-based light stabilizer represented by (4), gelation of the system can be avoided.

In the solventless coating composition of the present invention, when the silane compound represented by the general formula (IV) described above is used as the component (b-1), gelation of the system is prevented. All the hindered amine light stabilizers mentioned above can be used without occurring. It was also found that these hindered amine light stabilizers improve the weather resistance of the cured film of the coating composition of the present invention.

Further, in the coating composition of the present invention, various additives such as a surface smoothing agent, a surfactant and a storage stabilizer may be appropriately added and used, if necessary.

The method for producing the coating composition of the present invention is as follows:
Although not particularly limited, for example, the component (b) consisting of a silane compound and, if necessary, water and a catalyst are mixed with a dispersion liquid of colloidal silica, and the mixture is reacted under the above-mentioned reaction conditions. a) Mix the components. A method in which the dispersion medium of colloidal silica and the volatile matter generated by the hydrolysis reaction of the silane compound are then removed, and then the component (c) and, if necessary, other additives are added are particularly preferable.

When the silane compound represented by the general formula (IV) is used as the silane compound (b-1), the components (a) and (b) are preferably mixed by the following method. .

That is, first, a silane compound (b-2) represented by the general formula (V) is added to a dispersion liquid of silica fine particles to cause a hydrolysis reaction to perform surface modification with the hydrolyzed product, and the silica fine particles are Change the surface condition of. Next, the component (a) is added to this reaction system, and then the dispersion medium of the silica fine particles and most of the volatile components such as water are distilled off to replace the dispersion medium of the silica fine particles with the component (a). After that, the silane compound (b-1) represented by the general formula (IV) is added to cause a hydrolysis reaction to further modify the surface of the silica fine particles with the hydrolysis product.

This is because when the silane compound (b-1) represented by the general formula (IV) is added to a colloidal dispersion of silica fine particles using a volatile dispersion medium such as alcohol, the dispersion state of the silica fine particles is It changes and the silica fine particles aggregate and precipitate, or take a three-dimensional structure and cause gelation. In the case of such fine silica particles, the coating composition cannot be applied to an article. Therefore, by adopting such a two-step surface modification method, it becomes possible to produce the coating composition of the present invention using the silane compound of the general formula (IV) without gelation at all.

The method of applying the coating composition of the present invention to the surface of various molded articles includes brush coating method, casting method, roller method, bar coating method, spray coating method, air knife coating method, dipping method and the like. Is mentioned.

The coating amount of the coating composition of the present invention on the surface of the molded article is such that the thickness of the cured coating is 1 to 30 μm.
It is suitable to apply it so that it becomes m. Film thickness is 1 μm
If it is less than the above range, the abrasion resistance is poor, and if the film thickness exceeds 30 μm, the cured film tends to be cracked.

The molded article to which the coating composition of the present invention is applied may be various known molded articles that are required to have improved surface abrasion resistance and the like.

Generally, synthetic resin moldings such as polymethylmethacrylate, copolymers containing methylmethacrylate as a main constituent, polystyrene, styrene
Examples thereof include methyl methacrylate copolymer, styrene-acrylonitrile copolymer, polycarbonate, cellulose acetate butyrate resin, polyacryl diglycol carbonate resin, polyvinyl chloride resin, polyester resin and the like.

Further, the cured film obtained from the coating composition of the present invention has very excellent weather resistance, and therefore, for example, window glass for vehicles such as vehicles and airplanes, headlamp covers, windshields, roof materials; It is particularly useful for applications such as window glass, roofing materials, soundproof walls for roads, nameplates, faceplates for displays, etc. that are used outdoors.

[0085]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the examples. In addition, the part in an Example shows a weight part.

The various physical properties in the examples were measured and evaluated by the methods described below. 1) Scratch resistance No. 000 steel wool is attached to a 25φ circular pad,
The pad was placed on the surface of the sample held on the reciprocating abrasion test table, and reciprocally scratched 100 times under a load of 1000 g. Then, the scratched sample was washed and the haze value was measured with a haze meter. The steel wool scratch resistance (%) was represented by (haze value after scratch)-(haze value before scratch). 2) Abrasion resistance According to the Taber abrasion test method, CS-10F abrasion wheels and 50
A weight of 0 g was combined and the haze value after 100 rotations was measured with a haze meter. The haze value was measured at four locations around the orbit of the wear cycle, and the average value was calculated. The Taber abrasion resistance (%) was shown by (haze value after Taber test)-(haze value before Taber test). 3) Adhesion of cured film The sample is cut with a razor blade at 1 mm intervals to make 11 notches each in the vertical and horizontal directions to make 100 edges, and after closely adhering the commercially available cellophane tape, 90 ° C front direction When the film was rapidly peeled off, the number of cells (X) that the cured film remained without peeling from the molded product was expressed as X / 100. 4) Appearance With respect to the appearance of the molded product on which the cured coating was formed, defects such as banding, spots, cracks, and cloudiness were visually determined and evaluated as follows. ○: No particular defects were noticeable. X: Occurrence of yellowish color of 4.0 or more as a ΔYI value or occurrence of cracks, cloudiness and the like. 5) Weather resistance Sunshine weather meter (Suga Test Instruments Co., Ltd.,
WEL-SUN-DC type) with a black panel temperature of 63 ° C. and a cycle of 12 minutes of rainfall-48 minutes of drying for 1000
After exposure for 2000 hours, the appearance and adhesion of the molded product having the cured film formed thereon were evaluated. ⊚: No particularly noticeable defects. ◯: Some dirt is seen, but there is almost no problem. Δ: Adhesion is reduced. X: Occurrence of yellowish color of 4.0 or more as a ΔYI value or occurrence of cracks, cloudiness and the like. (The order of good weather resistance is indicated by ◎>○>△> x.)

[Example 1] (Preparation of coating composition) Isopropyl alcohol-dispersed colloidal silica (silica content 30% by weight, manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-ST) was added to 35 parts by weight of p.
-Vinylphenyltrimethoxysilane (hereinafter VPTM
2.0 parts by weight of S), 1.7 parts by weight of phenyltrimethoxysilane (hereinafter abbreviated as PTMS), and 1 part by weight of 0.01N aqueous hydrochloric acid solution were added, and the mixture was stirred at 40 ° C. for 1 hour. Then, 30 parts by weight of 1,6-hexanediol diacrylate (hereinafter abbreviated as C6DA), and trimethylolethane / acrylic acid / succinic acid (molar ratio 2/4 /
20 parts by weight of the condensate of 1) (hereinafter abbreviated as TAS) was added, and all volatile components were distilled off under reduced pressure. Then, 1.8 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as APO) as an active energy ray polymerization initiator and 2 as an ultraviolet absorber were added thereto.
-(2-hydroxy-5-t-butylphenylbenzotriazole (manufactured by Ciba Geigy, trade name: Tinuvin P
3.8 parts by weight of S; hereinafter abbreviated as UA-1) was added and dissolved to obtain a coating composition.

(Preparation of Surface Coated Molded Product) A polycarbonate plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialite, thickness) obtained by heating the coating composition thus obtained to 50 ° C. in a gear oven 2 mm) and then a polyester film (Diafoil, thickness 50 μm)
m), while tightly crimping with a sponge roll, and thoroughly squeezed. After leaving for 50 seconds in this state, 2m / m under a 120W / cm metal halide lamp (with parallel reflector, ozone-less type, distance between subject and lamp) adjusted to 13cm irradiation width
The polyester film was passed so that the surface side of the polyester film was irradiated at a speed of minutes. Then, only the polyester film is peeled off, and further passed under a high pressure mercury lamp of 120 W / cm (with parallel reflector, ozone type, irradiation width 13 cm, distance between subject and lamp 30 cm) at a speed of 1 m / min for coating. A resin plate whose surface was protected by the cured film of the composition was obtained. Table 3 shows the results of the evaluation performed on the obtained resin plate by the evaluation method described above.

[Examples 2 to 22 and Comparative Examples 1 to 8] Table 1
The coating compositions having various compositions shown in Table 1 were prepared in the same manner as in Example 1 to obtain a polycarbonate plate (Mitsubishi Rayon Co., Ltd.).
Made, product name: Diamond, thickness 2mm) or polymethylmethacrylate plate (Mitsubishi Rayon Co., Ltd., thickness 2)
mm) was applied and cured in the same manner as in Example 1 to obtain a resin plate whose surface was protected by a cured film. Then, with respect to each resin plate obtained here, the results of the evaluation performed in the same manner as in Example 1 are shown in Tables 3 and 4.

