JP3193832B2 - Coating composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to form a coating for surface protection by coating a surface of a steel plate such as stainless steel, a non-ferrous metal such as aluminum, an inorganic building material such as concrete or slate, or a plastic base material. The present invention relates to a coating composition used in the above.

[0002]

2. Description of the Related Art Conventionally, as a coating composition capable of forming a durable film for the purpose of protecting the surface of steel plates such as stainless steel, non-ferrous metals such as aluminum, inorganic building materials such as concrete and slate, and plastic base materials. A coating agent obtained by hydrolyzing or partially hydrolyzing a hydrolyzable organosilane and a coating agent obtained by mixing colloidal silica with this coating agent are known.

[0003] For example, JP-A-51-2736, JP-A-51-2737, and JP-A-53-130732.
JP-A-63-168470 discloses an organoalkoxysilane, a hydrolyzate of this organoalkoxysilane and / or a partial condensate thereof, and colloidal silica, wherein an alkoxy group is converted to silanol with excess water. A coating agent comprising:
The films obtained with these coating agents have high hardness, good weather resistance and are excellent for protecting substrates.

[0004] However, the coating agent proposed in the above-mentioned patent publication requires baking by a heat treatment at a high temperature of about 100 ° C. or more or a long time in order to obtain required film characteristics. There is a disadvantage that it may not be applicable depending on the size, heat resistance, and the place such as outdoors. In addition, these coating compositions have a problem that silanol obtained by hydrolysis of alkoxysilane has a high activity, and their condensation reaction gradually occurs even at room temperature, and gelation easily occurs, resulting in poor stability. In particular, when these coating compositions are used as a vehicle and a pigment is added to form a coating, there is a drawback that the stability is further deteriorated and the coating cannot be formed.

In Japanese Patent Application Laid-Open No. 64-168, a coating agent for converting an alkoxy group into a silanol group by adding water and a catalyst as a curing agent to a partially hydrolyzed product or a partially condensed product of an alkoxysilane immediately before coating is disclosed. Proposed.
The coating agent obtained in this way has good storage stability, and is relatively stable even when it is made into a paint by adding a pigment. However, in order to obtain the required film properties, it is necessary to perform baking by a heat treatment at a high temperature of about 100 ° C. or more or for a long time as in the case of the above-mentioned coating agent. Also, it may not be applicable depending on places such as outdoors.

On the other hand, silicone resins are known as vehicles for heat-resistant paints or weather-resistant paints. Most of these are composed of silanol group-containing organopolysiloxanes. Generally, such silanol group-containing organopolysiloxanes are often obtained by hydrolyzing organochlorosilanes to form a toluene or xylene solution, and furthermore, converting organoalkoxysilanes. Even when used, a silanol group is allowed to undergo a condensation reaction until the hydrolyzate is dissolved in toluene or xylene. The thus obtained silicone resin solution has a good stability even when a pigment is kneaded into the paint. However, paints using this silicone resin solution have the disadvantage that, like the above-mentioned coating agents, heat treatment must be carried out at a high temperature for a long time to form a heat-cured film. However, there is a limit in increasing the hardness of the film, and sufficient characteristics as a durable film cannot be obtained.

[0007] Further, for the purpose of eliminating the above-mentioned disadvantages,
JP-A-63-268772 proposes a coating agent comprising a prepolymer mainly composed of silicon alkoxide, a curing catalyst and water, and curing at around normal temperature. However, this coating agent has drawbacks such as poor coatability and curability, and its curability is easily affected by humidity.

In order to solve the above-mentioned drawbacks of each coating composition, Japanese Patent Application Laid-Open No. 4-175 / 1992
No. 388 discloses a silica-dispersed oligomer solution of an organosilane obtained by partially hydrolyzing a hydrolyzable organosilane in colloidal silica dispersed in an organic solvent or water, and an organopolysiloxane containing a silanol group in the molecule. And a catalyst as essential components, and a coating composition that cures at about normal temperature without being affected by humidity has been proposed. This coating composition is capable of forming a film having high hardness, excellent heat resistance, excellent weather resistance and the like and sufficient performance on the surface of the substrate.

[0009]

However, Japanese Patent Laid-Open No.
The coating composition proposed in Japanese Patent No. 175388 has a problem that the gloss of the coating film surface cannot be obtained stably. That is, there is a problem that the matting agent settles and agglomerates during the period of storing the coating composition, and the film after long-term storage does not have the same gloss as the film at the initial stage of preparation.

