JPH09111188A - Coating material composition - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To form a film having excellent scratch resistance, weather resistance, adhesiveness, anti-staining property, water resistance and chemical resistance, which is suitable for surface protection of articles directly exposed to the atmosphere. The provision of a coating material composition that can be used. SOLUTION: (A) Organic resin, and (B) Average composition formula (1)
: (X) _a (Y ') _b (R ¹ ) _c SiO _{(4-abc) / 2} (1) [wherein, X represents an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group, a haloalkyl group and An organic group having at least one selected from amino groups,
Y'is a hydrolyzable group or a mixture of a hydrolyzable group and a silanol group (provided that the proportion of silanol groups in Y'is 2
0% or less), R ¹ is a monovalent hydrocarbon group, a is a number from 0.05 to 0.90, b is a number from 0.12 to 1.88, and c is a number from 0.10 to 1.00, And a + b + c is 2.
It is a number in the range of 02 to 2.67. ], The organic group X
The amount of silicon atoms bonded to is 5 to 90 mol% based on all silicon atoms in the molecule, and the proportion of T units represented by R ¹ -SiO _3/2 is 10 to 95 mol% based on all siloxane units. And a silicone compound having an average degree of polymerization of 3 to 100,
A coating material composition containing:

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a building, a structure,
Alternatively, the present invention relates to a coating material composition which is useful for surface protection of articles that are directly exposed to the atmosphere such as devices such as automobiles and used outdoors.

[0002]

2. Description of the Related Art Conventionally, various outdoor paints having excellent weather resistance have been developed. In particular, silicone resin, fluororesin,
Or organic resin such as modified acrylic resin is
It is suitable as a base resin for outdoor paints because it is less deteriorated by acid rain. However, the coatings based on these resins have insufficient hardness, which may cause scratches on the surface or static electricity due to dust, dust, or contaminants floating in the air during exposure. Contaminants adhere to the surface of the coating film, or the coating film deteriorates due to the influence of acid rain, which has become a problem in recent years, and the protective function deteriorates over time. There was a drawback that it ended up.

As a material for forming a film having a high hardness, a silicone hard coating agent containing an alkyltrialkoxysilane (T unit source) and / or a tetraalkoxysilane (Q unit source) hydrolyzed as a main component is known. Has been. This material achieves high hardness by improving the crosslink density, but on the other hand, there is a drawback that satisfactory weather resistance cannot be obtained because the flexibility is poor and cracks occur over time.

Further, a method of introducing a silicone resin into an organic resin has also been studied for the purpose of obtaining good weather resistance,
Silicone-modified acrylic resin, silicone-modified polyester resin, silicone-modified epoxy resin and the like are already known. Although these silicone-modified resins have the effect of the introduced silicone resin, the decomposition by sunlight is considerably suppressed, but the cross-linking density is still insufficient and the surface hardness is insufficient, so that they are easily scratched or have insufficient adhesion. Moreover, there is a drawback that it is difficult to maintain a good appearance due to being contaminated by the influence of static electricity.

In order to prevent the adherence of contaminants floating in the air by lowering the surface resistivity of the coating film, an ionic surfactant, an antistatic agent, or a silanol exhibiting hydrophilicity is provided. Attempts have also been made to add a group precursor such as alkyl silicate to the coating material. According to this method, adsorption of pollutants can be effectively prevented temporarily, but since it is basically inferior in water resistance, it can be easily washed away by rainwater, etc., and its effect cannot be sustained. Not suitable for outdoor use.

Further, in order to make the effect of preventing the adsorption of contaminants permanent, a condensation reaction product of an alkyl silicate oligomer and a silane coupling agent, in particular, a pre-hydrolyzate of an epoxy-functional silane is added to the paint. Therefore, an organic coating composition which is particularly excellent in acid rain resistance has also been proposed (JP-A-6-306328). A coating composition excellent in stain resistance has also been proposed in which a similar material is added to a fluororesin system (JP-A-7-82520). Although this system can obtain good stain resistance to some extent, it contains a large amount of Q units derived from a tetrafunctional alkyl silicate oligomer as a constituent unit in order to improve hydrophilicity.
For this reason, when hydrolysis / condensation gradually progresses with time, the crosslinking density increases due to the large amount of Q units, resulting in partial stress generation, resulting in microcracks and a poor appearance. However, since the silanol group derived from the Q unit source is highly reactive, it condenses over time and the hydrophilicity gradually decreases. Further, when prepared by this method, it becomes a mixture of an alkyl silicate oligomer, a silane coupling agent oligomer, and a block condensate of both, and the epoxy group is not uniformly introduced into the alkyl silicate, and it is eluted by water. Alkyl silicate oligomers, which are easy to do, remain considerably, and as a result, the water resistance, especially the alkali resistance of the coating film is lowered.