Comparative Example 7 (Preparation of Coating Composition) 35 parts by weight of the same colloidal silica as used in Example 1 was mixed with γ-aminopropyltrimethoxysilane (hereinafter abbreviated as APTMS). Four
When parts by weight were added, the colloidal silica gelled,
Since it was deposited, it was not possible to obtain a coating composition. 30 parts by weight of C6DA and T
Even if 20 parts by weight of AS was further added, it remained a gelled product.

Comparative Example 8 (Preparation of Coating Composition) 35 parts by weight of the same colloidal silica as used in Example 1, 30 parts by weight of C6DA,
And 20 parts by weight of TAS, APTMS 3.4 was added.
Although a part by weight was added, gelling occurred and it was not possible to obtain a coating composition.

[Example 23] (Preparation of coating composition) To 35 parts by weight of the same colloidal silica as that used in Example 1, 1.7 parts by weight of PTMS and 0.8 parts by weight of deionized water were added to give 40 parts. Stir at 1 ° C for 1 hour. Then, 30 parts by weight of C6DA and 20 parts by weight of TAS were added, and most of the volatile components were distilled off under reduced pressure. Next, 1.7 parts by weight of APTMS was added, and the mixture was stirred at 40 ° C. for 1 hour to completely distill off the residual volatile matter. After that, APO
1.8 parts by weight and UA-1 3.8 parts by weight were added to obtain a coating composition.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was applied to a polycarbonate plate under the same conditions as in Example 1, and a polyester film (manufactured by Diafoil Co., thickness (50 μm) and tightly pressure-bonded using a sponge roll, and thoroughly squeezed so that the thickness of the coating layer was about 8 μm. 120 in this state
After leaving for 2 seconds, 80 W / c adjusted to an irradiation width of 13 cm
m metal halide lamp (with parallel reflector,
Ozone-less type, distance between subject and lamp is 30 cm)
The polyester film was passed at a speed of 0.5 m / min so that the polyester film surface side was irradiated. Then, only the polyester film is peeled off, and further passed under a high pressure mercury lamp of 120 W / cm (with parallel reflector, ozone type, irradiation width 13 cm, distance between subject and lamp 30 cm) at a speed of 1 m / min for coating. A resin plate whose surface was protected by the cured film of the composition was obtained. Tables 3 and 4 show the results of evaluations performed on the obtained resin plate in the same manner as in Example 1.

[Examples 24 and 25] Coating compositions having various compositions shown in Table 1 were prepared in the same manner as in Example 23,
Polycarbonate board (Mitsubishi Rayon Co., Ltd., trade name:
A resin plate, the surface of which was protected by a cured coating, was obtained by applying and curing the same on a dialite and a thickness of 2 mm) in the same manner as in Example 23. Table 4 shows the evaluation results obtained by the same method as in Example 1 for each resin plate obtained here.

[Example 26] (Preparation of coating composition) To 35 parts by weight of the same colloidal silica as used in Example 1, 1.7 parts by weight of PTMS, 1 part by weight of VPTMS, and 0 of deionized water were added. 0.8 parts by weight was added, and the mixture was stirred at 40 ° C. for 1 hour. After that, C6DA
30 parts by weight and 20 parts by weight of TAS were added, and most of the volatile components were distilled off under reduced pressure. Next, 0.8 part by weight of APTMS was added, and the mixture was stirred at 40 ° C. for 1 hour to completely distill off the residual volatile matter. Then 1.8 parts by weight of APO and UA
-1 3.8 parts by weight was added to obtain a coating composition.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was applied onto a polycarbonate plate under the same conditions as in Example 1 by the same procedure as in Example 23 and cured. A resin plate whose surface was protected by a cured film was obtained. Table 4 shows the results of evaluations performed on the obtained resin plate in the same manner as in Example 1.

Example 27 100 parts by weight of the same colloidal silica as used in Example 1 was mixed with γ-methacryloyloxypropylmethoxysilane (hereinafter referred to as MPTMS).
6.2 parts by weight, 10 parts by weight of PTMS, and 4 parts by weight of 0.01N aqueous hydrochloric acid solution are added, and the mixture is allowed to stand at 40 ° C. for 2 hours.
Stir for hours. Then, 20 parts by weight of C6DA, 80 parts by weight of bis (acryloyloxyethyl) hydroxyethyl isocyanurate (trade name: Aronix M-215 manufactured by Toagosei Co., Ltd.), 1.2 parts by weight of APO, and methylphenylglyoxylate of 0. 8 parts by weight, UA-11
0 parts by weight, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name: Sanol LS770) 0.4 parts by weight, isobutyl alcohol 270 parts by weight, n-butyl acetate 130 parts by weight, 3-methoxy-1-butanol 40 parts by weight may be added. Stir,
A coating composition was prepared.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was dip-coated at a rate of 0.3 cm / sec onto a polycarbonate plate under the same conditions as in Example 1 to form a film. Then, it was left at 80 ° C. for 10 minutes to evaporate the solvent in the coating composition. Then, using the high-pressure mercury lamp used in Example 1 without covering with a polyester film,
Curing is performed by irradiating active energy rays and curing the coating composition in the same manner as in Example 1 except that the distance between the polycarbonate plate and the lamp is 15 cm and the line speed is 1.5 m / min. A resin plate whose surface was protected by a coating film was obtained. Table 4 shows the results of evaluations performed on the obtained resin plate in the same manner as in Example 1.

[0099]

[Table 1]

[Table 2]

<Abbreviations in Tables 1 and 2> C6DA: 1,6-hexanedioldiacrylate TAS: Condensate of trimethylolethane / acrylic acid / succinic acid (molar ratio 2/4/1) C9DA: 1, 9-nonanediol diacrylate FA731A: tris (acryloyloxyethyl) isocyanurate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-7)
31A) DPHA: Dipentaerythritol hexaacrylate R-684: Dicyclopentanyl diacrylate (Nippon Kayaku Co., Ltd., trade name: Kayarad R-684) IBA: Isobornyl acrylate CHA: Cyclohexyl acrylate ADA: 1- Adamantyl acrylate DMADA: 3,5-dimethyl-1-adamantyl acrylate TBA: t-butyl acrylate CPTAA: cyclopentanyl acrylate CPTEA: cyclopentenyl acrylate THFA: tetrahydrofurfuryl acrylate M-215: bis (acryloyloxyethyl) hydroxyethyl isocyanate Nurate (manufactured by Toagosei Co., Ltd .; trade name: Aronix M-215) S-1: isopropyl alcohol-dispersed colloidal silica (silica content 0% by weight, manufactured by Nissan Chemical Industries, Ltd .; trade name: IPA-ST S-2: Water-dispersed colloidal silica (silica content 20% by weight, manufactured by Nissan Chemical Industry Co., Ltd .; trade name: Snowtex O) VPTMS: p-vinylphenyltrimethoxysilane PTMS: phenyltrimethoxysilane MPTMS: γ-methacryloyloxypropyltrimethoxysilane MTMS: methyltrimethoxysilane DMDMS: dimethyldimethoxysilane TMMS: trimethylmethoxysilane TMS: tetramethoxysilane VTMS: vinyltrimethoxysilane Methoxysilane PATMS: N-phenyl-γ-aminopropyltrimethoxysilane APTMS: γ-aminopropyltrimethoxysilane APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BAS) Ltd., trade name: LUCI
RIN-TPO) BAPO: bis (2,6-dimethoxybenzoyl)-
A mixture of 2,4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methyl-1-phenylpropan-1-one in a weight ratio of 1/3 (manufactured by Ciba-Geigy, trade name: CGI-1700) MPG: methyl Phenylglyoxylate (manufactured by Akzo Japan Ltd., trade name: VICURE-55) UA-1: 2- (2'-hydroxy-5'-tert-
Butylphenyl) benzotriazole (manufactured by Ciba Geigy; trade name: Tinuvin-PS) UA-2: 2- (2'-hydroxy-5'-tert-
Octylphenyl) benzotriazole (Ciba Geigy, trade name Tinuvin-329) HLS-1: bis (1-octoxy-2,2,6,6-)
Tetramethyl-4-piperidyl) sebacate (manufactured by Ciba Geigy, trade name: Tinuvin-123) HLS-2: 4-benzoyloxy-2,2,6,6-
Tetramethylpiperidine (manufactured by Sankyo Co., Ltd., trade name: SANOL LS-744) HLS-3: bis (2,2,6,6-tetramethyl-4)
-Piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name: Sanol LS-770) HLS-4: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (manufactured by Sankyo Co., Ltd., product) Name: Sanol LS-765)

