JPH11157014A - Resin molding with covering layer and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin molding having a covering layer excellent in wear resistance, weatherability and adhesion. SOLUTION: On the surface of a resin molding, a layer made of an acrylic crosslinked polymer, which has at least one SiO bond and includes 2 wt.% or less of Si atom is provided. Further, on the above-mentioned acrylic crosslinked polymer, a layer made of an acrylic crosslinked polymer, which has at least one SiO bond and includes 2-40 wt.% of Si atom is provided. A layer made of organopolysiloxane is formed on the layer just mentioned above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molded product comprising a resin molded product provided with a coating layer comprising a cured film having excellent abrasion resistance, weather resistance and adhesion, and a method for producing the same.

[0002]

2. Description of the Related Art Resin molded products manufactured from polymethyl methacrylate, polycarbonate, polystyrene, AS resin, etc. are not only lighter and more excellent in impact resistance than glass products, but also have good transparency and molding workability. Utilizing various advantages such as easiness, it is used in various fields.

[0003] On the other hand, however, these resin molded products are susceptible to damage due to contact, friction, scratching, etc., with other hard objects due to insufficient wear resistance of the surface. There is a strong need to improve the wear resistance of surfaces since damage can significantly reduce its commercial value or render it unusable in a short period of time.

As one of the methods for improving the disadvantages of such resin molded articles, for example, JP-A-53-102936, JP-A-53-104638, and JP-A-54-9 are known.
No. 7633, etc., a curing liquid composed of a compound having a plurality of (meth) acryloyloxy groups in a molecule is applied to a molded article, cured by an active energy ray such as heat or ultraviolet rays, and has abrasion resistance. A method for obtaining a molded article excellent in the above is disclosed. However, this method has an advantage that the curing liquid is relatively inexpensive and has excellent productivity, but since the cured film is an organic substance, the abrasion resistance of the coated molded article is limited.

On the other hand, as another method, a method is known in which a hydrolyzate of an organosilane compound is applied to a resin molded product, and a cured film of organopolysiloxane is formed by heat curing. According to this method, a high degree of abrasion resistance is obtained, but the adhesion to the surface of the molded product is often insufficient, and as a means for improving the adhesion, a method of forming a primer layer between the two is preferred. Has been proposed. For example, JP-A-52-138565 discloses a method using a thermoplastic acrylic primer, and JP-A-53-138476 uses an acrylic resin-based primer having a functional group such as an amino group. A method is disclosed.

[0006]

However, in such a resin molded article, it is known that the hardness of the lower layer (primer layer) of the coating layer greatly affects the wear resistance of the molded article. In the molded article obtained by the above method, sufficient consideration was not given to the hardness of the primer layer, so that sufficient wear resistance could not be obtained.

An object of the present invention is to provide a resin molded article having a coating layer having excellent wear resistance, weather resistance and adhesion on the surface and a method for producing the same.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a coating layer provided on the surface of a resin molded product has a three-layer structure using a specific cured coating component. As a result, it has been found that the above object can be achieved, and the present invention has been completed.

That is, the present invention provides a resin molded article comprising, on the surface thereof, a layer (A) comprising an acrylic cross-linked polymer having at least one SiO bond and containing less than 2% by weight of Si atoms, on which at least one layer is formed. With two SiO bonds
The resin molded article has a layer (B) composed of an acrylic cross-linked polymer containing 2 to 40% by weight of i atoms, and a coating layer on which a layer (C) composed of an organopolysiloxane is sequentially formed. .

The present invention further provides a polyfunctional (meth) acrylate monomer (m-1) having at least two (meth) acryloyloxy groups in a molecule on the surface of a resin molded product.
10 to 94% by weight and monofunctional (meth) copolymerizable with it
A coating agent (D) comprising 0 to 50% by weight of an acrylate monomer (m-2) and 6 to 90% by weight of a silane compound (s) is applied and cured to form at least one SiO 2
A layer (A) made of an acrylic cross-linked polymer having a bond and containing less than 2% by weight of Si atoms, and two or more Si atoms having at least one SiO bond on the layer (A);
After simultaneously forming a layer (B) composed of an acrylic cross-linked polymer containing 40% by weight, an organopolysiloxane compound or an organopolysiloxane compound mixed with colloidal silica is mainly contained on the layer (B). The method for producing a resin molded article according to the present invention is characterized in that a coating agent (E) is applied, dried, and thermally cured.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A resin molded article having a coating layer according to the present invention comprises an acrylic crosslinked polymer having at least one SiO bond and containing less than 2% by weight of Si atoms on the surface of the resin molded article. A layer (A) is provided, a layer (B) made of an acrylic cross-linked polymer having at least one SiO bond and containing 2 to 40% by weight of Si atoms is provided thereon, and an organopolysiloxane layer is further provided thereon. It is a resin molded product comprising three coating layers provided with (C).

