JPH11335625A - Coating resin composition and coated product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition excellent in curing property at lower and ordinary temperatures and capable of forming a film good in both crack resistance and wettability by employing the hydrolysates obtained by individually hydrolyzing two kinds of hydrolyzable organosilanes as a coating material component. SOLUTION: This composition comprises (A) a silica-dispersed oligomer solution of a mono- to trifunctional organosilane, which is obtained by partially hydrolyzing mono- to trifunctional hydrolyzable organosilane of the formula (R<1> is a 1-8C univalent hydrocarbon; (m) is an integer of 1 to 3; and X is a hydrolyzable group) in colloidal silica dispersed in an organic solvent, water or mixture solvent thereof by using 0.001 to 0.5 mol. of water based on 1 molar equivalent weight of the group X and (B) a silica-dispersed oligomer solution of a tetrafunctional organosilane, which is obtained by partially hydrolyzing a tetrafunctional hydrolysable organosilane of the formula: SiX4 in the same colloidal silica as in the component A by using 0.5 to 2.0 mol. of water based on 1 molar equivalent weight of the group X.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating which is excellent in curability at low temperature (100.degree. C. or lower) or normal temperature, and which can form a coating film having excellent crack resistance and water wettability (hydrophilicity). The present invention relates to a resin composition for use and a coated article using the same.

[0002]

2. Description of the Related Art Conventionally, as a paint excellent in weather resistance, durability and the like, for example, a silicone-based inorganic paint containing a silicone resin as a base resin (binder resin) is known. The silicone resin contained in the inorganic coating is obtained, for example, by hydrolyzing and polycondensing a hydrolyzable organosilane. Examples of the hydrolyzable organosilane as a raw material include bifunctional ones such as dimethyldimethoxysilane, trifunctional ones such as methyltrimethoxysilane, and tetrafunctional ones such as tetraethoxysilane (also referred to as TEOS or tetraethylorthosilicate). is there.

However, such a silicone-based inorganic paint has the following problems. When the silicone resin contains only a hydrolyzed polycondensate of a difunctional and / or trifunctional hydrolyzable organosilane, the obtained coating film is too soft, and the coating film strength is insufficient. Due to insufficient water wettability (hydrophilicity), the surface of the coating film is easily clouded or stained by water droplets.

On the other hand, when the silicone resin contains a hydrolyzed polycondensate of a tetrafunctional hydrolyzable organosilane, the coating strength and the coating strength are higher than in the case of only the above-mentioned difunctional and / or trifunctional. Water wettability on the surface is improved. These properties are most excellent when the silicone resin contains only a hydrolytic polycondensate of a tetrafunctional hydrolyzable organosilane.

However, a coating containing only a hydrolyzed polycondensate of a tetrafunctional hydrolyzable organosilane as a silicone resin is difficult to form a film because the tetrafunctional silicone resin is bulky. However, a normal coating thickness is too hard and cracks easily occur. In addition, the curing speed of the coating film is low due to steric hindrance of the tetrafunctional silicone resin, and it takes a very long time to cure the coating film, especially at room temperature. Further, tetrafunctional hydrolyzable organosilanes have higher reactivity with water than the difunctional and trifunctional ones, and the hydrolysis reaction easily proceeds during storage.
Lack of storage stability.

On the other hand, the bifunctional and trifunctional hydrolyzable organosilanes have the effect of improving the flexibility of the coating film to improve the crack resistance and, at the same time, have a higher water and water solubility than the tetrafunctional one. Is low in reactivity, and the curing rate of the hydrolyzed polycondensate is high, so that the bifunctional and / or trifunctional hydrolyzable organosilane is added to the tetrafunctional hydrolyzable organosilane, and the resulting mixture is hydrolyzed. There is known a coating material having improved storage stability, curing speed of a coating film, and crack resistance by decomposition and polycondensation (Japanese Patent Application Laid-Open No. Hei 6-1994).
No. 346025).

[0007]

However, the paint described in Japanese Patent Application Laid-Open No. 6-346025 is not satisfactory with respect to the water wettability of the coating film. Accordingly, an object of the present invention is to provide a resin composition for coating capable of forming a coating film having excellent curability at low or normal temperature, and also having excellent crack resistance and water wettability. To provide painted products.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result, as shown in the above-mentioned JP-A-6-346025, a difunctional and / or trifunctional paint. It is not a mixture obtained by mixing a functional hydrolyzable organosilane and a tetrafunctional hydrolyzable organosilane and then hydrolyzing the mixture. Instead, the difunctional and / or trifunctional hydrolyzable organosilane and the tetrafunctional hydrolyzable organosilane are mixed. It has been found that the use of a material obtained by separately hydrolyzing the above as a coating component also improves water wettability, and has completed the present invention.

That is, the resin composition for coating according to the present invention contains the following components (A) and (B). Component (A): represented by the general formula R ¹ _m SiX _4-m (1) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M represents an integer of 1 to 3, and X represents the same or different hydrolyzable group) in a colloidal silica in which a 1-3-functional hydrolyzable organosilane is dispersed in an organic solvent, water or a mixed solvent thereof. A silica-dispersed oligomer solution of a 1-3-functional organosilane, which is partially hydrolyzed under conditions using 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X) Is sometimes referred to as “silica-dispersed oligomer solution (A)”). Component (B): A tetrafunctional hydrolyzable organosilane represented by the general formula SiX ₄ (2) (where X represents the same or different hydrolyzable group) is mixed with an organic solvent, water or a mixture thereof. Silica of tetrafunctional organosilane obtained by partially hydrolyzing colloidal silica dispersed in a solvent under the condition of using 0.5 to 2.0 mol of water per 1 mol equivalent of the hydrolyzable group (X). Dispersed oligomer solution (hereinafter sometimes referred to as “silica dispersed oligomer solution (B)”).