[0101]

[Table 3]

[Table 4]

<Abbreviations in Tables 3 and 4> PC: Polycarbonate PMMA: Polymethylmethacrylate

The coating composition of the present invention is a coating composition which can be applied in both a solventless type and a solvent type,
A cured coating formed by applying and curing this on a substrate has excellent wear resistance and impact resistance, and has a good appearance. It also exhibits excellent weather resistance and is effective in preventing the occurrence of cracks in the coating film. Further, since the surface-coated molded product of the present invention is covered on the surface with a cured film having the above-mentioned effect, various problems such as deterioration of aesthetics due to scratches, which have been conventionally problematic in synthetic resin molded products, have been solved. A molded product can be obtained. Further, since the cured coating obtained from the coating composition of the present invention has very excellent weather resistance, for example, window glass for vehicles such as vehicles and airplanes, headlamp covers, windshields, roofing materials; window glass for buildings. , Roofing material; road soundproof wall; particularly useful for outdoor applications such as nameplates and faceplates for displays.

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[Procedure amendment]

[Submission date] April 27, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title: Coating composition, surface coated molding using the same, and method for producing the same

[Claims]

[Chemical 1] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
10 hydrocarbon group, R ³ is a hydrogen atom or 1 to 10 carbon atoms
10 hydrocarbon groups, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ and R ⁶ are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and m is 0 Represents an integer of 2. 5 to 95 parts by mole of at least one silane compound (b-1) selected from silane compounds represented by
The following general formula (IV)

[Chemical 2] (In the formula, R ⁷ and R ⁸ are the same or different and have 1 to 10 carbon atoms.
R ⁹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and p are integers from 0 to 3, and n
+ P is 0 to 3. ) A silane compound (b-
2) A coating composition comprising: silica fine particles whose surface is modified with a hydrolyzate of a mixture with 95 to 5 parts by mole, and an active energy ray polymerization initiator as a component (c).

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coating composition capable of forming a cured coating having excellent abrasion resistance and weather resistance by irradiation with active energy rays, and a cured product of the coating composition. As a molded article whose surface is covered, in particular, head lamp cover, windshield, vehicle window glass, vehicle roofing material, building window glass, building roofing material, road soundproof wall, name plate and display face plate, etc. The present invention relates to a surface-coated molded article having excellent wear resistance and weather resistance, which is used for.

[0002]

2. Description of the Related Art Recently, as an alternative to transparent inorganic glass,
It is widely practiced to use transparent plastic materials with good crush resistance.

However, the transparent plastic material is
Compared with inorganic glass, it has a serious problem that it has a soft surface and is easily scratched, and thus lacks abrasion resistance and weather resistance. Therefore, many attempts have heretofore been made to improve the wear resistance of transparent plastic materials.

As one of the most general methods, for example, as described in JP-A-53-102936, JP-A-53-104638, JP-A-54-97633 and the like, there are a plurality of molecules in a molecule. A molded product having a coating with excellent scratch resistance is obtained by applying a curing liquid mainly containing a compound having an acryloyloxy group or a methacryloyloxy group to the surface of the molded product and curing it by irradiation with active energy rays such as heat or ultraviolet rays. There is a way to get it. The curable liquid used in this method is relatively inexpensive and easily available, but since the cured coating film obtained is an organic substance, the wear resistance of the molded article having this coating is currently limited.

On the other hand, as a method for imparting higher surface hardness, for example, Japanese Patent Laid-Open Nos. 48-26822 and 59-59.
As disclosed in Japanese Patent No. 64671, etc., a method of applying an alkoxysilane compound to the surface of a plastic molded article to obtain a molded article having a coating cured by heat, or JP-A-56-106969, Kaihei 2-2
Japanese Patent No. 72041 discloses a method of applying a coating composition comprising colloidal silica and a curing liquid onto the surface of a plastic molded article to obtain a molded article having a coating cured by heat.

However, since the coating composition used in these methods uses an organic solvent in order to improve its coatability, cracks occur in the plastic molded article to be coated during the drying process. Or coating defects such as coating unevenness are likely to occur, and a problem may occur in the appearance of the obtained coated molded product. Further, it is inevitable that the organic solvent is released into the air in the coating process, which is not preferable from the viewpoint of global environment protection, which has been attracting attention in recent years.

Further, the coating film formed from these curing liquids is industrially disadvantageous because it consumes a large amount of energy because it is cured by heat and it takes a long time to cure.

On the other hand, Japanese Examined Patent Publication No. 62-21815, Japanese Examined Patent Publication No. 1-55307, No. 3-2168, No. 3-6190, Japanese Unexamined Patent Publication No. 59-204669, No. 62-256874. JP-A-2-6413
No. 8, gazette 4-18423 gazette, and gazette 4-21474.
No. 3, gazette No. 4-220411 gazette, and No. 5-9818.
No. 9, gazette 5-306374, gazette 6-2536.
No. 3, No. 6-41468, and No. 6-151.
Japanese Patent No. 694 discloses a coating composition composed of colloidal silica, an alkoxysilane having an acryl group or a methacryl group, and a polyfunctional acrylate.

These coating compositions can also be used as a solvent-free coating material, and a plastic molded article having a relatively excellent surface hardness can be obtained from this coating material. There was a problem that the cured film was hydrolyzed at the interface between the colloidal silica and the alkoxysilane to cause cracks and whitening, and the weather resistance was not sufficient. In order to solve these problems, the inventors of the present invention, as shown in JP-A-6-100789, have silica fine particles whose surface is modified with a hydrolyzate of an alkoxysilane having a styryl group, a polyfunctional acrylate, and It has been found that coating compositions comprising active energy ray polymerization initiators have good properties.

[0010]

However, although this coating composition also has superior performance to the conventional one, it cannot be said to be sufficient, and a cured film having high surface hardness and excellent weather resistance is obtained. The present situation is that an active energy ray-curable coating composition that can be used without a solvent that can be formed has not yet been obtained. The present invention has been obtained as a result of extensive studies to solve the above problems, the object is that it can be coated without using a solvent, and has a high surface hardness and good appearance and weather resistance. An active energy ray-curable coating composition capable of forming a cured coating having excellent abrasion resistance and scratch resistance. Another object of the present invention is to provide a molded product whose surface is coated with a cured product of this coating composition.

[0011]

[Means for Solving the Problems]

The inventors of the present invention have mainly used silica fine particles modified with a hydrolyzate of a silane compound (b-1) and a polyfunctional acrylate and / or methacrylate (hereinafter abbreviated as (meth) acrylate) as a main component. The cured film obtained from the coating composition that has been developed is considerably excellent, but in order to improve the point that it is inferior in weather resistance, the surface hardness development mechanism of this cured film and the factors affecting the weather resistance have been thoroughly studied. As a result of carrying out, the present invention was achieved. That is, the present invention provides, as the component (a), a crosslinkable polymerizable compound (a-) having at least two acryloyloxy groups and / or methacryloyloxy groups in the molecule.
1) or 50% by weight of the crosslinkable polymerizable compound (a-1)
50% by weight of the above compound (a-2) copolymerizable therewith
And a mixture of the following general formulas (I) to (III) as the component (b):

[Chemical 3] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
10 hydrocarbon group, R ³ is a hydrogen atom or 1 to 10 carbon atoms
10 hydrocarbon groups, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ and R ⁶ are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and m is 0 Represents an integer of 2. 5 to 95 parts by mole of at least one silane compound (b-1) selected from silane compounds represented by
The following general formula (IV)

[Chemical 4] (In the formula, R ⁷ and R ⁸ are the same or different and have 1 to 1 carbon atoms.
A hydrocarbon group of 0, R ⁹ is a hydrogen atom or a carbon number of 1 to 10
Hydrocarbon groups, n and p are integers of 0 to 3, and n + p is 0 to 3. ) A silane compound (b
-2) A coating composition comprising silica fine particles whose surface is modified with a hydrolyzate of a mixture with 95 to 5 parts by mole, and an active energy ray polymerization initiator as the component (c).