The present invention is an improvement of the coating composition proposed in Japanese Patent Application Laid-Open No. 4-175388, which is capable of curing and drying at room temperature or curing by accelerated heating at a relatively low temperature, and has heat resistance and weather resistance. It is an object of the present invention to provide a coating composition capable of forming a film excellent in the above properties and obtaining a stable gloss which does not change even when stored for a long period of time.

[0011]

The coating composition according to the present invention has a general formula: R ¹ _n SiX _4-n (1) wherein R ¹ is the same or different, substituted or unsubstituted carbon number. A monovalent hydrocarbon group of 1 to 8; n is an integer of 0 to 3; and X represents a hydrolyzable group). 3μ
m, water was added in an amount of 0.001 mol per mol of X1.
To those obtained by partial hydrolysis under the conditions of using 0.5 mol, the general formula _{^{OH (R 2 2 SiO) m}} H ... (2) ( wherein, R ² is a substituted or identical or different Silicone diol-containing fine particles containing 5 to 30% by weight of an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms and m representing 1 or more) and having a weight average molecular weight of 10,000 or less. Oxide dispersed oligomer (component A)
And an average composition formula R ³ _a Si (OH) _b O _{(4-ab) / 2} (3) (wherein, R ³ is the same or different and is a substituted or unsubstituted monovalent carbon having 1 to 8 carbon atoms. And a and b represent 0.2 ≦ a <2.0, 0.0001 ≦ b ≦ 3, a +
b <4 is a number that satisfies the relationship of (b <4), and a polyorganosiloxane containing a silanol group in the molecule (component B) and a catalyst (component C). Is what you do.

Further, in the present invention, the component A contains 5 to 30% by weight of a particulate oxide as a solid content, and at least 50 mol% of the hydrolyzable organosilane is an organosilane with n = 1, It is characterized in that 70 to 30 parts by weight of the B component (total 100 parts by weight of the A component and the B component) is added to 30 to 70 parts by weight.

The method for producing a coating composition according to the present invention is represented by the following general formula: R ¹ _n SiX _4-n (1) (wherein R ¹ is the same or different and is substituted or unsubstituted having 1 to 1 carbon atoms). 8 represents a monovalent hydrocarbon group, n represents an integer of 0 to 3, and X represents a hydrolyzable group).
m, water was added in an amount of 0.001 mol per mol of X1.
Together is partially hydrolyzed under the conditions used the 0.5 mol, the general formula _{^{OH (R 2 2 SiO) m}} H ... (2) ( wherein, R ² is the number of carbon atoms of the substituted or unsubstituted, identical or different 5 to 30% by weight of a silicone diol component having a weight average molecular weight of 10,000 or less represented by 1 to 8 monovalent hydrocarbon groups, and m represents 1 or more). A component) is prepared, and this component A is combined with the average composition formula R ³ _a Si (OH) _b O _{(4-ab) / 2} (3) (wherein R ³ is the same or different, substituted or unsubstituted) And a and b each represent 0.2 ≦ a <2.0, 0.0001 ≦ b ≦ 3, and a +
b <4 is a number that satisfies the relationship of b <4), and a polyorganosiloxane having a silanol group in the molecule (component B) and a catalyst (component C). .

Hereinafter, the present invention will be described in detail. The silicone diol-containing fine particle oxide-dispersed oligomer of the component A used in the present invention is a main component of a base polymer having a hydrolyzable group X as a functional group which is subjected to a curing reaction during film formation. This is achieved by adding a silicone diol represented by the above formula (2) and adding one or more hydrolyzable organosilanes represented by the above formula (1) to a powdery form. The hydrolyzable organosiloxane is obtained by partially hydrolyzing the hydrolyzable organosiloxane by adding a necessary amount of water while dispersing the fine particle oxide or after completing the dispersion of the fine particle oxide. The addition of the silicone diol may be performed before hydrolyzing the hydrolyzable organosilane, during the hydrolysis, or after the hydrolysis.

Here, the group R ¹ in the hydrolyzable organosilane represented by the general formula (1) represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Alkyl groups such as groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups;
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; halogen-substituted hydrocarbon group such as chloromethyl group, γ-chloropropyl group, 3,3,3-trifluoropropyl; and γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4- Examples thereof include a substituted hydrocarbon group such as an 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 hydrolyzable group X in the hydrolyzable organosilane represented by the above general formula (1) includes alkoxy, acetoxy, oxime (* 1), enoxy (* 2), amino Group, aminoxy group (* 3), amide group (* 4) and the like. Alkoxy groups are preferred because of their availability and ease of preparation of the particulate oxide dispersed oligomer solution.