[0010] The coated article according to the present invention is provided on the surface of a substrate,
A coating layer comprising a coated and cured film of the resin composition for coating of the present invention is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the coating resin composition of the present invention, that is, the silica-dispersed oligomer in the silica-dispersed oligomer solution (A) is subjected to a curing reaction when forming a cured coating film of the composition. It is a main component of a base polymer having a hydrolyzable group (X) as a functional group, and is a component that improves the curability of a coating film of the composition at low or normal temperature and the crack resistance ( In addition, when the crack resistance of the coating film is improved, the coating film can be made thicker.) This silica-dispersed oligomer solution (A)
For example, colloidal silica dispersed in an organic solvent or water (a mixed solvent of an organic solvent and water may be used) is added to one or two of a functionally hydrolyzable organosilane represented by the general formula (1). More than one species, and water (water previously contained in colloidal silica and / or water added separately) is used in an amount of 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X). It is obtained by partially hydrolyzing the hydrolyzable organosilane under conditions.

The group R ¹ in the 1-3-functional hydrolyzable organosilane represented by the general formula (1) is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. If it is not particularly limited, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group,
An alkyl group such as a hexyl group, a heptyl group and an octyl group;
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; vinyl groups and allyl group Alkenyl group; chloromethyl group, γ-chloropropyl group, halogen-substituted hydrocarbon group such as 3,3,3-trifluoropropyl group; γ-methacryloxypropyl group, γ-
Examples thereof include substituted hydrocarbon groups such as a glycidoxypropyl group, a 3,4-epoxycyclohexylethyl group, and a γ-mercaptopropyl group. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

The component (B) of the coating resin composition of the present invention, ie, the silica-dispersed oligomer in the silica-dispersed oligomer solution (B), has a functional property that is subjected to a curing reaction when forming a cured coating film of the composition. It is a main component of a base polymer having a hydrolyzable group (X) as a group and a component for improving the strength and water wettability of a coating film of the composition. This silica-dispersed oligomer solution (B) is, for example, mixed with colloidal silica dispersed in an organic solvent or water (which may be a mixed solvent of an organic solvent and water) by tetrafunctional hydrolysis represented by the general formula (2). One or two or more water-soluble organosilanes are added, and water (water previously contained in colloidal silica and / or water added separately) is added to water in an amount of 0.1 to 1 mol equivalent of the hydrolyzable group (X). It is obtained by partially hydrolyzing the hydrolyzable organosilane under the condition of using 5 to 2.0 mol.

In the general formulas (1) and (2), the hydrolyzable group X is not particularly limited.
Examples thereof include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, and an amide group. Among these, an alkoxy group is preferable because of its availability and ease of preparing the silica-dispersed oligomer solutions (A) and (B). When a plurality of Xs are contained in one molecule of the hydrolyzable organosilane, the plurality of Xs may be the same or different in each molecule of the hydrolyzable organosilane. X may be the same as or different from those used for preparing the component (A) and those used for preparing the component (B).

Specific examples of the above-mentioned 1-3-functional hydrolyzable organosilane used in the preparation of the silica-dispersed oligomer solution (A) include mono-monomers wherein m in the general formula (1) is an integer of 1 to 3. , Di- and tri-functional alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among them, alkoxysilanes are preferable because they are easily available and the silica-dispersed oligomer solution (A) is easily prepared.

Of the above alkoxysilanes, m
As the organotrialkoxysilane of = 1, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. Can be illustrated. Examples of the diorganodialkoxysilane having m = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane, and the like. Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of the hydrolyzable organosilanes represented by the general formula (1), preferably at least 50 mol% (more preferably at least 60 mol%, further preferably at least 70 mol%)
Above) is a trifunctional compound represented by m = 1. If the content is less than 50 mol%, sufficient hardness of the coating film cannot be obtained, and the dry curability of the coating film tends to be poor.

Specific examples of the tetrafunctional hydrolyzable organosilane used for preparing the silica-dispersed oligomer solution (B) are not particularly limited. For example, tetrafunctional alkoxysilanes, acetoxysilanes, Oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes, and the like. Among these, alkoxysilanes are preferred because they are easily available and paints can be easily prepared.

Specific examples of the tetrafunctional alkoxysilanes are not particularly limited, but include, for example, tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetra-t-t-silane.
Examples thereof include tetraalkoxysilanes such as butoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

The colloidal silica in the components (A) and (B) has the effect of increasing the hardness of the cured coating film of the resin composition for coating, and improving the smoothness and crack resistance. The colloidal silica is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. When using water-dispersible colloidal silica, water present as a component other than the solid content can be used for hydrolysis of the hydrolyzable organosilane, and as a curing agent for the coating resin composition. Can be used. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In the organic solvent-dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene Ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. Alternatively, two or more kinds can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

The colloidal silica in the components (A) and (B) has the above-mentioned effect. However, if the amount is too large, the cured film of the resin composition for coating becomes too hard and cracks of the film are generated. May be caused. For this reason, the colloidal silica is preferably used in an amount of 5 to 95% by weight (more preferably 10 to 90% by weight, more preferably Preferably 20 to 85% by weight). When the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, if the content exceeds 95% by weight, it becomes difficult to uniformly disperse the silica, and the component (A) tends to gel or crack.