Another aspect is a method for producing the coating composition by mixing the components (a), (b) and (c), wherein the silane compound is contained in a dispersion of silica fine particles. (B-2) is added to modify the surface of the silica fine particles with the hydrolyzate, and then the dispersion medium of the silica fine particles and water are distilled off after adding the component (a).
The method for producing a coating composition further comprises the step of subsequently adding a silane compound (b-1) to modify the surface of the silica fine particles with a hydrolyzate thereof. Further, a molded product whose surface is coated with a cured product of the coating composition is also an object of the present invention.

The inventors of the present invention have considered that (1) the weather resistance of the cured coating affects the degree of surface modification of the silica fine particles as factors affecting the surface hardness development mechanism and weather resistance of the conventional cured coating as described above. If the surface modification is not appropriate, the weather resistance will be reduced. (2) In order to express the surface hardness of the cured film to a high degree, between the silica fine particles and the polymerized and cured product of the polyfunctional (meth) acrylate. Silane compound (b-1) plays the role, and (3) silica fine particles and polyfunctional (meth) acrylate have a large number of bonding points. If too much, it becomes a factor that hinders the flexibility of the cured film, and the cured film expands and contracts during the high temperature / low temperature heat cycle test and the water absorption / drying water absorption cycle test in the weather resistance evaluation. Keep up without, defects such as cracks that appear found in the cured film.

Therefore, based on this finding, as a result of further studies in order to obtain a coating composition in which the surface hardness and weather resistance of the cured film are exhibited at the same time, the silane used for modifying the surface of the silica fine particles. As a compound, a silane compound (b-1) that causes a bond between the silica fine particles and the polymerization-cured product of a polyfunctional (meth) acrylate, and a silane compound (b-2) that does not cause a bond between them are used together. By doing so, it was clarified that the above performance can be exhibited.

That is, the silane compound (b-1) mainly serves to improve the surface hardness of the coating film, and the silane compound (b-).
2) acts on the surface modification of the silica fine particles and imparts flexibility to the cured film. Therefore, by using a coating composition containing the silica particles modified by both, high surface hardness and good weather resistance are exhibited. It has been found that a cured coating of this type is obtained.

The present invention will be described in detail below. The component (a) in the coating composition of the present invention is a crosslinkable polymerizable compound (a) having at least two acryloyloxy groups and / or methacryloyloxy groups (hereinafter abbreviated as (meth) acryloyloxy group) in the molecule. -1). The crosslinkable polymerizable compound (a-1) used in the present invention is
The residue that is a moiety other than the (meth) acryloyloxy group is a hydrocarbon or a derivative thereof, and the molecule may contain an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, or the like.

As the crosslinkable polymerizable compound (a-1),
Examples thereof include ester compounds obtained from polyhydric alcohols and (meth) acrylic acid or their derivatives, or ester compounds obtained from polyhydric alcohols and polyvalent carboxylic acids, and (meth) acrylic acid or their derivatives. .

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 300 to about 1000, propylene glycol, dipropylene glycol, 1,3-.
Propanediol, 1,3-butanediol, 2,3-
Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-
Nonanediol, neopentyl glycol (ie 2,2-dimethyl-1,3-propanediol), 2-
Ethylhexyl-1,3-hexanediol, 2,2 '
Divalent alcohols such as thiodiethanol and 1,4-cyclohexanedimethanol; trimethylolpropane (ie 1,1,1-trimethylolpropane), pentaglycerol (ie 1,1,1-trimethylolethane), Glycerol, 1,2,4-butanetriol,
Trihydric alcohols such as 1,2,6-hexanetriol; other pentaerythritol (that is, 2,2-bis (hydroxymethyl) -1,3-propanediol),
Examples include diglycerol and dipentaerythritol.

Specific examples of the crosslinkable polymerizable compound (a-1) obtained as a poly (meth) acrylate of a polyhydric alcohol include the following general formula (V).

[Chemical 5] (In the formula, q is an integer of 0 to 4, two or more of X ¹ present in the molecule are two or more (meth) acryloyloxy groups, and the remaining X ¹ are each independently a hydrogen atom, A compound represented by a hydroxyl group, an amino group, an alkyl group or a substituted alkyl group.).

Specific examples of the compound represented by the general formula (V) include trimethylolpropane tri (meth).
Acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate ) Acrylate, tripentaerythritol penta (meth) acrylate,
Examples include tripentaerythritol hexa (meth) acrylate and tripentaerythritol hepta (meth) acrylate.

Examples of poly (meth) acrylates of polyhydric alcohols other than the compound of the general formula (V) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth). ) Acrylate, 1,4-
Examples include butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and glycerin tri (meth) acrylate.

When an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid or a derivative thereof is used as the crosslinkable compound (a-1), particularly preferable ester compounds are diethylene glycol di (meth) acrylate and triethylene. Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaglycerol acrylate, dipentaglycerol pentaacrylate and the like.

The ester compound obtained from a polyhydric alcohol, a polyvalent carboxylic acid and (meth) acrylic acid or a derivative thereof which can be used as the crosslinkable polymerizable compound (a-1) is basically a polyhydric compound. It is obtained by reacting a mixture in which the hydroxyl groups of the alcohol and the carboxyl groups of both the polycarboxylic acid and (meth) acrylic acid or its derivative are finally equivalent.

Among these ester compounds, preferred are polyhydric alcohols which are dihydric alcohols, trihydric alcohols, or a mixture of dihydric alcohols and trihydric alcohols, and polyhydric carboxylic acids are dihydric alcohols. Examples thereof include esterified products obtained by using a carboxylic acid. Three
When a mixture of a dihydric alcohol and a dihydric alcohol is used, the molar ratio of the trihydric alcohol and the dihydric alcohol can be arbitrarily selected.

When the divalent carboxylic acid and (meth) acrylic acid or its derivative are used in combination, the molar ratio is 1 mol of the carboxyl group of (meth) acrylic acid or its derivative to the carboxyl of the divalent carboxylic acid. The number of groups is preferably within the range of 2 mol or less. When the divalent carboxylic acid is in excess of the above range, the viscosity of the ester produced becomes too high, which may make it difficult to form a coating film.

Examples of the divalent carboxylic acid or its derivative used in the synthesis of the above ester compound include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; tetrahydrophthalic acid and 3,6-endomethylenetetrahydrophthalic acid. Alicyclic dicarboxylic acids such as; phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids; other thioglycols, thiodivaleric acid, diglycolic acid, maleic acid, fumaric acid, itaconic acid, and their chlorides, An anhydride, an ester, etc. can be mentioned.

Specific examples of the above-mentioned ester compound used as the crosslinkable polymerizable compound (a-1) include malonic acid / trimethylolethane / (meth) acrylic acid and malonic acid /
Trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid /
Trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, adipic acid /
Trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, glutaric acid / tri Methylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylol Ethane / (meta)
Acrylic acid, sebacic acid / trimethylolpropane /
(Meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol /
(Meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, phthalic acid / glycerin /
(Meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / pentaerythritol / Saturated or unsaturated polyester poly (meth) by a combination of (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid, etc.
It is an acrylate.

Further, as the cross-linking polymerizable compound (a-1), for example, tolylene triisocyanate represented by the following general formula (VI)

[Chemical 6] (In the formula, R ¹⁰ represents an alkylene group having 1 to ¹⁰ carbon atoms.), Hexamethylene diisocyanate, tolylene diisocyanate, diphenylethane diisocyanate,
Polyisocyanates such as xylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate or trimethylhexamethylene diisocyanate, and acrylic monomers having active hydrogen, such as 2-hydroxyethyl (meth)
Acrylic monomer 1 per mole of isocyanate group, such as acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and N-hydroxy (meth) acrylamide.
Urethane (meth) acrylates obtained by reacting at least one mole by a conventional method; and poly [(meth) acryloyloxyethyl] isocyanurates such as tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid.