[0017]

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Such hydrolyzable organosilanes include mono-, di-, tri- and tetra-functional alkoxy groups wherein n in the above general formula (1) is an integer of 0 to 3. Examples include silanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Alkoxysilanes are preferred because they are easily available and easy to prepare a fine particle oxide dispersed oligomer solution.

In particular, tetramethoxysilane and tetraethoxysilane can be exemplified as the n = 0 tetraalkoxysilane, and methyltrimethoxysilane and methyltriethoxysilane as the n = 1 organotrialkoxysilane. , Methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Also, n = 2
Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having n = 3 include:
Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane. still,
Organosilane compounds, which are generally called silane coupling agents, can also be used as alkoxysilanes.

In the hydrolyzable organosilane represented by the general formula (1), at least 50 mol% of n = 1
Preferably, it is a trifunctional compound. It is more preferably at least 60 mol%, most preferably at least 70 mol%. If the trifunctional compound having n = 1 is less than 50 mol%, it is difficult to obtain a sufficient film hardness, and the dry curability may be inferior.

In the present invention, the powdery fine particle oxide in the component A is essential for controlling the gloss of the coating composition, and acts as a matting agent. As fine particle oxides, silicon oxide, aluminum oxide,
Titanium oxides and the like can be mentioned, and those whose surfaces have been subjected to silica treatment, alumina treatment, coupling treatment or the like for the purpose of enhancing dispersibility can be used.

The fine particle oxide is represented by the general formula (1)
Directly dispersed in the hydrolyzable organosilane represented by
The hydrolyzable organosilane is partially hydrolyzed with a required amount of water to prepare the component A. However, the component A is dispersed together with an organic solvent such as alcohol for the purpose of increasing the degree of dispersion of the powdery fine particle oxide, The component A may be prepared by partially hydrolyzing the hydrolyzable organosilane with a necessary amount of water. Kinds of the organic solvent include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate; diethylene glycol; Diethylene glycol derivatives such as diethylene glycol monobutyl ether; and diacetone alcohol. One or more selected from the group consisting of these can be used, but in combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, Methyl ethyl ketoxime can also be used.

The particle diameter of the fine particle oxide dispersed in the oligomer of the hydrolyzable organosilane of the component A is 0.2 to 0.2.
The range is 3 μm. If the particle diameter is less than 0.2 μm, it is difficult to control the gloss, and the particle diameter is 3 μm
If it exceeds 3, the film formability may be impaired. In the component A, the fine particle oxide is preferably in a range of 5 to 30% by weight as a solid content, more preferably 8 to 25% by weight.
It is contained in the range of weight%. If the content is less than 5% by weight, it is difficult to control the gloss, and the content is 30% by weight.
If it exceeds 300, there is a possibility that inconveniences such as impairment of the film-forming property of the film may be caused.

The silicone diol in the component A is essential for obtaining a stable gloss of the coating composition. A of the silicone diol represented by the general formula (2)
The mixing ratio in the components is 5 to 30% by weight. If it is less than 5% by weight, it is difficult to obtain long-term gloss stability, and if it exceeds 30% by weight, the curing of the coating film may be delayed. The silicone diol component has a weight average molecular weight of 10,000 or less, preferably 5,000.
It is better to use those having the following, more preferably 1000 or less. The weight average molecular weight of the silicone diol component is 1
Those having a molecular weight exceeding 0000 have poor compatibility with the resin and are difficult to use. Here, R ^{2 in} the general formula (2) of the silicone diol can be used without particular limitation as long as it is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. It includes the same hydrocarbon group as R ¹ in the formula (1).

The organosilane oligomer of the component A can be obtained by partially hydrolyzing the hydrolyzable organosilane of the general formula (1). The amount of water to the hydrolyzable organosilane, a water 0.001 mol of the hydrolyzable group X1 mol. Water usage is 0.00
Can not be is less than 1 mole obtain sufficient partial hydrolyzate, also the amount of water may turn poor stability of partial hydrolyzate exceeds 0.5 mol. The method of partial hydrolysis is not particularly limited, and a hydrolyzable organosilane and a necessary amount of water may be added and blended. At this time, the partial hydrolysis reaction proceeds at room temperature, but accelerates the partial hydrolysis reaction. For this purpose, heating may be performed at a temperature of 60 to 100 ° C. In order to further promote the partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluene An inorganic or organic acid such as sulfonic acid or oxalic acid may be used as a catalyst.