[0007]

Therefore, an object of the present invention is a coating material used for the purpose of protecting the surface directly exposed to the outdoors or for the purpose of maintaining the appearance and aesthetics, and solving the above problems. Another object of the present invention is to provide a coating material composition.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an oligomeric silicone having a specific functional group and a hydrolyzable group in the molecule at the same time. It has been found that these problems can be solved by blending the compound with a base component made of an organic resin.

According to the present invention, as a solution to the above problems, (A) an organic resin, and (B) an average composition formula (1): (X) _a (Y ') _b (R ¹ ) _c SiO 2 _{(4-abc) / 2} (1) [In the formula, X has at least one functional group selected from the group consisting of an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group, a haloalkyl group and an amino group. Is an organic group, Y ′ is a hydrolyzable group or a mixture of a hydrolyzable group and a silanol group (however, the proportion of silanol groups in Y ′ is 20 mol% or less), and R ¹
Is a monovalent hydrocarbon group, a is a number from 0.05 to 0.90, and b is
A number between 0.12 and 1.88, and c is a number between 0.10 and 1.00,
Moreover, a + b + c is a number in the range of 2.02 to 2.67. ]
And the amount of silicon atoms bonded to the organic group X having a functional group is 5 to 90 mol% with respect to all silicon atoms in the molecule, and the proportion of T units represented by R ¹ -SiO _3/2. Is 10 to 95 mol% with respect to all siloxane units, and the average degree of polymerization is 3
A coating material composition containing a silicone compound of about 100 is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) Organic resin As the organic resin used in the present invention, any organic resin can be used as long as it is an organic resin used for a known non-crosslinking type and crosslinking type coating material that has been conventionally suitably used for outdoor use. Is.

The non-crosslinking type coating material forms a film only when the solvent is vaporized. As an organic resin used for this type of coating material, foil, acrylic polymer, vinyl polymer, and Fluorine-based polymers and the like can be mentioned as specific examples.

The cross-linking type coating material is capable of cross-linking at room temperature or heating to form a cured film. The organic resin used in this type of coating material may be cross-linked as necessary depending on the type of cross-linking. An agent and optionally a catalyst are used in combination. Organic resins also need to have specific functional groups depending on the type of crosslinking. It is well known to those skilled in the art what kind of crosslinking agent, catalyst or functional group is required. Specifically, as such a crosslinkable organic resin system, an oxidation crosslinkable alkyd resin, a melamine crosslinkable or isocyanate crosslinkable polyester system, an acrylic resin, and a fluororesin, an epoxy crosslinkable epoxy resin,
And epoxy-containing modified acrylic resin, moisture-curable silicone-modified acrylic resin (that is, acrylic copolymer having an alkoxysilyl group in the side chain), moisture-curable silicone resin, addition type (that is, hydrosilylation crosslinking) Type)
Examples of the silicone resin, free radical cross-linking type silicone resin, UV curable type silicone resin and the like.

Among these resin systems, moisture curing type, addition type, free radical cross-linking type, and U which are particularly excellent in weather resistance.
It is preferable to use a V-curable silicone resin system, a melamine crosslinking type, an isocyanate curing type, an acid / epoxy curing type, and an alkoxysilyl crosslinking type acrylic resin system, and a fluororesin. In particular, in the case of the silicone resin used in the moisture-curable silicone resin system, those in which the organic substituent is a methyl group and / or a phenyl group are preferable. In addition, in the case of a silicone resin used in addition-type and UV-curable silicone systems, it is preferable that X of the component (B) described below does not contain an alkenyl group or a (meth) acryloyl group.