The amount of water used for preparing the silica-dispersed oligomer solutions (A) and (B) is as follows: (A) is based on the hydrolyzable group of the hydrolyzable organosilane represented by the general formula (1). (X) 0.001 per molar equivalent
In the range of from 0.5 to 0.5 mol, preferably in the range of from 0.01 to 0.4 mol. For (B), the hydrolyzable group of the hydrolyzable organosilane of the general formula (2) ( X) in the range of 0.5 to 2.0 moles per mole equivalent,
Preferably it is in the range of 0.5 to 1.0 mole. If the amount of water used is less than the above range, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds the above range, the stability of the partial hydrolyzate deteriorates. Here, the above-mentioned amount of water used in the partial hydrolysis reaction of each hydrolyzable organosilane is different when colloidal silica containing no water (for example, colloidal silica using only an organic solvent as a dispersion medium) is used. Is the amount of water added to the colloidal silica. When colloidal silica containing water (for example, colloidal silica using only water or a mixed solvent of an organic solvent and water as a dispersion medium of colloidal silica) is used, Is the amount of water previously contained in at least the colloidal silica of the water previously contained in water and the water separately added. If the amount of water was previously contained in the colloidal silica alone and the amount used was sufficient, it was not necessary to separately add water, but the amount of water was previously contained in the colloidal silica. If water alone is not sufficient for the above usage, it is necessary to separately add water until the usage reaches the above usage. In this case, the amount of water used is the total amount of water previously contained in the colloidal silica and water added separately. In addition, even in the case where only the water previously contained in the colloidal silica is sufficient for the above use amount, water may be separately added, and in such a case, the use amount of the water is included in the colloidal silica in advance. It is the total amount of water added and water added separately. However, this total amount is 0.5 mol per mol equivalent of the hydrolyzable group (X) with respect to the upper limit ((A)),
Water is separately added so as not to exceed (2.0 mol per mol equivalent of the hydrolyzable group (X) for (B)).

The method of partially hydrolyzing the hydrolyzable organosilane is not particularly limited with respect to both (A) and (B). For example, it is only necessary to mix the hydrolyzable organosilane with colloidal silica (colloidal silica). If the silica contains no water or does not contain the required amount, water is added and blended here). At this time, the partial hydrolysis reaction proceeds at room temperature, but if necessary, heating (for example, 60 to 1) may be performed to promote the partial hydrolysis reaction.
00 ° C.) or a catalyst may be used. The catalyst is not particularly limited, but includes, for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid,
One or more organic acids and inorganic acids such as benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid can be used. .

The silica-dispersed oligomer solutions (A) and (B) have a pH of preferably from 2.0 to 7.0, more preferably from 2.5 to 7.0 in order to stably obtain their performance over a long period of time. 6.5, more preferably 3.0 to 6.
It is good to set to 0. When the pH is out of this range, the amount of water used is particularly preferably (A) per mole equivalent of the hydrolyzable group (X).
The performance continuity of the component is significantly reduced under the condition of 0.3 mol or more, and the performance continuity of the component (B) is significantly reduced under the condition of 1.0 mol or more. When the pH of the component (A) or (B) is out of the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine, if the pH is more acidic than this range. If so, use an acidic reagent such as hydrochloric acid, nitric acid, or acetic acid to
H may be adjusted. However, the adjustment method is not particularly limited.

In the resin composition for coating of the present invention,
The mixing ratio of the components (A) and (B) is not particularly limited. For example, in terms of the total solid content in terms of the total condensed compound, the component (B) is:
Preferably 1 to 100 parts by weight, more preferably 1 to 50 parts
Parts by weight. When the component (B) exceeds 100 parts by weight,
The curability at low or normal temperature tends to decrease, and the coating film tends to be too hard and cracks tend to occur. If the component (B) is less than 1 part by weight, the coating film becomes too soft. There is a tendency that the strength of the coating film is reduced and the wettability of the coating film surface is reduced.

The coating resin composition of the present invention can further contain the following component (C), if necessary. Component (C): represented by the average composition formula R ² _a Si (OR ³ ) _b O _{(4-ab) / 2} (2) (where R ² is the same or different and substituted or unsubstituted and has 1 carbon atom) And R ³ represent the same or different substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, and a and b each represent 0.2 ≦ a ≦
2, 0.0001 ≦ b ≦ 3, a + b <4), a polyorganosiloxane containing an alkoxy group in the molecule (hereinafter referred to as “(alkoxy group-containing)
Polyorganosiloxane (C) ").

The alkoxy group-containing polyorganosiloxane (C) is a base polymer having a hydrolyzable group as a functional group subjected to a curing reaction.
A cross-linking agent for forming a three-dimensional cross-link in the cured film by a condensation reaction with the component (B), further absorbing cracks caused by the curing shrinkage of the component (B), and further preventing cracking of the coated film; It is a component that has the effect of making the coating film thicker.

