JP3247266B2 - Coating composition, surface-coated molded article using the same, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition capable of forming a cured film having excellent abrasion resistance and weather resistance by irradiating active energy rays, and a cured product of the coating composition. Molded products whose surface is coated, especially headlamp covers, windshields, vehicle windowpanes, vehicle roofing materials, building windowpanes, building roofing materials, road noise barriers, nameplates and display faceplates The present invention relates to a surface-coated molded article having excellent abrasion resistance and weather resistance used in the above.

[0002]

2. Description of the Related Art In recent years, as an alternative to transparent inorganic glass,
It is common practice to use transparent plastic materials with good crush resistance.

[0003] However, transparent plastic materials are
It has serious drawbacks such as insufficient wear resistance and insufficient weather resistance such that the surface is softer than that of inorganic glass and scratches easily occur. Therefore, many attempts have conventionally been made to improve the wear resistance of transparent plastic materials.

As one of the most common methods, for example, as described in JP-A-53-102936, JP-A-53-104638, and JP-A-54-97633, a plurality of A molding liquid having a coating excellent in abrasion 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 article and curing it by irradiation with active energy rays such as heat or ultraviolet rays. There is a way to get it. The curing liquid used in this method is relatively inexpensive and easily available, but the cured film obtained is an organic substance, and at present, there is a limit to the wear resistance of a molded article having this coating.

On the other hand, as a method for imparting a higher surface hardness, for example, Japanese Patent Application Laid-Open Nos.
As described in Japanese Patent Application Laid-Open No. 64671/1994, a method of applying an alkoxysilane compound to the surface of a plastic molded article and obtaining a molded article having a coating cured by heat, or Japanese Patent Application Laid-Open No. 56-106969, Kaihei 2-2
JP-A-72041 discloses a method of applying a coating composition comprising colloidal silica and a curing liquid to the surface of a plastic molded product and obtaining a molded product having a coating cured by heat.

However, since the coating composition used in these methods uses an organic solvent in order to improve the coating property, cracks occur in the plastic molded article to be coated in the drying step. And coating film defects such as uneven coating are likely to occur, and problems are likely to occur in the appearance of the resulting coated molded product. Further, in the coating process, the release of the organic solvent into the air is inevitable, which is not preferable from the viewpoint of global environmental protection, which has recently been receiving attention.

[0007] Further, the films made of these curing liquids are hardened by heat, so that they consume a large amount of energy and require a long time for the hardening, which is industrially disadvantageous.

On the other hand, JP-B-62-21815, JP-B-1-55307, JP-A-3-2168, JP-A-3-6190, JP-A-59-204669, and JP-A-62-256874. JP-A-2-6413
Nos. 8 and 4-18423 and 4-21474
No. 3, No. 4-220411, No. 5-9818
No. 9, No. 5-306374, No. 6-2536
No. 3, No. 6-41468, and No. 6-151.
No. 694 discloses a coating composition comprising 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. From these coating materials, plastic molded articles having relatively excellent surface hardness can be obtained. Hydrolysis was caused at the interface between the colloidal silica and the alkoxysilane, and cracks and whitening occurred in the cured film, and the weather resistance was insufficient. In order to solve these problems, the present inventors have, as shown in JP-A-6-100798, a silica fine particle whose surface is modified with a hydrolyzate of an alkoxysilane having a styryl group, a polyfunctional acrylate, and It has been found that a coating composition comprising an active energy ray polymerization initiator has good properties.

[0010]

However, although this coating composition has better performance than the conventional one, it is still not satisfactory, and a cured film having a high surface hardness and excellent weather resistance is obtained. At present, an active energy ray-curable coating composition that can be used even without a solvent that can be formed has not yet been obtained. The present invention has been obtained as a result of intensive studies in order to solve the above-described problems, the object of which is that it can be coated without using a solvent, and that the surface hardness is high and the appearance and weather resistance are good. An active energy ray-curable coating composition capable of forming a cured film having excellent abrasion resistance and abrasion resistance. Another object of the present invention is to provide a molded article whose surface is coated with a cured product of the coating composition.