The layer (A) in the molded article having the coating layer of the present invention improves the adhesion between the coating layer and the surface of the molded article, and the layer (B) provides the coating layer with excellent hardness. The layer (C) has a function of improving excellent adhesion to the layer (C), and has a function of imparting excellent wear resistance and weather resistance to the coating layer.

In the resin molded article having the coating layer of the present invention, the constitution of the layer (A) and the layer (B) is important. That is, the layer (A) contains less than 2% by weight of Si atoms, and the layer (B) contains 2% by weight of Si atoms.
It must be contained in the range of ４０40% by weight. This is because if the content of Si atoms in the layer (A) is 2% by weight or more, the adhesion between the coating layer and the surface of the molded article is deteriorated, and the content of Si atoms in the layer (B) is less than 2% by weight. In this case, the hardness of the coating layer becomes insufficient. On the other hand, when the content of Si atoms in the layer (B) exceeds 40% by weight, the adhesion between the layer (A) and the layer (B) decreases. That's why.

In the present invention, the layer (A) and the layer (B)
The component having at least one SiO bond contained in the acrylic cross-linked polymer constituting the above-mentioned compound has a cross-linked chain of the acrylic cross-linked polymer and SiO 2 as shown by the following formula (I).
The silane compound (s) having a bond is present by bonding. This example shows a case where colloidal silica whose surface is modified with a hydrolyzate of a silane compound is used as the silane compound (s).

[0015]

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In the present invention, the layer (A) and the layer (B)
Is a partial condensate of a silane compound copolymerizable with a (meth) acrylate monomer ((meth) acrylate is an acrylate or Methacrylate), colloidal silica whose surface is modified with a hydrolyzate of a silane compound copolymerizable with a (meth) acrylate monomer, or a mixture thereof.

Examples of the silane compound copolymerizable with the (meth) acrylate polymer used in the present invention include γ- (meth) acryloyloxypropyl trialkoxysilane and di (meth) acryloyl represented by the following formula (II): Oxydialkoxysilane, primary amino group-containing silane, secondary amino group-containing silane or mercapto group-containing silane and a polyfunctional (meth) acrylate monomer have a (meth) acryloyloxy group ( Silane compounds having an acryloyloxy group or a methacryloyloxy group; the same applies hereinafter). When these silane compounds (silane coupling agents) are used, a non-polymerizable silane coupling agent can be used in combination.

[0018]

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A silane compound obtained by a Michael addition reaction of a primary amino group-containing silane or a secondary amino group-containing silane with a polyfunctional (meth) acrylate monomer can be obtained, for example, by the following formula (III). it can.

[0020]

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A silane compound obtained by a Michael addition reaction between a mercapto group-containing silane and a polyfunctional (meth) acrylate can be obtained, for example, by the following formula (IV).

[0022]

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Examples of the amino group-containing silane compound used for obtaining the above silane compound include N- (2
-Aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and the like.

Examples of mercapto group-containing silane compounds include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane.
Mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropylbutyldimethoxysilane, δ- Mercaptobutyltrimethoxysilane, δ-mercaptopropyltriethoxysilane,
δ-mercaptobutylmethyldimethoxysilane, δ-mercaptobutylethyldimethoxysilane, δ-mercaptobutylmethyldiethoxysilane, δ-mercaptobutylethyldiethoxysilane, γ-mercaptoisobutyltrimethoxysilane, γ-mercaptoisobutylmethyldimethoxysilane, γ-mercaptobutyltrimethoxysilane, γ-mercaptobutylmethyltrimethoxysilane, γ-mercapto-2-hydroxypropyltrimethoxysilane, γ-mercapto-2-hydroxypropyltriethoxysilane, γ-mercapto-2-hydroxypropylmethyl Dimethoxysilane, γ-mercapto-2
-Hydroxypropylethyldiethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyldiethylethoxysilane, β-mercaptoethyltrimethoxysilane, β-mercaptoethyltriethoxysilane, γ-mercaptopropyltriaminosilane and the like. .

