JPH06128533A - Curable resin composition for topcoat - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition which cures at low temperatures, forms coating films excellent in the resistance to weather and to staining and has a low VOC value by mixing a specific functional resin, a specific silane compound and a metallic chelate compound together. CONSTITUTION:The composition comprises a resin containing a hydrolyzable group directly bonded to a silanol group and/or silicon atom, a hydroxyl group and an epoxy group as functional components; at least one silane compound selected from compounds of formulae I-III (wherein Rs may be the same or different and are each a 1-20C monovalent hydrocarbon group or haloalkyl group; R<1>s may be the same or different and are each a 1-5C alkyl or haloalkyl group; and n is an integer of 1-5); and a metallic chelate compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable resin composition for topcoating.

[0002]

2. Description of the Related Art Conventionally, in the field of constructions, etc. that require large-scale painting, it has excellent finished appearance and coating film performance (weather resistance, stain resistance, etc.), and is dried at room temperature. There is a strong demand for the development of a low temperature curable paint that cures. Further, in order to coat and dry outdoors, in recent years, water-based and low VOC (Volatile Organic Content) values have been demanded under the protection of the global environment.

At present, the paints occupying as the room temperature curable paints are, as a one-pack type, an oxidative curable type by an oxidative polymerization group,
Further, as the two-liquid type, an addition polymerization curing type by a reaction with an isocyanate group and a hydroxyl group, a moisture curing type by an alkoxysilane group and the like are mainly used.

However, the above-mentioned oxidation-curable coating is generally not dense in three-dimensional network structure as compared with curing of isocyanate, alkoxy, etc., and when the coating film is exposed to light, heat, etc. after curing. There is a problem that oxygen radicals are generated, and the bonds are broken by this, so that the weather resistance is deteriorated. In addition, although curing with isocyanate, alkoxysilane, etc. produces a dense three-dimensional network structure, the workability is poor due to the two-part type, and the coating performance is large due to the weather (moisture, etc.) during coating. There is a problem of being affected.

The applicant has made a metal chelate compound contained in a copolymer of a vinyl polymer containing an alkoxysilane group or a silanol group, a polymerizable unsaturated monomer containing an epoxy group and a polymerizable unsaturated monomer containing a hydroxyl group. A curable composition comprising the above is provided (Japanese Patent Laid-Open No. 2-233752). This curable composition is superior in low-temperature curability and coating film performance (weather resistance, stain resistance, etc.) to conventional oxidation-curable paints, urethane, and alkoxysilane-cured paints, but has a VOC value of 600.
It is as high as g / l, and there is a strong demand for lowering the VOC value from the viewpoint of environmental protection.

The present invention has been made for the purpose of developing a curable resin composition which is cured at a low temperature to form a coating film excellent in coating film performance (weather resistance, stain resistance, etc.) and has a low VOC value. It is a thing.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a silanol group and / or a hydrolyzable group directly bonded to a silicon atom, a hydroxyl group and an epoxy group are It was found that a resin composition obtained by mixing a specific silane compound and a metal chelate compound with a resin contained as a functional group component can solve all of the above-mentioned problems, and completed the present invention.

That is, the present invention provides (1) silanol groups and / or
Or a resin containing a hydrolyzable group directly bonded to a silicon atom, a hydroxyl group and an epoxy group as a functional group component, (2) at least one silane compound selected from the following general formulas (I) to (III),

[0009]

[Chemical 2]

[In the above formulas, R is the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a haloalkyl group, and R ¹ is the same or different and has 1 to 10 carbon atoms. 5
Is a monovalent alkyl group or haloalkyl group. Also,
n shows the integer of 1-5. ], And (3) metal chelate compound are contained, It is related with the curable resin composition for top coats characterized by the above-mentioned.

In the present invention, the hydrolyzable group contained in the resin (1) is hydrolyzed in the presence of water to form a hydroxysilane group, a tolyloxy group, a paramethoxyphenoxy group, a paranitrophenoxy group, a butanoyloxy group, Residues such as acyloxy groups such as benzoyloxy group, phenylacetoxy group and formyloxy group are included.

First, the resin (1) will be described.

The resin (1) includes silanol groups and /
Alternatively, a hydrolyzable group directly bonded to a silicon atom (hereinafter, these groups are simply referred to as “reactive silicon group”), an epoxy group and a functional group of a hydroxyl group are contained in the same resin or at least one of these functional groups. Included are resin mixtures in which the seeds are contained in discrete form.