[0011]

[Means for Solving the Problems]

The present inventors have proposed a silane compound (b-1)
Cured coatings obtained from conventionally developed coating compositions containing silica fine particles modified with a hydrolyzate and polyfunctional acrylate and / or methacrylate (hereinafter abbreviated as (meth) acrylate) as main components are considerably considerable. In order to improve the point that the cured film is excellent, but inferior in weather resistance, the present inventors have assiduously studied the mechanism of surface hardness development of the cured film and the factors affecting the weather resistance, and have reached the present invention. That is, the present invention provides, as a component (a), a crosslinked polymerizable compound (a-1) having at least two acryloyloxy groups and / or methacryloyloxy groups in a molecule, or the crosslinked polymerizable compound (a-1). A) a mixture of 50% by weight or more and 50% by weight of a compound (a-2) copolymerizable therewith; (b) a component represented by the following general formula (I) or (III):

Embedded image

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a hydrogen atom or a carbon atom 1
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, m is 0 Represents an integer of ２2. 5) to 95 of the silane compound (b-1)
A molar part and the following general formula (IV)

Embedded image (Wherein R ⁷ and R ⁸ are the same or different and have 1 to 1 carbon atoms)
10 hydrocarbon groups, R ⁹ is a hydrogen atom or a carbon number of 1 to 1
The hydrocarbon group of 0, n and p are integers of 0-3, and n + p is 0-3. A) a silica fine particle whose surface is modified with a hydrolyzate of a mixture of the silane compound (b-2) with 95 to 5 mol parts and a coating composition comprising an active energy ray polymerization initiator as the component (c). Things.

Another aspect is a method of 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 component (a) is added, and then the dispersion medium and water of the silica fine particles are distilled off.
A method for producing a coating composition, which comprises a step of adding a silane compound (b-1) and modifying the surface of the silica fine particles with a hydrolyzate thereof. Further, a molded article 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 considered that the above-mentioned conventional mechanism of the surface hardness development of the cured film and the factors affecting the weather resistance include (1) the weather resistance of the cured film affects the degree of surface modification of the silica fine particles. If the surface modification is not appropriate, it will lead to a decrease in weather resistance. (2) In order to express the surface hardness of the cured film to a high degree, it is necessary to dispose the silica fine particles and the polymerized and cured polyfunctional (meth) acrylate. The silane compound (b-1) plays a role in the above, and (3) the number of bonding points between the polymer fine particles of the silica fine particles and the polyfunctional (meth) acrylate is large. If it is too much, it becomes a factor that hinders the flexibility of the cured film, and the cured film expands and shrinks 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.

[0015] Based on this finding, the inventors further studied to obtain a coating composition exhibiting both the surface hardness and weather resistance of the cured film. As a result, the silane used for modifying the surface of the silica fine particles was examined. As the compound, a silane compound (b-1) that causes a bond between the silica fine particles and the polymerized and cured polyfunctional (meth) acrylate, and a silane compound (b-2) that does not cause a bond between the two are used in combination. By doing so, it has been clarified that the above performance can be exhibited.

That is, the silane compound (b-1) mainly works to improve the surface hardness of the coating film, and the silane compound (b-
2) works 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 fine particles modified with both, high surface hardness and good weather resistance are exhibited. It was found that a cured film was obtained.

Hereinafter, the present invention will be described in detail. The component (a) in the coating composition of the present invention is a crosslinked polymerizable compound (a) having at least two acryloyloxy groups and / or methacryloyloxy groups (hereinafter abbreviated as (meth) acryloyloxy groups) in the molecule. -1). The crosslinkable polymerizable compound (a-1) used in the present invention is
The residue 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 crosslinked polymerizable compound (a-1),
For example, an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid or a derivative thereof, or an ester compound obtained from a polyhydric alcohol, a polyvalent carboxylic acid, and (meth) acrylic acid or a derivative thereof can be given. .

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 1,000, 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 ′
Dihydric alcohols such as thiodiethanol and 1,4-cyclohexanedimethanol; trimethylolpropane (that is, 1,1,1-trimethylolpropane), pentaglycerol (that is, 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);
Diglycerol, dipentaerythritol and the like.

As specific examples of the crosslinked polymerizable compound (a-1) obtained as a polyhydric alcohol poly (meth) acrylate, the following general formula (V)

Embedded image (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 hydroxyl group, an amino group, an alkyl group or a substituted alkyl group).

As the compound represented by the general formula (V), specifically, 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, tripentaerythritol penta (meth) acrylate,
Examples thereof include tripentaerythritol hexa (meth) acrylate and tripentaerythritol hepta (meth) acrylate.