In order to obtain stable performance over a long period of time, the silicone diol-containing fine particle oxide-dispersed oligomer of the component A should have a pH of 2.0 to 7.0, more preferably a pH of 2.5 to 6 for the liquid. It is better to adjust the pH to a range of 0.5, even more preferably to a range of pH 3.0 to 6.0. If the pH is out of this range, the long-term deterioration of the performance of the component A may be remarkable particularly when the amount of water used is 0.3 mol or more per 1 mol of X. If the pH of the component A is outside this range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine when the pH is on the acidic side, and hydrochloric acid, nitric acid, The pH may be adjusted using an acidic reagent such as acetic acid. The method of this adjustment is not particularly limited.

The silanol group-containing polyorganosiloxane of the component B represented by the above-mentioned formula (3) is an important component which constitutes one of the features of the present invention. In equation (3),
As R ³ , the same as R ¹ in the above formula (1) can be exemplified, and preferably, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group, a γ-glycidoxypropyl group, A substituted hydrocarbon group such as a γ-methacryloxypropyl group and a 3,3,3-trifluoropropyl group, more preferably a methyl group and a phenyl group. In the formula (3), a and b are respectively 0.2 ≦ a <2.0,
It is a number that satisfies the relationship of 0.0001 ≦ b ≦ 3, a + b <4. If a is less than 0.2 or b exceeds 3, there are inconveniences such as cracks in the cured film, and a is 2.
When it is more than 0 and 4 or less, or when b is less than 0.0001, there is a disadvantage that curing does not proceed well.

The silanol group-containing polyorganosiloxane of the formula (3) is, for example, one or two of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and alkoxysilane corresponding thereto. It can be obtained by hydrolyzing the above mixture with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained, but such a polyorganosiloxane may be used.

The catalyst of the component C used in the present invention is the above-mentioned A
It promotes the condensation reaction between the component and the component B, and acts as a curing catalyst for curing the coating. Examples of such a catalyst include metal salts of carboxylic acids such as alkyl titanates, tin octylate and dibutyltin dilaurate and dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate; Carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N (-β-aminoethyl) -γ-aminopropyltrimethoxysilane; N (-β-aminoethyl)-
amine silane coupling agents such as γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali catalysts such as potassium hydroxide; tetraisopropyl There are titanium compounds such as titanate, tetrabutyl titanate, and titanium tetraacetylacetonate, and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane. There is no particular limitation as long as it is effective for the reaction.

The mixing ratio of the component A and the component B is 30
70 to 30 parts by weight of the component B is preferable to 70 to 70 parts by weight, and more preferably B to 40 to 60 parts by weight of the component A.
Component 60 to 40 parts by weight (provided that the total amount of component A and component B is 100 parts by weight). If the amount of the component A is less than 30 parts by weight, it is difficult to control the gloss of the coating, and if the amount of the component A exceeds 70 parts by weight, the film-forming properties of the coating may be impaired. The gloss of the coating can be easily adjusted by changing the mixing ratio of the component A and the component B within the above range. When the mixing ratio is adjusted so as to increase the amount of the component A, the gloss of the coating can be reduced. The glossiness of the film can be increased by adjusting the mixing ratio so that the amount of the component A can be reduced.

The amount of the catalyst of the component C is 0.0001 to 10 parts by weight based on 100 parts by weight of the total of the components A and B.
It is preferably in parts by weight. More preferably 0.00
0.5 to 8 parts by weight, most preferably 0.0007 to 0.0007 parts by weight.
5 parts by weight. If the added amount of the catalyst is less than 0.0001 part by weight, it may not be cured at room temperature, and if the added amount of the catalyst exceeds 10 parts by weight, the heat resistance and weather resistance of the coating may be deteriorated.

The coating composition according to the present invention can be used after being diluted with various organic solvents for ease of handling. The type of the organic solvent is selected according to the type or molecular weight of the monovalent hydrocarbon group of the component A or the component B. Examples of such an organic solvent include those shown as a dispersion solvent for the fine particle oxide. And one or more selected from the group consisting of these can be used.

The method for storing the coating composition according to the present invention generally takes a three-pack form in which the components A, B and C are separately stored.
Separate the mixed components and the B component into two packages, and mix them when using them. Also, mix all components and store them in one container. Is also possible. However, when the component A and the component C are mixed and stored, it is preferable that the pH of the component A is adjusted to 2 to 7, and then the component C is added and mixed. It is preferable to use water in which the amount of water used is 0.3 mol or less based on 1 mol of the hydrolyzable group X.