(B) Silicone Compound In the above-mentioned silicone compound (B), preferably, the amount of silicon atoms bonded to the organic group X having a functional group is 5 to 90 mol% with respect to all silicon atoms in the molecule. , R-SiO
The proportion of T units represented by _3/2 is 10 to 95 mol% with respect to all siloxane units. If the amount of silicon atoms bonded to the organic group X is less than 5 mol% with respect to all the silicon atoms in the molecule, the ability to fix the silicone compound (B) in the coating film is insufficient and the silicone compound (B) cannot be coated. It is not preferable because it easily elutes from the film. If it exceeds 90 mol%,
The hydrophilicity of the silicone compound (B) is insufficient, and good stain resistance cannot be obtained, which is not preferable. A particularly preferable content is 10 to 80 mol%. If the proportion of T units represented by R-SiO _3/2 is less than 10 mol% with respect to all siloxane units, flexibility and hydrophilicity given to the coating film are not sufficient, and cracks may occur, It is not preferable because good antifouling property cannot be obtained. On the other hand, if it exceeds 95 mol%, flexibility is sufficiently imparted, but hydrophobicity becomes too strong, hydrophilicity becomes insufficient, and good stain resistance cannot be obtained, which is not preferable. More preferable T unit content is 20 to
It is in the range of 90 mol%. In addition, T represented by R-SiO _3/2
Not only the oxygen atom forming the siloxane bond but also the oxygen atom of the hydroxyl group bonded to the silicon atom, for example, the alkoxy atom, the isopropenoxy group, the acetoxy group, or the like, which is an oxygen atom constituting the unit The oxygen atom of the organic group bonded to is also included.

The degree of polymerization of the silicone compound (B) is 3 to 1
It is better to satisfy the range of 00. If the degree of polymerization is less than 3, it is not suitable because it volatilizes, cannot impart sufficient hydrophilicity to the surface of the film, or is easily eluted from the film. On the other hand, if the degree of polymerization exceeds 100, the silicone compound (B) is not well dispersed in the formed film, making it difficult to form a uniform film, which is not preferable. Further, the degree of polymerization preferably satisfies the range of 5-80.

The functional group-containing organic group represented by X reacts with the organic resin (A) or the base material to form a chemical bond, forms a hydrogen bond with a polar structure, or has mutual affinity based on affinity. It acts to prevent the silicone compound (B) from being detached from the coating film and to improve the adhesiveness of the coating material layer to the substrate. As X, any kind of compound that acts in this way can be applied, and any known compound as an organic substituent of a so-called silane coupling agent can be used. This functional group reacts with the organic resin (A), or
By increasing the solubility in (A), it acts so that the silicone compound (B) can remain efficiently in the coating layer. Therefore, it is preferable to select the functional group to be adopted according to the type of the organic resin (A) used together. The functional group also acts to improve the adhesion between the coating layer and the substrate.

The functional group-containing organic group is preferably a hydrocarbon group having such a functional group and having 1 to 10 carbon atoms. The following can be mentioned as specific examples. γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) -ethyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, γ-mercaptopropyl group, β- (mercaptomethylphenyl ) Ethyl group, 6-mercaptohexyl group, 10-mercaptodecyl group, mercaptomethyl group, γ-methacryloxypropyl group, γ-
Methacryloxymethyl group, γ-acryloxypropyl group, γ-acryloxymethyl group, vinyl group, 5-hexenyl group, 9-decenyl group, p-styryl group, γ-chloropropyl group, γ-bromopropyl group, Trifluoropropyl group, perfluorooctylethyl group, γ-aminopropyl group, γ- (2-aminoethyl) aminopropyl group, p-
Aminomethylphenylethyl group and the like. These organic functional group-containing substituents may be contained alone in the silicone compound (B), or a plurality of kinds may be mixed.

In the general formula (1), Y'is a hydrolyzable group or a mixture of a hydrolyzable group and a silanol group, and the hydrolyzable group is, for example, the general formula (2) or (3) described later. ) Is mentioned.