The component (a) in the coating composition of the present invention comprises a crosslinkable polymerizable compound (a-1) as a main component (50% by weight).
A mixture of the above) and the compound (a-2) copolymerizable therewith may be used.

As the copolymerizable compound (a-2), for example, a compound having one (meth) acryloyl group in the molecule is used.

Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate, isobutyl (meth) acrylate, t-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5-dimethyl-1-
Adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth)
Acrylate, 1,4-butylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate,
(Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2 3,3-Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, N-hydroxybutyl (meth) acrylamide, hydroxymethyldiacetone (meth) acrylamide, N-hydroxyethyl-
N-methyl (meth) acrylamide etc. are mentioned.

Further, the following general formula (VII) or (VIII)

[Chemical 7] (Wherein, r is indicates 1 to 10, X ² represents a (meth) acryloyloxy group, R ^{1 1} is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, a benzyl group or substituted benzyl group .) And other mono (meth) acrylates.

Examples of the mono (meth) acrylate represented by the general formulas (VII) and (VIII) include methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate,
Examples thereof include phenoxy polyethylene glycol (meth) acrylate and butoxyethylene glycol (meth) acrylate.

Further, as the copolymerizable compound (a-2), for example, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxypropyl hydrogen Succinate, various known epoxy (meth) acrylates, urethane (meth) acrylates, and the like are also included.

The compound (a-2) is selected according to the intended use of the cured film obtained in the present invention, but when a film having high surface hardness is desired, a glass of a polymer of the compound (a-2) is used. Those having a high transition temperature are preferably used.

Specific compounds include t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 3,5-dimethyl-1-adamantyl (meth). Examples thereof include acrylate, dicyclopentanyl (meth) acrylate and dicyclopentenyl (meth) acrylate.

When using these compounds (a-2), it is necessary that the content of the compound (a) in the component (a) is 50% by weight or less, and preferably 30% by weight or less. The compound (a-
When 2) is included, the surface hardness of the cured film obtained by the present invention will be reduced.

The component (b) in the coating composition of the present invention is at least one silane compound (b- selected from the silane compounds represented by the general formulas (I) to (III).
A silica fine particle whose surface is modified with a hydrolyzate of a mixture of 1) and at least one silane compound (b-2) selected from the silane compounds represented by the general formula (IV).

The phrase "the surface is modified with a hydrolyzate" as used herein means that the hydrolyzate of the silane compound is retained on a part or all of the surface of the silica fine particles, and the surface characteristics of the silica fine particles are Means modified. It should be noted that this also includes silica fine particles that simultaneously retain those that have undergone the condensation reaction of the hydrolyzate of the silane compound.

The surface modification of the silica fine particles in the present invention can typically be easily carried out by causing hydrolysis of the silane compound or the hydrolysis and condensation reaction in the presence of the silica particles.

The fine silica particles are not particularly limited, but the average particle diameter of the fine silica particles is 1 nm to 1 μm.
Is preferable, and the average particle diameter is more preferably 5 to 200 nm. When transparency is required for a film formed from a coating material containing silica fine particles, it is preferable to use silica fine particles having an average particle diameter of 5 to 100 nm.

As the silica fine particles, for example, colloidal silica can be used. When using colloidal silica,
The dispersion medium is not particularly limited, but usually water; alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol; cellosolves; dimethylacetamide, toluene, xylene and the like are used. Particularly preferred dispersion media are alcohols, cellosolves, toluene, and water.

The silane compound (b-1) represented by the general formulas (I) to (III) used in the present invention causes a bond between the silica fine particles and the component (a) by irradiation with active energy rays. , Is a component that contributes to the development of the surface hardness of the cured coating formed by silica particles.

The silane compound (b) represented by the general formula (I)
Examples of -1) include p-vinylphenyltrimethoxysilane, (i.e. p-trimethoxysilylstyrene), p-vinylphenyltriethoxysilane, p-vinylphenyltriisopropoxysilane, p-vinylphenylmethyldimethoxysilane, p-vinylphenylmethyldiethoxysilane, p-vinylphenylethyldimethoxysilane, p-vinylphenylpropyldimethoxysilane, p-vinylphenylphenyldimethoxysilane, p-vinylphenyldimethylmethoxysilane, o-
Vinylphenyltrimethoxysilane, o-vinylphenylmethyldimethoxysilane, m-vinylphenyltrimethoxysilane, p-isopropenylphenyltrimethoxysilane, p-isopropenylphenylmethyldimethoxysilane, m-isopropenylphenyltrimethoxysilane, m -Isopropenylphenylmethyldimethoxysilane and the like.

A silane compound (b) represented by the general formula (II)
As -1), for example, vinyltrimethoxysilane,
Examples thereof include vinyltriethoxysilane, vinyltrin-butoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylethyltrimethoxysilane, vinyldimethylmethoxysilane, isopropenyltrimethoxysilane, and isopropenylmethyldimethoxysilane.

Specific examples of the silane compound (b-1) represented by the general formula (III) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane and γ. -Aminopropylmethyldiethoxysilane, γ-
Aminopropylethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-
Aminopropyltriethoxysilane, N-phenyl-γ
-Aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, N,
Examples thereof include N-dimethyl-γ-aminopropyltrimethoxysilane and N, N-diethyl-γ-aminopropyltrimethoxysilane.

The silane compounds (b-1) represented by the general formulas (I) to (III) may be used alone or in combination of two or more kinds.

However, among the silane compounds (b-1) represented by the general formula (III), for example, only silane compounds such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane are used. When the solventless coating composition of the invention is produced, the system gels, and the obtained coating composition cannot be applied, which is not preferable. However, only when the silane compound (b-2) described later is used in combination with the silane compound, a coating composition can be obtained without causing gelation of the system.

A silane compound (b) represented by the general formula (IV)
-2) contributes to the surface modification of the silica fine particles, but does not have the binding ability between the silica fine particles and the component (a).
It is a component that improves the flexibility of the cured film and eventually exhibits good weather resistance.

A silane compound (b) represented by the general formula (IV)
As specific examples of -2), tetramethoxysilane, tetraethoxysilane, tetra n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane,
Examples include phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and the like, and mixtures thereof.

The molar ratio of the silane compound (b-1) and the silane compound (b-2) used in the present invention is 5: 95-.
It is in the range of 95: 5, preferably 10:90 to 90 :.
The range is 10, and the range from 10:90 to 60:40 is particularly preferable.

When a coating composition containing silica fine particles modified with the silane compound (b-1) and the silane compound (b-2) used in a molar ratio outside the above range is used, a cured film The surface hardness is lowered and the weather resistance is deteriorated.

When colloidal silica is used as the silica fine particles, the silane compound is mixed in a dispersion of colloidal silica and hydrolyzed by water in this system or newly added water, so that the surface of the hydrolyzed product is obtained. The modified silica fine particles (b) can be obtained.

When carrying out the hydrolysis reaction of the silane compound, an inorganic acid or an organic acid can be used as a catalyst. Examples of the inorganic acid include hydrohalic acid such as hydrochloric acid, hydrofluoric acid and hydrobromic acid, and sulfuric acid, nitric acid, phosphoric acid and the like. Examples of the organic acid include formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid and the like.

It is preferable to use a solvent in order to carry out the reaction mildly and uniformly. As this solvent, those capable of compatibilizing the reaction product silane alkoxide with water and the catalyst are preferable.

Specific examples include water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl isobutyl ketone; and ethers such as tetrahydrofuran and dioxane.

As the solvent, the above-mentioned colloidal silica dispersion medium may be used as it is, or a necessary amount may be newly added. The solvent described above can also be used when newly added.

The amount of the solvent used is not particularly limited as long as it can dissolve the reactant uniformly, but if the concentration of the reactant is too dilute, the reaction rate may be significantly slowed down.
The hydrolysis and condensation reaction of the silane compound is from room temperature to 120 ° C.
The temperature is preferably about 30 minutes to 24 hours, more preferably about room temperature to the boiling point of the solvent for about 1 to 10 hours.

