JPH10158588A - Curable coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable coating composition that contains a film-forming resin composition which contains a curing agent, and pigments treated with a partially hydrolyzed condensate of an alkoxysilane compound, does not easily gel, has an excellent pigment dispersiveness, pigment dispersion stability, and realizes high-hardness coating films. SOLUTION: This curable coating composition comprises (A) a film-forming resin composition that contains a curing agent, such as a polyisocyanate compound blocked with lactams, oximes, and diketones, and (B) pigments treated with a partially hydrolyzed condensate of an alkoxysilane compound of the formula of (R<1> )p-Si-(OR2 )4-n (R1 is a 1-6C alkyl, epoxyalkyl, aryl, etc.; R2 is a l-6C alkyl or H; (n) is 0-2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a coated pigment which is hard to be solidified, and has good pigment dispersibility and pigment dispersion stability when used in a coating composition, and high hardness of a formed coating film. It relates to pigments with excellent expression.

[0002]

2. Description of the Related Art Various pigments are used for paints.
For example, color pigments (inorganic color pigments, inorganic fired pigments, organic color pigments), extender pigments, rust preventive pigments, design-imparting pigments (aluminum powder, mica-based pigments), matting materials (silica, alumina, etc.), and sauces There is a stopper (silica or the like). These pigments solidify during storage and transportation from production to use in paints due to the nature of the pigment's own components,
There are problems such as poor dispersion when blended into a paint and poor storage stability and color stability of the paint after pigment dispersion. For this purpose, paint pigments are generally subjected to surface treatment with fatty acids or resin acids. In addition, at the time of paint production, in order to maintain pigment dispersibility and storage stability and color stability after dispersion, the pigment is dispersed with a special dispersion resin, and a pigment dispersion paste is added thereto as a pigment dispersion paste. If available, enamel paints are manufactured by blending various paint additives. Generally, in this case, the pigment is dispersed after blending a dispersion resin whose acid-base properties are adjusted according to the acid-base properties of the pigment surface. In addition, in consideration of the hydrophilicity and hydrophobicity of the pigment surface (including the case where the surface is treated), a dispersion resin in which hydrophilicity and hydrophobicity are considered may be used.

[0003]

A curable coating containing a pigment which is hard to be solidified, has excellent pigment dispersibility when used in a coating composition, excellent pigment dispersion stability, and exhibits high hardness of a formed coating film. The composition is provided by any convenient method.

[0004]

According to the present invention, a commonly used pigment treated with a specific silane compound-based treating agent is incorporated into a curable coating composition or paint. The specific silane compound-based treating agent component is at least one kind of partially hydrolyzed condensate of an alkoxysilane represented by the following general formula. (R ¹ ) _n -Si- (OR ² ) _4-n

Wherein R ¹ is C _1-6 alkyl, epoxyalkyl, aryl or alkenyl, and R ² is
_1-6 alkyl, and n is 0, 1 or 2.

R ¹ is a C _1-6 alkyl group such as a methyl group, an ethyl group or a propyl group; a glycidoxypropyl group;
An epoxyalkyl group such as an epoxycyclohexylethyl group; an aryl group such as a phenyl group and a benzyl group; an alkenyl group such as a vinyl group, an allyl group, an acryloyloxypropyl group, and a methacryloyloxypropyl group. This organic group is used to modify the partially hydrolyzed condensate of the resulting organosilicon compound and to improve, for example, compatibility with the main resin. Usually, it may be an alkyl group.

R ² is a C _1-6 alkyl group or H,
Examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

[0008] Specific alkoxysilane compounds (hereinafter referred to as
Examples of “silane monomer”) include (tetrafunctional) tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; and others, methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxysilane. Silane,
Examples include trifunctional alkoxysilane compounds such as ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

The preferred number of n (ie, the number of alkoxy groups) is n = 0 (tetrafunctional) or n = 1 (3
Sensuality). When n> 2, the alkoxysilyl group is consumed when the organosilicon compound is hydrolyzed or condensed, and the reactive functional group (alkoxysilyl group or silanol group) of the partially hydrolyzed condensate of the organosilicon compound is consumed. The number decreases, the reactivity with the pigment surface decreases, and the curing reactivity of the film attached to the pigment surface decreases. The case where n = 0, that is, the case of tetraalkoxysilane is particularly preferred.

The preferred number of carbon atoms of the substituent R ² is C ₁ -C
₃ That is, the alkyl group is a methyl group, an ethyl group, or a propyl group. C ₁ and C ₂ are particularly preferred. If the carbon number is too large, the hydrolysis / condensation reaction becomes slow,
The production of a partially hydrolyzed condensate of the alkoxysilane compound cannot be easily performed, and the reactivity with the pigment surface decreases.

Examples of preferred alkoxysilane compounds are:
Examples include tetramethoxysilane, tetraethoxysilane, ethyltrimethoxysilane, and methyltriethoxysilane. Particularly preferred are tetramethoxysilane and tetraethoxysilane.

The partially hydrolyzed condensate of the alkoxysilane compound can be obtained by a known method. For example, in order to obtain a partially hydrolyzed condensate from a silane monomer, it can be obtained by adding a required amount of water and a catalyst and removing an alcohol generated by a hydrolysis / condensation reaction. In addition, oligomers (condensates)
, An oligomer having a higher degree of polymerization may be synthesized. The amount of water required here is determined from the desired hydrolysis rate. Here, the hydrolysis rate is a value calculated by the following equation, taking a tetraalkoxysilane monomer as an example. _{Si (OR) 4 + nH 2} O → Si (OR) 4 -n O n +2
_n ROH hydrolysis rate% = 2n / 4 × 100 = n / 2 × 100

The theoretical degree of hydrolysis for obtaining the partially hydrolyzed condensate is 0% <hydrolysis rate <100%. 100% hydrolyzate is complete the SiO ₂ solid, which rate of hydrolysis is more than 70% have a gelatinous gel or solid, and hydrolysis rate of 65% to 7
Those having a viscosity of up to 0% have a high viscosity and further react with a small amount of water in the air to form a gel, resulting in poor storage stability. Therefore, a hydrolysis rate of about 30 to 60% is most preferable. However, even when the hydrolysis rate is close to 100%, sufficient storage stability may be exhibited depending on the selection of an appropriate solvent and the like, and thus the hydrolysis rate is not limited to this range.

The water used for the hydrolysis is not particularly limited,
In general, if impurities such as ions remain in the coating film, the performance of the coating film deteriorates. Therefore, deionized water, pure water, or ultrapure water is used depending on the target coating film.

In order to obtain a partially hydrolyzed condensate by hydrolyzing and condensing the alkoxysilane compound, a catalyst can be used if necessary. Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acids such as carboxylic acid and sulfonic acid, and inorganic and organic bases such as ammonia, sodium hydroxide and amine. As the solvent, alcohol, ether,
Ketone or the like can be used.