The polyfunctional (meth) acrylate monomer used for obtaining the above-mentioned silane compound includes at least one of molecules in a molecule used for forming layers (A) and (B) described later. A polyfunctional (meth) acrylate monomer (m-1) having two (meth) acryloyloxy groups is used.

Here, “the surface was modified with the hydrolyzate”
The expression means that the hydrolyzate of the silane compound is held on a part or all of the surface of the colloidal silica by a condensation reaction, whereby the surface characteristics are modified. In addition, the one in which the condensation reaction of the hydrolyzate has advanced,
Colloidal silica retained at the same time is also included. This surface modification can be easily performed typically by hydrolyzing the silane compound in the presence of colloidal silica, or by causing a hydrolysis and condensation reaction. As a catalyst for performing the hydrolysis reaction of the silane compound, an inorganic acid or an organic acid can be used. Examples of the inorganic acid include, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like.
Examples of organic acids include formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid and the like.

In the hydrolysis reaction system of the silane compound, a solvent can be used in order to carry out the reaction mildly and uniformly. The solvent is desirably one that can dissolve the reactant silane alkoxide, 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. The amount of the solvent used is not particularly limited as long as there is an amount capable of uniformly dissolving the reactants. 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 carried out at a temperature of about room temperature to about 120 ° C. for about 30 minutes to about 24 hours, preferably at a temperature of about room temperature to about the boiling point of the solvent for about 1 to 10 hours. Will be

When the colloidal silica whose surface is modified by hydrolysis of the silane compound is obtained, the ratio of the silane compound to colloidal silica is 0.1 to 100 parts by weight of colloidal silica (solid content). It is preferably 500 parts by weight, more preferably 0.5 to 200 parts by weight.

The layer (A) comprises a polyfunctional (meth) having at least two (meth) acryloyloxy groups in the molecule.
Acrylate monomer (m-1) (hereinafter polyfunctional (meth)
Abbreviated as acrylate monomer (m-1). ) 50-1
00% by weight and 0 to 50% by weight of a monofunctional (meth) acrylate monomer (m-2) copolymerizable therewith (hereinafter abbreviated as a monofunctional (meth) acrylate monomer (m-2)).
And an acrylic crosslinked polymer obtained by copolymerization of less than 6% by weight of the silane compound (s).

The layer (B) comprises 10 to 94% by weight of a polyfunctional (meth) acrylate monomer (m-1) and 0 to 50% by weight of a monofunctional (meth) acrylate monomer (m-2). And an acrylic crosslinked polymer obtained by copolymerization of 6 to 90% by weight of the silane compound (s).

Polyfunctional (meth) acrylate monomer (m-1) and monofunctional (meth) acrylate monomer used for constituting the acrylic crosslinked polymer of layer (A) and layer (B) The following can be exemplified as (m-2). The polyfunctional (meth) acrylate monomer (m-1)
And the residue binding each (meth) acryloyloxy group of the monofunctional (meth) acrylate monomer (m-2) is a hydrocarbon or a derivative thereof, and an ether bond, a thioether -It may contain a ter bond, an ester bond, an amide bond, a urethane bond and the like.

The polyfunctional (meth) acrylate monomer (m-
Examples of 1) include polyhydric alcohol and (meth) acrylic acid (mean acrylic acid and / or methacrylic acid; the same applies hereinafter), or an ester obtained from a derivative thereof, or a polyhydric alcohol and polycarboxylic acid. And (meth) acrylic acid or a derivative thereof.

Examples of poly (meth) acrylates of polyhydric alcohols include polyethylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, 3-
Acryloyloxy-2-hydroxypropyl (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, a compound represented by the following formula (V), for example, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) A) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. .

