JPH093392A - Resin composition for coating, resin-coated material, and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn., for coating, capable of forming a coating having high hardness and weather resistance and high toughness, curable both at room temperature and by heating, and having good storage stability, a process for preparing the same, and a resin-coated material using the compsn. SOLUTION: This coating resin compsn. comprises: a silica-dispersed oligomer soln. of an organosilane prepd. by partially hydrolyzing a hydrolyzable organosilane represented by the formula R<1> n SiX4-n in colloidal silica dispersed in an org. solvent, water, or a mixed solvent composed of an org. solvent and water; an acrylic resin which is a copolymer of an acrylic ester or a methacrylic ester represented by the formula CH2 =CR<2> (COOR<3> ); and a curing catalyst as indispensable components. This compsn. may be prepd. by mixing the above components together according to a suitable method. This resin-coated material comprises a substrate having a surface bearing a cured resin layer formed of the compsn. This process for preparing a resin-coated material comprises the steps of: coating the surface of a substrate with the compsn.; and curing the coating.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coating, a resin coating and a method for producing them, and more specifically, a steel plate such as stainless steel; a non-ferrous metal such as aluminum; an inorganic building material such as concrete or slate; Plastic base material: a resin composition for coating, which can be coated on the surface of a base material such as wood and can be cured by leaving it at room temperature or by heat treatment to form a coating film having high hardness, heat resistance and weather resistance. And a method for producing the same, a resin coating having a cured resin layer of the resin composition for coating on the surface of the substrate, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a coating agent for forming a durable coating film for the purpose of surface protection of steel plates such as stainless steel, non-ferrous metals such as aluminum, concrete, inorganic building materials such as slate, wood, plastic substrates, etc. A coating agent obtained by hydrolyzing or partially hydrolyzing a hydrolyzable organosilane, or a coating agent in which colloidal silica is mixed with the coating composition is known.

For example, JP-A-51-2736 and JP-A-51-2736
JP-A-51-2737, JP-A-53-130732, JP-A-63-16
Japanese Patent No. 8470 proposes a coating agent composed of an organoalkoxysilane, a hydrolyzate of the organoalkoxysilane and / or a partial condensate thereof and colloidal silica, and converting an alkoxy group into silanol with excess water. ing. However, the coating films obtained with these coating agents have high hardness and excellent weather resistance and are excellent for substrate protection, but have poor toughness, and coating films with a thickness of 10 μm or more can be exposed to heat during outdoor curing. During use, cracks easily occur when a sudden temperature change occurs. In the coating process, it is difficult to strictly control the thickness of the coating film to 10 μm or less, and especially the coating surface, the periphery of the coated object, and the recesses on the coating surface easily exceed 10 μm, which causes manufacturing defects. Likely to happen. In addition, the coating film obtained with these coating agents requires heat treatment at a high temperature of about 100 ° C. or higher or for a long time in order to obtain desired coating film characteristics. There was an inconvenience that it could not be used in some places such as outdoors. Further, these coating compositions have a problem that the silanol obtained by hydrolysis of the alkoxysilane has high reactivity, their condensation reaction gradually occurs even at room temperature, easily gels, and has poor stability. In particular, when these coating compositions are used as vehicles and pigments are added to form paints, stability is further deteriorated, and there is a drawback that paints cannot be formed.

Further, as in JP-A 64-168, a coating agent for converting an alkoxy group to silanol by adding water and a catalyst as a curing agent to a partial hydrolyzate or partial condensate of an alkoxysilane immediately before coating. Is proposed. However, even with this coating agent, the toughness was poor, and
When the film thickness is m or more, cracks easily occur.
However, this coating agent has good storability and is relatively stable even if it is made into a paint by adding a pigment. It is necessary and cannot be used depending on the molding method and size of the base material, heat resistance, or location such as outdoors.

For the purpose of solving such a drawback, Japanese Patent Laid-Open No.
63-268772 proposes a coating agent which is composed of a prepolymer mainly composed of a silicon alkoxide, a curing catalyst and water and hardens at around room temperature, but the toughness is not improved, and after coating the precoat metal. Processing,
It is impossible to process the polycarbonate plate after coating. In addition, the coating properties and curability are poor, and the curability of the coating agent is susceptible to humidity.

Japanese Unexamined Patent Publication No. 4-175388 discloses a coating agent containing a partially hydrolyzed oligomer of organosilane, a silanol group-containing polyorganosiloxane, and a curing catalyst. ,
Although the paintability and the curability are improved and it is not affected by humidity, the toughness is not sufficiently improved.

To summarize the above, a coating agent containing organoalkoxysilane or a hydrolyzate of organoalkoxysilane as a main component has a coating film having high hardness, less scratches, and high weather resistance. However, due to poor toughness, cracks are likely to occur during the coating process or during use, and this is particularly noticeable when the film thickness is 10 μm or more. In addition, it requires baking at a high temperature of 100 ° C or higher, and although it can be painted in the factory, it is difficult to paint outdoors or on-site. Another drawback is that the coating liquid has high reactivity and is inferior in storage stability.

Further, it has an organic resin such as acrylic, polyester, epoxy, polyether or vinyl in the main chain,
Resins with hydrolyzable silane functional groups have also been reported.
For example, as seen in JP-A-5-287206 and JP-A-5-302007, since the main chain is an organic resin, it is inferior in weather resistance and hardness to a resin containing an organoalkoxysilane as a main component. . Alternatively, reactive resins having a linear polysiloxane as the main chain and having a polymerizable acrylic functional group at the terminal or side chain have also been proposed in JP-A-5-72928 and JP-A-5178998. But this is
Since the main chain is a linear polysiloxane, hardness cannot be obtained, and in some cases, it is a rubber elastic body and is not suitable as a coating resin.

By the way, the above-mentioned concrete, cement base material, and inorganic hardened material are materials having excellent heat resistance and durability, but if the surface is not coated, water will infiltrate, and the stain resistance and acid resistance will be improved. It has the disadvantage of being inferior. Furthermore, the unpainted appearance is often not aesthetic.
In order to make up for these drawbacks, it has been practiced to coat the surface thereof with an organic paint. However, organic coatings have the disadvantages of poor weather resistance and being easily scratched due to low film hardness.

Therefore, an attempt was made to apply an inorganic coating agent such as a water glass type instead of an organic type, but a satisfactory coating product was not obtained in terms of generation of efflorescence and porosity.

[0011]

The object of the present invention is to form a coating film having not only high hardness and weather resistance but also high toughness, cracks do not occur even at a film thickness of 10 μm or more, and at room temperature. Can be cured and dried at 100 ° C
Curing by heating promotion at the following low temperatures is also possible,
It has good storage stability and can obtain the above high-performance coating stably for more than 1 year, and it can be used as a stable vehicle when it is made into a paint by adding a pigment. It is intended to provide a coating resin composition that can be colored into a color and a method for producing the same, and a resin coating having a cured resin layer of the coating resin composition on the surface of a substrate and a method for producing the same.

[0012]

The resin composition for coating according to the present invention comprises (A) a general formula R ¹ _n SiX _4-n (I) (wherein R ¹ is the same or different and is substituted or unsubstituted). Represents a monovalent hydrocarbon group having 1 to 9 carbon atoms or a phenyl group,
n represents an integer of 0 to 3 and X represents a hydrolyzable functional group. ) Is a partially hydrolyzed hydrolyzable organosilane represented by colloidal silica dispersed in an organic solvent, water, or a mixed solvent thereof, and a silica-dispersed oligomer solution of organosilane, and (B) a general formula CH ₂ = CR ² (COOR ³ ) (II) (wherein R ² represents a hydrogen atom or a methyl group), and R ^{3 in} the formula is a substituted or unsubstituted C ¹ to C 9 group.
At least one first acrylic ester or methacrylic ester which is a monovalent hydrocarbon group, and R ³ in the formula, wherein R ³ is an epoxy group, a glycidyl group, or a carbonization containing them. At least one second acrylic ester or methacrylic ester which is a hydrogen group, and a hydrocarbon group represented by the general formula (II), wherein R ³ contains an alkoxysilyl group or a halogenated silyl group. An acrylic resin, which is a copolymer of at least one third acrylic ester or methacrylic ester, and (C) a curing catalyst are essential components.

The component (A) contains the hydrolyzable organosilane in an amount of 0.001 of water per equivalent of the hydrolyzable functional group (X).
It is preferably a silica-dispersed oligomer solution of organosilane which is partially hydrolyzed under the condition of using 0.5 mol. The component (A) is a silica component (containing Si
It is preferable that the solid content is 5 to 95% by weight as calculated as SiO ₂ .

It is preferable that at least 50 mol% of the hydrolyzable organosilane as the raw material of the component (A) is an organosilane of n = 1. The pH of the component (A) is 2.
It is preferably 0 to 7.0. The acrylic resin as the component (B) preferably contains, as a copolymerizable monomer, at least one selected from the group consisting of n-butyl methacrylate and n-butyl acrylate.

The acrylic resin as the component (B) preferably contains, as a comonomer, at least one selected from the group consisting of trimethoxysilylpropyl methacrylate and trimethoxysilylpropyl acrylate. The acrylic resin as the component (B) preferably contains, as a comonomer, at least one selected from the group consisting of glycidyl methacrylate and glycidyl acrylate.

The acrylic resin as the component (B) may further contain at least one selected from the group consisting of thiols, thiophenols and their derivatives. The acrylic resin as the component (B) preferably has a polystyrene reduced weight average molecular weight of 1,000 to 50,000.

In the coating resin composition of the present invention, 1 to 99 parts by weight of the component (B) is used relative to 1 to 99 parts by weight of the component (A) (provided that the components (A) and (B) are Total is 10
Is 0 parts by weight). The curing catalyst of the component (C) is selected from the group consisting of alkyl titanates, tin carboxylates, aluminum compounds, amine salts, amine silane coupling agents, halogenated silanes, acids and alkalis. It is preferably at least one kind.

The coating resin composition of the present invention comprises:
(D) Average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (III) (In the formula, R ⁴ is the same or different substituted or unsubstituted monovalent carbon atom having 1 to 9 carbon atoms. Represents a hydrogen group or a phenyl group,
a and b are 0.2 ≤ a ≤ 2, 0.0001 ≤ b ≤ 3, respectively
It is a number that satisfies the relationship of a + b <4. It is preferable that a polyorganosiloxane represented by the formula (1) and containing a silanol group in the molecule is further contained as an essential component.

In the coating resin composition further containing the component (D), 5 to 50 parts by weight of the component (B) and 1 to 94 parts by weight of the component (D) are added to 1 to 94 parts by weight of the component (A).
It is preferable that 94 parts by weight (however, the total of the component (A), the component (B), and the component (D) is 100 parts by weight). The polystyrene equivalent weight average molecular weight of the component (D) is preferably 700 to 20,000.

The coating resin composition of the present invention may further contain (E) a pigment as an essential component. The method for producing a coating resin composition according to the present invention,
The method includes a step of mixing a resin solution containing the component (A) and the component (B) with a resin solution containing the component (C).

Another method of producing a resin composition for coating according to the present invention is to mix a resin solution containing the component (A) and the component (C) with a resin solution containing the component (B). Including steps. Another method for producing a coating resin composition according to the present invention includes a step of mixing a resin solution containing the component (A) with a resin solution containing the component (B) and the component (C). .

Another method for producing a coating resin composition according to the present invention comprises a resin solution containing the component (A), the component (B) and the component (C), and the component (D). The step of mixing with a resin solution is included. Another method for producing a coating resin composition according to the present invention is a resin solution containing the component (A) and the component (C), and a resin solution containing the component (B) and the component (D). And mixing.