The partially hydrolyzed condensate of the alkoxysilane compound thus obtained is an oligomer,
Dimers, trimers, and higher multimers are mixed,
When the monomer is contained, the storage stability of the partially hydrolyzed condensate itself may be reduced, or the storage stability of a coating material using the same may be reduced. Further, it is not preferable because the coating film performance (for example, water resistance, acid resistance, alkali resistance, and crack resistance) of a coating material using the same may be reduced. Preferably, the amount of monomer is 1% by weight
Hereafter, the monomer is removed so as to be preferably 0.3% by weight or less. A known method may be used for removing the monomer.

Among the partially hydrolyzed condensates of the alkoxysilane compound, the partially hydrolyzed condensate of tetramethoxysilane is preferable because of its high reactivity. In this case, when used in the pigment treatment, it has high reactivity with the pigment surface, and is therefore preferable.

In the case of tetramethoxysilane, the degree of hydrolysis of the partially hydrolyzed condensate is preferably from 10 to 65.
%, More preferably 30 to 60%. Such a partially hydrolyzed condensate of tetramethoxysilane in which the monomer is removed to 1% by weight or less is commercially available, for example, MK silicate MS51 (hydrolysis rate about 40%, S
iO ₂ component about 52%), the MS56 (degree of hydrolysis about 50
%, SiO ₂ component about 56%) (both manufactured by Mitsubishi Chemical Corp.
Made).

The corresponding partially hydrolyzed condensate is produced in the same manner from tetraethoxysilane. Of the tetraethoxysilane partially hydrolyzed condensates, those having a SiO ₂ content of 40% are often used. ES-40 (Colcoat Co., Ltd.), silicate 40 (Tama Chemical Co., Ltd.), TE
S40 (Hoechst), Sylbond 40 (Stoffer), ethyl silicate 40 (Union Carbide)
It is commercially available from, for example. Those having other SiO ₂ contents can also be used. These condensates are oligomers, and include a mixture of monomers, dimers, trimers, and higher polymers. It is not preferable that a low molecular weight component such as a monomer is mixed, because the coating film performance (for example, water resistance, acid resistance, alkali resistance, and coating film crack) using the same is deteriorated. It can be used by selecting a small number. Further, it is preferable that the oligomer is further hydrolyzed and condensed by the above-described method to be used as a partially hydrolyzed condensate.

Usually, the partial hydrolysis condensate of tetraethoxysilane has a hydrolysis rate of 0 to 100%. A 100% hydrolyzate is a complete SiO ₂ solid, a hydrolyzate having a hydrolysis rate of more than 70% is a gelatinous gel or solid, and a hydrolyzate having a hydrolysis rate of 65% to 70% has a viscosity of up to 65% to 70%. It is high and further reacts with a small amount of water in the air to form a gel, and has poor storage stability and is very difficult to handle.

In such a case, it can be avoided by leaving the medium (organic solvent such as alcohol) for hydrolysis / condensation and leaving the partially hydrolyzed condensate in a diluted state.
The hydrolysis rate of the solution diluted with an organic solvent is preferably 2
0 to 100%. If it is less than 20%, the monomer tends to remain.

The alkoxysilane that is partially hydrolyzed and condensed to form particles, and a particle having an inertia radius determined by a small-angle X-ray scattering method can be used for the pigment surface treatment. In this case, the radius of gyration of the partially hydrolyzed condensate of the alkoxysilane compound is 100 ° (10 nm) or less. An ordinary partial hydrolysis condensate of tetraethoxysilane or the like may have an inertia radius of 10 to 20 °. Usually, even the finest particles of dry silica (such as fumed silica) and wet silica (silica sol) used in paints have a particle diameter of 100 ° (10 nm) or more. Partially hydrolyzed condensates are quite different.

The number of functional groups in the particulate tetraalkoxysilane partially hydrolyzed condensate is usually much larger than dry silica (fumed silica) or wet silica (silica sol) used in paints. Exists. In the case of tetraethoxysilane partially hydrolyzed condensate, usually S
It is 0.1 to 3 moles, preferably 0.5 to 2.7 moles, including Si-OH groups and Si-OR groups, per mole of i. The quantitative ratio of the silanol group to the alkoxy group varies depending on the type of the monomer used, the degree of the hydrolytic condensation, the solvent in the hydrolytic condensation step, and the dilution solvent after the condensation. For example, when an alcohol-based solvent is used, the alcohol is exchanged with the original alcohol group. As a result of examining the partially hydrolyzed condensate of tetraethoxysilane (IPA solvent suspension) by H-NMR integration ratio and CHN analysis of the isolated product, two days after hydrolysis, one mole of Si
—OH group: 0.72 ± 0.13 mol, Si—O—Et
Group: 0.64 ± 0.12 mol, Si—O—iPr group
30 ± 0.06 mol. On the other hand, fumed silica (Aerosil 200: particle size of about 100 mm, Nippon Aerosil Co., Ltd.)
), 2 x ^10-5 Si-OH groups per mole of Si
Mol, silica sol (Snowtex O: particle size about 100
Å; manufactured by Nissan Chemical Industries, Ltd.)
The amount is 4 × 10 ⁻⁵ mol of Si—OH group. Thus, it has a large amount of functional groups completely different from ordinary silica. This functional group improves the reactivity with the pigment surface.

Although the number of functional groups changes with time, when left at room temperature for 60 days after hydrolysis, 0.4 mol of SiOH groups and 0.36 SiOEt groups per mol of Si are used, respectively.
Mol, 0.17 mol of SiOiPr group, which indicates that the chemical stability during storage is excellent.

A typical particulate alkoxysilane partially hydrolyzed condensate is reactive ultrafine silica. this is,
PCT / JP94 / 02169 (WO95 / 1734)
9) is shown.

This is the amount required to hydrolyze and condense all the alkoxy groups of the starting material, starting from tetramethoxysilane or its partially hydrolyzed condensate,
That is, it is characterized in that it undergoes aging and hydrolysis and condensation in the presence of 0.5 mol times or more of water of an alkoxy group.

More specifically, the amount of water used is preferably 0.5 to 1 times, particularly preferably 0.5 to 0.75 times the alkoxy group. If the amount of water is too large, the liquid tends to gel, and if the amount of water is too small, the formation of reactive ultrafine silica is not sufficient,
The hardness of the obtained coating film may be poor.