The compounding ratio of the silica fine particles as the component (b) and the silane compound is not particularly limited, but the silane compound (b-1) is added to 100 parts by weight of the silica fine particles (solid content in the case of colloidal silica). And a silane compound (b-
The amount of the mixture of 2) is preferably in the range of 5 to 200 parts by weight, more preferably 10 to 100 parts by weight. Further, the compounding ratio of the component (a) and the component (b) is not limited, but it is preferable that the content of the component (b) is 1 to 200 parts by weight, particularly preferably 100 parts by weight of the component (a). Is in the range of 5 to 60 parts by weight.

In the coating composition of the present invention, the active energy ray used for curing is, for example, β ray,
Radiation such as γ-rays, X-rays, and accelerated electron beams, and ultraviolet rays are included. Since a polymerization reaction can occur in the coating composition of the present invention, it is necessary to add an active energy ray polymerization initiator (c). is there.

As a specific example of the component (c),
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin,
Toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-
1-one, 4- (2-hydroxyethoxy) phenyl-
(2-hydroxy-2-methylpropyl) ketone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone , 2, 4
Carbonyl compounds such as dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and methylphenylglyoxylate; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobis Azo compounds such as isobutyronitrile and azobis-2,4-dimethylvaleronitrile; peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzoyldiethoxyphosphine Oxide, bis (2,
Examples thereof include phosphine oxide compounds such as 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Among them, 2,4-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-
Dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide and methylphenylglyoxylate are preferred.

These active energy ray polymerization initiators are
They may be used alone or in combination of two or more. The blending amount of the active energy ray polymerization initiator (c) is
0.01 to 10 parts by weight is preferable with respect to 100 parts by weight of the component (a).

The coating composition of the present invention is basically provided without containing an organic solvent, but an organic solvent may be added and used if desired. As the organic solvent, those which can be uniformly mixed with the components (a) and (c) and which can uniformly disperse the component (b) can be used.

In particular, the boiling point at atmospheric pressure is 50 ° C. or higher and 200 ° C.
The following is suitable and the viscosity at room temperature (25 ° C.) is 10 centiboise or less. If the boiling point of the organic solvent is out of the above range, the coating solution may dry up, or inconvenience may occur such that it cannot be dried after coating.
Further, if the viscosity is out of the above range, the coatability tends to deteriorate.

As the organic solvent, for example, ethanol,
Alcohols such as isopropyl alcohol, normal propyl alcohol, normal butyl alcohol, and isobutyl alcohol; aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and methyl ethyl ketone;
Ethers such as dioxane; esters such as ethyl acetate and butyl acetate: N, N-dimethylformamides and the like. These organic solvents may be used alone or in admixture of two or more.

Further, the coating composition of the present invention preferably contains an ultraviolet absorber (d) for the purpose of preventing deterioration of the cured coating and protecting the substrate. As the ultraviolet absorber (d), benzophenone-based, benzotriazole-based, oxalic anilide-based, cyanoacrylate-based, and triazine-based ones are used. In the coating composition of the present invention, benzotriazole-based ones are used. Is preferably used.

Specific compounds include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-
5'-t-octylphenyl) benzotriazole, 2
-[2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl ) Benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5′-octoxycarbonylethylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-polyethyleneglycoxycarbonylethylphenyl) benzotriazole and the like can be mentioned. These ultraviolet absorbers (d) may be used alone or in combination of two or more kinds.

In the coating material composition of the present invention,
Further, a light stabilizer (e) can be contained, and among them, a hindered amine light stabilizer is preferably used. Specific examples of the light stabilizer (e) include bis (2,2
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,
2,6,6-tetramethylpiperidine, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy} -2,
2,6,6-tetramethylpiperidine, 8-acetyl-
3-dodecyl-7,7,9,9-tetramethyl-1,
3,8-Triazaspiro [4,5] decane-2,4-dione, 4- (meth) acryloyloxy-2,2,6
6-Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine and the like can be mentioned.

Among these, the most preferred compounds are bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, 4-benzoyloxy-
2,2,6,6-tetramethylpiperidine, bis (1-
Octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

As is generally known, depending on the type of these light stabilizers (e), precipitation may occur in the coating composition or gelation of the system may occur, making it impossible to apply. However, this can be avoided by selecting the composition of the component (a), the component (b-1) and the component (b-2) and adding a solvent. Specifically, in the solvent-free coating composition of the present invention, when the silane compounds represented by the general formulas (I) and (II) described above are used as the component (b-1). , Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-
The use of a hindered amine light stabilizer represented by the following general formula (IX), such as 4-piperidyl) sebacate, is not preferable because it causes gelation of the coating composition.

[0072]

[Chemical 8] (However, in the formula, R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹³ is a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁴ is a divalent hydrocarbon group having 4 to 12 carbon atoms. Represents.)

The coating composition of the present invention comprises the component (a) consisting of the component (a-1) and the component (a-2), and the component (b-1) and the component (b-2) (b). ) The above problems have been solved by selecting the composition of components and adding a solvent.

That is, among the coating compositions of the present invention,
In the solventless type, 4-benzoyloxy-
2,2,6,6-tetramethylpiperidine and bis (1-
Octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc., and the following general formula (X) or (XI)

[Chemical 9] (However, in the formula, R ¹⁵ may be a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁶ may be a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁷ may contain a carbon-carbon double bond. A hydrocarbon group having 1 to 12 carbon atoms, R ¹⁸ represents a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁹
Represents a divalent hydrocarbon group having 4 to 12 carbon atoms. It is preferable to use a hindered amine-based light stabilizer represented by (4).

However, in the solventless coating composition of the present invention, when the silane compound represented by the general formula (III) described above is used as the component (b-1), all the hindered amines described above are used. It has been found that light stabilizers can be used without gelation of the system. Furthermore, it was also found that these hindered amine light stabilizers improve the weather resistance of the cured coating film of the coating composition of the present invention.

In the coating composition of the present invention,
If necessary, various additives such as a surface smoothing agent, a surfactant and a storage stabilizer may be appropriately added and used.

The method for obtaining the coating composition of the present invention is not particularly limited, but for example, a dispersion liquid of colloidal silica is mixed with a component (b) consisting of a silane compound and, if necessary, water or a catalyst, The reaction is carried out under the reaction conditions described above, and the component (a) is mixed in the liquid after this reaction. Next, a method in which the dispersion medium of the colloidal silica and the volatile matter generated by the hydrolysis reaction of the silane compound are removed, and then the component (c) and other additives, if necessary, are added is particularly preferable.

When a silane compound represented by the general formula (III) is used as the silane compound (b-1), the components (a) and (b) are preferably mixed by the following method. .

That is, first, a silane compound (b-2) represented by the general formula (IV) is added to a dispersion liquid of silica fine particles to cause a hydrolysis reaction to perform surface modification with the hydrolyzed product, and the silica is Change the surface condition of the particles. Next, the component (a) is added to this reaction system, and then the dispersion medium of the silica fine particles and most of the volatile components such as water are distilled off to replace the dispersion medium of the silica fine particles with the component (a). After that, a silane compound (b-
1) is added to cause a hydrolysis reaction to further modify the surface of the silica fine particles with the hydrolysis product. When the silane compound (b-1) represented by the general formula (III) is added to a dispersion liquid of mochi polysilica fine particles in which a volatile dispersion medium such as alcohol is added, silica fine particles are precipitated and easily gelled.

By adopting such a two-step surface modification method, by adopting such a two-step modification method, the coating composition of the present invention using the silane compound of the general formula (III) is gelled. It is possible to manufacture in the state where there is no change.

The method of applying the coating composition of the present invention to the surface of various molded articles includes brush coating method, casting method, roller method, bar coating method, spray coating method, air knife coating method, dipping method and the like. Is mentioned.

The coating amount of the coating composition of the present invention on the surface of the molded article is such that the thickness of the cured coating is 1 to 30 μm.
It is suitable to apply it so that it becomes m. Film thickness is 1 μm
If it is less than the above range, the abrasion resistance is poor, and if the film thickness exceeds 30 μm, the cured film tends to be cracked.

The molded article to which the coating composition of the present invention is applied may be various known molded articles which are required to have improved surface abrasion resistance and the like.