Examples of the resin containing the reactive silicon group, the epoxy group and the hydroxyl group in the same resin include, for example, the reactive silicon group-containing polymerizable unsaturated monomer (a) and the epoxy group-containing polymerizable unsaturated monomer. A copolymer obtained by radically polymerizing the polymer (b), the hydroxyl group-containing polymerizable unsaturated monomer (c), and optionally other polymerizable unsaturated monomer (d) other than the above. Can be mentioned.

The copolymer has an average of 1 or more, preferably an average of 2 or more reactive silicon groups in one molecule, an average of 1 or more, preferably an average of 2 to 40 epoxy groups and 1 in one molecule. It is preferable to have an average of 2 to 200 hydroxyl groups in the molecule from the viewpoint of curability and coating film performance. In order to contain the number of these functional groups in the resin, the monomers (a) to (d) may be blended so that the blending ratio falls within the range.

The average molecular weight of the copolymer is about 1000.
˜200000, preferably 3000 to 100000 is desirable.

Examples of the reactive silicon group-containing polymerizable unsaturated monomer (a) include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- ( Silane compounds such as (meth) acryloxypropyltrisilanol, γ- (meth) acryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-styrylethyltrimethoxysilane, allyltriethoxysilane: the silane Compounds and reaction products with trialkoxy or trihydroxysilane compounds (for example, methyltrimethoxysilane, phenyltrimethoxysilane, methyltrisilanol) (for example, JP-A-2-16087).
Polysiloxane-based macromonomers described in JP-A No. 9) can be preferably used.

Epoxy group-containing polymerizable unsaturated monomer (b)
As the above, a polymerizable unsaturated monomer having an alicyclic epoxy group is preferable from the viewpoint of curability, and for example, JP-A-2-160
Examples thereof include alicyclic vinyl monomers represented by the general formulas (4) to (18) described in Japanese Patent No. 879.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer (c) include hydroxyethyl (meth) acrylate,
Hydroxyalkyl esters of (meth) acrylic acid such as hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; (poly) alkylene glycol mono such as ethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate (Meth) acrylates; hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether; allyl alcohols such as allyl alcohol, methallyl alcohol; addition of the above with lactones (eg ε-caprolactone, γ-valerolactone) The thing etc. are mentioned.

Further, other polymerizable unsaturated monomer (d)
As, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
C _1-24 alkyl or cycloalkyl esters of (meth) acrylic acid such as hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate,
Vinyl aromatic compounds such as styrene and vinyltoluene, perfluorobutylethyl (meth) acrylate,
Perfluoroisononylethyl (meth) acrylate,
Examples include perfluoroalkyl (meth) acrylates and (meth) acrylonitriles, olefins, fluoroolefins, vinyl esters, cyclohexyl or alkyl vinyl ethers, aryl ethers and the like.

The resin containing the functional groups of the reactive silicon group, the epoxy group and the hydroxyl group in a separated form is a mixed resin of the reactive silicon group-containing resin and the epoxy group-containing resin, and these resins. Two kinds of mixed resins having a hydroxyl group on one or both of them; two kinds of mixed resins of a reactive silicon group- and epoxy group-containing resin and a hydroxyl group-containing resin; a resin having a reactive silicon group, an epoxy group-containing resin and a hydroxyl group-containing resin 3 types of mixed resin of

The above-mentioned reactive silicon group-containing resin has an average of one or more reactive silicon groups in one molecule (in the case of containing a hydroxyl group, preferably one to 400 in average per molecule).
Resins having an average molecular weight of 1,000 to 200,000 can be used. Specifically, the resin includes the reactive silicon group-containing polymerizable unsaturated monomer (a) and, if necessary, the hydroxyl group-containing polymerizable unsaturated monomer (c) and the other polymerizable unsaturated. A (co) polymer obtained by radically polymerizing the monomer (d) can be used.

In addition to the above reactive silicon group-containing resin, the general formula Ph _n Si (OH) _4-n (IV) (wherein Ph represents a phenyl group and n represents an integer of 2 or 3). The phenyl silanol type compound represented by these can be used.
Specific examples of the compound include diphenylsilanediol and triphenylsilanol.

The epoxy group-containing resin has an average of 2 or more (preferably up to 300) epoxy groups per minute (in the case of containing a hydroxyl group, the average of 1 to 1 per molecule).
With an average molecular weight of 1000 to 2, preferably 400
00000 resins can be used. Specifically, the resin includes the epoxy group-containing polymerizable unsaturated monomer (b) and, if necessary, the hydroxyl group-containing polymerizable unsaturated monomer (c).
Also, a (co) polymer obtained by radical polymerization reaction of the other polymerizable unsaturated monomer (d) can be used.