When the hydrolysis and condensation are advanced by aging, a catalyst can be added as required. As the catalyst, for example, inorganic acids such as hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid,
Organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, sodium hydroxide, calcium hydroxide,
Alkaline catalysts such as ammonia, organic metals, metal alkoxides such as dibutyltin dilaurate, dibutyltin dioctate, organic tin compounds such as dibutyltin diacetate, aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (Butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate) and zirconium bis (isopropoxy) bis There are metal chelate compounds such as (acetylacetonate) and boron compounds such as boron butoxide and boric acid. However, the storage stability of the liquid composition and the reactivity with the pigment surface are excellent. That the point is, acetic acid, maleic acid, metal alkoxide, it is preferable to use one or more kinds of the boron compound.

In this case, reactive ultrafine silica particles are suspended in an organic or aqueous solvent. It also has a radius of inertia in small angle X-ray scattering measurement. Usually, radius of inertia 1
Ultrafine silica of 0 ° or less has been confirmed, and this is most preferred. In the GPC measurement, the weight average molecular weight is 1000 to 3000 in terms of standard polystyrene, and most of them is 1400 to 2000. For example, the number of moles of the hydroxyl group is 0.8 times or more the number of moles of the alkoxy group, and the reactivity is extremely high. It also has excellent storage stability. Since it can form a film by itself and is rich in reaction, a curable composition using this hardly needs to use a catalyst for curing it. This is the reason for “reactivity”.

The film obtained solely from the reactive ultrafine silica particles is particularly excellent in high hardness, heat resistance, stain resistance and boiling water resistance.

A diluent can be added at the time of aging when forming the reactive ultrafine particle silica, or to the partially hydrolyzed condensate of the produced alkoxysilane compound, and an organic solvent or water can be used according to the purpose. Can be.

As the organic solvent, those used in ordinary coating materials such as alcohols, glycols, hydrocarbons, ketos and ethers can be used. For example, as the alcohol, methanol, ethanol, isopropyl alcohol, n-butanol, i-butanol, n
-Propyl alcohol, octanol, acetone alcohol, etc .; glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Propylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc .; hydrocarbons such as benzene, toluene, xylene, kerosene, etc .; esters such as methyl acetate , Ethyl acetate, butyl acetate, acetovinegar The ketones; ethyl etc.
Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and the like; as ethers, ethyl ether, butyl ether, dioxane, furan, tetrahydrofuran and the like can be used.

When alcohols such as methanol, ethanol, isopropanol and butanol are used among these solvents, the storage stability of the partially hydrolyzed condensate is good. The amount of the diluent is 50 parts by weight based on 100 parts by weight of the partial hydrolysis condensate of tetramethoxysilane as an example.
It is preferred to add 〜5000 parts by weight, preferably 100-1000 parts by weight, of an alcoholic solvent. If the amount is less than 50 parts by weight, the storage stability of the resulting silicate compound or paint will decrease. If the amount is too large, it takes time to evaporate the solvent.

When water is used, the amount of water used for hydrolysis may be increased. Further, water may be added to the hydrolysis product. In the case of a tetramethoxysilane monomer, the amount of water is preferably 20 to 300 parts by weight in combination with water used for hydrolysis, based on 100 parts by weight of the monomer. When the diluent is water, the alkoxysilane condensate is more likely to gel than the organic solvent. In this case, gelation can be suppressed by maintaining the pH at 3 or less, preferably 1 to 2.

The partially hydrolyzed condensate of the alkoxysilane compound of the present invention, for example, an ordinary tetraalkoxysilane partially hydrolyzed condensate (for example, MKC silicate MS5
1 and MS56) tend to have a higher hardness when used in a curable resin composition or a paint than when they are not used.
It is considered that this is because the reactive functional group reacts with the hydroxyl group of the resin for the condensation or coating during the pigment treatment or the curing of the coating film to increase the apparent crosslink density.

Mixing of silane compound-based treating agent with pigment
The appropriate type and the amount of the silicate compound differ depending on the surface area of the pigment and the state of aggregation. When there is no aggregation and the specific surface area of the primary pigment particles is 1 m ² / g or more, it is preferable to previously treat the pigment surface with reactive ultrafine silica particles. The addition amount is 0.01 to 50 parts by weight, preferably 1 to 100 parts by weight of the pigment.
１５15 parts by weight.

On the other hand, when aggregation is observed in the pigment, if the surface of the pigment is previously treated with the reactive ultrafine silica, the crushability of the obtained surface-treated pigment is reduced. Partially hydrolyzed condensates of silanes are suitable. A hydrolysis rate of 40% to 50% is appropriate, and particularly, a hydrolysis rate of 40% is optimal. This hydrolysis condensate is commercially available, for example, MKC silicate M
S51 (manufactured by Mitsubishi Chemical Corporation). The addition amount is 1 to 50 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the pigment.
10 parts by weight.

Pigment surface treatment method In the case of the dry method, a silane compound-based treating agent is added while stirring the pigment powder with a stirring blade as in a Henschel machine. The addition method may be dropping or spraying. The spraying method is suitable for uniformly treating the pigment powder.

For example, when using a Henschel machine having a capacity of 500 l, about 100 kg of pigment powder is charged and stirred at a stirring blade rotation speed of 200 to 500 rpm for several minutes, and then a silane compound-based treating agent such as methyl silicate (Mitsubishi Chemical Corporation) 1-5 kg of MKC silicate MS51). After stirring for several minutes, the stirring is temporarily stopped, and the pigment powder and methyl silicate attached to the lid and the inner wall of the Henschel machine are scraped off. Thereafter, stirring is performed for tens of minutes, and the pigment powder may be taken out when the temperature reaches 90 ° C. or higher.

If the pigment surface is not uniformly treated by the spraying method, the treatment liquid may be diluted with a solvent in advance. As the type of the solvent, an alcohol solvent, particularly methanol or ethanol, is most suitable. The dilution amount is a partial hydrolysis condensate of tetraalkoxysilane such as MKC silicate MS
In the case of No. 51, 100 parts by weight of MKC silicate MS51
On the other hand, the amount of the solvent is optimally 100 to 200 parts by weight. still,
When the reactive ultrafine silica particles are used as the treatment liquid, there is almost no need for dilution since the solvent has already been added.

On the other hand, in the case of the wet method, it is necessary that the solvent used has good solubility of the silane compound-based treating agent. These solvents include water or organic solvents. As the organic solvent, those used in ordinary coating materials such as alcohols, glycols, hydrocarbons, ketos, and ethers can be used. For example, alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, i-butanol, n-propyl alcohol, octanol, acetone alcohol and the like; glycol derivatives include ethylene glycol,
Ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, etc .; hydrocarbons, such as benzene, toluene, xylene, kerosene, etc .; esters, methyl acetate, ethyl acetate, butyl acetate, ethyl acetoacetate, etc .; ketones, acetone , Methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, etc. The ethers, ethyl ether, butyl ether, dioxane, furan, and tetrahydrofuran can be used.