Generally, as a synthetic resin molded product, for example, polymethylmethacrylate, a copolymer having methylmethacrylate as a main constituent, polystyrene, styrene-
Examples thereof include methyl methacrylate copolymer, styrene-acrylonitrile copolymer, polycarbonate, cellulose acetate butyrate resin, polyacryl diglycol carbonate resin, polyvinyl chloride resin, polyester resin and the like.

Further, since the cured coating film obtained from the coating composition of the present invention is very excellent in weather resistance, for example, window glass for vehicles such as vehicles and airplanes, windshields, roofing materials, headlamp covers; It is especially useful for outdoor applications such as window glass, roofing materials, soundproof walls for roads, nameplates and face plates for displays.

[0086]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.
In addition, the part in an Example shows a weight part.

The various physical properties in the examples were measured and evaluated by the following methods. 1) Scratch resistance No. 000 steel wool is attached to a 25φ circular pad,
The pad was placed on the surface of the sample held on the reciprocating abrasion test table, and reciprocally scratched 100 times under a load of 1000 g. Then, the scratched sample was washed and the haze value was measured with a haze meter. The steel wool scratch resistance (%) was represented by (haze value after scratch)-(haze value before scratch). 2) Abrasion resistance According to the Taber abrasion test method, CS-10F abrasion wheels and 50
A weight of 0 g was combined and the haze value after 100 rotations was measured with a haze meter. The haze value was measured at four locations around the orbit of the wear cycle, and the average value was calculated. The Taber abrasion resistance (%) was shown by (haze value after Taber test)-(haze value before Taber test). 3) Adhesion of cured film The sample is cut with a razor blade at 1 mm intervals to make 11 notches each in the vertical and horizontal directions to make 100 edges, and after closely adhering the commercially available cellophane tape, 90 ° C front direction When rapidly peeled off, the number of cells (X) when the cured film remained without peeling from the molded product was indicated by X / 100. 4) Appearance With respect to the appearance of the molded product on which the cured film was formed, defects such as banding, spots, cracks, and cloudiness were visually determined and evaluated as follows. ○: No particular defects were noticeable. X: A yellowish color having a ΔYI value of 4.0 or more, or generation of spots, cracks, cloudiness, etc. is observed. 5) Weather resistance Sunshine weather meter (Suga Test Instruments Co., Ltd.,
WEL-SUN-DC type) with a black panel temperature of 63 ° C. and a cycle of 12 minutes of rainfall-48 minutes of drying for 1000
After exposure for 2000 hours, the appearance and adhesion of the molded product having the cured film formed thereon were evaluated. ⊚: No particularly noticeable defects. ◯: Some dirt is seen, but there is almost no problem. Δ: Adhesion is reduced. X: Occurrence of yellowish color of 4.0 or more as a ΔYI value or occurrence of cracks, cloudiness and the like. (The order of good weather resistance is indicated by ◎>○>△> x.)

[Example 1] (Preparation of coating composition) Isopropyl alcohol-dispersed colloidal silica (silica content 30% by weight, manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-ST) was added to 35 parts by weight of p.
-Vinylphenyltrimethoxysilane (hereinafter VPTM
2.0 parts by weight of S), 1.7 parts by weight of phenyltrimethoxysilane (hereinafter abbreviated as PTMS), and 1 part by weight of 0.01N aqueous hydrochloric acid solution were added, and the mixture was stirred at 40 ° C. for 1 hour. Then, 30 parts by weight of 1,6-hexanediol diacrylate (hereinafter abbreviated as C6DA) and 20 parts by weight of a condensate of trimethylolethane / acrylic acid / succinic acid (2/4/1) (hereinafter abbreviated as TAS). Parts were added, and all volatile components were distilled off under reduced pressure. Next, 1.8 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as APO) as an active energy ray polymerization initiator, and 2- (2-hydroxy-5-tert-) as an ultraviolet absorber. 3.8 parts by weight of butylphenylbenzotriazole (manufactured by Ciba-Geigy, trade name: Tinuvin PS; hereinafter abbreviated as UA-1) was added and dissolved to obtain a coating composition.

(Preparation of Surface Coated Molded Product) The coating composition thus obtained was heated at 50 ° C. in a gear oven to obtain a polycarbonate plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialite, thickness). 2 mm) and then a polyester film (Diafoil, thickness 50 μm)
m) and tightly pressure-bonded with a sponge roll, and thoroughly squeezed so that the thickness of the coating layer was about 8 μm. After leaving for 50 seconds in this state, under a 120 W / cm metal halide lamp (with parallel reflector, ozoneless type, distance between subject and lamp 30 cm) adjusted to 13 cm irradiation width, at a speed of 2 m / min. ,
The polyester film was passed such that the surface side was irradiated. Then, only the polyester film was peeled off, and a 120 W / cm high pressure mercury lamp (with a parallel reflector,
Ozone type, irradiation width 13 cm, distance between subject and lamp 30 cm) was passed at a speed of 1 m / min to obtain a resin plate whose surface was protected by a cured film of the coating composition. Table 2 shows the evaluation results of the obtained resin plate obtained by the above-described evaluation method.

[Examples 2 to 22 and Comparative Examples 1 to 6] Table 1
The coating compositions having various compositions shown in Table 1 were prepared in the same manner as in Example 1 to obtain a polycarbonate plate (Mitsubishi Rayon Co., Ltd.).
Made, product name: Diamond, thickness 2mm) or polymethylmethacrylate plate (Mitsubishi Rayon Co., Ltd., thickness 2)
mm) was applied and cured in the same manner as in Example 1 to obtain a resin plate whose surface was protected by a cured film. Table 2 shows the evaluation results obtained by the same method as in Example 1 for each resin plate obtained here.

Comparative Example 7 (Preparation of Coating Composition) 35 parts by weight of the same colloidal silica as used in Example 1 was added to γ-aminopropyltrimethoxysilane (hereinafter abbreviated as APTMS). Four
When parts by weight were added, colloidal silica gelled and was deposited, so that the coating composition could not be obtained. So, 30 parts by weight of C6DA,
And 20 parts by weight of TAS were added, but they were the same, and a coating composition could not be obtained.

[Comparative Example 8] (Preparation of coating composition) After adding 30 parts by weight of C6DA and 20 parts by weight of TAS to 35 parts by weight of the same colloidal silica as used in the examples, 3.4 parts by weight of APTMS. Was added, but gelation occurred, and it was not possible to obtain a coating composition.

[Example 23] (Preparation of coating composition) To 35 parts by weight of the same colloidal silica as used in Example 1, 1.7 parts by weight of PTMS and 0.8 parts by weight of deionized water were added to give 40 parts. Stir at 1 ° C for 1 hour. Then, 30 parts by weight of C6DA and 20 parts by weight of TAS were added, and most of the volatile components were distilled off under reduced pressure. Next, 1.7 parts by weight of APTMS was added, and the mixture was stirred at 40 ° C. for 1 hour to completely distill off the residual volatile matter. After that, APO
A coating composition was prepared by adding 1.8 parts by weight and UA-13.8 parts by weight.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was applied to a polycarbonate plate under the same conditions as in Example 1, and a polyester film (manufactured by Dia foil Co., thickness (50 μm) and tightly pressure-bonded using a sponge roll, and thoroughly squeezed to a coating layer thickness of 8 μm. After leaving for 120 seconds in this state, 80 W / cm adjusted to an irradiation width of 13 cm
Under a metal halide lamp (with parallel type reflector, ozone-less type, distance between subject and lamp: 30 cm) at 0.5 m / min so that the polyester film surface side was irradiated. Then, only the polyester film is peeled off, and further passed under a high pressure mercury lamp of 120 W / cm (with parallel reflector, ozone type, irradiation width 13 cm, distance between subject and lamp 30 cm) at a speed of 1 m / min for coating. A resin plate whose surface was protected by the cured film of the composition was obtained. Table 2 shows the evaluation results of the obtained resin plate obtained by the same method as in Example 1.

[Examples 24 and 25] Coating compositions having various compositions shown in Table 1 were prepared in the same manner as in Example 23,
Polycarbonate board (Mitsubishi Rayon Co., Ltd., trade name:
A resin plate, the surface of which was protected by a cured coating, was obtained by applying and curing the same on a dialite and a thickness of 2 mm) in the same manner as in Example 23. Table 2 shows the evaluation results obtained by the same method as in Example 1 for each resin plate obtained here.