Examples of poly (meth) acrylates of polyhydric alcohols other than the compound of the above general formula (V) include, for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. ) Acrylate, 1,4-
Examples thereof 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 polymerizable compound (a-1), particularly preferred ester compounds are diethylene glycol di (meth) acrylate and triethylene glycol. 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 polycarboxylic acid and (meth) acrylic acid or a derivative thereof, which can be used as the crosslinkable polymerizable compound (a-1), is basically a polyvalent alcohol. It is obtained by reacting a mixture such that the hydroxyl group of the alcohol and the carboxyl group of both the polyvalent carboxylic acid and the (meth) acrylic acid or a derivative thereof are finally equivalent.

Among these ester compounds, preferred are polyhydric alcohols such as dihydric alcohols, trihydric alcohols, and mixtures of dihydric alcohols and trihydric alcohols. Esterified products obtained by using a polyvalent carboxylic acid are exemplified. 3
When a mixture of a trihydric alcohol and a dihydric alcohol is used, the molar ratio between the trihydric alcohol and the dihydric alcohol can be arbitrarily selected.

When a divalent carboxylic acid and (meth) acrylic acid or a derivative thereof are used in combination, the molar ratio is such that one mole of the carboxyl group of the (meth) acrylic acid or a derivative thereof has one mole of the carboxyl group of the dicarboxylic acid. It is preferred that the group be in the range of 2 moles or less. If the amount of the divalent carboxylic acid is in excess of the above range, the viscosity of the resulting ester may be too high to form a coating film.

Examples of the divalent carboxylic acid or a derivative thereof used in the synthesis of the above ester compound include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid Alicyclic dicarboxylic acids such as; phthalic acid, isophthalic acid, aromatic dicarboxylic acids such as terephthalic acid; other thioglycols, thiodivalic acid, diglycolic acid, maleic acid, fumaric acid, itaconic acid, and chlorides thereof; Examples thereof include anhydrides and esters.

Specific examples of the above ester compound used as the crosslinkable polymerizable compound (a-1) include malonic acid / trimethylolethane / (meth) acrylic acid, 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.
Acrylate.

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

Embedded image (Wherein 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, for example, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, etc. are added to acrylic monomer 1 mole per isocyanate group.
Poly [(meth) acryloyloxyethyl] isocyanurate such as tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid, which is obtained by reacting at least one mole of the compound by a conventional method.

The component (a) in the coating composition of the present invention contains a cross-linkable polymerizable compound (a-1) as a main component (50% by weight).
Above) and a compound (a-2) copolymerizable therewith.

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, ethyl carbitol (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 3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, N-hydroxybutyl (meth) acrylamide, hydroxymethyldiacetone (meth) acrylamide, N-hydroxyethyl-
N-methyl (meth) acrylamide and the like can be mentioned.

In addition, the following general formula (VII) or (V
III)

Embedded image (Wherein, r represents 1 to 10, X ² represents a (meth) acryloyloxy group, and R ¹¹ represents an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group. )), And the like.

The mono (meth) acrylate represented by the general formulas (VII) and (VIII) includes, for example, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate,
Phenoxy polyethylene 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 hydrogen Succinate and various known epoxy (meth) acrylates and urethane (meth) acrylates are also included.

The compound (a-2) is selected according to the use of the cured film obtained in the present invention. If a film having a 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) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and the like can be mentioned.

When these compounds (a-2) are used, they need to be contained in the component (a) in a proportion of not more than 50% by weight, preferably not more than 30% by weight. Compound (a-) in component (a) at a ratio outside this range.
When 2) is contained, the surface hardness of the cured film obtained by the present invention decreases.

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

The expression “the surface has been modified with a hydrolyzate” as used herein means that the hydrolyzate of the silane compound is held on a part or all of the surface of the silica fine particles, and the surface characteristics of the silica fine particles are It means that it has been modified. In addition, the silica fine particles in which the condensation reaction of the hydrolyzate of the silane compound has been advanced are also included.

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

Although the silica fine particles are not particularly limited, the average particle diameter of the silica fine 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 size 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, and n-butanol; cellosolves; dimethylacetamide, toluene, xylene and the like are used. Particularly preferred dispersion media are alcohols, cellosolves, toluene, and water.