The reactive silicon group- and epoxy group-containing resin has an average of 1 or more, preferably 2 or more, average reactive silicon groups in one molecule, and 1 or more, and preferably 2 to 1 average in one molecule. It is preferable to contain 40 epoxy groups from the viewpoint of curability and coating film performance. The average molecular weight of the resin is preferably 1,000 to 200,000. Specifically, the resin includes the reactive silicon group-containing polymerizable unsaturated monomer (a), the epoxy group-containing polymerizable unsaturated monomer (b) and, if necessary, other polymerizable unsaturated monomer. A copolymer obtained by subjecting the body (d) to a radical polymerization reaction can be used.

As the hydroxyl group-containing resin, a resin having an average molecular weight of 1,000 to 200,000 per molecule can be used. Specifically, the resin is a (co) polymer obtained by radically polymerizing the hydroxyl group-containing polymerizable unsaturated monomer (c) and, if necessary, other polymerizable unsaturated monomer (d). Coalescence can be used.

In the case of a two-component mixed resin of a reactive silicon group-containing resin and an epoxy group-containing resin, the compounding ratio of the above resin is about 5 to 95% by weight of the former, preferably about 20 to 80% by weight of the latter. 5 to 95% by weight, preferably about 20 to 80
In the case of a mixed resin of two components of a resin containing a reactive silicon group and an epoxy group and a resin containing a hydroxyl group, the former is about 60-99.9% by weight, preferably about 80-.
The latter is about 0.1 to 40% by weight, preferably about 1 to 20% by weight at 99% by weight, and in the case of a three-component mixed resin of a reactive silicon group-containing resin, an epoxy group-containing resin and a hydroxyl group-containing resin Is about 5 to 95% by weight of the reactive silicon group-containing resin, preferably about 20 to 80% by weight, about 5 to 95% by weight of the epoxy group-containing resin, preferably about 20 to 80% by weight, and about 0. 1 to 40% by weight, preferably about 1 to 20% by weight is desirable.

Examples of the above resin include hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether. It is used in the form of a solution type, a dispersion type, a non-dispersion type or the like dissolved or dispersed in a solvent, an alcohol solvent such as butanol or propanol, or an aliphatic hydrocarbon such as pentane, hexane or heptane.

Next, the silane compounds represented by the general formulas (I) to (III) will be described.

In the general formulas (I) to (III), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. The “alkyl group” may be linear or branched and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl. , Neopentyl,
Examples thereof include n-heptyl, n-decyl and tetradecyl, and among these, a lower alkyl group having 1 to 5 carbon atoms is preferable. A "cycloalkyl group" can generally have 3 to 7 carbon atoms, for example a cyclohexyl group is preferred. The “aryl group” may be either monocyclic or polycyclic type, for example, phenyl, toluyl,
Examples thereof include xylyl and naphthyl, with a phenyl group being preferred. The “aralkyl group” is an alkyl group substituted with the above aryl group, and examples thereof include a benzyl group and a phenethyl group.

The haloalkyl group is a group in which at least one hydrogen atom of the above alkyl group is substituted with a halogen atom, for example, fluorine, chlorine, bromine, etc., and examples thereof include chloroethyl, chloropropyl, chlorobutyl, bromethyl and the like. .

Further, the monovalent alkyl group having 1 to 5 carbon atoms may be of a linear or branched type,
For example, methyl, ethyl, n-propyl, isopropyl,
Examples thereof include n-butyl, isobutyl, sec-butyl, and among these, methyl and ethyl are preferable.
The haloalkyl group is a group in which at least one hydrogen atom of the above alkyl group is substituted with a halogen atom, and examples thereof include chloroethyl and bromethyl.

In the above general formulas (I) to (III), R
Is particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group, and R ¹ is particularly preferably a methyl group or an ethyl group.

Specific examples of the silane compounds represented by the general formulas (I) to (III) include those represented by the general formula (I): dimethyldimethoxysilane, dimethyldiethoxysilane,
Diethyldiethoxysilane, diphenyldiethoxysilane, dimethyldibromoethoxysilane and 2-to these
Examples of the pentamer include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, and methyltrichloroethoxy. Silane, methyltribromoethoxysilane and 2-of these
Examples thereof include pentamers, and examples of the compound represented by the general formula (III) include tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, and dimers to pentamers thereof.