[0034]

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A saturated mixture obtained by reacting a mixture in which the hydroxyl groups of the polyhydric alcohol and the carboxyl groups of both the polycarboxylic acid and the (meth) acrylic acid are finally equal in amount is obtained. Among the unsaturated polyester poly (meth) acrylates, particularly preferred examples of the present invention include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, and 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) a Acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid /
Glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (Meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) 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, fumaric acid / glycerin / ( (Meth) acrylic acid, fumaric acid / pentane Risritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (Meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic acid, maleic anhydride /
Condensates formed by a combination of glycerin / (meth) acrylic acid, maleic anhydride / pentaerythritol / (meth) acrylic acid, and the like are included.

The polyfunctional (meth) acrylate monomer (m-
Other examples of 1) include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate,
A monomer such as 4,4'-methylenebis (cyclohexylisocyanate), isophorone diisocyanate or hexamethylene diisocyanate, or the following formula (VI) obtained by trimerization

[0037]

Embedded image And an acrylic monomer having active hydrogen, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth)
Acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 1,2,2
Urethane (meth) acrylate obtained by reacting 3-propanetriol-1,3-di (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl methacrylate or the like in a conventional manner, or tris (2-hydroxyethyl) isocyanur Examples thereof include poly [(meth) acryloyloxyethyl] isocyanurate such as acid di (meth) acrylate and tri (meth) acrylate, and known epoxy polyacrylate and urethane polyacrylate.

Monofunctional (meth) acrylate monomer (m-
Examples of 2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2, 2,
2-trifluoroethyl (meth) acrylate, 2,
2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be mentioned.

When forming the layers (A) and (B), the polyfunctional (meth) acrylate monomer (m-1), the monofunctional (meth) acrylate monomer (m-2) and the silane compound ( The above range is used for s), but in the layer (A), the polyfunctional (meth) acrylate monomer (m-1) is less than 50% by weight or the monofunctional (meth) acrylate monomer (m When -2) exceeds 50% by weight, the hardness of the coating layer decreases, and when the silane compound (s) is 6% by weight or more, the adhesion between the layer (A) and the resin molded product base material deteriorates. . In the layer (B), if the silane compound (s) is less than 6% by weight, the hardness of the coating layer decreases,
On the other hand, when the silane compound (s) exceeds 90% by weight, the adhesion between the layer (A) and the layer (B) is deteriorated. In the layer (B), when the use range of the polyfunctional (meth) acrylate monomer (m-1) and the monofunctional (meth) acrylate monomer (m-1) is out of the above range, the hardness of the coating layer is reduced. Decrease.

The thickness of the layer (A) is preferably 0.5 to 20 μm or less, and the thickness of the layer (B) is 0.5
It is preferably up to 20 μm. This is because when the thickness of the layer (A) and the layer (B) is less than 0.5 μm, the scratch resistance of the coating layer is deteriorated, while when the thickness of the layer (A) and the layer (B) exceeds 20 μm. This is because the flexibility deteriorates and cracks are easily generated by a slight deformation.

The layers (A) and (B) can contain various additives such as an ultraviolet absorber, a light stabilizer and a heat stabilizer, if necessary.

Examples of the ultraviolet absorber include benzotriazole, benzophenone, benzoate, cyanoacrylate and the like. Specifically, 2- (2 ′
-Hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2-
(2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis [4- ( 1,1,3,3, tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
n-octoxybenzophenone, 4-dodecyloxy-2
-Hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, phenyl salicylate, p-tert-butylphenyl Salicylate,
3-hydroxyphenylbenzoate, phenylene-
1,3-benzoate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-
And cyano-3,3'-diphenyl acrylate. The content of the ultraviolet absorbent is preferably 10 parts by weight or less based on 100 parts by weight of the layer (A) and the layer (B). The use of an amount exceeding 10 parts by weight is not preferred because the hardness of the coating layer is reduced.