The amount of the silane compound-based treating agent added to the pigment may be the same as in the dry method.

As the pigment to be used, various pigments usually used for paints can be used. For example, coloring pigments (inorganic coloring pigments, inorganic calcined pigments), extender pigments, rust-preventive pigments, design-imparting pigments (aluminum powder, mica-based pigments), matting materials (silica, alumina, etc.), Etc.). Among them, the coloring pigments include titanium oxide, zinc oxide, aluminum oxide, silicon dioxide, zirconium oxide, calcium carbonate, barium carbonate, barium sulfate, yellow iron oxide, red iron oxide, black iron oxide, iron-containing titanium oxide, and lower oxidation oxide. Examples thereof include titanium, cerium oxide, cobalt oxide, cobalt titanate, lithium cobalt titanate, titanium-titanium oxide sintered body, and carbon black.

The surface treatment of an ordinary pigment with a specific silicate compound in advance can provide a particularly high coating film hardness because the surface-treated pigment becomes a core of the specific silicate contained in the paint, It is considered that the crosslinking reaction proceeds further during coating.

[0045] Silicon added to the curable coating composition
Kate Condensate The curable coating composition of the present invention has the general formula:
(R ³ ) _m -Si- (OR ⁴ ) _4-m (where R ³ is C
_1-6 alkyl, epoxyalkyl, aryl or alkenyl; R ⁴ is C _1-6 alkyl or H;
Is 0, 1 or 2. )) (Hereinafter referred to as “component (C)”).
May be further included in the component (A) described below.

Here, a partially hydrolyzed condensate of an alkoxysilane compound as the component (C), for example, an ordinary tetraalkoxysilane partially hydrolyzed condensate (for example, MKC silicate MS51 or MS56, etc.) may be used as a curable resin composition. When used for objects or paints, hardness tends to be higher than when not used. This is presumably because the reactive functional group reacts with the treated pigment, condenses, or reacts with the resin for coating during curing of the coating film, thereby increasing the apparent crosslink density.

On the other hand, the dry silica or wet silica used for the coating material is generally as large as 100 ° even if it is small,
Since the number of reactive functional groups (silanol groups) per mole is small, an increase in apparent crosslink density cannot be expected, and the coating film hardness is hardly obtained. In addition, due to the interaction between the surface silanol groups and the interaction with the hydroxyl groups of the resin, even a small amount (approximately 1%) has structural viscosity in the paint and has the effect of preventing sagging. As in the present invention, when the concentration is further increased, for example, 10% by weight, the fluidity of the paint is lost,
It cannot be painted.

As the component (C), it is particularly preferable to use the reactive ultrafine particle silica described above. In this case, the film obtained alone has high hardness, heat resistance, stain resistance, and boiling water resistance. However, it has high reactivity with the treated pigment and with the resin, and when cured, can improve the hardness and alkali resistance of the coating film.

Further, the use of particularly preferred reactive ultrafine particle silica exerts the following effects different from ordinary tetraalkoxysilane partially hydrolyzed condensates.

Particle Synergy and Reactive (Self-Condensable) Synergistic Effect The reactive ultrafine silica particles have particle properties and have various and many reactive functional groups as described above. It is considered that, due to the reactivity with the pigment and the condensation of the ultrafine particles themselves, hard aggregates are likely to be formed in the film as compared with the non-particulate tetraalkoxysilane partially hydrolyzed condensate, and the resin component = sea / high hardness component = It is thought that the so-called sea / island structure of the island is easily formed. Therefore, it has the flexibility and strength required for the coating film, and has the ability to suppress cracks in the coating film, and the hardness of the film is easily obtained.

When the surface of the pigment is treated with a silane compound-based treating agent and added to the film-forming resin composition and the silane compound, the reaction between the treated pigment and the silane compound and the reaction of the silane compound itself are further enhanced. It is thought that the chemical resistance and extremely high hardness of the obtained coating film develop. In particular, when reactive ultrafine silica particles are used as the silane compound, the effect is remarkable.

The component (C) is the same as the component (A) except for the component (C).
1 part by weight of non-volatile components per 100 parts by weight of non-volatile components
It is preferable that the amount is from 300 to 300 parts by weight, preferably from 10 to 200 parts by weight. In this range, the hardness of the coating film is significantly improved,
At the same time, the storage stability and paintability of the paint are excellent.

Film-forming resin composition As the film-forming resin composition, generally used resins can be used. Preferably, in order to further improve the chemical resistance of the obtained coating film, it is optimal to mix the treated pigment and the silicate condensate with the combination of the polyol resin system and the isocyanate. In addition, a melamine resin or a benzoguanamine resin may be used as the curing agent, and an alkyl etherified product thereof is particularly preferable. Hereinafter, the polyol resin system combined with the isocyanate will be described in detail.

Polyol resins which form cured coatings by urethane crosslinking are well known. Typical examples of these are (modified) acrylic polyol resins, (modified) polyester polyol resins, (modified) fluorinated polyol resins, and (modified) silicone polyol resins.

The hydroxyl value of the polyol resin is 5 to 3
00, the number average molecular weight is 500-20,000. Preferably, the hydroxyl number is between 30 and 200 and the number average molecular weight is between 1,800 and 20,000. If the hydroxyl value is 5 or less, the amount of the curable reactive group is too small, and the curability decreases. If the amount is too large, a hydrophilic group remains in the cured film, and the water resistance, acid resistance, and alkali resistance of the coating film decrease. If the molecular weight is too small, the strength of the film will be reduced, and if it is too large, the viscosity of the coating will be too high and the coatability will be reduced.

Depending on the purpose of the coating, these resins may be modified in other segments. For example, acrylic polyol and polyester polyol resins may be modified with other types of segments commonly used in coatings such as silicone. Also, functional groups other than hydroxyl groups,
For example, it may be modified to have a carboxyl group, an alkoxysilyl group or the like. This type of modification may be carried out as appropriate according to the requirements of the target coating film. In the case of modification so as to have an alkoxysilyl group, the modification is preferably performed so that the alkoxysilyl equivalent of the component (A) becomes 650 or more.

The other physical properties are designed so as to fall within the range to be provided as a film-forming resin for paint. For example, the glass transition temperature (Tg) is from -20C to 60C. When the Tg is low, the formed coating film becomes soft. On the other hand, if the Tg is too high, the coating film tends to be non-uniform, and the formed coating film is too hard, which tends to cause cracks. The acid value is less than 30, and when the acid value is higher than this, when the alkoxysilyl group remains in the component (C) to be combined, it serves as a catalyst for the hydrolysis and condensation reaction, and the stability of the paint ( (Moisture curability under open air, storage stability).

Hereinafter, each polyol resin will be described in detail.