In the above average composition formula (3) representing the alkoxy group-containing polyorganosiloxane (C), R ² represents
There is no particular limitation, and the same as R ¹ in the above formula (1) are exemplified. Preferably, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a γ-glycidoxypropyl group, Substituted hydrocarbon groups such as a γ-methacryloxypropyl group, a γ-aminopropyl group and a 3,3,3-trifluoropropyl group, more preferably a methyl group and a phenyl group.

In the above formula (3), R ³ is not particularly limited as long as it is the same or different and substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, Examples thereof include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Further, in the above formula (3), a and b are numbers satisfying the above-mentioned relationship, respectively, and if a is less than 0.2 or b exceeds 3, there are inconveniences such as cracks in the cured film.
When a is more than 2 and 4 or less, or b is 0.0
If it is less than 001, curing does not proceed well.

The alkoxy group-containing polyorganosiloxane (C) is not particularly limited.
It can be obtained by hydrolyzing trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, or one or a mixture of two or more of the corresponding alkoxysilanes with a predetermined amount of water by a known method.

In the coating resin composition of the present invention, the component (B) is used in the above-mentioned general formula (1) when the tetrafunctional hydrolyzable organosilane represented by the general formula (2) is partially hydrolyzed. It may be obtained by coexisting the above-mentioned 1-3 functional hydrolyzable organosilane. As described above, the component (B) obtained by co-existing the 1-3-functional hydrolyzable organosilane and the 4-functional hydrolyzable organosilane and partially hydrolyzing them is used only as the 4-functional hydrolyzable organosilane. The reactivity of the partially hydrolyzed product in the component (B) with water is reduced by the addition of the 1-3 functionally hydrolyzable organosilane as compared with that obtained by partial hydrolysis, and Since the progress of the further hydrolysis reaction of the partial hydrolyzate is suppressed, the storage stability is excellent. The amount of the 1-3 functional hydrolyzable organosilane used for the preparation of the component (B) is preferably 1 to 50 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the tetrafunctional hydrolyzable organosilane. ４０40 parts by weight. 1 to 3 functional hydrolyzable organosilane used
When the amount is less than 10 parts by weight, the effect of improving the storage stability of the component (B) is hardly obtained.

The resin composition for coating according to the present invention does not need to contain a curing catalyst, but is used for the purpose of accelerating the condensation reaction between the component (A) and the component (B), thereby accelerating the curing of the coating film. If necessary, a curing catalyst can be further contained. The curing catalyst is not particularly limited, for example, alkyl titanates; tin octylate,
Metal salts of carboxylic acids such as dibutyltin dilaurate and dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate and ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; tetraethylpentamine Amines such as N-β-aminoethyl-γ-
Amine silane coupling agents such as aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum alkoxides and aluminum chelates Aluminum compounds; alkali metal salts such as lithium acetate, lithium formate, sodium formate, potassium phosphate, potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; methyltrichlorosilane, dimethyldichlorosilane And halogenated silanes such as trimethylmonochlorosilane. However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction between the component (A) and the component (B).

The mixing ratio of the curing catalyst in the resin composition for coating is not particularly limited. For example, based on the solid content, the conversion amount of the component (A) and the conversion amount of the component (B) are calculated. The amount is preferably in the range of 0.0001 to 10 parts by weight, more preferably in the range of 0.0005 to 8 parts by weight, and still more preferably in the range of 0.0007 to 5 parts by weight with respect to 100 parts by weight in total. It is. If the amount of the curing catalyst is less than 0.0001 part by weight, the room-temperature curability tends to decrease, and sufficient film hardness tends not to be obtained.
If the amount exceeds 10 parts by weight, the heat resistance and weather resistance of the cured film may be reduced, and the hardness of the cured film may be too high to cause cracks.

The coating resin composition of the present invention comprises:
The hydrolyzable group of the organosilane oligomer in the component (A) and the hydrolyzable group of the organosilane oligomer in the component (B) undergo a condensation reaction when left at room temperature or heated at a low temperature to form a cured film. I do. Therefore, such a coating resin composition is hardly affected by humidity even when it is cured at room temperature. Also,
Heat treatment can also promote the condensation reaction to form a cured film.

The resin composition for coating of the present invention can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. The pigment that can be used is not particularly limited. For example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide;
Inorganic pigments such as barium sulfate, red iron oxide, and composite metal oxides are preferred, and one or two or more selected from these groups may be used in combination. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, dispersant, dispersing aid, thickener,
Use of a coupling agent or the like is possible. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment. For example, it is preferably 5 to 100 parts by weight of the total condensed compound in the total amount of the resin composition for coating on a solid content basis. -80 parts by weight, more preferably 10-
70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it is more than 80 parts by weight, the smoothness of the coating film may be deteriorated.