Another method for producing a resin composition for coating according to the present invention is a resin solution containing the above-mentioned component (A), the above-mentioned component (B) and the above-mentioned component (C), the above-mentioned component (C) and the above-mentioned component. The step of mixing with a resin solution containing the component (D) is included.
The resin coating according to the present invention, on the surface of the substrate,
It has a cured resin layer of the coating resin composition according to the present invention.

The resin coating according to the present invention may have two or more resin layers on the surface of the above-mentioned substrate, if necessary, and in that case, at least one of these resin layers is provided. Is a cured resin layer of the coating resin composition according to the present invention. The resin coating according to the present invention preferably further has a primer layer as a first layer between the base material and the resin layer.

The primer layer has a solid content of at least one selected from the group consisting of epoxy resin, acrylic resin, acrylic silicone resin, chlorinated rubber resin, urethane resin, phenol resin, polyester resin and melamine resin. It is preferably a cured resin layer of a primer composition containing at least wt%. The primer layer contains (a-1) 100 parts by weight of an isocyanate prepolymer that contains two or more isocyanate groups in one molecule but does not contain a urethane bond, and (b-1) one or more in one molecule. 1 to 100 parts by weight of an organosilicon compound containing a mercapto group and two or more alkoxyl groups, (c-1) 100 parts by weight or less of an epoxy resin-modified silicone resin, and (d-1) an organotin compound and / or A cured resin layer of a primer composition containing 0.01 to 30 parts by weight of an organic acid salt of tin as an essential component is preferable.

The isocyanate group contained in the component (a-1) is preferably not directly bonded to the benzene ring. The primer layer is (a-2) ethylene-type monomer 99.5
~ 75 mol% and the general formula RSiX _m R ' _(3-m) (In the formula, R represents a monovalent hydrocarbon group containing a vinyl group, and R'represents 1 to 1 carbon atoms.
Represents a monovalent hydrocarbon group of 10 and X is selected from the group consisting of an alkoxyl group having 1 to 4 carbon atoms, an alkoxyalkoxyl group having 2 to 6 carbon atoms and an oxime group having 2 to 4 carbon atoms. Which represents a hydrolyzable group, and m represents an integer of 1 to 3) a hydrolyzable group-containing vinyl-based copolymer obtained by copolymerization with 0.5 to 25 mol% of an unsaturated group-containing silicon compound represented by A cured resin layer of a primer composition containing 100 parts by weight of the polymer and 0.1 to 50 parts by weight of the epoxy resin-modified silicone resin (b-2) is preferable.

The primer layer may contain a pigment, if necessary. At least one of the resin layers may be a cured resin layer having a pattern pattern formed by division coating and / or overcoating of a resin composition containing at least two kinds of pigments. At least one of the resin layers is a cured resin layer of a coating resin composition containing at least one pigment, and a cured resin layer of a pigment-free coating resin composition is formed on the cured layer. It may have been done.

The resin coating according to the present invention includes
At least one of bending, drawing, punching, punching, cutting, and pressing may be performed. The base material is preferably a steel plate, a non-ferrous metal, a hardened inorganic material, glass, plastic or wood.

The inorganic cured product has a bulk density of 0.5 g / cm ³ or more, and its dimensional change from saturated water absorption to complete drying is 0.5.
% Or less is preferable. The inorganic cured product may have a tongue-processed portion and / or an uneven pattern, if necessary. The method for producing a resin coating product according to the present invention includes a step of forming at least one resin layer on the surface of a base material. At least one of the resin layers is
It is formed by coating the surface of the substrate with the coating resin composition according to the present invention and then curing the coating resin composition.

In the method for producing a resin coating product according to the present invention, before forming the resin layer, the primer composition is coated on the surface of the substrate, and the primer composition is cured to give the above-mentioned base. The method may further include the step of forming a primer layer as the first layer on the surface of the material. The method for producing a resin coating product according to the present invention is, after forming the primer layer and / or the resin layer on the surface of the base material, bending, drawing, punching, punching, and cutting. The method may further include a step of performing at least one of press working.

The method for producing a resin coating product according to the present invention may further include a step of forming at least one resin layer after the above-mentioned processing.
The base material is a steel plate, a non-ferrous metal, an inorganic hardened body, glass,
It is preferably plastic or wood. It is preferable that the inorganic cured body has a bulk density of 0.5 g / cm ³ or more, and the dimensional change from the time of saturated water absorption to complete drying is 0.5% or less.

The inorganic cured product may have a tongue-processed portion and / or an uneven pattern, if necessary.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION First, a coating resin composition according to the present invention will be described. The coating resin composition according to the present invention contains the above-mentioned component (A), the above-mentioned component (B) and the above-mentioned component (C) as essential components and, if necessary, further comprises the above-mentioned component (D).

The silica-dispersed oligomer as the component (A) is the main component of the base polymer having the hydrolyzable group (X) as a functional group that is involved in the curing reaction when forming a coating film.
This is obtained by adding colloidal silica dispersed in an organic solvent or water (including a mixed solvent of an organic solvent and water) to the above general formula.
It is obtained by adding one or more hydrolyzable organosilanes represented by (I) and partially hydrolyzing the hydrolyzable organosilane with water in colloidal silica or separately added water. .

The group R ¹ in the hydrolyzable organosilane represented by the general formula (I) represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, such as methyl group and ethyl group. Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; 2-phenylethyl group, 2-phenylpropyl group, 3-phenylpropyi group Aralkyl groups such as phenyl groups; aryl groups such as phenyl groups and tolyl groups; alkenyl groups such as vinyl groups and allyl groups; chloromethyl groups, γ-chloropropyl groups, 3,3,3-trifluoropropyl groups Such halogen-substituted hydrocarbon groups; γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl Examples thereof include substituted hydrocarbon groups such as groups. Among them, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

As the hydrolyzable group X, an alkoxy group,
Acetoxy group, oxime group (-ON = CR (R ')), enoxy group
(-OC (R) = C (R ') R "), amino group, aminoxy group (-ON (R)
R '), amide group (-N (R) -C (= O) -R') (where R, R ', R "
Are, for example, each independently a hydrogen atom or a monovalent hydrocarbon group) and the like. Among these, an alkoxy group is preferable because it is easily available and a silica-dispersed organosilane oligomer solution is easily prepared.

Examples of such hydrolyzable organosilanes include mono-, di-, tri-, and tetra-functional alkoxysilanes in which n in the general formula (I) is an integer of 0 to 3. , Acetoxysilanes, oximesilanes, enoxysilanes, aminosilanes, aminoxysilanes,
Amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and a silica-dispersed organosilane oligomer solution is easily prepared.

In particular, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane of n = 0, and methyltrimethoxysilane, methyltriethoxysilane and methyltriisosilane can be exemplified as the organotrialkoxysilane of n = 1. Propoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,
Examples thereof include 3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane of n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.As the triorganoalkoxysilane of n = 3, Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane.

Of these hydrolyzable organosilanes represented by the general formula (I), 50 mol% or more is preferably trifunctional represented by n = 1, and more preferably 60 mol.
% Or more. If it is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the dry curability may be poor. The colloidal silica in the component (A) is necessary to increase the hardness of the coating film of the coating resin composition of the present invention. As such colloidal silica, water dispersible or organic solvent dispersible colloidal silica can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the content of silica can be determined from this value. Further, when using water-dispersible colloidal silica, water present as a component other than solid content is
It can be used for hydrolysis of the hydrolyzable organosilane as the component (A). These are usually made of water glass, but such colloidal silica can be easily obtained as a commercial product. The organic solvent-dispersed colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Commercially available products of such an organic solvent-dispersible colloidal silica can be obtained similarly to the water-dispersible colloidal silica. The type of organic solvent in which colloidal silica is dispersed is, for example,
Lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; And diacetone alcohol and the like, and one kind or a mixture of two or more kinds selected from the group consisting of these can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone oxime and the like can also be used in combination with these hydrophilic organic solvents.

In the component (A), the colloidal silica is preferably 5 to 95% by weight, more preferably 2% by weight, based on the solid content of the silica content (the weight of the contained Si converted to SiO ₂ ).
It is contained in the range of 0 to 85% by weight. Content is 5% by weight
If less than 95%, the desired coating hardness cannot be obtained, and 95 weight
If it exceeds%, it becomes difficult to uniformly disperse the silica, and the component (A) may gel.

The silica-dispersed oligomer as the component (A) can be obtained by partially hydrolyzing the hydrolyzable organosilane represented by the general formula (I) in water-dispersed colloidal silica or organic solvent-dispersed colloidal silica. . The amount of water added to the hydrolyzable organosilane is
(X) 0.001 to 0.5 mol of water is preferable with respect to 1 equivalent. If the proportion is less than 0.001 mol, a sufficient hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. The method of partial hydrolysis is not particularly limited, and it suffices to mix the hydrolyzable organosilane and colloidal silica and add a necessary amount of water, and the partial hydrolysis reaction proceeds at room temperature. Further, for the purpose of promoting the partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid,
Organic and inorganic acids such as citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid and oxalic acid may be used as a catalyst.

In order to obtain long-term storage stability, the component (A) preferably has a liquid pH of 2.0 to 7.0, more preferably 3.0 to 6.0. If the pH is out of this range, the long-term storability of the component (A) may be significantly deteriorated, especially under the condition that the amount of water used is 0.3 mol or more per X1 equivalent. When the pH of the component (A) is out of the above range, if it is on the acidic side of this range, ammonia, a basic reagent such as ethylenediamine may be added to adjust the pH, and if it is on the basic side, The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid or acetic acid. However, the adjustment method is not particularly limited.

The acrylic resin as the component (B) is an important component having an action of improving the toughness of the coating film obtained from the coating resin composition of the present invention, and is represented by the above general formula (II). It is a copolymer of first, second and third acrylic or methacrylic acid esters. The first acrylic acid ester or methacrylic acid ester has the formula (I
R ^{3 in} I) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and other alkyl groups; cyclopentyl, cyclohexyl, and other cycloalkyl groups; 2-phenylethyl, 2-phenylpropyl Group, aralkyl group such as 3-phenylpropyl group; aryl group such as phenyl group and tolyl group; halogenated hydrocarbon group such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group A hydroxyhydrocarbon group such as a 2-hydroxyethyl group; and the like.
Further, the second acrylic acid ester or methacrylic acid ester is a compound in which R ³ in the formula (II) is an epoxy group, a glycidyl group or a hydrocarbon group containing them, for example, a γ-glycidoxypropyl group. At least one kind. The third acrylic acid ester or methacrylic acid ester is a hydrocarbon group in which R ³ in the formula (II) contains an alkoxysilyl group or a halogenated silyl group, for example, a trimethoxysilylpropyl group, a dimethoxymethylsilylpropyl group, a monohydric group. At least one of methoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group, dichloromethylsilylpropyl group, chlorodimethylsilylpropyl group is there. The component (B) is the first, second, or
A third acrylic acid ester or methacrylic acid ester copolymer, which is an acrylic acid ester or methacrylic acid ester copolymer containing at least one kind and a total of at least three kinds respectively, and the above-mentioned first, second, and third acrylic acid esters. Or 1 or 2 or more of methacrylic acid esters, or 1 further selected from acrylate or methacrylic acid esters other than the above.
It may be a copolymer containing two or more species.