(Modified) Acrylic Polyol Resin An acrylic polyol resin is obtained by copolymerizing a hydroxyl group-containing acrylic monomer and another ethylenically unsaturated monomer by a conventional method.

Examples of the hydroxyl group-containing acrylic monomer include 2-hydroxyethyl (meth) acrylate,
And hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate and 4-hydroxybutyl methacrylate.

Further, various monomers can be used in order to adjust the physical properties of the coating film so as to match the intended coating material. For example, in order to impart flexibility to a coating film and enhance processability as a PCM, a monomer containing a soft segment,
For example, an ε-caprolactone-modified acrylic monomer can be used. These are commercially available, for example,
2- commercially available from Daicel Chemical Industries, Ltd. as Praxel-FA series and Praxel FM series
A hydroxyethyl (meth) acrylate / ε-caprolactone adduct, a polyalkylene glycol mono (meth) acrylate, or the like can be used in combination.

Monomers copolymerizable with the hydroxyl group-containing acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl Alkyl (meth) acrylates such as -butyl acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate; aromatic vinyl compounds such as styrene and vinyl toluene; acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, and the like. . Glycidyl (meth) acrylate having an epoxy group can also be used. In addition, if necessary, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
There are amino group-containing monomers such as (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-butoxymethyl (meth) acrylamide and N-methylacrylamide, and acrylamides.

As mentioned above, acrylyl polyol resins can be modified to have alkoxysilyl as a pendant group. For this purpose, one group having a polymerizable unsaturated bond to silicon, 0 to 2 hydrocarbon groups (typically methyl), and 1 to 3 alkoxy groups (typically methoxy or ethoxy) are used. The bound monomer is
It may be copolymerized with the above-mentioned hydroxyl group-containing acrylic monomer and other ethylenically unsaturated monomers.

Typical examples of the alkoxysilyl group-containing monomer described above include the following. Vinylmethyldimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloylpropylmethyldimethoxysilane (KBM5
02), γ-methacryloyloxypropyltrimethoxysilane (KBM503), γ-[(2-propene-2
-Yloxycarbonyl) benzoyloxy] propylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane (KBE502), and γ-methacryloyloxypropyltriethoxysilane (KBE503)

KBM502, KBM503, KBE50
2 and KBE503 are both commercially available from Shin-Etsu Chemical Co., Ltd. These alkoxysilyl group-containing monomers are preferably used so that the acrylic polyol resin has an alkoxysilyl equivalent described later.

Here, “alkoxysilyl equivalent” means the resin molecular weight per alkoxysilyl group.
The alkoxysilyl group-containing modified acrylic polyol resin that can be used in the present invention has an alkoxysilyl equivalent of 650 or more, preferably 900 or more, and more preferably 1500. If the alkoxysilyl equivalent is less than this value, a -Si-O-Si- bond or -Si-O
Although —C— bonds are easily formed and the coating film hardness is developed, it is not preferable because it has an adverse effect on acid resistance and alkali resistance. Further, since the alkoxysilyl group is excessively present, problems such as gelation by moisture and generation of cracks after forming a coating film are likely to occur.

(Modified) Polyester Polyol Resin As is well known, a polyester resin is a polycondensate of an acid component mainly composed of a polyvalent carboxylic acid and an alcohol component mainly composed of a polyhydric alcohol.

Examples of the acid component include terephthalic acid, isophthalic acid, phthalic acid or anhydride thereof, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, and anhydrides thereof; succinic acid, Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Further, lactones such as γ-butyrolactone and ε-caprolactone; and corresponding hydroxycarboxylic acids and aromatic oxymonocarboxylic acids such as p-oxyethoxybenzoic acid; and trimellitic acid, trimedic acid, and pyromellitic acid. The polyvalent carboxylic acid having a valency or higher can be contained in a small proportion.

As the alcohol component, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexane Diol, 1,4-cyclohexanedimethanol, bisphenol A alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,2-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol , 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,2 -Dodecanediol, 1,2-octane There are aliphatic glycols having a side chain such as decanediol. The alcohol component may also include a small proportion of trihydric or higher polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol and the like.

The polyester polyol resin may be combined with another component (such as a silicone component) if necessary.
For example, using a (poly) siloxane having a hydroxyalkyl group as an alcohol component and a usual condensation reaction with an acid component,
Silicone components can be introduced. Such resins are also commercially available, for example, TA22-29 from Hitachi Chemical.
3J (hydroxyl number about 170, Mn = about 2400).

(Modified) Fluorinated Polyol Resin The fluorinated polyol resin includes a hydroxyl group-containing radically polymerizable unsaturated monomer (a), a fluoroolefin monomer (b), and if necessary, other radically polymerizable unsaturated monomer. (C) is obtained by copolymerization with (c).

Examples of the hydroxyl group-containing radically polymerizable unsaturated monomer (a) include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether and hydroxypentyl vinyl ether; ethylene glycol monoallyl ether, diethylene glycol monoallyl ether And hydroxyallyl ethers such as triethylene glycol monoallyl ether.

Examples of the fluoroolefin monomer (b) include so-called difluorinated olefin monomers, olefin trifluoride monomers, and tetrafluoroolefin monomers, and specifically, vinyl fluoride, vinylidene fluoride, and trifluorinated chloride. Examples include ethylene and ethylene tetrafluoride.

Other radically polymerizable unsaturated monomers (c)
Can be appropriately selected from known monomers in accordance with required coating film properties. For example, ethylene, propylene,
Α-olefins such as isobutylene; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, and vinyl caprylate And fatty acid isopropenyl esters such as aliphatic isopropenyl such as isopropenyl acetate and isopropenyl propionate.

The fluorine-based polyol resin may have an acid value if necessary. In this method, a part of the hydroxyl group of the fluorine-based polyol resin may be subjected to an addition reaction with a polybasic acid anhydride (for example, succinic anhydride or the like) by an ordinary method.

Further, as the fluorine-based polyol resin, the above-mentioned acrylic polyol resin is added to a fluorine-containing polymer having no hydroxyl group, for example, a polymer obtained by copolymerizing (b) alone or (b) and (c). Blended materials are also included.

The acrylic polyol resin to be blended is
The above-mentioned hydroxyl group-containing radical polymerizable unsaturated monomer (a) and / or 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-methacrylic acid
Hydroxyl group-containing radically polymerizable unsaturated monomers such as hydroxyethyl and hydroxypropyl methacrylate; alkyl esters of acrylic acid or methacrylic acid; or ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid; styrene, α -Vinyl aromatic monomers such as methylstyrene and vinyltoluene; amides such as amide compounds of acrylic acid or methacrylic acid and derivatives thereof; and those obtained by copolymerizing acrylonitrile or methacrylonitrile.