The compounding amount of the silane compound (2) is about 0.1 to 5 with respect to 100 parts by weight (solid content) of the resin (1).
0 parts by weight, preferably about 10 to 30 parts by weight is desirable.
When the compounding amount of the compound (2) is less than about 0.1 part by weight,
The VOC value becomes large and the curability is lowered, and excellent coating performance (weather resistance, stain resistance, etc.) cannot be obtained. On the other hand, if the blending amount exceeds 50 parts by weight, the appearance of the coating film and the like deteriorate, which is not preferable.

The metal compound (3) used in combination with the resin (1) and the silane compound (2) is particularly aluminum, zirconium, containing a compound capable of forming a keto-enol tautomer as a stable ligand, Chelate compounds such as titanium are desirable. Examples of the compound capable of forming the keto / enol tautomer include β-diketones (acetylacetone etc.), acetoacetates (methyl acetoacetate etc.), malonates (ethyl malonate etc.), and a hydroxyl group at the β-position. It is possible to use a ketone having a group such as diacetone alcohol and an aldehyde having a hydroxyl group at the β-position such as salicylaldehyde. Particularly, preferable results are obtained by using acetoacetic acid esters and β-diketones.

Preferred specific examples of the metal chelate compound include tris (ethylacetoacetate) aluminum, monoacetylacetonato bis (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (n-butylacetate). ) Aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, monoacetylacetonato bis (propionylacetonato) aluminum, tris (propionate) aluminum Aluminum chelate compounds such as; Titanium compounds such as tris (ethylacetoacetate titanium, tris (acetylacetonato) titanium) Over preparative compounds; tetrakis (n
Zirconium chelate compounds such as -propylacetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethylacetoacetate) zirconium and the like are suitable.

These metal chelate compounds can be used alone or in combination of two or more.

Among the above metal chelate compounds, it is preferable to use the aluminum chelate compound because a resin composition having a good balance of performances such as storage stability, curability and finished appearance can be obtained.

The mixing ratio of the metal chelate compound is preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid content of the resin (1). If it is less than this range, the curability tends to decrease, while if it exceeds this range, it tends to remain in the cured product to lower the water resistance, which is not preferable.

The curable resin composition of the present invention may contain a polyfunctional epoxy compound, an ultraviolet absorber, and
A light stabilizer, a fluidity modifier, a coloring pigment, an extender pigment, a pigment dispersant, polymer fine particles and other additives can be added.

The curable resin composition of the present invention can be used in paints, adhesives, inks and the like.

Since the curable resin composition of the present invention has a particularly low VOC value and excellent weather resistance and stain resistance, it is used for exterior coating of buildings, general industrial applications and the like. It is advantageous to use it as a resin composition.

Next, one example in which the curable resin composition of the present invention is applied as a building resin will be described.

The architectural paint can be used in both color and clear. As the color paint, the curable resin composition containing a coloring pigment can be used. As the coloring pigment, it is possible to use both inorganic and organic high weather resistance coloring pigments used in conventional architectural coatings, for example, inorganic pigments such as rutile titanium oxide or carbon black, quinacridone red. Organic pigments such as quinacridone-based pigments, azo-based pigments such as Pigment Red, and phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green can be used. Further, it can also be used in a metallic finish paint prepared by mixing metal flake powder and mica powder.

In the present invention, a primer can be applied to the surface of a building (concrete, mortar, etc.) and then applied. At this time, the paint used for the primer may be any of epoxy type, ketimine curing type, and zinc rich inorganic type, and is not limited thereto.

The coating of the composition of the present invention is not particularly limited and can be carried out by a conventionally known means, but preferably, it can be applied by brush coating, roller coating, air spray coating or the like. The coating film thickness is usually about 10 in dry film thickness.
The range of 400 to 400 μm, preferably about 100 to 200 μm is desirable. Also, the coating film is cured and dried at room temperature,
It is also possible to cure it by baking. In that case, 5 minutes ~ 3 hours at 40 ℃ ~ 100 ℃, 100 ℃ ~
It can be performed at a temperature of 140 ° C. for about 5 minutes to 30 minutes.

[0048]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a curable resin composition which can be cured at a low temperature to form a coating film excellent in coating film performance (weather resistance, stain resistance, etc.) and has a low VOC value. Provided.