Examples of light stabilizers include tetrakis (1,
2,2,6,6-pentamethyl-4-piperidyl) 1,
2,3,4 butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)
1,2,3,4 butanetetracarboxylate, 4-methacryloyloxy-1,2,2,6,6-pentamethyl-piperidine, 1- [2- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionyloxy]
Ethyl] -4- [3- (3,5-di-t-butyl-4-
[Hydroxyphenyl) propionyloxy] -2,2,2
6,6-tetramethylpiperidine, bis (2,2,6,
6-tetramethyl-4-piperidyl) sebacate, 4-
Benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4
-Piperidyl) sebacate, dimethyl succinate-1-
(2-hydroxyethyl) -4-hydroxy-2,2,
6,6-tetramethylpiperidine polycondensate is exemplified. The content of the light stabilizer is preferably 3 parts by weight or less based on 100 parts by weight of the layer (A) and the layer (B). The use of an amount exceeding 3 parts by weight is not preferred because it lowers the hardness of the coating layer.

In the present invention, the layer (C) provided on the layer (B) is composed of a cured coating of an organopolysiloxane or an organopolysiloxane filled with colloidal silica. The organopolysiloxane that can be used in the present invention is a silane represented by the following general formulas (VII) and (VIII) and silanes selected from partial hydrolysates and condensation products thereof. .

[0045]

Embedded image R _a ¹³ Si (OR ¹⁴ ) _4-a (VII)

[0046]

Embedded image R _b ¹⁵ Si (OCOR ¹⁶ ) _4-b (VIII)

Here, R ¹³ and R ¹⁴ are selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and are preferably an alkyl group having 1 to 8 carbon atoms and a phenyl group. , A is 0 or 1, and R ¹⁵
And R ¹⁶ can be a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, preferably an alkyl group having 1 to 8 carbon atoms and a phenyl group, and b is
0 to 2.

The thickness of the layer (C) is not particularly limited but is preferably in the range of 0.5 to 20 μm. If the thickness of the layer (C) is too small, the abrasion resistance of the coating layer deteriorates. If the thickness is too large, the flexibility deteriorates, and cracks are easily generated by a slight deformation.

Examples of the resin molded article as the base material include polymethyl methacrylate, a copolymer containing methyl methacrylate as a main component, polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, polycarbonate, Molded articles obtained from polyvinyl chloride resin, polyester resin and the like can be mentioned.

The resin molded article having a coating layer according to the present invention is characterized in that the surface of the resin molded article has 50 to 100% by weight of a polyfunctional (meth) acrylate monomer (m-1) and a monofunctional (meth) acrylate monomer. (M-2) After applying a coating agent comprising 0 to 50% by weight and less than 6% by weight of the silane compound (s), the coating agent is cured by heat curing, ultraviolet curing, electron beam curing or the like to form at least one SiO bond. Has 2 Si atoms
Forming a layer (A) made of an acrylic cross-linked polymer containing less than 10% by weight, and forming a polyfunctional (meth) on the layer (A);
After applying a coating agent comprising 10 to 94% by weight of acrylate monomer (m-1), 0 to 50% by weight of monofunctional (meth) acrylate monomer (m-2) and 6 to 90% by weight of silane compound Cured by heat curing, ultraviolet curing, electron beam curing or the like to form a layer (B) made of an acrylic cross-linked polymer having at least one SiO bond and containing 2 to 40% by weight of Si atoms, On the layer (B), a coating agent comprising an organopolysiloxane compound or an organopolysiloxane compound filled with colloidal silica is applied, and then heat-condensed and solidified to form an organopolysiloxane layer (C). Can be obtained by

However, individually performing the three-layer coating in this manner is troublesome and costly, and therefore has at least one SiO bond and has two Si atoms.
Simultaneously coats a layer (A) composed of an acrylic cross-linked polymer containing less than 2% by weight and a layer (B) composed of an acrylic cross-linked polymer containing at least one SiO bond and containing 2 to 40% by weight of Si atoms. Is preferred. That is, the polyfunctional (meth) acrylate monomer (m-1) 10
To 94% by weight of a monofunctional (meth) acrylate monomer (m
-2) 0 to 50% by weight and silane compound (s) 6 to 9
When a coating agent (D) consisting of 0% by weight is applied to the surface of the molded article and ultraviolet curing is performed, the silane compound (s) is aggregated on the surface layer of the applied surface, and has at least one SiO bond and has Si atoms. A layer (A) composed of an acrylic crosslinked polymer containing less than 2% by weight and a layer (B) composed of an acrylic crosslinked polymer having at least one SiO bond and containing 2 to 40% by weight of Si atoms are separated. These two layers are formed at the same time.