Further, in the general formula (1), R ¹ is a monovalent hydrocarbon group, specifically having 1 to 10 carbon atoms,
More specifically, examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a decyl group. The silicone compound represented by the general formula (1) is, for example, a compound represented by the general formula (2): Si (X) _d (Y) _e (R ¹ ) _f (2) [wherein, X and R ¹ are as described above. Where Y is a hydrolyzable group, d is an integer of 1 or 2, e is an integer of 2 or 3, f is an integer of 0 or 1, and d + e + f = 4. ] The silane coupling agent represented by the general formula (3)
Si (Y) ₃ (R ¹ ) (3) [wherein Y and R ¹ are as described above] and an alkoxysilane mixture containing a trifunctional hydrolyzable silane,
It is obtained by subjecting to partial co-hydrolysis / condensation.

The silane coupling agent represented by the general formula (2) has two or three hydrolyzable groups Y (D unit source) capable of forming a siloxane bond by a hydrolysis / condensation reaction. (T unit source) can be used.

The hydrolyzable group (Y) of the trifunctional hydrolyzable silane represented by the general formula (3) partially forms a silanol group by partial hydrolysis and condensation, and other Some form siloxane bonds. Furthermore, some of the hydrolyzable groups remain in the silicone compound (B) as they are.

This trifunctional hydrolyzable silane is a so-called T unit source and, by crosslinking, an effect of imparting hardness to the coating film obtained from the composition, and an effect of imparting contradictory softness and flexibility. And, due to the effect of the silanol groups generated, it imparts appropriate hydrophilicity to the silicone compound (B) and the coating film, and the action of neutralizing electricity, and when the remaining substituents are alkyl groups, imparts lubricity to the film surface. It is considered to have the action of Especially,
Speaking of the static elimination property, the silanol group derived from the T unit source has little polarization, and therefore, unlike the silanol group derived from the Q unit source, the condensation activity is low, so that stable hydrophilicity and static elimination property are maintained over time. You can do it.

In the general formulas (2) and (3), the monovalent hydrocarbon group R ¹ has ¹ to 10 carbon atoms, and a methyl group, an ethyl group and a propyl group are particularly preferable. Among them, the methyl group is particularly preferable because it has the least hydrophobicity and is rich in lubricity.

In the general formulas (2) and (3), as the hydrolyzable group Y, conventionally known ones can be used, and the following can be exemplified. Methoxy group, ethoxy group, butoxy group, isopropenoxy group, acetoxy group, butanoxime group, amino group and the like. These hydrolyzable groups may be used alone or in combination. The application of a methoxy group or an ethoxy group is particularly preferable because good storage stability can be imparted to the coating material and good hydrolysis resistance can be obtained at an early stage due to its suitable hydrolyzability.

In the above synthetic reaction, a bifunctional dialkyldialkoxysilane (D unit source) or a tetrafunctional tetraalkoxysilane may be used, if necessary, together with the trifunctional hydrolyzable silane of the general formula (3). (Q unit source) may be added. Since the Q unit may cause stress in the film, it is necessary to carefully determine the addition amount even when the Q unit source is added to the coating material composition. In contrast, the Q unit source should be limited to 30 parts by weight or less. Further, the D unit remarkably improves the flexibility of the film, but on the other hand, it remarkably lowers the hydrophilicity. Therefore, it is necessary to carefully add the D unit source, and the D unit is 30 parts by weight per 100 parts by weight of the T unit. It should be limited to the following parts.

Partial cohydrolysis of the silane coupling agent of the general formula (2), the trifunctional hydrolyzable silane of the general formula (3), and other hydrolyzable silane optionally used in combination
The condensation can be performed by various conventionally known methods. Specifically, the following examples can be given,
It is not limited to the method described below.

(A) A predetermined amount of silane coupling agent and 3
Partial co-hydrolysis of a silane mixture containing a functional hydrolyzable silane (T unit source) in the presence of a hydrolysis / condensation catalyst.
Method of condensation. (B) A method of reacting a predetermined amount of a silane coupling agent with an oligomer or resin obtained by partially hydrolyzing a silane mixture containing a predetermined amount of a trifunctional hydrolyzable silane (T unit source).

(C) A method of reacting a co-hydrolyzate of a silane mixture containing a predetermined amount of a silane coupling agent with a trifunctional hydrolyzable silane (T unit source) or a partially hydrolyzed product thereof in advance. Among these methods, the method (a) is capable of uniformly introducing the functional group-containing organic group, the hydrolyzable group, and the T unit into the silicone compound (B) to be obtained, and can form a film. It is particularly preferable because it is possible to easily improve both durability such as flexibility, antifouling property, chemical resistance such as acid rain resistance and the like in terms of durability and prevent cracking of the film.