The general formula (I) or (II ) used in the present invention
The silane compound (b-1) represented by I) generates a bond between the silica fine particles and the component (a) by irradiation with an active energy ray, and contributes to the development of the surface hardness of the cured film by the silica fine particles. Component.

The silane compound (b) represented by the general formula (I)
As -1), for example, p-vinylphenyltrimethoxysilane, (ie, 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.

[0046]

Specific examples of the silane compound (b-1) represented by the general formula (III) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 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-aminopropylmethyldiethoxysilane, N,
N-dimethyl-γ-aminopropyltrimethoxysilane, N, N-diethyl-γ-aminopropyltrimethoxysilane and the like can be mentioned.

The silane compound (b-1) represented by the general formula (I) or (III ) is used alone or in combination of two or more.

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 solvent-free coating composition of the present invention is produced, the system is gelled, so that 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, the coating composition can be obtained without causing gelation of the system.

The silane compound (b) represented by the general formula (IV)
-2) contributes to the surface modification of the silica fine particles, but has no binding ability between the silica fine particles and the component (a),
It is a component that improves the flexibility of the cured film and, consequently, exhibits good weather resistance.

The silane compound (b) represented by the general formula (IV)
Specific examples of -2) include 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) to the silane compound (b-2) used in the present invention is from 5:95 to
95: 5, preferably 10:90 to 90:
It is particularly preferably in the range of 10:90 to 60:40.

When the coating composition containing the silica fine particles modified in such a manner that the molar ratio of the silane compound (b-1) to the silane compound (b-2) is out of the above range is used, the cured coating film The surface hardness decreases and the weather resistance deteriorates.

When colloidal silica is used as silica fine particles, a silane compound is mixed in a dispersion of colloidal silica and hydrolyzed with water in the system or newly added water. Modified silica fine particles (b) can be obtained.

In conducting 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, sulfuric acid, nitric acid, and phosphoric acid. 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. The solvent is preferably one that can make the reactant silane alkoxide compatible with water and a catalyst.

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 dispersion medium of colloidal silica may be used as it is, or a new required amount may be added. The solvent mentioned above can be used also when newly adding.

The amount of the solvent used is not particularly limited as long as the reactants can be uniformly dissolved. However, if the concentration of the reactants is too low, the reaction rate may be significantly reduced.
The hydrolysis and condensation reaction of the silane compound is performed at room temperature to 120 ° C.
It is preferably carried out at a temperature of about 30 minutes to 24 hours, more preferably at room temperature to about the boiling point of the solvent for about 1 to 10 hours.

The mixing ratio of the silica fine particles of the component (b) to 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 in the range of 5 to 200 parts by weight, more preferably 10 to 100 parts by weight. The mixing ratio of component (a) to component (b) is not limited, but component (b) is preferably in the range of 1 to 200 parts by weight, and particularly preferably 100 parts by weight of component (a). Ranges from 5 to 60 parts by weight.

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

Specific examples of the component (c) include:
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-
Hydroxycyclohexylphenyl 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 di-tert-butyl peroxide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzoyldiethoxyphosphine Oxide, bis (2,
And 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 include:
They may be used alone or in combination of two or more. The compounding amount of the active energy ray polymerization initiator (c) is
The amount is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the component (a).

The coating composition of the present invention is basically provided as containing no organic solvent, but may be used by adding an organic solvent if desired. As the organic solvent, a solvent 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 normal pressure is 50 ° C. or more and 200 ° C.
Those having a viscosity of not more than 10 and a viscosity at room temperature (25 ° C.) of not more than 10 cV are suitable. If the boiling point of the organic solvent is out of the above range, the coating solution may be dried, or inconvenience such as being unable to dry after coating may occur,
On the other hand, when the viscosity is out of the above range, the coatability tends to decrease.

Examples of the organic solvent include 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-dimethylformamide; These organic solvents can be used alone or in combination 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 film and protecting the substrate. As the ultraviolet absorbent (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. These ultraviolet absorbents (d) may be used alone or in combination of two or more.