The dyes that can be used are not particularly limited, but include, for example, azo, anthraquinone, indicoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinone imine,
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye. For example, it is preferably 5 to 100 parts by weight of the total condensed compound in the total amount of the coating resin composition on a solid content basis. The amount is from 80 to 80 parts by weight, more preferably from 10 to 70 parts by weight. When the amount of the dye is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

In addition, a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the coating resin composition within a range that does not adversely affect the effects of the present invention. The resin composition for coating is
It can be used by diluting it with various organic solvents, if necessary, for ease of handling, or it may be diluted with the same organic solvent. The type of the organic solvent can be appropriately selected according to the type of the monovalent hydrocarbon group contained in each component, the molecular weight of each component, and the like. Examples of such an organic solvent are not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl acetate And ethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol and the like. ,
One or more selected from the group consisting of these can be used. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method for producing the resin composition for coating is not particularly limited, and the respective components may be mixed using ordinary methods and equipment. Regarding the form of each component when introduced into the coating resin composition, a liquid itself, a solution dissolved in a solvent, a liquid such as a dispersion dispersed in a dispersion medium, a powder or the like There is no particular limitation irrespective of the solid state. When each component is introduced in the form of a solution or dispersion, for example, water, the above-mentioned organic solvent, or a mixture of water and the above-mentioned organic solvent can be used as the solvent or dispersion medium. Each component may be added separately, or two or more components may be mixed in advance and then mixed with the remaining components, or all components may be mixed simultaneously. The timing of mixing and the like are not particularly limited.

The method of applying the resin composition for coating is not particularly limited, and may be any of various common methods such as brushing, spraying, dipping (dipping), roll, flow, curtain, knife coating, spin coating and the like. An application method can be selected. The method of curing the coating film of the resin composition for coating may be a known method, and is not particularly limited. In addition, the temperature at the time of curing is not particularly limited, and desired cured film performance,
A wide range of room temperature to heating temperature can be taken according to the heat resistance of the substrate.

The thickness of the cured coating film formed from the coating resin composition is not particularly limited. For example, the thickness may be 10 μm or less so that cracks and peeling do not occur. 5 μm or less is preferable, and 2 μm or less is preferable in order to exert more effectively or shorten the curing time at room temperature, and to stably adhere and hold the applied cured film for a long period of time.

The substrate on which the resin composition for coating of the present invention is applied (which is also the substrate used for the coated article of the present invention) is not particularly limited, and examples thereof include inorganic substrates, organic substrates, Examples thereof include an inorganic-organic composite substrate, and a coated substrate having at least one inorganic film and / or at least one organic film on any of these surfaces.

The inorganic substrate is not particularly limited, and examples thereof include a metal substrate; a glass substrate; an enamel; an inorganic building material such as a water glass decorative plate and an inorganic cured product; and ceramics. The metal substrate is not particularly limited. For example, non-ferrous metals [for example, aluminum (JIS-H4000 etc.), aluminum alloys (duralumin etc.), copper, zinc etc.], iron, steel [for example, rolled steel (JIS) -G3101 etc.), hot-dip galvanized steel (JIS
-G3302 etc.), (rolled) stainless steel (JIS-G
4304, G4305, etc.), tinplate (JIS-G3)
303 etc.) and other metals in general (including alloys).

The glass substrate is not particularly limited, and examples thereof include sodium glass, Pyrex glass, quartz glass, and alkali-free glass. The enamel is obtained by baking and coating a glassy enamel on a metal surface. Examples of the base metal include a mild steel plate, a steel plate, cast iron, and aluminum, but are not particularly limited. The enamel may be a normal enamel, and is not particularly limited.

The water glass decorative board refers to, for example, a decorative board obtained by applying sodium silicate to a cement base such as a slate and baking it. The inorganic hardened material is not particularly limited. For example, a fiber reinforced cement board (J
IS-A5430, etc.), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminate board (JIS-A5426)
Gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A6901 etc.)
A5402), ceramic tile (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540)
6), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), and all types of base materials obtained by curing and molding inorganic materials such as ordinary bricks (JIS-R1250 etc.).

The ceramic substrate is not particularly limited, and examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like. As an organic substrate,
Although not particularly limited, for example, plastic, wood,
Examples include wood and paper. As a plastic substrate,
Although not particularly limited, for example, a thermosetting or thermoplastic plastic such as a polycarbonate resin, an acrylic resin, an ABS resin, a vinyl chloride resin, an epoxy resin, and a phenol resin, and a reinforcement of these plastics with an organic fiber such as a nylon fiber. Fiber reinforced plastic (FRP).

The inorganic-organic composite base material is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. The organic film constituting the coating substrate is not particularly limited, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, etc. A cured film of a coating material containing an organic resin may be used.

The inorganic coating constituting the coating substrate is not particularly limited, and includes, for example, a cured coating of a coating material containing an inorganic resin such as a silicone resin. When applying the coating resin composition to the substrate, depending on the material and surface condition of the substrate, if the coating resin composition is applied as it is, it may be difficult to obtain adhesion or weather resistance. A primer layer may be previously formed on the surface of the base material before forming a cured coating film of the coating resin composition. The primer layer is not particularly limited, whether organic or inorganic.Examples of the organic primer layer include nylon resin,
Alkyd resin, epoxy resin, acrylic resin, organically modified silicone resin (for example, acrylic silicone resin), chlorinated rubber resin, urethane resin, phenol resin,
A solid content of at least one organic resin selected from the group consisting of polyester resin and melamine resin
Examples of the inorganic primer layer include a cured resin layer of an inorganic primer composition containing 90% by weight or more as a solid content of an inorganic resin such as a silicone resin. And the like.

The thickness of the primer layer is not particularly limited, but is preferably, for example, 0.1 to 50 μm, and 0.5 to 50 μm.
-10 μm is more preferred. If the thickness is too thin, adhesion and weather resistance may not be obtained, while if too thick, foaming or the like may occur during drying. A substrate having at least one organic primer layer and / or inorganic primer layer on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

The primer layer may contain a coloring agent such as a pigment or a dye for toning, if necessary. Examples of usable colorants include those described above as those that can be added to the coating resin composition. The preferred numerical range of the amount of the coloring agent to be added to the primer layer is the same as in the case of the coating resin composition described above. However, although it is based on solid content, it is specified not with respect to 100 parts by weight of the total condensed compound but with respect to 100 parts by weight of the total resin in the total amount of the primer composition.