Thus, the coating composition according to the present invention comprises polycarbonate resin, acrylic resin, ABS
It can be applied for surface protection of plastics such as resin, metals such as aluminum, stainless steel, copper, iron, duralumin, or wall materials made of paper, wood, glass, cement or plaster, etc. It can also be applied to surface protection of acrylic, alkyd, polyester, epoxy, urethane paints and the like.
The thickness of the coating is preferably from 1 to 35 μm when applied to applications that require long-term high-temperature durability. If the coating has a thickness of more than 35 μm, cracks may occur in a test for boiling water resistance.

The coating composition according to the present invention can be coated by a usual coating method. For example, various coating methods such as brush coating, spraying, dipping, flow, roll, curtain, and knife coating are selected. be able to. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be determined as needed. In addition, the coating composition contains a leveling agent, a thickener, a pigment, a dye, an aluminum paste, a glass frit, a metal powder, an antioxidant, an ultraviolet absorber, and the like, if necessary, without affecting the present invention. It can be added in a range.

[0036]

Next, the present invention will be further described with reference to examples. Unless otherwise specified in the examples, all parts are by weight.
And “%” represents “% by weight” in all cases. It goes without saying that the present invention is not limited to these examples. (Preparation Example A-1 of Component A) 80 parts of methyltrimethoxysilane as a hydrolyzable organosilane of the general formula (1), 2.5 parts of water,
0.5 parts of N hydrochloric acid solution, 14 parts of Nippon Aerosil Co., Ltd. "Aerosil # 380" as the particulate silicon oxide, R ² in the general formula (2) is the weight average molecular weight in methyl about 10
The silicone diol-containing aerosil-dispersed silicone oligomer was obtained by adding 6 parts of the silicone diol of Example No. 00 and stirring for about 45 minutes with a paint shaker. This A component is referred to as “A-1”.

(Preparation Example A-2 of Component A) Except that the amount of the silicone diol was changed to 20 parts, Preparation Example A-
In the same manner as in Example 1, an aerosil-dispersed silicone oligomer containing silicone diol was obtained. This A component is referred to as “A-2”
And (Preparation Example A-3 of Component A) A silicone diol-containing aerosil-dispersed silicone oligomer was obtained in the same manner as in Preparation Example A-1, except that 20 parts of toluene was mixed and the amount of the silicone diol was changed to 35 parts. Was. This A component is referred to as “A-3”.

(Preparation Example A-4 of Component A) Preparation Example A-1 except that the amount of the silicone diol was changed to 3 parts.
In the same manner as described above, a silicone diol-containing aerosil-dispersed silicone oligomer was obtained. This A component is referred to as “A-4”. (Preparation Example A-5 of Component A) A silicone diol-containing aerosil-dispersed silicone oligomer was obtained in the same manner as in Preparation Example A-1, except that the amount of the silicone diol was changed to 50 parts. This A component is referred to as “A-5”.

Table 1 shows the amounts of the components A in Preparation Examples A-1 to A-5. Table 1 shows the average particle diameter of the fine particle oxide dispersed in the component A. The particle diameter was measured by SEM photograph observation.

[0040]

[Table 1]

(Example of adjusting component B) A flask equipped with a stirrer, a humidifying jacket, a condenser, a dropping funnel and a thermometer was charged with methyltriisopropoxysilane 220.
A mixture of 1 part (1 mol) and 150 parts of toluene was weighed, and 108 parts of a 1% aqueous hydrochloric acid solution was added dropwise to the mixture over 20 minutes to hydrolyze methyltriisopropoxysilane. Stop stirring 40 minutes after dropping,
The lower layer of a mixture of water and isopropyl alcohol containing a small amount of hydrochloric acid was separated out of the two layers, and then the remaining hydrochloric acid in the resin solution of toluene was removed by washing with water, and the toluene was further removed under reduced pressure. Thereafter, by diluting with isopropyl alcohol, isopropyl alcohol 4 of a silanol group-containing organopolysiloxane having an average molecular weight of 2,000 was obtained.
A 0% solution was obtained. This B component is referred to as “B-1”.

(Examples 1 to 5, Comparative Examples 1 and 2) Components A, B and C were used as catalysts for component C using N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane.
The components were mixed in the components and ratios shown in Tables 2 and 3 (all C components were 2 parts) to obtain coating compositions of Examples 1 to 5 and Comparative Examples 1 and 2.

About the above-mentioned component A, 1 day, 90 days, 1 day
After storing for 80 days, the appearance of the component A was observed, and the results are shown in Tables 2 and 3. In Tables 2 and 3, "Appearance of component A"
“○” indicates no matting agent (Aerosil) sedimentation, “X” indicates
Indicates sedimentation. Example 1 obtained as described above
The coating compositions of Comparative Examples 1 to 5 and Comparative Examples 1 and 2 were applied to a test piece ("Alster" manufactured by Nippon Test Panel Co., Ltd.) to a thickness of about 10 [mu] m by spray coating and cured at room temperature. One week later, the properties of the coating were tested. The results are shown in Tables 2 and 3. In addition, the test of the film property was based on the following evaluation method. Drying time: The time during which no tack remains when the film surface is pressed with a finger. -Coating hardness: Pencil hardness test method (according to JIS K 5400)-Gloss: Specular gloss measurement method (according to JIS K 5400), and color difference meter ("Z" manufactured by Nippon Denshoku Industries Co., Ltd.)
Measure the 60-degree specular gloss of -80 ").

[0044]

[Table 2]

[0045]

[Table 3]

As shown in Tables 2 and 3, in each of the examples, the curability and hardness of the film cured at room temperature are good, and the change in gloss due to the difference in the storage period of the component A is small. There were few.

[0047]

As described above, the coating composition according to the present invention comprises the above-mentioned A component, B component and C component, and can be dried rapidly, cured at room temperature and dried at a relatively low temperature. Can be cured by accelerated heating, and can form a film having excellent heat resistance and weather resistance. Therefore, it can be applied to a substrate having no heat resistance and can be applied at a work site where heat is not applied, and its industrial and industrial value is extremely large. In addition, the storage stability is enhanced by the action of the silicone diol component blended in the component A, and the stability of gloss can be enhanced.

Claims (5)

(57) [Claims] 1. A compound represented by the general formula: R ¹ _n SiX _4-n (wherein, R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n represents 0 to 3) An integer, X represents a hydrolyzable group), a hydrolyzable organosilane represented by the following formula:
m, water was added in an amount of 0.001 mol per mol of X1.
To 0.5 those obtained by partial hydrolysis under the conditions used the molar formula OH (R ^{₂ 2} SiO) in _m H (wherein, R ² is a substituted or unsubstituted carbon atoms of the same or different A silicone diol-containing fine particle oxide-dispersed oligomer containing 5 to 30% by weight of a silicone diol component having a weight-average molecular weight of 10,000 or less represented by the following formula (1): (A component)
And an average composition formula R ³ _a Si (OH) _b O _{(4-ab) / 2} (wherein, R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. , A and b are respectively 0.2 ≦ a <2.0, 0.0001 ≦ b ≦ 3, a +
b <4 is a number that satisfies the relationship of (b <4), and a polyorganosiloxane having a silanol group in the molecule (component B) and a catalyst (component C). Coating composition. 2. The composition according to claim 1, wherein the component A has a fine particle oxide content of 5%.
The coating composition according to claim 1, wherein the composition is contained in an amount of from 30 to 30% by weight. 3. The coating composition according to claim 1, wherein at least 50 mol% of the hydrolyzable organosilane is n = 1. 4. 70 to 30 parts by weight of component B with respect to 30 to 70 parts by weight of component A (provided that the total of component A and component B is 100
The coating composition according to any one of claims 1 to 3, further comprising: 5. A compound of the general formula R ¹ _n SiX _4-n (wherein R ¹ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n is 0 to 3) An integer, X represents a hydrolyzable group), a hydrolyzable organosilane represented by the following formula:
m, water was added in an amount of 0.001 mol per mol of X1.
Together is partially hydrolyzed under the conditions used the 0.5 mol, the general formula OH (R ^{₂ 2} SiO) in _m H (wherein, R ² is the same or different substituted or unsubstituted C1-8 A monovalent hydrocarbon group, m represents 1 or more), and 5 to 30% by weight of a silicone diol component having a weight average molecular weight of 10,000 or less is blended to form a silicone diol-containing fine particle oxide-dispersed oligomer (A component). Prepared by mixing the component A with an average composition formula R ³ _a Si (OH) _b O _{(4-ab) / 2} (wherein R ³ is the same or different and is a substituted or unsubstituted C 1-8 A and b represent 0.2 ≦ a <2.0, 0.0001 ≦ b ≦ 3, a +
b <a number that satisfies the relationship of <4), comprising a polyorganosiloxane containing a silanol group in the molecule (component B) and a catalyst (component C). Method of manufacturing a product.