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

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 generally known, depending on the type of the light stabilizer (e), precipitation occurs in the coating composition, gelation of the system occurs, and application is impossible. Care must be taken, but this can be avoided by selecting the composition of component (a), component (b-1), and component (b-2) and by adding a solvent. Specifically, in the solvent-free coating composition of the present invention, when the silane compounds represented by the above-mentioned general formulas (I) and (II) are used as the component (b-1). , Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-
It is not preferable to use a hindered amine-based light stabilizer represented by the following general formula (IX) such as (4-piperidyl) sebacate because gelling of the coating composition occurs.

[0072]

Embedded image (Where 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,
¹⁴ represents a divalent hydrocarbon group having 4 to 12 carbon atoms. )

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

That is, among the coating compositions of the present invention, the solvent-free coating compositions include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and bis (1
-Octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate or the like represented by the following general formula (X) or (X
I)

Embedded image (Where R ¹⁵ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R ¹⁶ is a hydrocarbon group having 1 to 4 carbon atoms;
¹⁷ has 1 carbon atom which may contain a carbon-carbon double bond.
And R ¹⁸ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁹ represents a divalent hydrocarbon group having 4 to 12 carbon atoms. It is preferable to use the hindered amine light stabilizer represented by the formula (1).

However, when the silane compound represented by the general formula (III) is used as the component (b-1) in the solvent-free coating composition of the present invention, all of the above hindered amines are used. It has been found that the system light stabilizer can be used without causing gelation of the system. Further, they have 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,
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. For example, a component (b) composed of a silane compound and, if necessary, water or a catalyst are mixed with a dispersion of colloidal silica. The reaction is performed under the above-described reaction conditions, and the component (a) is mixed into the liquid after the reaction. Next, it is particularly preferable to remove the volatile matter generated by the hydrolysis reaction of the dispersion medium of colloidal silica and the silane compound, and then add the component (c) and, if necessary, other additives.

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 of silica fine particles to cause a hydrolysis reaction, and a surface modification with the hydrolyzate is performed. Changes the surface state of the fine particles. Next, after adding the component (a) to the reaction system, most of the volatile medium such as the dispersion medium of the silica fine particles and water is distilled off to replace the dispersion medium of the silica fine particles with the component (a). Thereafter, the silane compound represented by the general formula (III) (b-
1) is added to cause a hydrolysis reaction, and further surface modification of the silica fine particles with the hydrolyzate is performed. When the silane compound (b-1) represented by the general formula (III) is added to a dispersion of rice cake multi-silica fine particles in a volatile dispersion medium such as alcohol, silica fine particles are precipitated and easily gelled.

By employing such a two-step surface modification method, by employing such a two-step modification method, the coating composition of the present invention using the silane compound of the general formula (III) can be gel-coated. It can be manufactured without any modification.

The coating composition of the present invention can be applied to the surface of various molded products by brushing, casting, roller, bar coating, spray coating, air knife coating, dipping, etc. Is mentioned.

The coating amount of the coating composition of the present invention on the surface of the molded article is preferably 1 to 30 μm.
m. 1 μm thick
When the thickness is less than 30 μm, the abrasion resistance is poor, and when the thickness exceeds 30 μm, the cured coating tends to crack.

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

In general, synthetic resin molded articles include, for example, polymethyl methacrylate, copolymers having methyl methacrylate as a main component, polystyrene, styrene-
Examples include methyl methacrylate copolymer, styrene-acrylonitrile copolymer, polycarbonate, cellulose acetate butyrate resin, polyacryl diglycol carbonate resin, polyvinyl chloride resin, and polyester resin.

Further, the cured film obtained from the coating composition of the present invention is very excellent in weather resistance, and thus, for example, window glass, windshield, roofing material, headlamp cover for vehicles such as vehicles and airplanes; It is particularly useful for outdoor applications such as windowpanes, roofing materials, soundproof walls of roads, nameplates and display panels.