The form of the substrate is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Further, the base material may be a molded body of a material having these shapes, or a structure partially provided with at least one of the material having the shape or the molded body. The base material may be made of the above-mentioned various materials alone, a composite material obtained by combining at least two of the above-described various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

A coating film formed from the resin composition for coating of the present invention (also a coating film of the coated product of the present invention)
By equipping it with at least a part of various materials or articles, it can be suitably used for, for example, the following applications. Building-related members or articles, for example, exterior materials (eg, exterior wall materials, roof materials such as flat tiles, Japanese tiles, metal tiles, etc.), interior materials, ceiling materials, kitchens, bath related products, PVC rain gutters, etc. Rain gutters such as resin rain gutters, stainless steel rain gutters, and other metal rain gutters, gates and members used therefor (for example, gates, gate posts, gate walls, etc.), fences (fences) and members used therefor, Garage doors, home terraces, doors, pillars, car ports, bicycle parking ports, sign posts, home delivery posts, wiring boards such as switchboards and switches, gas meters, intercoms, TV doorphones and camera lens parts, electric locks, entrance poles, porch Windows (eg, daylighting windows, skylights, open / close windows such as louvers, etc.) and members for use therewith (eg, Frame, shutters,
Blinds, etc., automobiles, railway vehicles, aircraft, ships, machinery, civil engineering / road peripherals (for example, concrete protective walls, road decorative panels, soundproof walls, tunnel interior panels, various display devices, guardrails, car stops, railroads, traffic Sign boards and posts, traffic lights, post cones, etc.), advertising towers,
Outdoor or indoor lighting fixtures and members for use therein (eg, members made of at least one material selected from the group consisting of glass, resin, metal, and ceramics), solar cell glass, agricultural vinyl And glass houses, outdoor units for air conditioners, VHF, UHF,
Antennas such as BS / CS.

The coating resin composition of the present invention may be directly applied to at least a part of the above-mentioned various materials or articles and cured, but is not limited thereto. A film obtained by applying the composition to the surface of the film substrate and curing the composition may be attached to at least a part of the above-mentioned various materials or articles. As the material of the base material of such a film, for example, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (P
P) Resins such as resins and their composite resins, but are not particularly limited.

[0053]

The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. In addition, this invention is not limited to a following example. First, prior to the following Examples and Comparative Examples, the components (A) and (B) used for them were prepared as follows. (Preparation Example of Component A): <Preparation Example A-1> 34 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane, is mixed with an acidic colloidal silica, isopropanol-dispersed organosilica sol (trade name “MTST”; 47 parts (manufactured by Kogyo Co., Ltd., solid content: 30%) were added under stirring. 25 of the obtained liquid
By aging at a temperature of 1 ° C. for one week, a silica-dispersed oligomer solution of organosilane was obtained. This is called A-1.
The solid content in terms of the total condensed compound was 37.8%.

Conditions for preparing A-1:-Number of moles of water per mole equivalent of hydrolyzable group 0.06 mole-Content of silica component (A-1) 46.1%-Hydrolysis with m = 1 Preparation Example A-2> 34 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane, and 34 parts of an acidic colloidal silica, an isopropanol-dispersed organosilica sol (trade name “MTST”, catalyst 47 parts of Kasei Kogyo Co., Ltd., solid content 30%) and 0.6 parts of water were added under stirring.
The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called A-2. The solid content in terms of the total condensed compound is 37.
8%.

Preparation conditions of A-2:-Number of moles of water per mole equivalent of hydrolyzable group 0.1 mol-Silica content of component (A-2) 45.7%-Hydrolysis of m = 1 Preparation Example A-3> 34 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane, is mixed with an isopropanol-dispersed organosilica sol as acidic colloidal silica (trade name “MTST”, catalyst 47 parts of Kasei Kogyo Co., Ltd., solid content 30%) and 6 parts of water were added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is A-
No. 3. The solid content in terms of the total condensed compound is 36.6%
Met.

Preparation conditions of A-3: 0.5 mole of water per 1 mole equivalent of hydrolyzable group 0.5% silica content of component (A-3) 44.3% Hydrolysis of m = 1 <Preparation Example A-4> Isopropanol-dispersed organosilica sol (trade name: MTST) was added to 27.2 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane. 47 parts of Catalyst Kasei Kogyo Co., Ltd., solid content 30%), 0.6 part of water and 6.8 parts of alkoxy oligomer (trade name "KC89", manufactured by Shin-Etsu Chemical Co., Ltd.) as component (C). It was added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is A-4
Called. The solid content in terms of the total condensed compound was 37.8%.

Preparation conditions of A-4: ・ mol number of water per 1 mol equivalent of hydrolyzable group 0.1 mol ・ silica content of component (A-4) 45.7% ・ hydrolysis with m = 1 Preparation Example A-5> 27.2 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane, is mixed with isopropanol-dispersed organosilica sol, an acidic colloidal silica (trade name “MTST”). And 47 parts of water, 0.6 parts of water, and an alkoxy oligomer (trade name "X40-922") as a component (C).
6.8 parts ("0", Shin-Etsu Chemical Co., Ltd.) was added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called A-5. The solid content in terms of the total condensed compound was 37.8%.