In the present invention, the silane compound (2) is an important constituent component, and by using this component,
In particular, low temperature curing and low VOC value are possible.

The compound (2) has a function as a diluting solvent for dissolving the resin (1) in the paint (before coating),
After coating, the functional group in the compound (2) reacts with the functional group of the resin (1) to exert a function as a crosslinking agent,
Since it remains as a cross-linking agent component in the cured coating film and is changed to a non-volatile substance, a low VOC value (340 g / 1) can be achieved.

[0051]

EXAMPLES The present invention will be described in detail below with reference to examples.

Production Example of Polysiloxane Macromonomer 2720 g of methylmethoxysilane, 256 g of γ-methacryloxypropyl trimethoxysilane, 1134 g of deionized water, 2 g of 6% acetic acid, and 1 g of hydroquinone.

The above mixture was reacted at 80 ° C. for 5 hours to obtain a polysiloxane macromonomer. The number average molecular weight of the obtained polysiloxane-based macromonomer was 2000, and it had one vinyl group (polymerizable unsaturated bond) and four hydroxyl groups per molecule on average.

Production Example of Resin (a) 200 g of the polysiloxane macromonomer, 300 g of n-butyl methacrylate,

[0055]

[Chemical 3]

[0056]

The above mixture was added dropwise to 1000 g of an equal weight mixture of butanol and xylene and reacted at 120 ° C. to obtain a copolymer having a solid content of 50%. The number average molecular weight of the copolymer was about 40,000.

Production Example of Resin (b) γ-methacryloxypropyl trimethoxysilane 100 g, methyl methacrylate 400 g,

[0059]

[Chemical 4]

[0060]

The above mixture was added dropwise to 1000 g of an equal weight mixture of butanol and xylene, and the reaction was carried out at 120 ° C. to obtain a transparent copolymer having a solid content of 50% by weight and a copolymer average molecular weight of about 30,000.

Production Example of Resin (c) 100 g of the polysiloxane macromonomer, 50 g of γ-methacryloxypropyl methyldimethoxysilane, 200 g of methyl methacrylate, 150 g of n-butyl acrylate,

[0063]

[Chemical 5]

[0064]

The above mixture was added dropwise to 1000 g of an equal weight mixture of butanol and xylene and reacted at 120 ° C. to obtain a transparent copolymer having a solid content of 50% by weight and a copolymer average molecular weight of about 20,000.

Production Example of Resin (d) γ-methacryloxypropyl trimethoxysilane 100 g, methyl methacrylate 400 g, n-butyl acrylate 400 g, 2-hydroxyethyl acrylate 100 g, azoisobutyronitrile 10 g.

The above mixture was added dropwise to 1000 g of an equal weight mixture of butanol and xylene and reacted at 120 ° C. to obtain a transparent copolymer having a solid content of 50% by weight and a copolymer average molecular weight of about 30,000.

Production Example of Resin (e)

[0069]

[Chemical 6]

[0070]

The above mixture was added dropwise to 1000 g of an equal weight mixture of butanol and xylene and reacted at 120 ° C. to obtain a transparent copolymer having a solid content of 50% by weight and a copolymer average molecular weight of about 30,000.

Examples 1 to 13 and Comparative Examples 1 to 5 Using the copolymers obtained in the above Production Examples, the top coat paints for construction of the present invention and the comparative construction were produced with the composition (solid content) shown in Table 1. . Titanium oxide was dispersed for 30 minutes using a paint shoeker using each copolymer.

The resin f used in Example 13 is diphenylsilanediol. Further, the resin g used in Comparative Example 4 was a low temperature curable acrylic resin coating (trademark: Multitile Topcoat AC, manufactured by Kansai Paint Co., Ltd.), and the resin h used in Comparative Example 5 was a low temperature curable acrylic resin / Polyisocyanate resin (trademark; multi-tile topcoat PU,
Kansai Paint Co., Ltd.).

[0074]

[Table 1]

[0075]

[Table 2]

Table 1 also shows the results of the storage stability test investigated as follows.

Storage stability: According to the storage stability test method of JIS-K-5400, it was allowed to stand at 40 ° C. for 3 months. The paint before storage, viscosity change, and sedimentation state were examined.