As the silane coupling agent of the general formula (2), conventionally known ones can be used, and examples thereof include vinyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane and γ-glycid. Xypropyl methyl diethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-acryloxypropyl・ Trimethoxysilane, γ-aminopropyl ・
Triethoxysilane, 5-hexenyl trimethoxysilane, p-styryl trimethoxysilane, trifluoropropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyl diisopro Penoxysilane etc. can be illustrated.

Examples of the trifunctional hydrolyzable silane represented by the general formula (3) include methyl trimethoxysilane and methyl.
Triethoxysilane, methyl triisopropoxysilane, methyl tributoxysilane, ethyl trimethoxysilane, propyl trimethoxysilane, hexyl
Trimethoxysilane, phenyl trimethoxysilane,
Examples thereof include decyl trimethoxysilane, methyl triacetoxysilane, methyl tributanoxysilane, and methyl triisopropenoxysilane.

Examples of the bifunctional hydrolyzable silane and the tetrafunctional hydrolyzable silane used as necessary include, for example,
Dimethyl-dimethoxysilane, dimethyl-diethoxysilane, dimethyl-dibutoxysilane, methyl-phenyl-dimethoxysilane, diphenyl-dimethoxysilane,
Examples thereof include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and the like.

As the hydrolysis / condensation catalyst used when carrying out the hydrolysis / condensation reaction, various conventionally known catalysts can be applied. Specific examples include organic acids such as acetic acid, butyric acid, maleic acid and citric acid, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, basic compounds such as triethylamine, organic metals such as tetrabutyl titanate and dibutyltin dilaurate. Salts, KF, NH ₄ F
F-containing compounds such as The above catalysts may be used alone or in combination of two or more. The amount of the catalyst used may be in the range of 0.0001 to 1 mol% based on all the reaction components.

In carrying out the hydrolysis / condensation reaction,
You may use a solvent as needed. Usable solvents include methanol, ethanol, isopropanol,
Examples thereof include alcohols such as t-butanol, ketones such as acetone and methyl isobutyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate, and aromatics such as toluene. In particular, solvents such as methanol, ethanol and acetone are preferable.

The amount of water used for the partial cohydrolysis / condensation reaction is determined by the desired degree of polymerization. If added in excess, the hydrolyzable groups will be destroyed, eventually leading to gelation, so it must be determined strictly. Especially when an F-containing compound is used as a catalyst, the F-containing compound has the ability to completely proceed with hydrolysis and condensation. Therefore, the degree of polymerization can be determined by selecting the amount of water to be added, and an arbitrary molecular weight can be set. Therefore, it is preferable. That is, in order to prepare the target product having the average degree of polymerization M, (M-1) mol of water may be used with respect to M mol of the hydrolyzable silane compound. In the case of other catalysts, it is necessary to slightly increase the amount.

The hydrolysis / condensation reaction is carried out at room temperature or 150
It may be carried out in a temperature range of ℃ or less. If the temperature is lower than room temperature, the reaction proceeds slowly, which is not practical, and if the temperature exceeds 150 ° C., the organic functional groups such as epoxy group and mercapto group are thermally decomposed, which is not preferable.

The proportion of the silicone compound (B) in the composition is preferably 0.1 to 50 parts by weight, more preferably 1.0 to 20 parts by weight, based on 100 parts by weight of the resin solids contained in the composition. desirable. When the amount of the silicone compound (B) is too small, the resulting film has insufficient scratch resistance, stain resistance, weather resistance, chemical resistance, and water resistance, while when it exceeds 50 parts by weight, the film becomes too hard. The water resistance, weather resistance and flexibility of the film deteriorate.

Other Components In addition to the components (A) and (B) described above, the composition of the present invention usually contains an organic solvent. Organic resin as organic solvent
Any compound can be used without particular limitation as long as it dissolves or disperses (A) and does not substantially react with the silicone compound (B). Specifically, acetic acid esters (for example,
Ethyl acetate, propyl acetate etc.), ketones (eg methyl isobutyl ketone etc.), aromatic hydrocarbons (eg xylene, toluene etc.), aliphatic hydrocarbons (eg heptane etc.), alcohols (eg Examples thereof include propyl alcohol) and ethers (eg, ethyl cellosolve, butyl cellosolve, etc.). These organic solvents can be used alone or in combination of two or more.