Preparation conditions for A-5:-Number of moles of water per mole equivalent of hydrolyzable group: 0.1 mole-Silica content of component (A-5): 45.7%-Hydrolysis with m = 1 Preparation Example A-6> 34 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane, is mixed with 34 parts of an acidic colloidal silica, i.e., an organosilica sol dispersed with an acidic colloidal silica (trade name "MTST", catalyst 47 parts of Kasei Kogyo Co., Ltd., solid content 30%) and 12 parts of water were added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is A
-6. The solid content in terms of the total condensed compound is 33.2.
%Met.

Preparation conditions for A-6: 1.0 moles of water per 1 mole equivalent of hydrolyzable group, silica content of component (A-6) 45.7%, hydrolysis of m = 1 <Preparation Example A-7> Isopropanol-dispersed organosilica sol (trade name: MTST) was added to 27.2 parts of methyltrimethoxysilane, which is a trifunctional hydrolyzable organosilane. (Catalyst Kasei Kogyo Co., Ltd., solid content 30%), 47 parts of water, 0.6 parts of water and 6.8 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, were added thereto with stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called A-7. The solid content in terms of the total condensed compound was 36.6%. (Preparation Example of Component B): <Preparation Example B-1> In 34 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, isopropanol-dispersed organosilica sol (trade name: “MTST”, manufactured by Catalyst Chemical Industry Co., Ltd.) Co., Ltd., solid content 30
%) 47 parts, water 6 parts and isopropanol 783 parts were added with stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called B-1. The solid content in terms of the total condensed compound was 2.7%.

Preparation conditions of B-1:-The number of moles of water per 1 molar equivalent of the hydrolyzable group: 0.5 mol-The silica content of the component (B-1): 60.0% <Preparation Example B-2> 34 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, is mixed with an isopropanol-dispersed organosilica sol as acidic colloidal silica (trade name: "MTST", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 30).
%) 47 parts, water 12 parts and isopropanol 837 parts were added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called B-2. The solid content in terms of the total condensed compound was 2.6%.

Preparation conditions for B-2:-1.0 mol of water per 1 mol equivalent of hydrolyzable group-Silica content of component (B-2) 58.3% <Preparation Example B-3> 34 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, is mixed with an isopropanol-dispersed organosilica sol as acidic colloidal silica (trade name: "MTST", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 30).
%), 12 parts of water and 945 parts of isopropanol were added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called B-3. The solid content in terms of the total condensed compound was 2.6%.

Preparation conditions for B-3: 2.0 moles of water per 1 mole equivalent of hydrolyzable group, and a silica content of component (B-3) of 52.2% <Preparation Example B-4> To 27.2 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, 47 parts of isopropanol-dispersed organosilica sol (trade name: “MTST”, manufactured by Catalyst Chemical Industry Co., Ltd., solid content 30%), which is an acidic colloidal silica, 24 parts of water, 6.8 parts of methyltrimethoxysilane, a trifunctional hydrolyzable organosilane, and 945 parts of isopropanol were added with stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is B-4
Called. The solid content in terms of the total condensed compound was 2.4%.

Preparation conditions of B-4: 2.0 moles of water per mole equivalent of hydrolyzable group 2.0 moles of silica component (B-4) 55.9% <Preparation Example B-5> 34 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, is mixed with an isopropanol-dispersed organosilica sol as acidic colloidal silica (trade name: "MTST", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 30).
%) 47 parts, water 0.6 parts and isopropanol 734
Parts were added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called B-5. The solid content in terms of the total condensed compound was 2.9%.

Preparation conditions of B-5: 0.1 mol of water per 1 mol equivalent of hydrolysable group 0.1 mol of silica content of component (B-5) 59.6% <Preparation Example B-6> 34 parts of tetraethoxysilane, which is a tetrafunctional hydrolyzable organosilane, is mixed with an isopropanol-dispersed organosilica sol as acidic colloidal silica (trade name: "MTST", manufactured by Catalyst Chemical Industry Co., Ltd., solid content 30).
%) 47 parts, water 48 parts and isopropanol 1160
Parts were added under stirring. The obtained liquid was aged at 25 ° C. for one week to obtain a silica-dispersed oligomer solution of organosilane. This is called B-6. The solid content in terms of the total condensed compound was 1.9%.

Preparation conditions of B-6:-number of moles of water per mole equivalent of hydrolysable group: 4.0 moles-content of silica component (B-6) 57.6% A- obtained above In each of the solutions 1 to A-7 and B-1 to B-6, no gelation or turbidity was observed even after one month, and the following Examples and Comparative Examples were performed using them. <Examples 1 to 11 and Comparative Examples 1 to 7>
By mixing with the composition shown in No. 3, a resin composition for coating was obtained.

The resin composition for coating was applied to an aluminum substrate by a spray coating method, and the coated film was dried and cured at room temperature for one week to obtain a coated product. The cured film had a thickness of 2 μm. <Examples 12 to 20> A resin composition for coating was obtained by mixing the components with the formulations shown in Tables 4 and 5.

The resin composition for coating was applied to an aluminum substrate by a spray coating method, and the coated film was dried and cured at room temperature for one week to obtain a coated product. The cured film had a thickness of 7 μm. <Examples 21 to 25> A resin composition for coating was obtained by mixing the components in the proportions shown in Table 6.