[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 measurement and evaluation of various physical properties in the examples were performed 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 a sample held on a reciprocating abrasion test table and subjected to 100 reciprocal scratches under a load of 1000 g. Thereafter, the scratched sample was washed, and the haze value was measured with a haze meter. The scratch resistance (%) of steel wool resistance was represented by (haze value after abrasion)-(haze value before abrasion). 2) Wear resistance According to the Taber abrasion test method, CS-10F wear wheel and 50
The haze value was measured with a haze meter when the weights of 0 g were combined and rotated 100 times. The haze value was measured at four points around the orbit of the wear cycle, and the average value was calculated. Taber abrasion (%) was represented by (haze value after Taber test)-(haze value before Taber test). 3) Adhesion of the cured film The sample was cut with a razor blade at 1 mm intervals at 11 mm intervals in the vertical and horizontal directions to make 100 goban eyes. The number of squares (X) when the cured film remained without peeling off from the molded product when it was rapidly peeled off was indicated by X / 100. 4) Appearance Defects such as banding, spots, cracks, and cloudiness were visually determined with respect to the appearance of the molded article having the cured film formed thereon, and evaluated as follows. ：: No noticeable defect. X: Yellowish color with △ YI value of 4.0 or more or occurrence of bumps, cracks, clouding, etc. is observed. 5) Weather resistance Sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.
(WEL-SUN-DC type) with a black panel temperature of 63 ° C. and a rainfall of 12 min.
After 2,000 hours of exposure, the appearance and adhesion of the molded article having the cured film formed thereon were evaluated. A: No noticeable defect. ：: Some adhesion of dirt is observed, but there is almost no problem. Δ: Adhesion decreased. ×: Yellowish color or cracks, clouding, and the like having a ΔYI value of 4.0 or more are observed. (The order of good weather resistance is represented by ◎>○>△> ×)

Example 1 (Preparation of coating composition) Isopropyl alcohol-dispersed colloidal silica (silica content: 30% by weight, manufactured by Nissan Chemical Industries, Ltd., trade name: I
PA-ST) 35 parts by weight, 2.0 parts by weight of p-vinylphenyltrimethoxysilane (hereinafter abbreviated as VPTMS), 1.7 parts by weight of phenyltrimethoxysilane (hereinafter abbreviated as PTMS), 0.01 N Of hydrochloric acid was added and stirred at 40 ° C. for 1 hour. Thereafter, 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) Was 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) was added thereto as an active energy ray polymerization initiator.
2- (2-hydroxy-5-ter) as an ultraviolet absorber
t-butylphenylbenzotriazole (Ciba Geigy, trade name: Tinuvin PS; hereinafter abbreviated as UA-1)
3.8 parts by weight were added and dissolved to obtain a coating composition.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was heated to 50 ° C. in a gear oven at a polycarbonate plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialite, thickness). 2 mm) and tightly pressed with a sponge roll while covering with a polyester film (manufactured by Diafoil Co., Ltd., thickness: 50 μm), and squeezed well so that the thickness of the coating layer was about 8 μm. . After leaving for 50 seconds in this state, irradiation width 1
Passes under a 120 W / cm metal halide lamp adjusted to 3 cm (with parallel reflector, ozoneless type, distance between subject and lamp 30 cm) at a speed of 2 m / min so that the polyester film surface side is irradiated. I let it. Next, only the polyester film was peeled off, and the film was passed under a high-pressure mercury lamp of 120 W / cm (with a parallel reflector, ozone type, irradiation width of 13 cm, distance between the subject and the lamp of 30 cm) at a speed of 1 m / min. A resin plate whose surface was protected by a cured coating of the composition was obtained. Table 2 shows the results of the evaluation performed on the obtained resin plate by the evaluation method described above.

[Examples 2 to 21 and Comparative Examples 1 to 6] Coating compositions of various compositions shown in Table 1 were prepared in the same manner as in Example 1, and polycarbonate plates (manufactured by Mitsubishi Rayon Co., Ltd., Name: Dialite, 2 mm thick) or polymethyl methacrylate plate (Mitsubishi Rayon Co., Ltd.)
A resin plate having a surface protected by a cured film was obtained by applying and curing the same method as in Example 1 on the thickness of 2 mm). Table 2 shows the results of the evaluation performed on each of the obtained resin plates in the same manner as in Example 1.

Comparative Example 7 (Preparation of Coating Composition) γ-aminopropyltrimethoxysilane (hereinafter abbreviated as APTMS) was added to 35 parts by weight of the same colloidal silica as used in Example 1. When 4 parts by weight were added, the colloidal silica was gelled and precipitated, and could not be used as a coating composition. Therefore, C6DA (30 parts by weight) and TAS (20 parts by weight) were added thereto, but the results were the same and could not be used as the coating composition.

Comparative Example 8 (Preparation of Coating Composition) To 35 parts by weight of the same colloidal silica used in the examples, 30 parts by weight of C6DA and 20 parts by weight of TAS were added, and then 3.4 parts by weight of APTMS. Was added, but gelation occurred, and the composition could not be obtained as a coating composition.