If desired, the composition may further contain, for example, a colorant, a filler, a curing catalyst, an anti-sagging agent, an anti-cissing agent, an ultraviolet absorber, an ultraviolet stabilizer and the like.

Coating Treatment The base material to which the coating material composition of the present invention can be applied is not particularly limited, but examples thereof include inorganic base materials such as slate and concrete, steel, aluminum, zinc, stainless steel and these. Examples thereof include metallic substrates such as those surface-treated with chromic acid and zinc phosphate, and plastic substrates such as polyvinyl chloride, polyethylene terephthalate and polyethylene. Further, a base material obtained by coating a known primer, an intermediate coating material, a top coating material or the like on these base materials, if necessary, can also be used.

The coating method can be carried out by means such as brush coating, spray coating, roller coating and dip coating. The coating amount is generally in the range of 1 to 100 μm, preferably 10 to 60 μm.

[0041]

The alkylsilane compound or its hydrolysis / condensation product (resin) has hitherto been known as a material exhibiting water repellency or imparting water repellency. According to the present invention, when the trifunctional hydrolyzable alkylsilane is hydrolyzed under the above-mentioned suitable reaction conditions, a linear oligomer having an alkoxy group pendant on the side chain is selectively obtained. Unexpectedly, it was found that the one in which an organic functional group was introduced into a part of the chain exhibited hydrophilicity. That is, the alkoxy group present in the side chain is converted into a silanol group because it is hydrolyzable, but its activity is low,
It is considered that the ability to condense is weak, and a considerable amount of silanol groups remain as it is, and it exhibits a good and continuous hydrophilicity and static elimination function. In addition, since the silicone compound thus obtained is rich in linear structure, even if the crosslinking progresses to some extent and the hardness increases, the coating film is highly flexible, and while achieving high hardness, no cracks occur. , It has excellent scratch resistance, and at the same time, it is difficult for contaminants to adhere to it, and it is easy to fall off. In addition, it has a unique property of having hydrophilicity.

Since the silanol group derived from the Q unit derived from tetraalkoxysilane is remarkably polarized and rich in reaction activity, the crosslinking density further increases with the lapse of time. As a result, the appearance becomes defective due to cracking, and conversely, the hydrophilicity is low. On the other hand, the silanol group belonging to the T unit employed in the present invention has a weak reaction activity and remains stable on the surface of the coating film even after the completion of the curing reaction, so that it has a durable hydrophilic property. And antifouling property are obtained. Furthermore, unlike the Q unit, the T unit imparts flexibility to the cured film as described above. Therefore, both high hardness retention and flexibility are achieved. Also, if a large amount of Q units are contained,
Although the hydrophilicity of the silicone compound itself is too high, it tends to fall off from the coating film, but since the system of the present invention containing mainly T units is moderately hydrophilic, the characteristic level tends to maintain the initial value. . Further, since it imparts lubricity to the film in which the alkyl group attached to the T unit is obtained, it provides good scratch resistance, weather resistance, and stain resistance.

In the composition of the present invention, the excellent effect of the present invention can be obtained only by using the silicone compound (B) satisfying the above three conditions-T unit structure, organic functional group and hydrolyzable silyl group. .

[0044]

The present invention will be described in detail below with reference to examples. In the following description, "part" and "%" are based on weight.

Synthesis Example-1 118 g (0.50 mol) of γ-glycidoxypropyltrimethoxysilane and 68 g of methyltrimethoxysilane were placed in a 1,000 ml reaction vessel equipped with a thermometer, a nitrogen introducing tube and a dropping funnel.
(0.50 mol), 320 g of methanol (10 mol) and 0.06 g of KF
(0.001 mol) was charged, and 14.4 g (0.80 mol) of water was stirred at room temperature.
l) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and then heated and stirred for 2 hours under methanol reflux. Then, the low boiling components were distilled off under reduced pressure and further filtered to obtain 120 g of a colorless transparent body. The substance thus obtained is used as GPC
As a result of the measurement, the average degree of polymerization was 5.2 (setting degree of polymerization = 5), which was almost as set.