The coating resin composition was applied to an aluminum substrate by a spray coating method, and the coating film was dried and cured at room temperature for 3 days to obtain a coated product. The cured film had a thickness of 2 μm. The coating film performance of the coating resin composition and the coated product obtained as described above was evaluated by the following method. <Evaluation method> (Crack resistance): After boiling in boiling water for 2 hours, a coating film having no crack was regarded as having no abnormality.

(Contact angle (water wettability)): The cured film was exposed to 60 ° outdoors (Kadoma City, Osaka Prefecture) for one month, and then evaluated by measuring the contact angle between the cured film and water. The contact angle was measured by dropping 0.2 cc of distilled water onto the surface of the cured film and then observing it with a magnifying camera. The smaller the contact angle, the higher the water wettability.

(Appearance): A cured film having neither crack nor cloudiness was regarded as having no abnormality. (Surface hardness): According to a pencil hardness test (according to JIS-K5400). The results are shown in Tables 1 to 6.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

[Table 6]

[0077]

According to the present invention, a coating film formed from the resin composition for coating according to any one of claims 1 to 4 can be cured at a low or normal temperature because the composition contains the component (A). In addition, the composition has excellent crack resistance and the composition contains the component (B), so that the composition has excellent weather resistance, durability, coating film strength, and water wettability.

The coating film of the resin composition for coating is as follows:
Because of its excellent crack resistance, it can be made thicker, and because of its excellent water wettability, it can exhibit properties such as rainwater washing antifouling property and antifogging property. Since the resin composition for coating is an inorganic resin, it is possible to form a coating film that is hardly deteriorated by ultraviolet rays because the performance of the coating film is hardly impaired by the addition of various additives. In addition, since various colors can be toned, the design is high and the range of use is wide.

The above resin composition for coating can be cured not only under heat but also at low or normal temperature, so that it can be used in a wide range of dry curing conditions or temperature. Therefore, not only can a substrate having a shape difficult to apply heat uniformly, a substrate having a large size or a substrate having poor heat resistance be coated, but also when performing a coating operation outdoors or the like. Since it can be painted even when it is difficult to apply heat, its industrial value is high.

Since the resin composition for coating according to the second aspect further contains the component (C), the occurrence of cracks in the coating film is further prevented, and the coating film can be made thicker. 4. The resin composition for coating according to claim 3, wherein the component (B) is a 1- to 3-functional compound of the general formula (1) upon partial hydrolysis of the tetrafunctional hydrolyzable organosilane of the general formula (2). Since a product obtained by coexisting a hydrolyzable organosilane is used, compared with a case in which only a tetrafunctional hydrolyzable organosilane is partially hydrolyzed and used as the component (B), 1 By adding the trifunctional hydrolyzable organosilane, the reactivity of the partial hydrolyzate in the component (B) to water decreases, and the further hydrolysis of the partial hydrolyzate during storage is suppressed. Therefore, the storage stability of the component (B) is excellent.

The resin composition for coating according to the fourth aspect further comprises a curing catalyst, so that the curing time of the coating film can be shortened. Since the coated article according to claim 5 includes a coating layer formed of a cured coating film of the resin composition for coating according to any one of claims 1 to 4, the coated resin composition or And has the above-mentioned various excellent properties and advantages derived from the coating film formed therefrom.

Claims (5)

[Claims] 1. A coating resin composition comprising the following components (A) and (B). Component (A): represented by the general formula R ¹ _m SiX _4-m (1) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M represents an integer of 1 to 3, and X represents the same or different hydrolyzable group) in a colloidal silica in which a 1-3-functional hydrolyzable organosilane is dispersed in an organic solvent, water or a mixed solvent thereof. A silica-dispersed oligomer solution of a 1-3-functional organosilane, which is partially hydrolyzed under the conditions of using 0.001 to 0.5 mol of water per 1 mol equivalent of the hydrolyzable group (X). Component (B): A tetrafunctional hydrolyzable organosilane represented by the general formula SiX ₄ (2) (where X represents the same or different hydrolyzable group) is mixed with an organic solvent, water or a mixture thereof. Silica of tetrafunctional organosilane obtained by partially hydrolyzing colloidal silica dispersed in a solvent under the condition of using 0.5 to 2.0 mol of water per 1 mol equivalent of the hydrolyzable group (X). Dispersed oligomer solution. 2. The coating resin composition according to claim 1, further comprising the following component (C). Component (C): represented by the average composition formula R ² _a Si (OR ³ ) _b O _{(4-ab) / 2} (3) (where R ² is the same or different and substituted or unsubstituted and has 1 carbon atom) And R ³ represent the same or different substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, and a and b each represent 0.2 ≦ a ≦
2, 0.0001 ≦ b ≦ 3, a + b <4), a polyorganosiloxane containing an alkoxy group in the molecule. 3. The component (B) is used in the step of partially hydrolyzing the tetrafunctional hydrolyzable organosilane represented by the general formula (2). The coating resin composition according to claim 1, which is obtained by coexisting a hydrolyzable organosilane. 4. The coating resin composition according to claim 1, further comprising a curing catalyst. 5. A coated article comprising, on a surface of a substrate, a coating layer comprising a cured coating film of the resin composition for coating according to any one of claims 1 to 4.