Fluororesins or fluorinated polyol resins are commercially available, and include difluorinated polyvinylidene fluoride (PVDF), fluorinated fluoroethylene vinyl ether copolymer (FEVE), and tetrafluorinated FEVE.
There is a system. The PVDF system is available, for example, as Elf Atochem from Kaina 500. Since this resin does not have a hydroxyl group, the above hydroxyl group-containing acrylic polyol resin is blended and used. As the trifluoride type FEVE system, for example, Lumiflon series of Asahi Glass Co., Ltd., Fluonate series of Dainippon Ink and Chemicals, Inc., and Cefral Coat series of Central Glass Co., Ltd. can be used. Further, as the tetrafluoride type FEVE type, those commercially available from Daikin Industries, Ltd. as Zeffle series can be used. In addition, as a so-called fluorinated acrylic resin, Cotax available from Toray Industries, Inc. can be used. These can be used as they are or, if necessary, by blending with a hydroxyl group-containing acrylic polyol resin to adjust the hydroxyl value.

Preferred fluorine polyol resins are tetrafluoride FEVE and trifluoride FE from the viewpoint of durability.
VE system.

(Modified) Silicone Polyol Resin The silicone polyol resin as used herein refers to an organopolysiloxane having at least two alcoholic hydroxyl groups in a molecule, and the modified silicone polyol resin refers to another organopolysiloxane. Refers to a polyol resin blended or grafted with a resin.

Such an organopolysiloxane can be represented by the following composition formula. (R _a ) _n (R _b ) _m Si (O) _{(4-nm) / 2} (1)

Here, _Ra is methyl, C _1-20 alkoxy, aryl, hydrogen, aryloxy, one of C _2-100 containing an ester bond, an ether bond, a urethane bond or a carbon-carbon unsaturated bond in the chain. A valent organic group, R _b
Is a monovalent organic group containing an ester bond, an ether bond, a urethane bond or a carbon-carbon unsaturated bond in the chain and having an alcoholic hydroxyl group at a terminal, and m and n are 0 <
It means a positive real number that satisfies the conditions of n <4, 0 <m <4, and 2 ≦ n + m ≦ 4. The silicone polyol resin applicable to the composition formula (1) is described in JP-A-2-61481.
It is described in. The disclosure of which is incorporated herein by reference. In the resin of the composition formula (1), _Ra is HOC ₂ H ₄
OC ₃ H ₆ —, R _b is methyl, propyl or phenyl, n and m are 0 <n <2, 0 <m <2, and n
A positive real number that satisfies + m <3 is preferable from the viewpoint of ease of production, coating workability, and curability. Above all,
Equation (2)

[0083]

Embedded image

R _a is methyl or phenyl, R _b is HOC ₂ H ₄ OC ₃ H _6- ,
x is 0 or 1, y is 1 to 20, z is 1 to 10, further preferable because the silicone polyol containing 10 to 50 mol% of phenyl as R _a compatibility is good with other resins.

Examples of specific silicone polyols corresponding to the formula (2) are described in JP-A-2-61481 cited above.

This silicone polyol resin is used in combination with another polyol resin. Such resins contain hydroxyl groups and have a hydroxyl number of 5-30.
0, preferably 30 to 200, and the type is not particularly limited. For example, the acrylic polyol resin, the polyester polyol resin, the fluorine-based polyol resin, and the like are used. Also, alkyd resin,
Acrylic-modified alkyd resins, acrylic-modified polyester resins, epoxy resins obtained from bisphenol A and epichlorohydrin, and the like can also be used. The silicone polyol resin may be blended with another polyol resin, or the whole or a part thereof may be reacted in advance. The method includes, for example, reacting an unsaturated double bond and a compound having a functional group other than a hydroxyl group with a trisiloxane having a hydroxyalkyl group, for example, a compound such as maleic anhydride to obtain an unsaturated double bond. By incorporating a component having the following, and by addition polymerization of this part and a double bond part such as acrylic or vinyl monomer,
Both can be combined.

The combination ratio of the silicone polyol to the other polyol resin may be 3 to 7 for the silicone polyol resin.
A wide range such as 97 to 30 parts by weight of another polyol resin is possible with respect to 0 parts by weight. Preferably, the former 5
The latter is 95 to 60 parts by weight relative to 40 parts by weight.
When the ratio of the silicone polyol resin falls below the lower limit, the characteristics of the silicone (for example, weather resistance, chemical resistance, etc.) are not sufficiently exhibited. When the ratio exceeds the upper limit, the compatibility of the resin is reduced.

By combining with these resins,
The compatibility between the silicone polyol resin and other additives, the pigment dispersion (stability), and various physical properties (eg, adhesion, elongation, hardness, etc.) according to the intended coating film can be adjusted.

Polyisocyanate In the case of curing by heating and baking, a polyisocyanate obtained by blocking a polyisocyanate compound with a blocking agent is used. The polyisocyanate compound is
A compound having at least two isocyanate groups in one molecule. Examples of polyisocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and trimethylhexamethylene diisocyanate (TMDI); alicyclic diisocyanates such as isophorone diisocyanate (IPDI); and aromatics such as xylylene diisocyanate (XDI). Aliphatic diisocyanates; tolylene diisocyanate (TD
I), 4,4-diphenylmethane diisocyanate (M
Aromatic diisocyanates such as DI); dimer acid diisocyanate (DDI), hydrogenated TDI (HT
DI), hydrogenated diisocyanates such as hydrogenated XDI (H6XDI) and hydrogenated MDI (H12MDI); dimers, trimers, and higher molecular weight polyisocyanates of these diisocyanate compounds; trimethylolpropane Such as polyhydric alcohol or water, or an adduct with a low molecular weight polyester resin.

As the blocking agent, known agents can be used, for example, oximes such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime and benzophenone oxime;
phenols such as m-cresol and xylenol; alcohols such as methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol and ethylene glycol monoethyl ether; lactams such as ε-caprolactam; diethyl malonate; Diketones; and mercaptans such as thiophenol. In addition, there are many ureas such as thiourea; imidazoles; carbamic acids and the like.

The blocked isocyanate compound is obtained by reacting the above isocyanate compound with a blocking agent by a conventional method until free isocyanate groups disappear.
These are commercially available, Desmodur series (Sumitomo Bayer Urethane Co., Ltd.), Vernock D series (Dainippon Ink and Chemicals, Inc.), Takenate B series (Takeda Pharmaceutical Co., Ltd.), Coronate 2500 series (Nippon Polyurethane Co., Ltd.) Industrial Co., Ltd.) can be obtained. Isocyanate curing agents blocked with oximes or lactams are preferred.

In the case where no blocking agent is used in (b),
The component (A) is packaged separately from the component (A) and used as a two-pack type paint, and is mainly used as a normal-dry paint or a forced-dry paint.