When the epoxy equivalent was measured by the epoxy ring-opening method with hydrochloric acid, it was found to be 292 g / mol (set value 296 g
/ Mol), and it was confirmed that the epoxy group was introduced in a predetermined amount. When the amount of alkoxy groups was quantified by alkali cracking, it was 28.7% by weight (theoretical value: 29.2% by weight). Further, from the ¹ H-NMR measurement result, the structure of the obtained substance was a structure represented by the following general formula.

Average composition formula

Embedded image Furthermore, when ²⁹ Si-NMR was measured, the existence state of each silicon atom was assigned as follows.

[0048]

Embedded image [In the formula, R is a methyl group or a γ-glycidoxypropyl group, and Z is a hydrogen atom or a methyl group. From this analysis result, it was found that the present silicone compound has most of the linear structure portion. The compound thus obtained is designated as A.

In the same manner as above, the compounds B to H having the set structures shown in Table 1 and the comparative compound J were prepared by changing the kinds and amounts of the silane coupling agent, alkyltrialkoxysilane, and catalyst used. Was prepared. The following method was also examined instead of the partial cohydrolysis / condensation method.

Method-II A method in which trialkoxysilane is hydrolyzed in advance and then reacted and condensed with a silane coupling agent.

Method-III A method in which the silane coupling agent is hydrolyzed in advance, and then trialkoxysilane is reacted and condensed with.

[0052]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 3 With the formulations shown in Table 2, coating materials of Examples 1 to 8 and Comparative Examples 1 to 3 were prepared. In the silicone resin, the organic substituents are all methyl groups, D unit / T unit = 25/75 (molar ratio),
An oxime-curing type having a solid content of 25% was used. As the base material, a polished mild steel plate having a thickness of 0.3 mm was used. The coating was air spray coating so that the dry film thickness was about 30 μm. The curing was completed by leaving it at 20 ° C. for 24 hours.

The performance evaluation test of the obtained coating film was carried out as follows. (In addition, the evaluation of the coating film was performed in the same manner after Example 9 as well.) Coating hardness: Pencil hardness / JIS K 5400. Adhesion: Cross-cut peeling test / JIS K 5400
Compliant with. Weather resistance: 3000 on a sunshine weatherometer
By observing the appearance of the coating film after irradiation for a certain time
Compliant with 00. ◯: Good with no change visually. B: Appearance change (swelling, cracking, peeling, etc.) is visually observed. X: A visually noticeable change in appearance is observed. Bad. Scratch resistance: Rub the surface with # 0000 steel wool,
The appearance was visually evaluated. ◯: No scratches were observed, which was good. Δ: About 1 to 5 scratches were recognized. X: Scratched significantly. Anti-contamination property: exposed to the outdoors for half a year, and visually evaluated the appearance. Good: No trace of contamination was observed on the surface of the coating film, which was good. Δ: Some traces of contamination were found on the surface of the coating film. X: Significant contamination was observed on the coating film surface. Bad. Water resistance: The coating appearance after the test plate was immersed in water for 1 week was visually evaluated. Δ: Appearance change (swelling, peeling, etc.) is visually observed. X: Remarkably defective appearance is visually observed. The coating film performance test results are shown in Table 2.

[0055]

[Table 2]

[0056] In Example 9-16, the formulation of Comparative Examples 4-6 in Table 3 described in Example 9-16 to prepare a coating material of Comparative Example 4-6. The silicone-modified acrylic resin has an average molecular weight of 6000 obtained by copolymerizing an acrylic monomer containing 5 mol% of methacryloxypropyltrimethoxysilane and 10 mol% of glycidyl methacrylate and has a solid content of 50%.
And an average molecular weight of 40 containing 5 mol% of acrylic acid
At 00, a solid content of 50% was mixed and used. The base material is 0.
Polished mild steel plate with a thickness of 3 mm was used. The coating was air spray coating so that the dry film thickness was about 30 μm.
The curing was completed by leaving it at 150 ° C. for 30 minutes. The coating film performance test results are shown in Table 3.