The first acrylic acid ester or methacrylic acid ester is an essential component for improving the toughness of the coating film, and further has an effect of improving the compatibility of the components (A) and (D). There is also. For this purpose, the substituted or unsubstituted hydrocarbon group of R ³ preferably has a volume of a certain amount or more, and preferably has 2 or more carbon atoms. The second acrylic ester or methacrylic ester is an essential component for improving the adhesion of the coating film to the substrate. The third acrylic acid ester or methacrylic acid ester forms a chemical bond between the component (B) and the component (A), and optionally the component (D) when the coating film is cured. The component (B) is fixed in the coating film. The third acrylic acid ester or methacrylic acid ester also has the effect of improving the compatibility of the component (B) with the component (A) and optionally the component (D).

The molecular weight of the acrylic resin as the component (B) is (A)
It is greatly related to the compatibility with the components and (D) component used as necessary. When the polystyrene-converted weight average molecular weight of the acrylic resin of the component (B) exceeds 50,000, phase separation occurs,
The coating film may be whitened. Therefore, it is desirable that the polystyrene-converted weight average molecular weight of the acrylic resin as the component (B) be 50,000 or less. Further, the lower limit of the polystyrene reduced weight average molecular weight of the acrylic resin as the component (B) is preferably 1,000. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease and cracking tends to occur,
Not preferred. The second acrylic acid ester or methacrylic acid ester having an epoxy group is preferably 2% or more in terms of the monomer molar ratio in the copolymer. If it is less than 2%, the adhesion of the coating film will be insufficient. The third acrylic acid ester or methacrylic acid ester having an alkoxysilyl group or halogenated silyl group is preferably in the range of 2 to 50% in terms of monomer molar ratio in the copolymer. If it is less than 2%, the compatibility of the component (B) with the component (A) and optionally the component (D) is poor, and the coating film may be whitened. If it exceeds 50%, (B)
The bond density between the component and the component (A) and optionally the component (D) becomes too high, and the original purpose of the component (B) is not improved in toughness.

As the method for synthesizing the component (B), a radical polymerization method by solution polymerization, emulsion polymerization, suspension polymerization in a known organic solvent, or anionic polymerization method or cationic polymerization method is used. is not. In the radical polymerization method by solution polymerization, for example, the first, second and third acrylic acid ester or methacrylic acid ester monomers are dissolved in an organic solvent in a reaction vessel by a known method, and further radical polymerization is performed. An initiator is added, and the mixture is heated and reacted under a nitrogen stream. The organic solvent is not particularly limited, but for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, etc. are used. Further, the radical polymerization initiator is not particularly limited, but for example, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, azo, etc. Bisisobutyronitrile, hydrogen peroxide-F
e ²⁺ salt, persulfate-NaHSO ₃ , cumene hydroperoxide
-Fe2 ⁺ salt, benzoyl peroxide-dimethylaniline, peroxide-triethylaluminum, etc. are used. In order to control the molecular weight, a chain transfer agent can be added. The chain transfer agent is not particularly limited, and examples thereof include quinones such as monoethylhydroquinone and p-benzoquinone; mercaptoacetic acid-ethyl ester, mercaptoacetic acid-n-butyl ester, mercaptoacetic acid. 2-Ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane, 2-mercaptoethanol and other thiols; di-3-chlorobenzenethiol, p-toluenethiol, benzenethiol and other thiophenols; γ-mercaptopropyltrimethoxysilane, etc. , Phenylpicrylhydrazine, diphenylamine, and tert-butylcatechol can be used.

The curing catalyst which is the component (C) is composed of the component (A),
It accelerates the condensation reaction of the component (B) and optionally the component (D) to cure the coating film. Examples of such catalysts include alkyl titanates; tin carboxylates such as tin octylate, dibutyltin dilaurate and dioctyltin dimaleate; dibutylamine-2-
Amine salts such as hexoate, dimethylamine acetate, ethanolamine acetate; carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropylmethyldimethoxy Amine-based silane coupling agents such as silanes; acids such as p-toluenesulfonic acid, phthalic acid, hydrochloric acid; aluminum compounds such as aluminum alkoxides and aluminum chelates; alkali catalysts such as potassium hydroxide, tetraisopropyl titanate, tetrabutyl titanate, Titanium compounds such as titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane, etc., but (A) component, (B) composition If it is not particularly limited and is optionally used (D) to be valid in the condensation of the components.

The silanol group-containing polyorganosiloxane of the component (D), which is optionally used, has the above average composition formula
It is a component represented by (III), which participates in the formation of a cured coating film through a condensation reaction with the components (A) and (B) and further improves the smoothness, mechanical strength and toughness of the coating film. Examples of R ⁴ in formula (III) include the same as R ¹ in formula (I) above, but preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, and γ-glycid Substituted hydrocarbon groups such as xypropyl group, γ-aminopropyl group and 3,3,3-trifluoropropyl group are more preferable, and methyl group and phenyl group are more preferable. Further, in the formula, a and b are numbers satisfying the above relationship, and when a is less than 0.2 or b is more than 3, cracks are likely to occur in the cured coating film. Further, when a is more than 2 and 4 or less, or b is less than 0.0001, curing does not proceed.

As such silanol group-containing polyorganosiloxane, for example, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyltrichlorosilane, or one or a mixture of two or more corresponding alkoxysilanes is known. It can be obtained by hydrolyzing with a large amount of water according to the above method. When a silanol group-containing polyorganosiloxane is obtained by hydrolysis using an alkoxysilane by a known method, there is a case where an unhydrolyzed alkoxysilane remains. That is, a polyorganosiloxane in which a silanol group and an alkoxy group coexist may be obtained, but in the present invention, such a polyorganosiloxane may be used.

The polystyrene-converted weight average molecular weight of the silanol group-containing polyorganosiloxane of the component (D) is 700 to
It is preferably 20,000. If the molecular weight is lower than this range, the toughness of the coating film is low, and cracks tend to occur easily.On the other hand, if the molecular weight is higher than the above range, the resin in the coating film tends to undergo phase separation and whitening, Not preferable.

The mixing ratio of the component (A) and the component (B) is preferably 1 to 99 parts by weight of the component (A) and 99 to 1 parts by weight of the component (B),
More preferably, the component (A) is 5 to 95 parts by weight, and the component (B) is 95 to 5 parts by weight (however, the total of the component (A) and the component (B) is 100 parts by weight). Also in this case, if the amount of the component (A) exceeds 99 parts by weight, cracks are likely to occur in the coating film, and if it is less than 1 part by weight, the hardness of the coating film cannot be obtained.

When the coating resin composition further contains the component (D), the mixing ratio of the component (A), the component (B) and the component (D) is 1 to 94 parts by weight of the component (A), 5 to 50 parts by weight of ingredients,
The component (D) is preferably 1 to 94 parts by weight, the component (A) is 20 to 94 parts by weight, the component (B) is 5 to 50 parts by weight, and the component (D) is preferably 20 to 94 parts by weight (however, (A)). The total of the component, the component (B) and the component (D) is 100 parts by weight). When the amount of the component (A) exceeds 94 parts by weight, the coating film tends to crack, and when it is less than 1 part by weight, the hardness of the coating film cannot be obtained. If the amount of component (B) exceeds 50 parts by weight, the weather resistance of the coating film cannot be obtained, and if it is less than 5 parts by weight, sufficient toughness cannot be obtained.

The amount of the component (C) added is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the total of the component (A), the component (B) and the component (D) which is optionally used. . 0.
If it is less than 001 parts by weight, it may not be cured at room temperature, and if it exceeds 10 parts by weight, heat resistance and weather resistance may deteriorate. The coating resin composition of the present invention can be made into a paint by adding a pigment. Pigments to be added are preferably organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa Yellow, inorganic pigments such as titanium oxide, barium sulfate, rouge, and complex metal oxides. One or two or more selected may be used in combination.
The amount of the pigment added is not particularly limited because the hiding property varies depending on the type of pigment, but it is based on 100 parts by weight of the total solid content of the component (A), the component (B), and the component (D) that is optionally used. , Preferably 5 to 80 parts by weight. If it is less than 5 parts by weight, the hiding property may be poor, and if it exceeds 80 parts by weight, the smoothness of the coating film may be poor. The pigment may be dispersed by a usual method. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used.

The thickness of the coating film is not particularly limited, and is 0.1 to 100.
1 μm to 50 μm in order that the coating film can be stably adhered and held for a long time without cracks or peeling.
m is preferred. The coating resin composition of the present invention,
The coating can be carried out by a usual coating method, and various coating methods such as brush coating, spraying, dipping, flow, roll, curtain and knife coating can be selected. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be determined as needed.

The coating resin composition of the present invention may further contain a leveling agent, a thickener, a pigment, a dye, an aluminum paste, a glass frit, a metal powder, an antioxidant, an ultraviolet absorber, etc., if necessary. It can be added within a range that does not adversely affect the effects of the present invention. The method for producing the coating resin composition of the present invention is not particularly limited, but for example, the following (1), (2) or
The method of (3) can be mentioned.

(1) A method comprising a step of mixing a resin solution containing the component (A) and the component (B) with a resin solution containing the component (C). (2) A method including a step of mixing a resin solution containing the component (A) and the component (C) with a resin solution containing the component (B). (3) A method including a step of mixing a resin solution containing the component (A) with a resin solution containing the component (B) and the component (C).

When the coating resin composition of the present invention further contains the component (D), the method for producing the coating resin composition is not particularly limited, but for example, the following ( 4), (5) or (6)
And the like. (4) A method comprising a step of mixing a resin solution containing the component (A), the component (B) and the component (C) with a resin solution containing the component (D).

(5) A method comprising a step of mixing a resin solution containing the component (A) and the component (C) with a resin solution containing the component (B) and the component (D). (6) A method comprising a step of mixing a resin solution containing the component (A), the component (B) and the component (C) with a resin solution containing the component (C) and the component (D). In the above methods (1) to (6), the more specific method of mixing the components is not particularly limited, but, for example, in the case of the method (4), the component (A) is included. The resin solution is mixed with the resin solution containing the component (B), and then further mixed with the resin solution containing the component (C) (here, after mixing, the mixture is heated at 60 ° C. to accelerate the reaction). It is also possible), and a method of further mixing the resin solution containing the component (D). It should be noted that the mixing of the respective components may be carried out by a known method, for example, using an ordinary stirring device, but it is not limited to this.

Next, the resin coating according to the present invention will be described. This resin coating product has a cured resin layer of the coating resin composition according to the present invention on the surface of the substrate. The thickness of the cured resin layer is not particularly limited and may be 0.1 to 100 μm, but is preferably 1 to 50 μm in order for the cured resin layer to be stably adhered and held for a long period of time without cracking or peeling. .

The resin-coated product according to the present invention may have two or more resin layers on the surface of the substrate, if necessary. In that case, at least one of these resin layers may be a cured resin layer of the coating resin composition according to the present invention. That is, it is not necessary that all of the two or more resin layers are the cured resin layer of the coating resin composition of the present invention, and the cured resin layer of the coating resin composition of the present invention and the coating resin other than the present invention A cured resin layer of the resin composition may be mixed.

The coating resin composition other than the present invention that can be used is not particularly limited, but examples thereof include phthalic acid resin enamel (for example, Unipack 200 manufactured by Nippon Paint Co., Ltd.), polyurethane resin coating (for example, Toaurethane manufactured by Tope). # 100), acrylic resin (for example, AP enamel manufactured by Kansai Paint Co., Ltd.), and the like. These are used for the purpose of, for example, protecting an organic coating film having poor weather resistance and low film hardness, and imparting a design property to the coating film of the coating resin composition of the present invention with an organic coating.