[0093] In the Example 2 2] 35 parts by weight same colloidal silica as used in Example 1 (Preparation of coating composition), was added 0.8 parts by weight PTMS1.7 parts by weight of deionized water Stirred at 40 ° C. for 1 hour. After that, C6DA
Was added and 20 parts by weight of TAS were added, and the volatile components were almost distilled off under reduced pressure. Subsequently, 1.7 parts by weight of APTMS was added, and the mixture was stirred at 40 ° C. for 1 hour, and residual volatile components were completely distilled off. Thereafter, 1.8 parts by weight of APO 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., Ltd., 50 μm)
, And tightly compressed with a sponge roll, and squeezed well so that the thickness of the coating layer became 8 μm. After leaving for 120 seconds in this state, 0.5 m / min under an 80 W / cm metal halide lamp (with a parallel reflector, an ozone-less type, a distance between the subject and the lamp of 30 cm) adjusted to an irradiation width of 13 cm. The polyester film was passed at a speed such that the polyester film side was irradiated. Subsequently, only the polyester film was peeled off, and further 120
W / cm high-pressure mercury lamp (with parallel reflector, ozone type, irradiation width 13 cm, distance between subject and lamp 30
cm) at a speed of 1 m / min to obtain a resin plate whose surface is protected by a cured coating of the coating composition. Table 2 shows the results of evaluation of the obtained resin plate in the same manner as in Example 1.

[0095] [Example 2 3 and 2 4 Table coating composition of the various compositions shown in 1 was prepared in the same manner as in Example 2 2, a polycarbonate plate (Mitsubishi Rayon Co., Ltd., trade name: Dia light, on the thickness of 2 mm), coated in the same manner as in example 2 2, by curing, to obtain a resin plate surface is protected by the cured film. Table 2 shows the results of the evaluation performed on each of the obtained resin plates in the same manner as in Example 1.

[Example 25 ] (Preparation of coating composition) In 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 0.8 parts by weight of deionized water, and the mixture was stirred at 40 ° C. for 1 hour. Thereafter, 30 parts by weight of C6DA and 20 parts by weight of TAS were added, and the volatile components were almost distilled off under reduced pressure. Next, 0.8 parts by weight of APTMS was added, and the mixture was stirred at 40 ° C. for 1 hour, and residual volatiles were completely distilled off. After that, APO
1.8 parts by weight and 3.8 parts by weight of UA-1 were added to obtain a coating composition.

[0097] (Preparation of surface-coated molded product) The thus coating composition obtained, applied in the same manner as in Example 2 2 On a polycarbonate plate the same conditions as in Example 1, to be cured As a result, a resin plate whose surface was protected by the cured film was obtained. Table 2 shows the results of evaluation of the obtained resin plate in the same manner as in Example 1.

Example 2 6 Colloidal silica 100 similar to that used in Example 1
To the parts by weight, 5.6 parts by weight of VPTMS, 10 parts by weight of PTMS, and 4 parts by weight of a 0.01 N hydrochloric acid aqueous solution were added.
Stirred at 40 ° C. for 2 hours. Thereafter, 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 0.1 part by weight of methylphenylglyoxylate. 8 parts by weight, U
10 parts by weight of A-1, 0.4 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name: Sanol LS770), and 270 parts by weight of isobutyl alcohol Then, 130 parts by weight of n-butyl acetate and 40 parts by weight of 3-methoxy-1-butanol were added and stirred well to obtain a coating composition.

(Preparation of Surface-Coated Molded Product) The coating composition thus obtained was dip-coated on a polycarbonate plate under the same conditions as in Example 1 at a rate of 0.3 cm / sec to form a coating. Then, it was left at 80 ° C. for 10 minutes to evaporate the solvent in the coating composition. Next, the same as Example 1 except that the polyester film was not covered, the high-pressure mercury lamp used in Example 1 was used, the distance between the polycarbonate plate and the lamp was 15 cm, and the line speed was 1.5 m / min. By irradiating with an active energy ray to cure the coating composition, a resin plate whose surface was protected by a cured film was obtained. Table 2 shows the results of evaluation of the obtained resin plate in the same manner as in Example 1.