Coating film performance test An epoxy-based undercoat paint (trademark: Epomarin undercoat, manufactured by Kansai Paint Co., Ltd.) was applied to a mortar plate (prepared according to JIS-R-5201) and a flexible plate (JIS-A-5403 acceptable product). 80 g / m ² , followed by an epoxy-based intermediate coating (trademark: Epomarin Sealer, Kansai Paint Co., Ltd.)
About 80 g / m ² was applied with a brush. Thereafter, the paints of Examples and Comparative Examples were applied with a brush at about 200 g / m ² (twice coating), and cured for 7 days in a thermostatic chamber at a temperature of 20 ° C. and a humidity of 70% to obtain test pieces.

Table 2 shows the results of various performance tests of these test bodies.
Shown in.

[0080]

[Table 3]

The test method and evaluation were carried out based on the following.

Coating surface gloss: JIS K-5400 7.6
It was measured according to. (Reflectance of 60 degrees).

Pencil hardness: Measured according to JIS K-5400.

Adhesiveness: JIS K-5400 8.5.
10 squares of 1mm x 1mm according to the 2nd tape method
Zero pieces were prepared, and the degree of peeling of the squares when the tape was adhered to the surface and peeled off was evaluated. When the number of goggles was 99 or more, the mark was ◯, when the number of goggles was 98 to 90, the mark was Δ, and when the number of goggles was 89 or less, the mark was x.

Water resistance: After being immersed in water at 40 ° C. for 20 days, the above adhesion was examined.

Acid resistance: About 10 drops of a 40% aqueous solution of sulfuric acid was dropped on a flexible plate test body, allowed to stand horizontally at 40 ° C., water was evaporated and then washed with water to evaluate the coated surface state.

Contamination resistance: A test dust No. 12 specified in JIS-Z-8901 was rubbed against the test piece, washed with water and then compared with an uncontaminated portion. Those that did not change at all were evaluated as ◯, those that contaminate were evaluated as Δ, and those that significantly contaminate were evaluated as x.

Weather resistance: 2000 with a sunshine carbon arc lamp type weather resistance tester according to JIS-B-7753.
The appearance of the coating film (gloss, crack, discoloration, etc.) after the time test was compared and evaluated with the coated plate before the test. Good results with almost no change were evaluated as ◯, gloss retention ratios of 80% or less were evaluated as Δ, and gloss retention ratios of 50% or less as cracked or discolored were evaluated as x.

VOC value: The weight of the volatile solvent in the paint used to obtain a coating film having a unit volume, which is represented by the following formula.
The unit is g / l.

VOC = (100-N) × Dm Here, N is the nonvolatile content (% by weight) of the paint when the viscosity of the paint is adjusted to 3 poise (20 ° C.), and Dm is the specific gravity at 25 ° C. (g / ml). ) Are shown respectively.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Okamoto 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (7)

[Claims] 1. A resin containing (1) a silanol group and / or a hydrolyzable group directly bonded to a silicon atom, a hydroxyl group and an epoxy group as a functional group component, (2) the following general formula (I):
To at least one silane compound selected from (III), [In the above formulas, R is the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a haloalkyl group, and R ¹ is the same or different and is alkyl having 1 to 5 carbon atoms. Represents a group or a haloalkyl group. Moreover, n shows the integer of 1-5. ), And (3) a metal chelate compound are contained, The curable resin composition for topcoats characterized by the above-mentioned. 2. The resin (1) contains a hydrolyzable group directly bonded to a silanol group and / or a silicon atom, a hydroxyl group and an epoxy group as a functional group component, and these functional groups are contained in the same resin. The curable resin composition according to claim 1, wherein (1) The resin contains as a functional group component a hydrolyzable group directly bonded to a silanol group and / or a silicon atom, a hydroxyl group and an epoxy group, and at least one of these functional groups is separated. The curable resin composition according to claim 1, which is a resin mixture contained in the form described above. 4. A radical-polymerizable unsaturated monomer having a hydrolyzable group directly bonded to a silanol group and / or a silicon atom, which contains a hydrolyzable group directly bonded to a silanol group and / or a silicon atom. The curable resin composition according to claim 2 or 3. 5. The resin mixture is a silanol group-containing compound,
The curable resin composition according to claim 3, which is a resin mixture of a hydroxyl group-containing resin and an epoxy group-containing resin. 6. A resin mixture comprising a silanol group-containing compound,
The curable resin composition according to claim 3, which is a resin mixture with a resin containing a hydroxyl group and an epoxy group. 7. A silanol group-containing compound is represented by the general formula Ph _n Si (OH) _4-n (IV) (wherein Ph represents a phenyl group and n represents an integer of 2 or 3). 7. A phenylsilanol compound.
The curable resin composition described.