The thickness of the cured resin layer of the coating resin composition other than the present invention described above is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 50 μm. If it is less than 0.1 μm, there are problems that it is difficult to obtain a uniform coating film and the hiding property is poor. If it exceeds 100 μm, there is a problem that cracks are likely to occur in the coating film.

In order to obtain high adhesion, the resin coating according to the present invention has a primer layer as a first layer between the substrate and the resin layer (the lowest layer when there are a plurality of resin layers). It is preferable to further have The thickness of the primer layer is not particularly limited, but is 0.1 to 50 μm.
m is preferable, and 0.5-10 μm is more preferable. If the thickness is too thin, there is a problem that it is difficult to obtain a uniform coating film.
If the thickness is too thick, foaming etc. may occur during drying.

As the primer layer, for example, at least one selected from the group consisting of epoxy resin, acrylic resin, acrylic silicon resin, chlorinated rubber resin, urethane resin, phenol resin, polyester resin and melamine resin is used as a solid. Examples include a cured resin layer of a primer composition containing 10% by weight or more. The primer layer is not limited to the above. For example,
(a-1) 100 parts by weight of an isocyanate prepolymer which contains two or more isocyanate groups in one molecule but does not contain a urethane bond, and (b-1) one or more mercapto groups and 2 in one molecule. 1 to 100 parts by weight of an organosilicon compound containing one or more alkoxyl groups, and (c-1) 100 parts by weight or less of epoxy resin-modified silicone resin (as solid content)
And (d-1) an organic tin compound and / or an organic acid salt of tin.
It may be a cured resin layer of a primer composition containing 01 to 30 parts by weight as an essential component.

When the isocyanate group contained in the component (a-1) is required not to be discolored by light,
It is preferably not directly bonded to the benzene ring. Said
Specific examples of the component (a-1) are not particularly limited,
Examples thereof include hexamethylene diisocyanate, tolylene diisocyanate, m-xylylene diisocyanate, tris (2-hydroxyethyl) isocyanate, and the like, and further, partial hydrolysis products and trimers thereof, and further isocyanate mixtures thereof. Examples include reaction products. Among them, from the viewpoint of weather resistance,
For this purpose, those having no urethane bond and having no isocyanate group directly bonded to the benzene ring are preferred. For example, those having a buret bond such as the following formulas (IV) and (V), the following formulas (VI), (VII), (VIII) and (I
Examples thereof include those having an isocyanurate ring such as X). These may be used alone or in combination of two or more.

[0066]

Embedded image

The organosilicon compound as the component (b-1) is
Reacts with organic compounds and reacts with mercapto groups and inorganic compounds
Adhesion with a silane coupling agent having an alkoxy group
Acts as a sex improver. Such an organosilicon compound
Is not particularly limited, for example, HS (CH_Two)_Three
Si (OCH_Three)_Three, HS (CH_Two)_ThreeSi (OC_TwoH_Five)_Three, HS (CH_Two)_TwoSi (OC
H_Three) _Three, HS (CH_Two)_TwoSi (OC_TwoH_Five)_Three, HS (CH_Two)_ThreeSi (CH_Two) (OCH_Three)_Two
And silanes thereof and hydrolysates thereof. This
These may be used alone or in combination of two or more.

The blending amount of the organosilicon compound as the component (b-1) is such that the isocyanate prepolymer 1 as the component (a-1) is used.
1 to 100 parts by weight, preferably 3 to 00 parts by weight
˜50 parts by weight. If the ratio is less than 1 part by weight, the adhesiveness may not be sufficiently exhibited and the strength of the coating may be poor, and if it exceeds 100 parts by weight, the adhesiveness tends to be rather deteriorated.

The epoxy resin-modified silicone resin as the component (c-1) contributes to the improvement of the adhesiveness and ultraviolet resistance of the primer. Epoxy resin component, glycidyl group, 3,
It is a low molecular weight compound or polymer containing a compound having oxirane oxygen such as 4-oxycyclohexyl group, and various acid anhydrides, amines and the like may be used as a curing agent. The curing agent components are not particularly limited, and include phthalic anhydride,
Examples thereof include maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, dodecylsuccinic anhydride, and the like, which may be used alone or in combination of two or more.

The compounding amount of the epoxy resin-modified silicone resin as the component (c-1) is 10 as a solid component based on 100 parts by weight of the isocyanate prepolymer as the component (a-1).
It is 0 part by weight or less, preferably 3 to 50 parts by weight. If the above proportion exceeds 100 parts by weight, not only the weather resistance and the adhesiveness may be impaired, but also the stability of the primer resin solution is not preferable.

The organotin compound and / or tin organic acid salt as the component (d-1) serves as a reaction catalyst for the isocyanate group, alkoxysilyl group, silanol group and the like contained in other primer components. Such tin compounds are not particularly limited, but include tin carboxylates such as tin octylate, dibutyltin acetate, dibutyltin laurate, dibutyltin malate, dibutyltin phthalate and other organotin carboxylates and compounds thereof. Examples thereof include deesterification reaction products with alkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and reaction products with organic tin oxides such as dibutyltin oxide and esters thereof.

The blending amount of the component (d-1) is 0.01 to 30 parts by weight, preferably 0.05 to 1 part by weight, relative to 100 parts by weight of the isocyanate prepolymer of the component (a-1).
0 parts by weight. If the blending amount is less than 0.01 parts by weight, the adhesiveness, particularly the water resistance of the adhesive, may be deteriorated. Workability tends to cause problems.

The primer composition comprising each of the above components is appropriately diluted with an organic solvent for the purpose of facilitating the coating operation and imparting storage stability. The solvent is not particularly limited, but examples thereof include carboxylic acid esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic compounds such as toluene, xylene and benzene; diethyl ether, tetrahydrofuran. , Ethers such as dioxane, and heterocyclic compounds containing oxygen can be used. These solvents may be used alone or in combination of two or more.

The primer layer is not limited to the above-mentioned ones. For example, (a-2) ethylene type monomer 99.5 to
75 mol% and the general formula RSiX _m R ' _(3-m) (In the formula, R represents a monovalent hydrocarbon group containing a vinyl group, and R'represents 1 to 10 carbon atoms.
Represents a monovalent hydrocarbon group, and X is a hydrolyzate selected from the group consisting of an alkoxyl group having 1 to 4 carbon atoms, an alkoxyalkoxyl group having 2 to 6 carbon atoms and an oxime group having 2 to 4 carbon atoms. Represents a decomposable group, m represents an integer of 1 to 3) and a hydrolyzable group-containing vinyl-based copolymer obtained by copolymerization with 0.5 to 25 mol% of an unsaturated group-containing silicon compound represented by It may be a cured resin layer of a primer composition containing 100 parts by weight of the combined product and (b-2) 0.1 to 50 parts by weight of an epoxy resin-modified silicone resin as essential components.

The ethylene type monomer as the raw material of the component (a-2) is not particularly limited, but for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, Alkyl (meth) acrylates such as butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate; conjugated dienes such as styrene, vinyltoluene, α-methylstyrene; carbon number 1 such as vinyl acetate, vinyl propionate Examples thereof include vinyl esters of saturated fatty acids of -12.

Similarly, the general formula of the raw material of the component (a-2)
In the unsaturated group-containing silicon compound represented by RSiX _m R ′ _(3-m) , the vinyl group-containing monovalent hydrocarbon group R is
Vinyl, allyl, 3-acryloxypropyl, 3-methacryloxypropyl, p-vinylphenyl, etc. are recommended due to their availability of raw materials and ease of synthesis. Examples of the hydrolyzable group X include C1-C4 alkoxy groups such as methoxy, ethoxy, p-propoxy, and n-butoxy; C2-C6 alkoxyalkoxyl groups such as methoxyethoxy, ethoxyethoxy, and acetoxy. Examples thereof include an acyloxy group having 2 to 4 carbon atoms; and an oxime group having 2 to 4 carbon atoms such as methylethylketoxime. The number m of the hydrolyzable group X is selected from an integer of 1 to 3, and is preferably 2 or 3, and particularly preferably 3 from the viewpoint of forming a network structure in a short time. Specific examples of these unsaturated group-containing silicon compounds include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (ethoxyethoxy) silane, vinyltris (methylethylketoxime) silane, allyltrimethoxysilane, and allyltrimethoxysilane. Ethoxysilane, allyltris (methylethylketoxime) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltris (ethoxyethoxy) silane, 3-acryloxypropyltris (methylethylketoxime) Silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane,
Examples thereof include 3-methacryloxypropyltris (ethoxyethoxy) silane and 3-methacryloxypropyltris (methylethylketoxime) silane.

The hydrolyzable group-containing vinyl copolymer as the component (a-2) is prepared by adding the above ethylene type monomer and unsaturated group-containing silicon compound, for example, in the presence of an organic solvent and a free radical initiator. It is obtained by reacting under the temperature of 50 to 150 ° C. The free radical initiator is not particularly limited, but for example, an azo compound or an organic peroxide can be used, and specifically, azobisisobutyronitrile, t-
Examples thereof include butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and acetone peroxide. The amount of the free radical initiator is not particularly limited, but 0.01 to 1% by weight is suitable with respect to the total amount of the ethylene type monomer and the unsaturated group-containing silicon compound. Further, when carrying out this polymerization, a chain transfer agent such as n-propanethiol, 1-hexanethiol, 1-decanethiol, benzenethiol, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane is used. It is also possible to control the molecular weight.

The ratio of the ethylenic monomer to the unsaturated group-containing silicon compound is preferably 0.5 to 25 mol% of the unsaturated group-containing silicon compound with respect to 99.5 to 75 mol% of the ethylene type monomer. When the amount of the unsaturated group-containing silicon compound used is less than this range, the weather resistance of the coating film is deteriorated, which is not preferable.

The epoxy resin-modified silicone resin of the component (b-2) is not particularly limited.
Examples thereof include the same epoxy resin-modified silicone resin as the component (c-1). The amount of the epoxy resin-modified silicone resin as the component (b-2) used is 0.1 to 50 parts by weight as a solid content based on 100 parts by weight of the hydrolyzable group-containing vinyl copolymer as the component (a-2). It is desirable to be a department. If the amount used is less than 0.1 part by weight, the weather resistance and the toughness of the film may be impaired, and if it exceeds 50 parts by weight, the adhesiveness will be reduced, such being undesirable.

The primer composition containing the component (a-2) and the component (b-2) may further contain a curing catalyst, if necessary. The amount of the curing catalyst used is preferably less than 20 parts by weight with respect to 100 parts by weight of the hydrolyzable group-containing vinyl copolymer. If the amount used exceeds 20 parts by weight, it will exude to the surface of the primer coating and the adhesiveness will be impaired, such being undesirable. Specific examples of the curing catalyst include, but are not limited to, dibutyltin laurate, dibutyltin acetate, butyltin tri (2-ethylhexoate), stannous caprylate, tin naphthenate, tin oleate, iron- 2-ethylhexoate, lead-2-ethyloctoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexoate, titanium naphthenate, zinc naphthenate, Organic carboxylic acid metal salts such as cobalt naphthenate and zinc stearate; Organic titanate esters such as tetrabutyl titanate and tetra (isopropenyloxy) titanate;
Organic titanium compounds such as organosiloxy titanium and β-carbonyl titanium; aminoalkyl group-substituted alkoxysilanes such as γ-aminopropyltriethoxysilane and N- (trimethoxysilylpropyl) ethylenediamine; amines such as hexylamine and dodecylamine phosphate Compounds or salts thereof; Quaternary ammonium salts such as benzenetriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, lithium oxalate; dialkylhydroxylamines such as dimethylhydroxylamine, diethylhydroxylamine;
Examples thereof include guanidine compounds such as tetramethylguanidine, and guanidine group-containing silane or siloxane compounds.

Any of the above primer compositions may further contain other additives such as coloring pigments such as titanium oxide, carbon black and iron oxide, if necessary. The method for coating the primer composition is not particularly limited, and for example, brush coating, spraying, roll coater, flow coater, etc. can be used, and the coating film thickness is
0.5 to 10 μm is desirable. The dry curing is not particularly limited, but can be carried out, for example, in a dryer at 80 ° C. for 10 to 20 minutes.

At least one of the resin layers is divided and / or coated with a resin composition containing at least two kinds of pigments.
Alternatively, it may be a cured resin layer having a pattern pattern formed by overcoating. At least one of the resin layers is
A cured resin layer of a coating resin composition containing at least one pigment, and a cured resin layer of a pigment-free coating resin composition may be formed on the cured layer.

The resin coating product according to the present invention includes:
At least one of bending, drawing, punching, punching, cutting, and pressing may be performed. Next, a method for producing a resin coating product according to the present invention will be described. This manufacturing method is
The step of forming at least one resin layer on the surface of the base material is included. At least one of the resin layers is formed by coating the surface of the substrate with the coating resin composition according to the present invention and then curing the coating resin composition.

The method for producing a resin coating product according to the present invention may further include a step of forming a primer layer as a first layer on the surface of the base material before forming the resin layer. Further, prior to the formation of the primer layer, depending on the type of the base material, sealing may be performed by a solvent-based, water-soluble or emulsion-based sealer to adjust the variation of suction on the surface of the base material. The sealer used is not particularly limited, and acrylic type,
A latex type etc. can be used.

In the method for producing a resin coating product according to the present invention, after the primer layer and / or the resin layer is formed on the surface of the base material, bending, drawing, punching, and punching are performed. The method may further include a step of performing at least one of cutting, cutting and pressing. The method for producing a resin coated product according to the present invention further comprises at least 1 after performing the above-mentioned processing.
It may further include a step of forming one resin layer.

Next, the base material used in the present invention will be described. Specific examples of the base material are not particularly limited, for example, polycarbonate resin, acrylic resin,
Plastics such as ABS resin; non-ferrous metals such as aluminum, duralumin and copper; steel plates such as stainless steel and iron;
Glass; wood; paper; wall materials such as cement and gypsum; inorganic hardened materials; ceramics such as alumina. Furthermore, regardless of the substrate, the coating resin composition according to the present invention may be used for surface protection of acrylic, alkyd, polyester, epoxy, and urethane coatings.

The following are specific examples of the inorganic hardened material. There is no particular limitation on the hydraulic inorganic adhesive material as a raw material for the inorganic hardened body, and for example, one or more selected from Portland cement, blast furnace cement, blast furnace slag, calcium silicate, gypsum, etc. may be used. Can be used. Usually, an inorganic filler, a fibrous material, or the like is blended in the adhesive material. They are not particularly limited, as the inorganic filler, fly ash, microsilica, silica sand and the like, as the fibrous material, pulp, synthetic fibers, inorganic fibers such as asbestos, metal fibers such as steel fibers. They are selected and used alone or in combination of two or more.

The inorganic hardened material thus constituted is molded by a method such as extrusion molding, casting, paper molding, press molding or the like, and is not particularly limited, but it is not limited to autoclave curing, steam curing, Room temperature curing is suitable. The resulting inorganic cured product has a bulk density of 0.5 g / cm ³ or more, and its dimensional change from saturated water absorption to complete drying is 0.5%.
The following are preferable, and more preferably:
A material having a bulk density of 0.7 g / cm ³ or more and a dimensional change of 0.4% or less is selected. When the bulk density is less than 0.5 g / cm ³ , since the primer composition and the resin composition for coating of the present invention are strongly sucked, the adhesion performance is difficult to be exhibited and the appearance of the coating film is deteriorated. There is a fear.

The inorganic cured product may have a tongue-finished portion and / or an uneven pattern, if necessary. Examples of such an inorganic cured product include, but are not limited to, those processed into the dimensions (unit: mm) and shapes shown in FIGS. 1 and 2.

[0090]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the present invention is not limited to the following Examples. In the following, all "parts" represent "parts by weight" and "%" all represent "% by weight". First, an example of a method for preparing the component (A) will be described. (Preparation Example A-1) IPA-ST (isopropanol dispersed colloidal silica sol in a flask equipped with a stirrer, heating jacket, condenser and thermometer: particle size 10 to 20 nm, solid content 30%, water content 0.5%, Nissan Chemical Industries (Made by the company) 100 g, methyltrimethoxysilane 68 g, and water 2.2 g are added and stirred.
Hydrolysis was carried out at a temperature of 65 ° C. for 5 hours and cooled to obtain component (A). It had a solids content of 36% when left at room temperature for 48 hours. The component (A) obtained here is called A-1. Preparation conditions for A-1: -Number of moles of water to 1 mol of hydrolyzable groups 0.1-Silica content of component (A) 47.3% -Mole% of hydrolyzable organosilane with n = 1 100 mol% (preparation Example A-2) MA-ST (methanol dispersed colloidal silica sol: particle size 10 to 20 nm, solid content 30%) in a flask equipped with a stirrer, heating jacket, condenser and thermometer.
, Moisture 0.5%, manufactured by Nissan Chemical Industries, Ltd.) 100g, methyltrimethoxysilane 68g, phenyltrimethoxysilane 49.5g
, 16.0 g of water and 0.1 g of acetic anhydride were added and stirred with stirring 60
Hydrolysis was carried out at a temperature of ℃ for 5 hours and cooled to obtain the component (A). This product has a solid content of 48 hours when left at room temperature.
41%. The component (A) obtained here is referred to as A-2. Preparation conditions for A-2: -Mole number of water to 1 mol of hydrolyzable group 0.4-Silica content of component (A) 31.3% -Mole% of hydrolyzable organosilane with n = 1 100 mol% (B ) The method for preparing the components is as follows.

Preparation Example B-1 A flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas introducing / exhausting hole and a thermometer was charged with n-butyl methacrylate.
(BMA) 5.69 g (40 mmol), trimethoxysilylpropyl methacrylate (SMA) 1.24 g (5 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), and γ as a chain transfer agent.
-Mercaptopropyltrimethoxysilane 0.784g (4mmo
To a reaction solution prepared by dissolving l) in 8.49 g of toluene was added dropwise a solution of 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene under a nitrogen stream, and the mixture was reacted at 70 ° C. for 2 hours. A polymer having a weight average molecular weight of 1,000 was obtained, and this acrylic resin solution was used as it was as the component (B). this
It is called B-1. The molecular weight was determined by gel permeation chromatography (measurement model: HLC-802UR, manufactured by Tosoh Corporation) to find a standard polystyrene conversion value. The subsequent molecular weight was measured in the same manner. B-1 preparation conditions: -Monomer molar ratio BMA / SMA / GMA = 8/1 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-2) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 4.98 g (35 mmol), trimethoxysilylpropyl methacrylate (SMA) 2.48 g (10 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784 To a reaction solution prepared by dissolving g (4 mmol) in 9.26 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-2. Preparation conditions for B-2: -Monomer molar ratio BMA / SMA / GMA = 7/2 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-3) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 4.27 g (30 mmol), trimethoxysilylpropyl methacrylate (SMA) 3.73 g (15 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784 To a reaction solution prepared by dissolving g (4 mmol) in 10.10 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-3. Preparation conditions for B-3: -Monomer molar ratio BMA / SMA / GMA = 6/3 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-4) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 3.56 g (25 mmol), trimethoxysilylpropyl methacrylate (SMA) 4.97 g (20 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784 To a reaction solution prepared by dissolving g (4 mmol) in 10.90 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-4. Preparation conditions for B-4: -Monomer molar ratio BMA / SMA / GMA = 5/4 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-5) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 2.84 g (20 mmol), trimethoxysilylpropyl methacrylate (SMA) 6.21 g (25 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784. To a reaction liquid prepared by dissolving g (4 mmol) in 11.68 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-5. Preparation conditions for B-5: -Monomer molar ratio BMA / SMA / GMA = 4/5 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-6) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 2.13 g (15 mmol), trimethoxysilylpropyl methacrylate (SMA) 7.45 g (30 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784 To a reaction solution prepared by dissolving g (4 mmol) in 12.47 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-6. Preparation conditions for B-6: -Monomer molar ratio BMA / SMA / GMA = 3/6 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-7) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 1.42 g (10 mmol), trimethoxysilylpropyl methacrylate (SMA) 8.69 g (35 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784. To a reaction solution prepared by dissolving g (4 mmol) in 13.27 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-7. Preparation conditions for B-7: -Monomer molar ratio BMA / SMA / GMA = 2/7 / 1-Weight average molecular weight 1,000-Solid content 40% (Preparation Example B-8) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 0.711 g (5 mmol), trimethoxysilylpropyl methacrylate (SMA) 9.93 g (40 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.784 To a reaction solution prepared by dissolving g (4 mmol) in 14.06 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-8. Preparation conditions for B-8: -Monomer molar ratio BMA / SMA / GMA = 1/8 / 1-Weight average molecular weight 1,000-Solid content 40% (Comparative Preparation Example B'-1) Preparation Example B-1 Do the same operation as n-butyl methacrylate (BMA) 7.11 g (50 mmol), trimethoxysilylpropyl methacrylate (SMA) 0 g (0 mmol), glycidyl methacrylate (GMA) 0 g (0 mmol), γ-mercaptopropyltrimethoxysilane 0.784 g (4 mmol) of toluene
Azobisisobutyronitrile was added to the reaction solution dissolved in 7.7 g.
A solution prepared by dissolving 0.025 g (0.15 mmol) in 3 g of toluene was added dropwise and reacted. This is referred to as comparative component B'-1. Preparation conditions for B'-1: -Monomer molar ratio BMA / SMA / GMA = 10/0 / 0-Weight average molecular weight 1,000-Solid content 40% (Comparative Preparation Example B'-2) Preparation Example B- Do the same operation as 1 n-butyl methacrylate (BMA) 0 g (0 mmol), trimethoxysilylpropyl methacrylate (SMA) 12.4 g (50 mmol), glycidyl methacrylate (GMA) 0 g (0 mmol), γ-mercaptopropyltrimethoxysilane 0.784 g (4 mmol) of toluene
To the reaction solution dissolved in 15.6 g, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise and reacted. This is referred to as comparative component B'-2. Preparation conditions for B'-2: -Monomer molar ratio BMA / SMA / GMA = 0/10 / 0-Weight average molecular weight 1,000-Solid content 40% (Comparative Preparation Example B'-3) Preparation Example B- Do the same operation as 1 n-butyl methacrylate (BMA) 0 g (0 mmol), trimethoxysilylpropyl methacrylate (SMA) 0 g (0 mmol), glycidyl methacrylate (GMA) 7.1 g (50 mmol), γ-mercaptopropyltrimethoxysilane 0.784 g (4 mmol) of toluene 7.
Azobisisobutyronitrile was added to the reaction solution dissolved in 65 g.
A solution prepared by dissolving 0.025 g (0.15 mmol) in 3 g of toluene was added dropwise and reacted. This is referred to as comparative component B'-3. B'-3 preparation conditions: -Monomer molar ratio BMA / SMA / GMA = 0/0 / 10-Weight average molecular weight 1,000-Solid content 40% Next, an example of the preparation method of component (D) explain.

Preparation Example D-1 A flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer is charged with a solution of 220 g (1 mol) of methyltriisopropoxysilane in 150 g of toluene, and 108 g of a 1% hydrochloric acid aqueous solution. Was added dropwise to the above mixed solution in 20 minutes to hydrolyze methyltriisopropoxysilane. After 40 minutes from the dropping, the stirring was stopped, the lower layer water / isopropyl alcohol mixed solution containing a small amount of hydrochloric acid separated into two layers was separated, and the hydrochloric acid remaining in the resin solution of toluene remaining afterwards was removed by washing with water. Further, toluene was removed under reduced pressure and diluted with isopropyl alcohol to obtain a 40% isopropyl alcohol solution of a silanol group-containing organopolysiloxane having a weight average molecular weight of about 2,000. This is called D-1.

Preparation Example D-2 A flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer was charged with 1,000 g of water and 50 g of acetone, and 44.8 g (0.3 mol) of methyltrichlorosilane and phenyltriphenylsilane were added. A solution of 84.6 g (0.4 mol) of chlorosilane dissolved in 200 g of toluene was hydrolyzed while being added dropwise with stirring. After 40 minutes from dropping, the stirring was stopped, the reaction solution was transferred to a separating funnel and allowed to stand still, and then the lower layer hydrochloric acid water separated into two layers was separated, and then,
Water and hydrochloric acid remaining in the toluene solution of the organopolysiloxane in the upper layer are removed together with excess toluene by vacuum stripping, and the weight average molecular weight is about 3,000.
Of silanol group-containing organopolysiloxane of toluene
A 60% solution was obtained. This is called D-2.

-Examples 1 to 20 and Comparative Examples 1 to 8- (Coating resin composition as clear paint) The components shown in Tables 1 to 4 were mixed in the proportions shown in the same table, and all were mixed with isopropyl alcohol. It was diluted to a solid content of 25% to obtain a coating resin composition. The obtained coating resin composition was spray-painted on an aluminum-blown test piece (trade name: Ulster; manufactured by Nippon Test Panel Co., Ltd .; dimensions 150 mm x 70 mm x 0.3 mm) to give a cured coating film thickness of 30 μm. Apply and cure at a curing temperature of 100 ° C for 20
Films were cured by curing for minutes and tested for film properties. The coating film properties were tested by the following evaluation methods.

Adhesion: Adhesion to the substrate is evaluated by a cross-cut adhesive tape (using cellophane tape) peeling test. Coating film hardness: According to pencil hardness test (according to JIS K5400). Solvent resistance: The coating film was gently pressed with a gauze impregnated with toluene and rubbed 100 times in a reciprocating manner.

Boiling resistance: After 16 hours of boiling water test, the test piece was allowed to stand for 1 hour and the state of the coating film was observed. Weather resistance: After irradiating 2500 hours with a sunshine weatherometer (according to JIS K5400), the coating film was observed and the one with no change was regarded as good. As can be seen from Tables 1 to 4, the coating resin compositions of the Examples have coating films with respect to adhesion, coating hardness, solvent resistance, boiling water resistance and weather resistance as compared with Comparative Examples. It was good.

-Examples 21-28 and Comparative Examples 9-16
-(Coating resin composition as clear paint) The components shown in Tables 5 to 7 are mixed in the ratio shown in the same table, and all are diluted with isopropyl alcohol to a solid content of 25% to prepare a coating resin composition. I got a thing. The coating film production method and the coating film evaluation method are the same as those shown in Tables 1 to 4.
The method for preparing the new component (B) is shown below.

(Preparation Example B-9) The same operation as in Preparation Example B-1 was carried out to obtain 5.69 g (40 mmol) of n-butyl methacrylate (BMA) and 1.24 g (5 m of trimethoxysilylpropyl methacrylate (SMA).
mol), glycidyl methacrylate (GMA) 0.71 g (5 mmol),
γ-mercaptopropyltrimethoxysilane 0.196g (1m
To a reaction solution prepared by dissolving (mol) in 8.49 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise and reacted. This is called B-9. Preparation conditions for B-9: ・ Monomer molar ratio BMA / SMA / GMA = 8/1/1 ・ Weight average molecular weight 3,000 ・ Solid content 40% (Preparation Example B-10) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 5.69 g (40 mmol), trimethoxysilylpropyl methacrylate (SMA) 1.24 g (5 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.098 To a reaction solution prepared by dissolving g (0.5 mmol) in 8.49 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-10. Preparation conditions for B-10: -Monomer molar ratio BMA / SMA / GMA = 8/1 / 1-Weight average molecular weight 5,000-Solid content 40% (Preparation Example B-11) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 5.69 g (40 mmol), trimethoxysilylpropyl methacrylate (SMA) 1.24 g (5 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0.0392 To a reaction solution prepared by dissolving g (0.2 mmol) in 8.49 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is called B-11. Preparation conditions for B-11: -Monomer molar ratio BMA / SMA / GMA = 8/1 / 1-Weight average molecular weight 12,000-Solid content 40% (Preparation Example B-12) Same as Preparation Example B-1 N-butyl methacrylate (BMA) 5.69 g (40 mmol), trimethoxysilylpropyl methacrylate (SMA) 1.24 g (5 mmol), glycidyl methacrylate (GMA) 0.71 g (5 mmol), γ-mercaptopropyltrimethoxysilane 0 g Toluene (0 mmol) 8.
Azobisisobutyronitrile was added to the reaction solution dissolved in 49 g.
A solution prepared by dissolving 0.025 g (0.15 mmol) in 3 g of toluene was added dropwise and reacted. This is called B-12. Preparation conditions for B-12: -Monomer molar ratio BMA / SMA / GMA = 8/1 / 1-Weight average molecular weight 36,000-Solid content 40% (Comparative Preparation Example B'-4) Preparation Example B-1 N-butyl methacrylate (BMA) 3.56 g (25 mmol), trimethoxysilylpropyl methacrylate (SMA) 6.20 g (25 mmol),
Glycidyl methacrylate (GMA) 0 g (0 mmol), γ-mercaptopropyltrimethoxysilane 0.784 g (4 mmol) dissolved in toluene 11.6 g, azobisisobutyronitrile 0.025 g (0.15 mmol) dissolved in toluene 3 g What was done was dripped and it was made to react. This is referred to as comparative component B'-4. Preparation conditions for B'-4: -Monomer molar ratio BMA / SMA / GMA = 5/5 / 0-Weight average molecular weight 1,000-Solid content 40% (Comparative Preparation Example B'-5) Preparation Example B- Perform the same operation as 1 n-butyl methacrylate (BMA) 3.56 g (25 mmol), trimethoxysilylpropyl methacrylate (SMA) 0 g (0 mmol), glycidyl methacrylate (GMA) 3.55 g (25 mmol), γ-mercaptopropyltrimethoxy To a reaction solution prepared by dissolving 0.784 g (4 mmol) of silane in 7.7 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is referred to as comparative component B'-5. Preparation conditions for B'-5: -Monomer molar ratio BMA / SMA / GMA = 5/0 / 5-Weight average molecular weight 1,000-Solid content 40% (Comparative Preparation Example B'-6) Preparation Example B- Perform the same operation as 1 n-butyl methacrylate (BMA) 0 g (0 mmol), trimethoxysilylpropyl methacrylate (SMA) 6.20 g (25 mmol), glycidyl methacrylate (GMA) 3.55 g (25 mmol), γ-mercaptopropyltrimethoxy To a reaction solution prepared by dissolving 0.784 g (4 mmol) of silane in 11.6 g of toluene, a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise for reaction. This is referred to as comparative component B'-6. Preparation conditions for B'-6: -Molar molar ratio BMA / SMA / GMA = 0/5 / 5-Weight average molecular weight 1,000-Solid content 40% As shown in Tables 5 to 7, coatings of Examples The coating composition of the resin composition for use had better adhesion, coating hardness, solvent resistance, boiling water resistance, and weather resistance than those of Comparative Examples.

-Examples 29-38 and Comparative Examples 17-2
0- (Resin composition for coating containing pigment) Tables 8 to 9
The pigment mixture consisting of 100 g of white pigment titanium oxide (R-820, manufactured by Ishihara Sangyo Co., Ltd.) and 1 g of Benagi (manufactured by Toda Kogyo Co., Ltd.) was dispersed in 90 g of the component (A) using a gran mill. It was Add (A) component and (B) component to this,
The components were prepared so that the weight ratio of component (A): component (B): pigment = 10: 4: 10. This ratio is 18: 8: 50 in terms of solid content ratio. Further, the amounts of the components (C) and (D) shown in Tables 8 to 9 were added to obtain coating liquids. All were diluted with isopropyl alcohol to a solid content of 25%, a coating film was formed in the same manner as shown in Tables 1 to 4, and the coating film characteristics were tested. As the test method, in addition to the method described above, the gloss was evaluated by a gloss meter (60 degree gloss).

As can be seen from Tables 8 to 9, the coating resin compositions of the examples have adhesive films, coating film hardness, solvent resistance, boiling water resistance, weather resistance and The gloss was good.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

[Table 6]

[0107]

[Table 7]

[0108]

[Table 8]

[0109]

[Table 9]

-Examples 39 to 54-Various substrates were coated with the resin composition for coating of Example 1 to prepare resin coatings, and the coating film characteristics were evaluated in the same manner as in Example 1. . As a substrate,
The following were used. Glass plate: Soda glass plate (size 76 mm x 52 mm x 0.
7 mm).

Aluminum plate: Surface alumite treated aluminum plate (dimensions 150 mm × 70 mm × 0.3 mm). Stainless steel plate: SUS303 plate (dimensions 150 mm x 70 mm x 0.
5mm). PC board: Polycarbonate board (Dimension 10 mm x 10 mm x
2.5 mm). PMMA board: Polymethylmethacrylate board (size 10 mm x 1
0 mm x 2.5 mm).

Inorganic board: "Multi Siding" manufactured by Matsushita Electric Works, Ltd. (acrylic emulsion sealer-coated cement-based board with a bulk density of 1.0 g / cm ³ and a dimensional change of 0.3% from saturated water absorption to complete drying) (Dimension 150 mm x 70 mm x 5
mm). Processed inorganic plate: The above-mentioned inorganic plate processed into the dimensions and shapes shown in FIGS.

Alumina plate: Alumina sintered plate for electronic circuit board manufactured by Matsushita Electric Works, Ltd. If necessary, an epoxy sealer "Epo E Sealer" (manufactured by Isamu Paint Co., Ltd.) was used as a primer.
Even if no primer is used, there is no particular problem with the adhesion, but if sufficient adhesion is required even after treatment with boiling water for 5 hours, it is preferable to use a primer.

The results are shown in Tables 10-12. Tables 10-12
As can be seen from the above, sufficient coating film performance was obtained with any base material. It is one of the features of the present invention that a coated product free from cracks can be obtained even when a substrate having a surface irregularity such as a processed inorganic plate is used. -Examples 55 to 62- The resin coated product of the present invention can be processed after coating as long as it is a processable substrate. Stainless steel plate (SUS30
3) (Dimension 150 mm × 70 mm × 0.5 mm) was treated with a primer (Epo E Sealer (manufactured by Isam paint)), further coated with the coating resin composition of Example 1, and the following processing was performed.

Bending: bending at 90 ° with R5. Punching: Punching a hole with a diameter of 50 mm with a punching press. Drilling: Drilling a hole with a diameter of 5 mm. Cutting process: Cutting with a press cutter. Further, a coated product obtained by subjecting the same processed product to the above primer treatment and resin coating in the same manner as above was simultaneously prepared, and the coating film performance was evaluated.

The results are shown in Tables 13-14. Table 13-
As can be seen from No. 14, in all cases, sufficient coating film performance was obtained. -Examples 63 to 70-The primer is not limited to the above epoxy-based primer, and the following paints that are already commercially available,
The coatings were evaluated in the same manner as above using the primer. The coating specifications are for each primer,
According to the specifications of the paint, each was applied so that the film thickness was around 1 μm.

Epoxy type: Epo E sealer (made by Isamu paint). Acrylic type: Permalock (made by Rock Paint). Acrylic silicon type: Neosilica # 5000 (made by Isamu paint). Chlorinated rubber type: Laval # 100 primer (made by Shinto paint). Urethane type: Epicon Primer CL (Chinese paint).

Phenol type: New Aknon primer (manufactured by Kansai Paint). Polyester type: Polybest putty # 100 (manufactured by Dainippon Paint). Melamine type: Amilak (made by Kansai Paint). The results are shown in Tables 15 to 16. As can be seen from Tables 15 to 16, there are suitability and unsuitability depending on the use and the required characteristics, but the coating film characteristics showed good results.

-Examples 71-75 and Comparative Examples 21-2
3- Next, a preparation example of a primer composition containing the components (a-1) to (d-1), which is particularly suitable for producing a resin coating, will be described. (Preparation of solution S-1): The following components were mixed and added dropwise to a mixture of 350 parts of water and 50 parts of methanol in a container equipped with a reflux condenser while stirring at a temperature of 50 ° C. Decomposed and condensed.

Dimethylchlorosilane 7 parts Methyltrichlorosilane 40 parts Diphenylchlorosilane 48 parts Phenyltrichlorosilane 78 parts Toluene 95 parts The produced polymethylsiloxane was washed with water to remove by-produced hydrogen chloride. This was heated under reduced pressure to remove water remaining as a part of the solvent to obtain a silicone resin toluene solution having a concentration of 50%. Then, a solution containing the following components was prepared, the temperature was gradually raised with stirring while removing toluene, and when the temperature reached 230 ° C., heating was continued for another 5 hours while maintaining the temperature.

Bisphenol A epichlorohydrin type epoxy resin 70 parts (epoxy equivalent 500) phthalic anhydride 5 parts linseed oil fatty acid 10 parts toluene 75 parts Here, the above silicone resin toluene solution 50 parts and the whole solid Toluene in an amount of 50% was added and stirred until the solution became transparent to obtain a toluene solution S-1 of epoxy resin-modified silicone resin.

(Preparation of solution S-2): The following components were mixed,
While maintaining the temperature at 50 ° C., the mixture was dropped into 320 parts of water while stirring, and a silicone resin xylene solution having a concentration of 60% was obtained in the same manner as in the preparation example of S-1. Dimethylchlorosilane 51 parts Methyltrichlorosilane 15 parts Diphenylchlorosilane 44 parts Phenyltrichlorosilane 52 parts Xylene 50 parts Then, a solution containing the following components was prepared, and 51 parts of the above silicone resin solution was added thereto, and the solution was refluxed for 3 hours. The mixture was heated and stirred.

Bisphenol A epichlorohydrin type epoxy resin 54 parts (epoxy equivalent 500) dodecyl succinic anhydride 25 parts xylene 23 parts Furthermore, a required amount of xylene is added, and a 50% xylene solution of epoxy resin-modified silicone resin is added. Got the S-2.

(Preparation of Solution S-3): The following components were mixed and kept at a temperature of 25 ° C. or lower: methanol 40 parts-water 1
The 5 parts mixture was added dropwise with stirring. Then with stirring 70
The temperature was raised to 0 ° C., the mixture was heated under reflux for 1 hour, then cooled, 40 parts of methanol was added, and the layers were separated. 2 parts of calcium carbonate was added to the collected polyorganosiloxane layer to neutralize the by-produced hydrogen chloride, and then heated under reduced pressure to remove methanol and low-boiling compounds to obtain a liquid polyorganosiloxane.
To 50 parts of this polyorganosiloxane was added the following, and the mixture was heated for 3 hours under reflux of xylene. After cooling and filtration, 50% xylene solution S-3 of epoxy resin-modified silicone resin was obtained.

Novolak type epoxy resin (epoxy equivalent 180) 45 parts Phthalic anhydride 3.5 parts Xylene 100 parts After cooling and filtration, 50 parts of epoxy resin-modified silicone resin
% Xylene solution S-3 was obtained.

The following was used as the isocyanate composition. (Solution I-1): 75% butyl acetate solution of isocyanate prepolymer mixture represented by the chemical formula (VI) (Solution I-2): 75% acetic acid of isocyanate prepolymer mixture represented by the chemical formula (IV) Butyl Solution (Solution I-3): 50% Ethyl Acetate Solution of Isocyanate Prepolymer Mixture Represented by Chemical Formula (IX) The primer compositions were prepared in the ratios shown in Tables 17 to 18. Using the obtained primer composition and the coating resin composition of Example 1, a resin coating was prepared by the same method as described above, and evaluated by the same method as described above. The primer composition was spray coated and cured by heating at 80 ° C for 20 minutes.

The results are shown in Tables 17-18. Tables 17-18
As can be seen from the above, in Examples, the coating film performance is good, and after the 5000-hour accelerated weathering test with a sunshine weatherometer, there is no peeling of the coating film and no discoloration is visually observed. Met. -Examples 76 to 81 and Comparative Examples 24 to 26-Next, preparation examples of primer compositions containing the above-mentioned components (a-2) to (b-2), which are particularly suitable for producing resin coatings. Will be explained.

First, in the preparation of the hydrolyzable group-containing vinyl copolymer, a reaction vessel equipped with a stirrer, a cooler and a thermometer was charged with the monomers shown in Table 19, and the amount of the monomer was doubled. Of toluene and the indicated chain transfer agent and polymerization initiator were added, and the mixture was reacted with stirring at 70 ° C. for 2 hours under a nitrogen gas atmosphere while stirring uniformly. The resulting hydrolyzable group-containing vinyl copolymers were designated as P-1 to P-6, respectively. The molecular weight was measured by the method described above. The solutions S-1 to S-3 described above were used as the epoxy resin-modified silicone resin.

Using the obtained primer composition and the coating resin composition of Example 1, a resin coating was prepared in the same manner as described above, and evaluated in the same manner as described above. The results are shown in Tables 20-21. -Examples 82-85-Next, the Example which uses a coloring primer is shown. Example 7
Using the primer composition used in 1 above, the following 4 kinds of pigments were added thereto, treated with a sand mill for 60 minutes, and used as it was as a primer composition.

White: White pigment (manufactured by Ishihara Sangyo) 45% added to the solid content of the primer. Yellow: Yellow pigment (manufactured by Dainichiseika Kogyo Co., Ltd.) 60% added to the solid content of the primer. Brown: Brown pigment (manufactured by Dainichiseika Co., Ltd.) 30% added to the primer solids. Black: Black pigment (Dainichi Seika Kogyo Co., Ltd.) 25% added to the solid content. The primer composition was spray coated and cured by heating at 80 ° C. for 20 minutes. Then, the coating resin composition of Example 1 was applied so as to have a thickness of 30 μm, and the coating was performed at 80 ° C. for 20 minutes.
Heat cured for a minute. The results are shown in Table 22.

-Example 86- Next, Table 23 shows an example of imparting a high-grade appearance to an inorganic cured body by recoating. The following two kinds of pigments were added to the coating resin composition of Example 1 to prepare two kinds of enamel. This was added to the inorganic cured product shown in FIGS. 1 and 2 with a primer composition (used in Example 76. 1 μm thick), a coating resin composition (used in Example 1; pigment 1; 10 μm thick). , Coating resin composition (Example 1
The pigment used in Example 1; Pigment 2; 10 μm thick) was applied in this order by spraying, and then cured by heating. The heat curing was performed at 80 ° C. for 20 minutes in all cases. As a result, as shown in Table 23, there was no problem in coating film performance. In addition, the film thickness of the convex portion and the concave portion was different depending on the flow of the paint, and therefore, the appearance of the convex portion and the concave portion having different colors and gloss was obtained.

Examples 87 to 90 Next, Table 24 shows examples in which a primer-treated substrate was coated with a commercially available coloring paint or the coloring paint according to the present invention and further coated with a transparent paint according to the present invention. Show.
As a result, it is possible to obtain a coating product in which the coating surface of a commercially available paint is further protected and coated. Commercially available intermediate coating was spray coated according to the manufacturer's specifications. As shown in Table 24, there is no problem in the coating film performance in any of the cases.
A coating having excellent durability was obtained.

-Examples 91 to 94-Next, a base material which has not been treated with a primer is coated with a commercially available coloring paint or the coloring paint according to the present invention, and further,
Table 25 shows an example of coating with a clear paint according to the present invention. As can be seen from Table 25, in all cases, sufficient coating performance with excellent durability was obtained.

[0134]

[Table 10]

[0135]

[Table 11]

[0136]

[Table 12]

[0137]

[Table 13]

[0138]

[Table 14]

[0139]

[Table 15]

[0140]

[Table 16]

[0141]

[Table 17]

[0142]

[Table 18]

[0143]

[Table 19]

[0144]

[Table 20]

[0145]

[Table 21]

[0146]

[Table 22]

[0147]

[Table 23]

[0148]

[Table 24]

[0149]

[Table 25]

[0150]

The coating resin composition of the present invention comprises:
The (A), (B), (C) component, or the (A), (B),
(C), (D) component as an essential component, high toughness, high hardness, high weather resistance and adhesion, solvent resistance, boiling water resistance, further to form a coating film excellent in high speed drying You can Since this coating film has excellent toughness, cracks do not occur at a film thickness of up to 50 μm, there is little coating unevenness, and the adaptability to irregularities of the substrate is wide. Further, it is possible to widely deal with dimensional changes due to temperature and humidity of the base material. Further, the coating resin composition of the present invention is capable of both room temperature curing and heat curing,
It can be used in a wide range of dry curing conditions or temperature.
Therefore, it can be applied to substrates with poor heat resistance, and
Its industrial value is high because it can be painted even at work sites where heat cannot be applied. Furthermore, the coating resin of the present invention has high stability during storage, can be stored for a long time even when a pigment is dispersed and blended, and can be arbitrarily colored.

According to the method for producing a coating resin composition of the present invention, the coating resin composition having the above-mentioned excellent performance can be easily obtained. The resin coating according to the present invention has a cured resin layer of the coating resin composition on the surface of the base material, and thus has high toughness, high hardness, high weather resistance, adhesion, solvent resistance, and boiling water resistance. Further, it has a coating film excellent in high speed drying property. Since this coating film has excellent toughness, cracks do not occur at a film thickness of up to 50 μm, coating unevenness is small, and adaptability to irregularities of the substrate is wide. Further, it is possible to widely deal with dimensional changes due to temperature and humidity of the base material.