[Example 26] (Preparation of coating composition) 35 parts by weight of the same colloidal silica as used in Example 1 was added to 1.7 parts by weight of PTMS, 1 part by weight of VPTMS, and 0.8 parts of deionized water. The weight part was added and it stirred at 40 degreeC for 1 hour. After that, C6DA
30 parts by weight and 20 parts by weight of TAS were added, and most of the volatile components were distilled off under reduced pressure. Next, 0.8 part by weight of APTMS was added, and the mixture was stirred at 40 ° C. for 1 hour to completely distill off the residual volatile matter. Then 1.8 parts by weight of APO and UA
-1 3.8 parts by weight was added to obtain a coating composition.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was applied and cured on a polycarbonate plate under the same conditions as in Example 1 by the same method as in Example 23. A resin plate whose surface was protected by a cured film was obtained. Table 2 shows the evaluation results of the obtained resin plate obtained by the same method as in Example 1.

[Example 27] 100 parts by weight of the same colloidal silica as used in Example 1 was mixed with VPTMS5.
6 parts by weight, 10 parts by weight of PTMS, and 4 parts by weight of 0.01 N hydrochloric acid aqueous solution were added, and the mixture was stirred at 40 ° C. for 2 hours.
Then, 20 parts by weight of C6DA, bis (acryloyloxyethyl) hydroxyethyl isocyanurate (manufactured by Toagosei Co., Ltd., trade name: Aronix M-215) 80
Parts by weight, APO 1.2 parts by weight, methylphenylglyoxylate 0.8 parts by weight, UA-1 10 parts by weight, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Sankyo ), Product name: SANOL LS77
0) 0.4 parts by weight, 270 parts by weight of isobutyl alcohol, 130 parts by weight of n-butyl acetate, 3-methoxy-1-
40 parts by weight of butanol was added and well stirred to obtain a coating composition.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained is dip-coated at a rate of 0.3 cm / sec onto a polycarbonate plate under the same conditions as in Example 1 to form a film. Then, it was left at 80 ° C. for 10 minutes to evaporate the solvent in the coating composition. Then, using the high-pressure mercury lamp used in Example 1 without covering with a polyester film,
Curing is performed by irradiating active energy rays and curing the coating composition in the same manner as in Example 1 except that the distance between the polycarbonate plate and the lamp is 15 cm and the line speed is 1.5 m / min. A resin plate whose surface was protected by a coating film was obtained. Table 2 shows the evaluation results of the obtained resin plate obtained by the same method as in Example 1.

[0100]

[Table 1]

[0101]

[Table 2]

<Abbreviations in Table 1> C6DA: 1,6-hexanediol diacrylate TAS: trimethylolethane / acrylic acid / succinic acid (molar ratio 2/4/1) condensate C9DA: 1,9-nonane Diol diacrylate FA731A: tris (acryloyloxyethyl) isocyanurate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-7)
31A) DPHA: Dipentaerythritol hexaacrylate R-684: Dicyclopentanyl diacrylate (Nippon Kayaku Co., Ltd., trade name: Kayarad R-684) IBA: Isobornyl acrylate CHA: Cyclohexyl acrylate ADA: 1- Adamantyl acrylate DMADA: 3,5-dimethyl-1-adamantyl acrylate TBA: t-butyl acrylate CPTAA: cyclopentanyl acrylate CPTEA: cyclopentenyl acrylate THFA: tetrahydrofurfuryl acrylate M-215: bis (acryloyloxyethyl) hydroxyethyl isocyanate Nurate (manufactured by Toagosei Co., Ltd .; trade name: Aronix M-215) S-1: isopropyl alcohol-dispersed colloidal silica (silica content 0% by weight, manufactured by Nissan Chemical Industries, Ltd .; trade name: IPA-ST S-2: Water-dispersed colloidal silica (silica content 20% by weight, manufactured by Nissan Chemical Industry Co., Ltd .; trade name: Snowtex O) VPTMS: p-vinylphenyltrimethoxysilane MPTMS: γ-methacryloyloxypropyltrimethoxysilane PTMS: phenyltrimethoxysilane MTMS: methyltrimethoxysilane DMDMS: dimethyldimethoxysilane TMMS: trimethylmethoxysilane TMS: tetramethoxysilane VTMS: vinyltrimethoxysilane Methoxysilane PATMS: N-phenyl-γ-aminopropyltrimethoxysilane APTMS: γ-aminopropyltrimethoxysilane APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BAS) Ltd., trade name: LUCI
RIN-TPO) BAPO: bis (2,6-dimethoxybenzoyl)-
A mixture of 2,4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methyl-1-phenylpropan-1-one in a weight ratio of 1/3 (manufactured by Ciba-Geigy, trade name: CGI-1700) MPG: methyl Phenylglyoxylate (manufactured by Akzo Japan Ltd., trade name: VICURE-55) UA-1: 2- (2'-hydroxy-5'-tert-
Butylphenyl) benzotriazole (manufactured by Ciba Geigy; trade name: Tinuvin-PS) UA-2: 2- (2'-hydroxy-5'-tert-
Octylphenyl) benzotriazole (Ciba Geigy, trade name Tinuvin-329) HALS-1: bis (1-octoxy-2,2,6,6)
-Tetramethyl-4-piperidyl) sebacate (manufactured by Ciba Geigy, trade name: Tinuvin-123) HALS-2: 4-benzoyloxy-2,2,6,6
-Tetramethylpiperidine (manufactured by Sankyo Co., Ltd., trade name: SANOL LS-744) HALS-3: bis (2,2,6,6-tetramethyl-
4-piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name:
SANOL LS-770) HALS-4: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name: SANOL LS-765)

[0103]

[Table 3]

[0104]

[Table 4]

<Abbreviations in Table 2> PC: Polycarbonate PMMA: Polymethylmethacrylate

The coating composition of the present invention is a coating composition which can be applied in both a solventless type and a solvent type,
A cured coating formed by applying and curing this on a substrate has excellent wear resistance and impact resistance, and has a good appearance. It also exhibits excellent weather resistance and is effective in preventing the occurrence of cracks in the cured coating. Further, since the surface-coated molded product of the present invention is covered on the surface with a cured film having the above-mentioned effect, various problems such as deterioration of aesthetics due to scratches, which have been conventionally problematic in synthetic resin molded products, have been solved. A molded product can be obtained. Further, the cured coating obtained from the coating composition of the present invention has very excellent weather resistance, and therefore, for example, window glass for vehicles such as vehicles and airplanes, headlamp covers, windshields, roofing materials; windows for buildings. It is particularly useful for applications such as glass, roofing materials, soundproof walls for roads, nameplates, faceplates for displays, etc. that are used outdoors.

Claims (3)

[Claims] 1. As component (a), at least 2 in the molecule.
Cross-linkable compound (a-1) having one acryloyloxy group and / or methacryloyloxy group, or 50 wt% or more of the cross-linkable compound (a-1) and a compound (a- 2) A mixture of 50% by weight or less, the following general formulas (I) to (IV) as the component (b): (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
10 hydrocarbon group, R ³ is a hydrogen atom or 1 to 10 carbon atoms
10 hydrocarbon groups, R ⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ and R ⁶ are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and m is 0 Represents an integer of 2. 5 to 95 parts by mole of at least one silane compound (b-1) selected from silane compounds represented by
The following general formula (V): (In the formula, R ⁷ and R ⁸ are the same or different and have 1 to 10 carbon atoms.
R ⁹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and p are integers from 0 to 3, and n
+ P is 0 to 3. ) A silane compound (b-
2) A coating composition comprising: silica fine particles whose surface is modified with a hydrolyzate of a mixture with 95 to 5 parts by mole, and an active energy ray polymerization initiator as a component (c). 2. A molded product whose surface is coated with the cured product of the coating composition according to claim 1. 3. The method for producing a coating composition according to claim 1, wherein the silane compound (b-2) is added to the dispersion liquid of the silica fine particles (b), and the silica fine particles (b) are hydrolyzed. Of the silica fine particles (b), and then the dispersion medium of the silica fine particles (b) and water are distilled off. Then, the silane compound (b-1) is added and A method for producing a coating composition, which comprises a step of modifying the surface of silica fine particles.