[0057]

[Table 3]

[0058] In Example 17 to 24, the formulation of Comparative Example 7-9 in Table 4, Example 17 to 24 to prepare a coating material of Comparative Example 7-9. Fluororesin is linear and has an average molecular weight of 18
It is a type that cures 00 perfluoropolyether with hexamethylene diisocyanate and has a solid content of 50%.
Was used. As the base material, a polished mild steel plate having a thickness of 0.3 mm was used. The coating was air spray coating so that the dry film thickness was about 30 μm. The curing was completed by leaving it at 150 ° C. for 30 minutes. The coating film performance test results are shown in Table 4.

[0059]

[Table 4]

Examples 25 to 32, Comparative Examples 10 to 12 With the formulations shown in Table 5 , Examples 25 to 32 and Comparative Examples 10 to 1
Two paints were made. The silicone hard coating agent was a type in which all organic substituents were methyl groups and colloidal silica was used in combination, and the solid content was 20%. A primer containing a silicone-modified acrylic resin and a modified aminosilane compound as main components and having a solid content of 10% was applied to a substrate in advance. The substrate used was a 0.5 mm thick polycarbonate plate. The coating was performed by dip coating so that the dry film thickness of the primer was 3 μm and the hard coating agent was about 2 μm. Primer at 120 ℃ for 30 minutes, hard coat agent at 120 ℃
The mixture was heated for 1 hour to complete the curing. The coating film performance test results are shown in Table 5.

[0061]

[Table 5]

[0062]

EFFECTS OF THE INVENTION The cured coating film obtained from the coating material composition of the present invention has excellent abrasion resistance even when exposed to the outdoors (a) because of its high surface hardness and rich lubricity, (b) At the same time, the entire film has a highly flexible structure, and it has good weather resistance without cracks even in the outdoors where there is a large difference in global warming. (C) A large amount of potentially hydrophilic polar groups are present on the surface. Existing on the surface and removing the static electricity accumulated on the surface,
It suppresses the attachment of pollutants, and (d) has the function of easily washing away the contaminants and acid rain adhering to the surface due to the hydrophilic effect brought by the polar group, and (e) the polar group has little change over time and is a film. Stable stain resistance and chemical resistance are maintained, and (f) the organic functional groups have high adhesion to various substrates and form a film with good water resistance. is there. In addition, boiling water, acidic solution,
The elution and hydrolysis of the coating film are suppressed even in an alkaline solution and the like, and it exhibits excellent durability such as anti-staining property, boiling water resistance, and chemical resistance.

Claims (4)

[Claims] 1. An (A) organic resin, and (B) an average composition formula (1).
: (X) _a (Y ') _b (R ¹ ) _c SiO _{(4-abc) / 2} (1) [wherein, X represents an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group, a haloalkyl group and An organic group having at least one functional group selected from the group consisting of amino groups, Y'is a hydrolyzable group or a mixture of a hydrolyzable group and a silanol group (provided that the proportion of silanol groups in Y'is Is 20 mol% or less), and R ¹
Is a monovalent hydrocarbon group, a is a number from 0.05 to 0.90, and b is
A number between 0.12 and 1.88, and c is a number between 0.10 and 1.00,
Moreover, a + b + c is a number in the range of 2.02 to 2.67. ]
And the amount of silicon atoms bonded to the organic group X having a functional group is 5 to 90 mol% with respect to all silicon atoms in the molecule, and the proportion of T units represented by R ¹ -SiO _3/2. Is 10 to 95 mol% with respect to all siloxane units, and the average degree of polymerization is 3
A coating material composition containing a silicone compound of about 100. 2. The content of the silicone compound (B) is
The composition according to claim 1, which is 0.1 to 50 parts by weight based on 100 parts by weight of the solid component of the composition. 3. The silicone compound has the general formula (2): Si (X) _d (Y) _e (R ¹ ) _f (2) [wherein, X and R ¹ are as described above, and Y is It is a hydrolyzable group, d is an integer of 1 or 2, e is an integer of 2 or 3, f is an integer of 0 or 1, and d + e + f = 4. And a trifunctional hydrolyzable silane represented by the general formula: Si (Y) ₃ (R ¹ ) (3) [wherein Y and R ¹ are as described above]. An alkoxysilane mixture containing
The composition according to claim 1, which is obtained by subjecting to partial cohydrolysis / condensation. 4. The organic resin (A) is an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group,
The composition according to claim 1, which contains a functional group capable of reacting with a haloalkyl group, an amino group and a hydrolyzable silyl group.