The resin coating material according to the present invention can be produced by using the above coating resin composition capable of both room temperature curing and heat curing, so that it can be produced in a wide dry curing condition range or temperature range. Therefore,
Since a base material having poor heat resistance can be used, and it can be manufactured even at a work site where heat is not applied, its industrial value is high. Furthermore, the resin coating of the present invention has high stability during storage, can be stored for a long time even when the pigment is dispersed and compounded, and can be produced using a coating resin composition that can be arbitrarily colored, High design and wide range of use.

According to the method for producing a resin coated product of the present invention, the above excellent resin coated product can be easily obtained.

[Brief description of drawings]

FIG. 1 is a plan view showing an example of a processed inorganic cured body used in the present invention.

FIG. 2 is a cross-sectional view showing a concavo-convex portion of the processed inorganic cured body of FIG.

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[Procedure amendment]

[Submission date] April 11, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

[0066]

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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 143/04 PGL C09D 143/04 PGL 183/04 PMQ 183/04 PMQ // C04B 41/64 C04B 41/64 (72) Minoru Inoue Minoru Inoue 1048, Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd. (72) Motozen Haruna, 1048, Kadoma, Kadoma City, Osaka Prefecture (72) Inventor, Sunaga Ken No. 6, 2-31, Roppongi, Minato-ku, Tokyo Within Toshiba Silicon Co., Ltd. (72) Inventor Yasuyo Iwabuchi, No. 6, 2-31, Roppongi, Minato-ku, Tokyo Toshiba Silicone Co., Ltd. (72) Norio Sato, Tokyo 6-23-1, Roppongi, Minato-ku, Tokyo Inside Toshiba Silicon Co., Ltd.

Claims (44)

[Claims] (A) General formula R ¹ _n SiX _4-n (I) (In the formula, R ¹ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms or a phenyl group. Indicates
n is an integer of 0 to 3, and X is a hydrolyzable functional group. ) A hydrolyzable organosilane represented by the formula (1) is partially hydrolyzed in colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, and a silica-dispersed oligomer solution of organosilane, ₂ = CR ² (COOR ³ ) (II) (in the formula, R ² represents a hydrogen atom or a methyl group), and R ^{3 in} the formula is a substituted or unsubstituted 1 to 9 carbon atom At least one first acrylic acid ester or methacrylic acid ester which is a valent hydrocarbon group, and a hydrocarbon represented by the general formula (II), wherein R ³ is an epoxy group, a glycidyl group or a hydrocarbon containing them. At least one second acrylic ester or methacrylic ester which is a group, and R ^{3 in} the formula represented by the general formula (II), wherein the hydrocarbon group contains an alkoxysilyl group or a halogenated silyl group. There is at least 1 The third acrylic resin is a copolymer of acrylic acid ester or methacrylic acid ester, (C) a coating resin composition for a curing catalyst, and the essential components of the. 2. The component (A) comprises the hydrolyzable organosilane in an amount of 0.001 of water based on 1 equivalent of the hydrolyzable functional group (X).
The coating resin composition according to claim 1, which is a silica-dispersed oligomer solution of organosilane, which is partially hydrolyzed under the condition of using 1 to 0.5 mol. 3. The component (A) is a silica component (containing Si is SiO ₂
The resin composition for coating according to claim 1 or 2, containing 5 to 95% by weight as a solid content. 4. The resin composition for coating according to claim 1, wherein at least 50 mol% of the hydrolyzable organosilane as a raw material of the component (A) is an organosilane with n = 1. Stuff. 5. The coating resin composition according to claim 1, wherein the component (A) has a pH of 2.0 to 7.0. 6. The acrylic resin as the component (B) contains, as a comonomer, at least one selected from the group consisting of n-butyl methacrylate and n-butyl acrylate. The resin composition for coating according to any one of 1 to 6 above. 7. The acrylic resin as the component (B) contains, as a comonomer, at least one selected from the group consisting of trimethoxysilylpropyl methacrylate and trimethoxysilylpropyl acrylate.
The resin composition for coating according to any one of 1 to 6. 8. The acrylic resin as the component (B) contains, as a comonomer, at least one selected from the group consisting of glycidyl methacrylate and glycidyl acrylate. The resin composition for coating according to item 4. 9. The (B) component acrylic resin further contains at least one selected from the group consisting of thiols, thiophenols and their derivatives.
The resin composition for coating according to any one of 1 to 8. 10. The coating resin composition according to any one of claims 1 to 9, wherein the acrylic resin as the component (B) has a polystyrene reduced weight average molecular weight of 1,000 to 50,000. 11. The component (A) is used in the amount of 1 to 99 parts by weight as described above.
The coating resin according to any one of claims 1 to 10, which contains 1 to 99 parts by weight of the component (B) (however, the total of the components (A) and (B) is 100 parts by weight). Composition. 12. The component (C) curing catalyst comprises alkyl titanates, tin carboxylates, aluminum compounds,
The coating resin composition according to any one of claims 1 to 11, which is at least one selected from the group consisting of amine salts, amine-based silane coupling agents, halogenated silanes, acids and alkalis. . 13. (D) Average composition formula R ⁴ _a Si (OH) _b O _{(4-ab) / 2} (III) (wherein, R ⁴ is the same or different, substituted or unsubstituted carbon number 1 to 9 represents a monovalent hydrocarbon group or a phenyl group,
a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3,
It is a number that satisfies the relationship of a + b <4. ), And the resin composition for coating according to any one of claims 1 to 12, further comprising a polyorganosiloxane having a silanol group in the molecule as an essential component. 14. 1 to 94 parts by weight of the component (A), 5 to 50 parts by weight of the component (B) and 1 to 94 parts by weight of the component (D) (provided that the component (A), (B ) And (D) components total 10
The resin composition for coating according to claim 13, which is 0 part by weight). 15. The polystyrene-reduced weight average molecular weight of the component (D) is 700 to 20,000.
The resin composition for coating according to item 4. 16. The resin composition for coating according to claim 1, which further comprises (E) a pigment as an essential component. 17. A method for producing a resin composition for coating, comprising the step of mixing a resin solution containing the component (A) and the component (B) with a resin solution containing the component (C). 18. A method for producing a resin composition for coating, comprising the step of mixing a resin solution containing the component (A) and the component (C) with a resin solution containing the component (B). 19. A resin solution containing the component (A), and
A method for producing a coating resin composition, which comprises a step of mixing a component (B) and a resin solution containing the component (C). 20. The component (A), the component (B) and the component
A method for producing a resin composition for coating, comprising the step of mixing a resin solution containing the component (C) and a resin solution containing the component (D). 21. A resin composition for coating, which comprises a step of mixing a resin solution containing the component (A) and the component (C) with a resin solution containing the component (B) and the component (D). Manufacturing method. 22. A resin solution containing the component (A), the component (B) and the component (C), and the component (C) and the component (C).
A method for producing a resin composition for coating, which comprises a step of mixing with a resin solution containing the component (D). 23. A resin coated product having a cured resin layer of the resin composition for coating according to claim 1 on the surface of a substrate. 24. The coating resin composition according to claim 1, wherein the surface of the substrate has two or more resin layers, and at least one of these resin layers. The resin coated product according to claim 23, which is the cured resin layer of. 25. The resin coated product according to claim 23, further comprising a primer layer as a first layer between the base material and the resin layer. 26. The resin coated product according to claim 24, further comprising a primer layer as a first layer between the base material and the resin layer. 27. The primer layer is at least one selected from the group consisting of epoxy resin, acrylic resin, acrylic silicon resin, chlorinated rubber resin, urethane resin, phenol resin, polyester resin and melamine resin.
The resin coating according to claim 25 or 26, which is a cured resin layer of a primer composition containing 10% by weight or more of seed as a solid content. 28. The primer layer comprises (a-1) 100 parts by weight of an isocyanate prepolymer which contains two or more isocyanate groups in one molecule but does not contain a urethane bond, and (b-1) one molecule. Organosilicon compounds 1-10 containing at least one mercapto group and at least two alkoxyl groups therein
0 parts by weight, (c-1) 100 parts by weight or less of an epoxy resin-modified silicone resin, (d-1) an organic tin compound and / or an organic acid salt of tin 0.01 to
30 parts by weight, and the resin coating according to claim 25 or 26 which is a cured resin layer of a primer composition containing as an essential component. 29. The resin coated product according to claim 28, wherein the isocyanate group contained in the component (a-1) is not directly bonded to the benzene ring. 30. The primer layer comprises (a-2) an ethylene type monomer of 99.5 to 75 mol% and a general formula RSiX.
_m R ' _(3-m) (In the formula, R represents a monovalent hydrocarbon group containing a vinyl group, R'represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is a carbon number. An alkoxyl group having 1 to 4 carbon atoms of 2
An unsaturated group-containing silicon represented by a hydrolyzable group selected from the group consisting of an alkoxyalkoxy group of 6 and an oxime group of 2 to 4 carbon atoms, and m represents an integer of 1 to 3). 100 parts by weight of a hydrolyzable group-containing vinyl copolymer obtained by copolymerizing with 0.5 to 25 mol% of a compound, and (b-2) 0.1 to 50 parts by weight of an epoxy resin-modified silicone resin are essential components. The resin coating according to claim 25 or 26, which is a cured resin layer of the primer composition. 31. The resin coating product according to claim 25, wherein the primer layer contains a pigment. 32. At least one of the resin layers is a cured resin layer having a patterned pattern formed by division coating and / or recoating of a resin composition containing at least two kinds of pigments. 31. The resin coated product according to any of 31. 33. At least one of the resin layers is a cured resin layer of a coating resin composition containing at least one pigment, and a pigment-free coating resin composition is provided on the cured layer. The resin coated product according to any one of claims 23 to 32, wherein a cured resin layer is formed. 34. At least one of bending, drawing, punching, punching, cutting and pressing.
The resin coated product according to any one of claims 23 to 33, which has been subjected to two processes. 35. The base material is a steel plate, a non-ferrous metal, a hardened inorganic material, glass, plastic or wood.
The resin coated product according to any one of 3 to 34. 36. The inorganic cured product has a bulk density of 0.5 g / cm ³ or more, and the dimensional change from the time of saturated water absorption to the complete drying is
The resin coated product according to claim 35, which has a content of 0.5% or less. 37. The resin coated product according to claim 35 or 36, wherein the inorganic cured body has a tongue-finished portion and / or an uneven pattern. 38. A step of forming at least one resin layer on the surface of a substrate, wherein at least one of the resin layers comprises the coating resin composition according to any one of claims 1 to 22. A method for producing a resin coated product, which is formed by coating the surface of a base material and then curing the coating resin composition. 39. Before forming the resin layer, a primer composition is coated on the surface of the base material and the primer composition is cured to form a primer layer as a first layer on the surface of the base material. 39. The method for producing a resin coating according to claim 38, further comprising a step of forming. 40. At least one of bending, drawing, punching, punching, cutting, and pressing after forming the primer layer and / or the resin layer on the surface of the base material. The method for producing a resin-coated product according to claim 38 or 39, further comprising the step of performing one process. 41. The method further comprising the step of forming at least one resin layer after the processing.
The method for producing a resin-coated product according to. 42. The base material is a steel plate, a non-ferrous metal, a hardened inorganic material, glass, plastic or wood.
The method for producing a resin coated product according to any one of 8 to 41. 43. The inorganic cured body has a bulk density of 0.5 g / cm ³ or more, and its dimensional change from the time of saturated water absorption to the absolute dryness is
The method for producing a resin coated product according to claim 42, wherein the content is 0.5% or less. 44. The method for producing a resin coated article according to claim 42 or 43, wherein the inorganic cured body has a tongue-finished portion and / or an uneven pattern.