It is usual to use a catalyst for the curing reaction with isocyanate. Examples of the catalyst include organotin compounds such as dibutyltin laurate, dibutyltin octate, and dibutyltin diacetate; aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (acetylacetonate), and titanium bis (acetylacetonate). ) Bis (acetylacetonate), titanium bis (isopropoxy)
Bis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate)
And other metal chelate compounds. Tin-based catalysts are common.

The isocyanate is basically blended so as to have an isocyanate group equivalent to or more than the hydroxyl value of the film-forming resin component. Actually, a composition in the range of 0.8 to 1.5 times the equivalent may be used. Preferably, the equivalent is 1.0 to 1.2 times. If the amount is less than the equivalent, the curability is reduced and only a soft coating film is obtained, and not only the hardness but also the chemical resistance and the stain resistance are reduced. In addition, if the amount is too large, not only the effect of the addition is not obtained, but also the coating properties (strength, hardness, workability) designed by the physical properties of the main resin due to the incorporation of a large amount of (block) isocyanate compound. Etc.) and chemical resistance. Further, yellowing and weather resistance of the coating film are liable to decrease.

The amount of the catalyst component to be added is usually 0.02 to 100% by weight of the (block) isocyanate curing agent component.
It is 5 parts by weight, preferably 0.1 to 1 part by weight. Even if it is added in a large amount, a catalytic effect corresponding to it is not seen.

[0096] paint paint is mixed film-forming resin component (A) uniformly, the treatment according to the invention is carried out by adding an additive of pigments and other conventional were made to it. Generally, the component (A) or a pigment-dispersed paste prepared using a dedicated pigment-dispersing resin is dispersed in the component (A), and the last remaining component (B) and, if applicable, (C) )), And, if necessary, a solvent and other conventional additives to give a one-pack coating.

In the case of a two-pack type paint, a dispersion paste of the pigment of the present invention is prepared, and if necessary, a mixture of a main resin varnish and various additives is used as a main agent liquid, and a mixture of a curing agent and a catalyst is used. A hardener liquid is used, and the two are mixed immediately before coating.

The pigment is dispersed using a usual machine such as a roller mill, a paint shaker, a pot mill, a disper, a bead mill, and the like. The compounding amount of the pigment may be a general one.
00 parts by weight. The compounding amount is required color, hiding power,
It is determined in consideration of various conditions such as coating film strength.

In the paint of the present invention, solvents and other various additives (for example, anti-dripping agent, leveling regulator, ultraviolet ray inhibitor, antifoaming agent, surface modifier, viscosity modifier, Dispersants, waxes, matting agents, etc.).

In addition to the pigment of the present invention, a pigment which has not been subjected to the treatment of the present invention can also be blended. Examples of such materials include titanium dioxide, carbon black, iron oxide, various calcined pigments, coloring pigments such as cyanine blue and cyanine gray, extenders such as calcium carbonate, clay and barium sulfate, metal powders such as aluminum powder, and silica. And a matting agent such as alumina.

The organic solvent may be one generally used for paints, for example, aromatic hydrocarbons such as toluene, xylene, Solvesso 100 and Solvesso 150;
Esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone; alcohols such as butanol, octanol and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monobutyl ether and ethylene glycol Monomethyl ether, diethylene glycol monoethyl ether,
Glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate can be used.
It can be selected in consideration of solubility, evaporation rate, safety and the like.

Coating Method Coating can be performed by a general coating method such as a roll coater, an air spray, an airless spray, and a curtain flow coater. Use them according to your purpose. The baking conditions are
The temperature is appropriately changed according to the dissociation temperature of the blocking agent of the block isocyanate.
This is performed at 0 ° C. for 30 seconds. The baking conditions are set according to the reaction temperature of the curing agent used. For example, when a block isocyanate curing agent is used, it is appropriately changed according to the dissociation temperature of the blocking agent of the block isocyanate. In the case of baking in a short time of about 30 seconds to about 2 minutes as in the case of PCM, the temperature is controlled by the reached plate temperature, and the temperature is controlled to 190 ° C.
Generally, the temperature is set to 230 ° C. In the case of a dry coating at room temperature, it can be used by leaving it to dry for 1 to 7 days after coating. The condition of drying at 60 ° C. to 110 ° C. for several minutes to 30 minutes is called forced drying, but this method is also possible depending on the composition of the paint.

The paint according to the present invention can be applied directly to the substrate with one coat, but it is preferable to apply the primer after applying a primer in order to ensure adhesion and corrosion resistance. The primer may be a conventional one, and an epoxy resin primer, a polyurethane-modified epoxy resin primer, or a polyester resin primer is used. The baking method may be 2 coats / 2 bake which is generally performed, or 2 coats / bake.
One bake may be used.

Applicable Materials Materials to which the present invention is applied include, for example, steel materials such as carbon steel, high-strength steel, and high-strength steel, plated steels of various metals, alloy steels such as stainless steel, cast iron, galvanized steel sheets, and zinc-alloyed steel. Forming of the above-mentioned metal material from plates and sheets, such as galvanized steel sheets, zinc / aluminum-plated steel sheets, aluminum-plated steel sheets, aluminum or aluminum alloys, copper or its alloys, titanium or its alloys, cold-rolled steel sheets, metal deposits, etc. Things. Organic materials such as plastic, FRP
Inorganic materials such as composite plastic materials, artificial marble, and slate are also possible. These materials may be directly coated or may be subjected to surface treatment. Generally, a metal material is subjected to a zinc phosphate treatment, a reactive chromate treatment, and a coating chromate treatment. Also, a thin film type organic composite coating on chromate is possible.

[0105]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

In the following Production Examples, Examples and Comparative Examples, parts and percentages are by weight unless otherwise specified.

Production Example 1 Synthesis of Reactive Ultrafine Particle Silica 50 equipped with a stirrer, a condenser for reflux and a thermometer
234 parts of tetramethoxysilane and 74 parts of methanol were added to a 0 ml four-necked round bottom flask and mixed.
22.2 parts of 05% hydrochloric acid was added to carry out a hydrolytic condensation reaction at an internal temperature of 65 ° C. for 2 hours. Next, the condenser was replaced with a distillation tube, the temperature was raised until the internal temperature reached 130 ° C., and the mixture was discharged with methanol. Thus, a partially hydrolyzed condensate was obtained (hydrolysis rate: 40%). Oligomers having a degree of polymerization of 2 to 8 were confirmed, and the weight average molecular weight was 550. The monomer amount in the obtained partially hydrolyzed condensate (hereinafter, referred to as tetramethoxysilane oligomer) was 5%. Subsequently, the tetramethoxysilane oligomer was charged into the flask heated to 130 ° C., and the temperature was raised to 150 ° C. and kept for 3 hours while excluding the vaporized monomer from the system together with the inert gas. The amount of the monomer in the tetramethoxysilane oligomer after the removal of the monomer thus obtained was 0.2%. Next, 6.52 parts of dechlorinated water, 0.31 part of aluminum (tris) acetylacetonate were added to 30.77 parts of the obtained tetramethoxysilane oligomer,
62.4 parts of ethyl carbitol was added as a solvent.
The amount of water is 1.13 times the amount that can theoretically completely hydrolyze and condense the tetramethoxysilane oligomer.
The mixture was allowed to stand at room temperature for 1 day to obtain a colorless, transparent, and homogeneous liquid composition containing the reactive ultrafine silica particles.

Production Example 2 Treatment of Pigment 1500 parts of a commercially available titanium dioxide pigment (manufactured by Ishihara Sangyo Co., Ltd., trade name: TAIPEK CR-97) was charged into a Henschel stirrer (capacity: 7 l, 2200 rpm), and then MS51 (Mitsubishi Chemical) 30 parts of MKC silicate MS51 (manufactured by Co., Ltd., SiO ₂ content: 52 wt%) was added. After stirring for 5 minutes, the stirring was temporarily stopped, and the pigment and MS5 attached to the lid of the Henschel stirrer and the inner wall of the container were stirred.
1 was stirred and stirred again for 25 minutes to take out the powder. The powder temperature at the time of removal was about 95 ° C. The texture was smooth and free of pigment.

Production Example 3 Treatment of Pigment The same as Production Example 2 except that the addition amount of MS51 was increased from 30 parts to 75 parts.

Production Example 4 Treatment of Pigment Instead of MS51, MS56 (manufactured by Mitsubishi Chemical Corporation, product name: MKC silicate MS51, SiO ₂ content: 57 wt.
%) Except that% was used.

Production Example 5 Treatment of Pigment The same as Production Example 4 except that the amount of MS56 added was increased from 30 parts to 75 parts.

Production Example 6 Treatment of Pigment The same as Production Example 2 except that 420 parts of reactive ultrafine silica particles were added instead of MS51.

Production Example 7 Treatment of Pigment Instead of 1500 parts of commercially available titanium dioxide pigment (manufactured by Ishihara Sangyo Co., Ltd., product name: TAIPEK CR-97), 150 parts of commercially available titanium dioxide pigment (manufactured by Teica Co., product name: JR) 150
Production Example 2 was the same as Production Example 2 except that a mixture obtained by adding 256 parts of reactive ultrafine silica to 0 parts was used.

Examples 1 to 6 and Comparative Examples 1 and 2 (1) Raw material of paint a. Polyester / polyol resin Hitachi Chemical Polymer Co., Ltd., product name TA22-293J, weight average molecular weight 12,400, hydroxyl value 171, solvent diethylene glycol monomethyl ether, nonvolatile content 50% b. Blocked isocyanate MEK oxime block with product name BL3175 HMDI manufactured by Sumitomo Bayer Urethane Co., Ltd. Solvent naphtha 100, nonvolatile content 75% c. Organic tin dibutyltin dilaurate manufactured by Sankyo Co., Ltd. d. Diluent solvent Ethyl carbitol (2) Method for preparing paint A paint was prepared by passing three times using three rolls in the amounts shown in Tables 1 to 3. (3) Coating method The substrate of tin plate JIS G 3303 was washed with a toluene solvent and wiped off with acetone. Continue bar coater (#
50). After air drying for about 1 minute
Heat curing was performed at 30 ° C. for 30 minutes. (4) Coating film evaluation method a. Coating thickness: Measured with a step-type thickness gauge. b. Smoothness: Observed by visual observation. c. Pencil hardness: according to JIS S-6006. d. Acid resistance: The coating film after immersion in a 5% HCl solution at 20 ° C. for 24 hours is visually observed. ◎: No change
：: slight change e. Alkali resistance: 24 at 20 ° C. in 5% NaOH solution
The coating film after immersion for a time is visually observed. ◎: No change
：: slight change The results are shown in Tables 1 to 3.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 18/62 C08G 18/62 18/80 18/80 (72) Inventor Keita Mizutani 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (13)

[Claims] (A) a film-forming resin composition containing a curing agent, and (B) a general formula (R ¹ ) _n -Si- (O
R ² ) _{4-n wherein} R ¹ is C _1-6 alkyl, epoxyalkyl, aryl or alkenyl, and R ² is
_1-6 alkyl or H, and n is 0, 1 or 2. A) a pigment that has been treated with a partially hydrolyzed condensate of an alkoxysilane compound of (a). 2. Component (A) is (C) a general formula: (R ³ ) _m
—Si— (OR ⁴ ) _{4-m wherein} R ³ is C _1-6 alkyl, epoxyalkyl, aryl or alkenyl; R ⁴ is C _1-6 alkyl or H; Or 2.) The curable coating composition according to claim 1, comprising a partially hydrolyzed condensate of an alkoxysilane compound. 3. The component (A) is selected from the group consisting of a polyol resin having a hydroxyl value of 5 to 300 and a number average molecular weight of 500 to 20,000, a polyisocyanate compound, a block polyisocyanate compound and an amino resin. The curable coating composition according to claim 1, comprising a cured agent that reacts with the polyol resin. 4. The curable coating composition according to claim 3, wherein the polyol resin is selected from the group consisting of an acrylic polyol resin, a polyester polyol resin, a fluorinated polyol resin, and a silicone polyol resin. 5. The method according to claim 1, wherein said curing agent is a polyisocyanate compound blocked by a member selected from the group consisting of lactams, oximes and diketones, and is cured by heat baking. 4. The curable coating composition according to 3. 6. The curable coating composition according to claim 1, wherein R ² is a methyl group and n = 0. 7. In the preparation of the component (B), the composition is treated with 0.01 to 50 parts by weight of the partially hydrolyzed condensate based on 100 parts by weight of an untreated raw pigment.
A curable coating composition according to claim 6. 8. The hydrolyzed condensate of the component (C), wherein R ⁴ is a methyl group and m = 0, has an inertial radius of 10 ° or less, and has a functional group Si—OR group. Si-
The curable composition according to any one of claims 2 to 7, wherein the reactive ultrafine silica has a molar ratio of OH groups (moles of Si-OH groups / moles of Si-OR groups) of 0.8 or more. Coating composition. 9. 10 parts by weight of component (A)
To 200 parts by weight of the component (B).
The curable coating composition according to claim 1. 10. The curable coating composition according to claim 9, further comprising 1 to 300 parts by weight of the component (C). 11. A curable paint containing the curable coating composition according to claim 1 as a film-forming component. 12. A coating film formed from the curable paint according to claim 11. 13. An object having the coating according to claim 12.