A layer (A) comprising an acrylic cross-linked polymer having at least one SiO bond and containing less than 2% by weight of Si atoms, and a layer (A) having at least one SiO bond and
In order to separate the layer (B) composed of the acrylic crosslinked polymer containing 2 to 40% by weight of atoms, the temperature at which the coating agent (D) is applied to the surface of the molded article is important,
The temperature of the surface of the molded product is preferably in the range of 20 to 120 ° C. This is because, when the temperature of the surface of the molded article when the coating agent (D) is applied to the surface of the molded article is less than 20 ° C., the acrylic cross-linking having at least one SiO bond and containing less than 2% by weight of Si atoms. Separation of the layer (A) made of a polymer and the layer (B) made of an acrylic crosslinked polymer having at least one SiO bond and containing 2 to 40% by weight of Si atoms did not proceed, and further a coating layer When the coating agent (D) is applied to the surface of the molded product and the temperature of the surface of the molded product exceeds 120 ° C., the appearance of the coating layer deteriorates. That's why.

Examples of the method of applying the coating agent (D) to the surface of the resin molded product include a spray coating method, a bar coating method, a roller coating method, a casting method, a dipping method, an air knife coating method, and a brush coating method. No.

The method for curing the applied coating agent (D) includes thermal curing, ultraviolet curing, and electron beam curing.

When curing is carried out by heat curing or ultraviolet rays, it is necessary to add a polymerization initiator to the coating agent. Among the polymerization initiators, examples of the polymerization initiator used for thermosetting include lauroyl peroxide, benzoyl peroxide, propionoyl peroxide, tertiary butyl peroxylaurate, dicumyl peroxide, and ditertiary butyl peroxide. Oxides, peroxide initiators such as cumene hydroperoxide,
2,2′-azobisisobutyronitrile, 1,1′-azobis-1-cyclopentanonitrile, dimethyl-2,
2'-azobisisobutyrate, 1,1'-azobiscyclohexanecarbonitrile, 4,4'-azobis-4
-Cyanovaleic acid, 2,2'-azobis-2-
An azo initiator such as benzylpropionitrile and the like can be mentioned.

Examples of the polymerization initiator used for ultraviolet curing include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p
-Methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy -2-methyl-1
-Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4- Examples thereof include dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. These polymerization initiators may be used alone or in combination of two or more. The addition amount of the polymerization initiator is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the coating agent (D).

The coating agent (D) used in the present invention comprises:
Basically, those that do not contain organic solvents are used,
If necessary, an organic solvent can be contained and used. As this organic solvent, a polyfunctional (meth) acrylate monomer (m-1), a monofunctional (meth) acrylate monomer (m-2) and a polymerization initiator can be uniformly mixed, and a coating agent A solvent capable of uniformly dispersing (D) is used. In addition, the boiling point at normal pressure is 50 ° C or more and 200 ° C.
It is suitable to satisfy the condition that the viscosity at room temperature (25 ° C.) is 10 centipoise or less. Specifically, ethanol, isopropyl alcohol, normal propyl alcohol, alcohols such as normal butyl alcohol, benzene, aromatic hydrocarbons such as toluene, acetone, ketones such as methyl ethyl ketone, ethers such as dioxane, ethyl acetate, Esters such as butyl acetate; N, N-dimethylformamide; These organic solvents can be used alone or in combination of two or more.

Further, the coating agent used in the present invention may contain various additives such as the above-mentioned ultraviolet absorber, light stabilizer and surface smoothing agent, surfactant, heat stabilizer and storage stabilizer, if necessary. Can be added.

Next, on the cured layer (B), a coating agent (E) comprising the above-mentioned silane and an organopolysiloxane compound selected from a partial hydrolyzate and a condensation product of the silane is applied to form a coating (20). ~ 130 ° C
To form a layer (C). The coating agent (E) is adjusted to have a solid content of about 10 to 100% by weight using water or an organic solvent, preferably alkanol, as a solvent. At this time, colloidal silica may be contained in an amount of 10 to 70% by weight. The method for applying the coating agent (E) to the surface of the resin molded product is not particularly limited, and a known method can be used.

Hereinafter, the present invention will be described in detail with reference to examples. Measurement and evaluation of various physical properties in the examples were performed by the following methods.

1) Adhesion of the coating film The sample was cut with eleven vertical and horizontal lines at 1 mm intervals with a razor blade to make 100 grids, and the cellophane tape was adhered well. The number of squares N when the coating film is left without being peeled when it is suddenly peeled.
Was calculated and indicated by N / 100.

2) Wear Resistance Using a CS-10F wear wheel, a wear test was performed at 500 rotations with a load of 500 g per wheel by the Taber abrasion test method, and the haze value of the worn portion was measured with a haze meter. The haze was measured at four points on the track of the wear cycle, and the average value was calculated. Taber abrasion (%) is represented by (haze value after Taber test)-(haze value before Taber test).

3) Weather resistance Sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.)
Exposure was carried out at 63 ° C. and in the presence of rain, and the appearance of the sample after 3000 hours of exposure was visually observed.

Example 1 133 parts by weight of isopropanol and 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd .; hereinafter abbreviated as C6DA) 1
04 parts by weight, γ-mercaptopropyltrimethoxysilane (brand name KBM-803, manufactured by Shin-Etsu Silicone Co., Ltd.)
A mixture consisting of 30 parts by weight and 0.6 part by weight of triphenylphosphine (hereinafter, abbreviated as TPP) was added at room temperature for 7 hours.
Stir for 2 hours. Next, 125 parts by weight of stirred isopropanol-dispersed colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-ST, solid content: 30% by weight)
100 parts by weight of the above mixture stirred for 72 hours and 0.1 part by weight.
4.5 parts by weight of 01N hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 4 hours. Thereafter, 40.5 parts by weight of dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA) and 21.9 parts by weight of C6DA were added, and the mixture was stirred uniformly. Obtained.

Next, the obtained filler dispersion 10
0, parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (B
ASF, Lucirin TPO, TP
Abbreviated as O. 2.8 parts by weight, 1 part by weight of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.), 2-
6 parts by weight of (2'-hydroxy-5'-tert-butylphenyl) benzotriazole (trade name: Tinuvin PS, manufactured by Ciba Geigy), and bis (2,2,6,6) as a light stabilizer
1 part by weight of -tetramethyl-4-piperidyl) sebacate (manufactured by Sankyo Co., Ltd., trade name: SANOL LS770) was added, and the mixture was stirred and dissolved to prepare a coating agent (D).

Next, the coating agent (D) was coated with a polycarbonate plate (dialite P, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) having a length of 300 mm, a width of 300 mm and a thickness of 2 mm, the surface temperature of which was set to 45 ° C. by a flow method. And the thickness of the coating layer was set to 8 μm. This plate is lifted 150
The coating agent (D) was cured by passing at a speed of 3.0 m / min under a metal halide lamp having an output of 120 w / cm ² placed at a position of 150 mm and then the plate was placed at a position of 150 mm above. Output 120w /
The layer (A) and the layer (B) were formed by passing under a cm ² high-pressure mercury lamp at a speed of 3.0 m / min.

Next, on this layer (B), a coating agent (E) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Top KP85) containing colloidal silica, organotrialkoxysilane, a curing catalyst and a solvent was flow-processed. And cured at 120-130 ° C. for 1 hour.
A layer (C) of μm was formed. Table 1 shows the evaluation results of the obtained plates.

[Embodiment 2] In the embodiment 1, the DPHA
Instead of using a polyester acrylate obtained by a condensation reaction of trimethylolethane / succinic acid / acrylic acid (molar ratio 2: 1: 4), a coating layer was formed on a plate in the same manner as in Example 1. The results in Table 1 were obtained.

Example 3 100 parts by weight of the filler dispersion prepared in Example 1 was mixed with TPO as a photopolymerization initiator.
2.8 parts by weight, 1 part by weight of benzophenone, and 6 parts by weight of 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole (trade name: Tinuvin PS, manufactured by Ciba Geigy) as an ultraviolet absorber are coated. Agent (D) was prepared. This coating agent (D) is 300 mm long and 3 mm wide by setting the surface temperature to 65 ° C. by the flow method.
It was applied to a methacrylic resin plate (Acrylite L, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 00 mm and a thickness of 3 mm, and the thickness of the coating layer was set to 8 μm. Other conditions were the same as in Example 1, a coating layer was formed on the plate, and the results in Table 1 were obtained.

Comparative Example 1 Table 1 shows the evaluation results of the untreated polycarbonate plates used in Example 1.

Comparative Example 2 DPHA 40 parts by weight, C6
After mixing 60 parts by weight of DA, 2.8 parts by weight of TPO and 1 part by weight of benzophenone, the mixture was stirred and dissolved to prepare a coating agent. This coating agent was applied to a 2 mm-thick polycarbonate plate (manufactured by Mitsubishi Rayon Co., Ltd.
The product was applied to Dialite P). Other conditions were the same as in Example 1, a coating layer was formed on the plate, and the results in Table 1 were obtained.

[0072]

[Table 1]

[0073]

As is clear from the results of the above examples, the resin molded article having the coating layer of the present invention has excellent abrasion resistance, good weather resistance and good adhesion. So
For example, it can be used for applications that require such performance, such as window glass, signboards, covers for lighting equipment, optical parts, and automobile-related parts.

Claims (7)

[Claims] 1. A resin molded product having at least one S
Layer (A) comprising an acrylic crosslinked polymer having an iO bond and containing less than 2% by weight of Si atoms, and an acrylic crosslinker having at least one SiO bond and containing 2 to 40% by weight of Si atoms. A resin molded article having a coating layer in which a layer (B) made of a polymer and a layer (C) made of an organopolysiloxane are further formed on the layer (B). 2. An acrylic crosslinked polymer constituting the layer (A) is a polyfunctional (meth) acrylate monomer (m-1) having at least two (meth) acryloyloxy groups in a molecule. A polymer comprising 100% by weight and 0 to 50% by weight of a monofunctional (meth) acrylate monomer (m-2) copolymerizable therewith and less than 6% by weight of a silane compound (s); The constituent acrylic cross-linked polymer is a polyfunctional (meth) acrylate monomer having at least two (meth) acryloyloxy groups in the molecule (m
-1) 10 to 94% by weight and a monofunctional (meth) acrylate monomer (m-2) copolymerizable therewith, 0 to 50% by weight
The resin molded article having a coating layer according to claim 1, which is a polymer comprising 6 to 90% by weight of a silane compound (s). 3. The layer (C) comprising: an organopolysiloxane;
The resin molded article having a coating layer according to claim 1 or 2, which is an organopolysiloxane filled with colloidal silica. 4. A partial condensate of a silane compound copolymerizable with a (meth) acrylate monomer and / or hydrolysis of a silane compound copolymerizable with a (meth) acrylate monomer. The resin molded article having a coating layer according to claim 2 or 3, wherein the resin molded article is colloidal silica whose surface is modified with an article. 5. 10 to 94% by weight of a polyfunctional (meth) acrylate monomer (m-1) having at least two (meth) acryloyloxy groups in the molecule on the surface of a resin molded product and copolymerization therewith A coating agent (D) comprising 0 to 50% by weight of a possible monofunctional (meth) acrylate monomer (m-2) and 6 to 90% by weight of a silane compound (s) is applied and cured to form at least one SiO 2 A layer (A) made of an acrylic cross-linked polymer having a bond and containing less than 2% by weight of Si atoms, and 2 to 40% by weight of Si atoms having at least one SiO bond on the layer (A) After simultaneously forming a layer (B) made of the acrylic cross-linked polymer contained, an organopolysiloxane compound or an organopolysiloxane compound mixed with colloidal silica is formed on the layer (B). The method for producing a resin molded article having a coating layer according to claim 1, wherein the coating agent (E) as a main component is applied, dried, and thermally cured. 6. The surface of the silane compound (s) is a partial condensate of a silane compound copolymerizable with a (meth) acrylate monomer and / or a hydrolyzate of a silane compound copolymerizable with a (meth) acrylate. Is a modified colloidal silica, The method for producing a resin molded article having a coating layer according to claim 5, wherein 7. The coating layer according to claim 5, wherein the surface temperature of the molded article when applying the coating agent (D) to the surface of the resin molded article is 20 to 120 ° C. Method of manufacturing resin molded products.