[0100]

[Table 1]

[0101]

[Table 2]

<Abbreviations in Table 1> C6DA: 1,6-hexanediol diacrylate TAS: Condensate of trimethylolethane / acrylic acid / succinic acid (molar ratio 2/4/1) 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 (trade name: Kayarad R-684, manufactured by Nippon Kayaku Co., Ltd.) 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-dispersible colloidal silica (silica content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd .; trade name: Snowtex O) VPTMS: p-vinylphenyltrimethoxysilane MPTMS: γ-methacryloyloxypropyltrimethoxysilane PTMS: phenyltrimethoxysilane MTMS: methyltrimethoxysilane DMDMS: dimethyldimethoxysilane TMMS: trimethylmethoxysilane TMS: tetramethoxysilane VTMS: vinyltri 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)-
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 K.K., 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 (trade name: Tinuvin-123, manufactured by Ciba Geigy) 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: polymethyl methacrylate

The coating composition of the present invention is a coating composition that can be applied in either a solventless type or a solvent type.
A cured film formed by applying and curing the composition on a substrate is excellent in abrasion resistance and impact resistance and has a good appearance. In addition, it exhibits excellent weather resistance and is also effective in preventing the occurrence of cracks and the like in the cured film. In addition, since the surface-coated molded product of the present invention is covered with a cured film having the above-mentioned effect on the surface, various problems such as a decrease in aesthetics due to scratches, which have conventionally been a problem in a synthetic resin molded product, have been solved. A molded article can be obtained. Further, the cured coating 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, headlamp covers, windshields, roof materials; windows for buildings It is particularly useful for applications used outdoors, such as glass, roofing materials, soundproof walls of roads, various faceplates such as nameplates and display faceplates.

Claims (6)

(57) [Claims] 1. A crosslinked polymerizable compound (a-1) having at least two acryloyloxy groups and / or methacryloyloxy groups in the molecule as the component (a), or the crosslinked polymerizable compound (a-1) A mixture comprising 50% by weight or more and a compound (a-2) copolymerizable therewith; as a component (b), a compound represented by the following general formula (I): (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a hydrogen atom or a carbon atom 1
A hydrocarbon group of 10 to 10; m represents an integer of 0 to 2; 5 to 95 mol parts of the silane compound (b-1) represented by the following general formula (IV): (Wherein, R ⁷ and R ⁸ are the same or different and have 1 to 1 carbon atoms.
0 is a hydrocarbon group, and R ⁹ is a hydrogen atom or a group having 1 to 10 carbon atoms.
And n and p are integers of 0 to 3, and n + p is 0 to 3. ) (B)
-2) A coating composition comprising: silica fine particles whose surface is modified with a hydrolyzate of a mixture of 95 to 5 mol parts; and an active energy ray polymerization initiator as a component (c). 2. The silane compound (b-1) has the following general formula:
(III) ## STR3 ## (Wherein, R ² is a hydrocarbon group having 1 to 10 carbon atoms, and R ³ is water
An atom or a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is carbon atom
The divalent hydrocarbon groups of formulas 1 to 10, R ⁵ and R ⁶ are the same
One or different hydrogen atoms or hydrocarbons having 1 to 10 carbon atoms
And m represents an integer of 0 to 2. Coating composition which is a silane compound represented by). 3. The component (a) is a component (a-1)
0% by weight or more and 30% by weight or less of a polymerizable compound having one acryloyl group or methacryloyl group in the molecule as the component (a-2), based on 100 parts by weight of a mixture comprising: 5 to 60 parts by weight of (c) 0.01 to 10 parts by weight of the coating composition according to claim 1 or 2 . 4. (d) The benzotriazole-based ultraviolet absorber as the component and / or (e) a hindered amine light stabilizer further claim 1 or 2 in serial <br/> placing coating composition containing as component . 5. A molded product having a surface coated with a cured product of the coating composition according to claim 1 or 2 . 6. The method for producing a coating composition according to claim 1, wherein a silane compound (b-2) is added to a dispersion of the silica fine particles (b) and the hydrolyzate thereof is used to produce silica fine particles. Modifying the surface of (b),
(A) After adding the component, the dispersion medium and water of the silica fine particles (b) are distilled off, and then the silane compound (b-1) is added and the surface of the silica fine particles is modified with the hydrolyzate. A method for producing a coating composition, comprising: