JP2000080354A - Rustproof and stain resistant coating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having excellent rustproof and stain resistant effects by blending a curable liquid silicone resin, a silicone resin, a poly-di- organosiloxane, a silane mixture having a hydrolyzable group, a dimethyl- silicone oil and an organic solvent. SOLUTION: This is a liquid composition containing 100 pts.wt. of a curable liquid silicone resin of the formula: RaSiXbO(4-(a+b))/2, 5-20 pts.wt. of a silicone resin comprising 50-99 mol% of R1mSiO(4-m)/2 unit and 1-50 mol% of R23SiO1/2 unit, 5-100 pts.wt. of a poly-di-organosiloxane of formula I, 5-100 pts.wt. of a silane mixture having two hydrolyzable groups of the formula: R42Si(OR5)2, 0.2-5 pts.wt. of a dimethyl-silicone oil of formula II and 800-1,500 pts.wt. of a hydrocarbon solvent and/or a volatile silicone. In the formulas, R, R1, R2 and R4 are each a monovalent hydrocarbon; R3 is a monovalent organic group; R5 is a 1-4C alkyl; X and Y are each hydroxyl or the like; 0.8<=a<2; 1.3<=b<2; 0<=c<=5,000; and 0<m<2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust-proof and stain-resistant protective coating composition applied to a substrate, and more particularly, to a metal material represented by aluminum, alumite, or the like, or a metal material used in contact with the metal material. By applying it to the surface of inorganic materials such as mortar, it forms a transparent film and imparts excellent rust prevention and protection effects.It also has excellent water resistance and can be easily applied at room temperature and high temperature. The present invention relates to a stain-resistant protective coating composition.

[0002]

Technical Background of the Invention and Problems There is a problem that the surface of a metal material typified by aluminum, alumite, etc. is deteriorated by acid rain, salt damage, etc., and the appearance is deteriorated. Further, there is a problem that rust is generated on a wheel surface of an automobile wheel or the like under the influence of wear powder of a brake pad, and the generated rust cannot be easily removed. Moreover,
When inorganic materials such as mortar are installed or painted on metal materials, when rust is generated on the metal materials, the rust penetrates into the inorganic materials and appears as stains on the base material surface, discoloring the appearance Bring. The generation of rust gives an impression that the quality of the molded product or the exterior surface is deteriorated. In order to solve such a problem, a conventionally known method of applying a rust inhibitor (Japanese Patent Laid-Open No. 51-906)
No. 82) and a method of further using an amino-modified siloxane as a rust inhibitor (see Japanese Patent Application Laid-Open No. 6-57458).
Has been proposed. However, generally known rust inhibitors containing wax, vaseline, paraffin, carnauba wax and the like as main components are insufficient in water resistance, and have a problem in rust prevention during flooding or rainfall. In addition, even when amino-modified siloxane is used as a rust preventive agent, it is more likely to cause yellowing on the substrate surface and to prevent rust in an environment where the film strength of the rust preventive agent is insufficient and easily affected by physical effects. Improvement was desired. It is well known to use rust-preventive oil made from mineral oil as a rust-preventing method for metal materials, and rust-preventive oil is used as a temporary rust preventive during the storage, molding process or transportation of metal materials. However, the film easily falls off, and has not been able to provide a stable rust prevention effect for a long time. On the other hand, a method is known in which a coating agent containing a silane compound or polysiloxane as a main component is applied to a porous inorganic material such as concrete to impart water repellency to prevent deterioration (Japanese Patent Application Laid-Open No. Sho 57-79). 1268
No. 78, Japanese Patent Application Laid-Open No. 62-19736, Japanese Patent Application Laid-Open
JP-A-150477), there is no description about the rust preventive effect, and further improvement was required.

[0003]

The object of the present invention is to solve the above-mentioned problems, have an excellent rust-preventing and anti-fouling effect, and apply a natural chemical,
Shields deteriorated parts and abrasions caused by physical factors,
Abrasion resistance, weather resistance, water repellency, and improved aesthetics can be imparted. Furthermore, dirt and rust are less adhered, and even if rust and dirt adhere, they can be easily removed. It is an object of the present invention to provide a film-forming type rust-proof / stain-resistant protective coating composition capable of protecting the composition in a beautiful state.

[0004]

The present inventors have conducted various studies to achieve the above object. As a result, by combining specific siloxane components, a rust-proof and stain-resistant protective coating composition having the above characteristics can be obtained. This led to the completion of the present invention. That is, the present invention provides: (A) a compound represented by the following general formula: R _a SiX _b O _{(4- (a + b)) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, X
Represents a hydroxyl group or a hydrolyzable group, a and
b is a number that has the following relationship: 0.8 ≦ a <2 1.3 ≦ b <2) curable liquid silicone resin 100 parts by weight represented by ^{_{(B) R 1 m SiO (}} 4-m) / 2 units 50 to 99 mol% and R ² ₃ SiO _{1 / 2 to} 1 mol% (wherein R ¹ and R ^{2 each} represent a substituted or unsubstituted monovalent hydrocarbon group, and m is a number of 0 <m <2). 20 parts by weight (C) Polydiorganosiloxane represented by the general formula (I)
5-100 parts by weight

[0005]

Embedded image

(Wherein, R ³ represents a monovalent organic group, Y represents a hydroxyl group or a hydrolyzable group, and c represents 0 ≦ c ≦
It is an integer satisfying 5000. ) (D) formula _{^{R 4 2 Si (OR 5)}} 2 ( wherein, R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ⁵ is from 1 to 4 carbon atoms A silane mixture having two hydrolyzable groups represented by the following formula: 5 to 100 parts by weight (E) a viscosity at 25 ° C represented by the general formula (II) of 50 to 2,000.
00cP dimethyl silicone oil 0.2 to 5 parts by weight

[0007]

Embedded image

(Wherein d is dimethyl silicone oil
(F) It represents any integer having a viscosity at 25 ° C of 50 to 200,000 cP.) (F) It contains 800 to 1500 parts by weight of one kind of hydrocarbon solvent and / or volatile silicone and / or a mixture thereof, and Rust prevention with a viscosity of 1 to 1000 cP
It is a stain-resistant protective coating composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) used in the coating composition of the present invention
The component is a curable liquid silicone resin represented by the following general formula, which stably disperses each component in the coating composition of the present invention, improves the adhesion of the coating film to the substrate, and improves the durability. It is a component for holding. R _a SiX _b O _{(4- (a + b)) / 2} (where R is a substituted or unsubstituted monovalent hydrocarbon group, X
Represents a hydroxyl group or a hydrolyzable group, a and
b is a number that has the following relationship: 0.8 ≦ a <21.3 ≦ b <2) wherein R is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and may be a methyl group, an ethyl group, a propyl group, a butyl group. Group, amyl group, hexyl group, octyl group, decyl group, alkyl group having 1 to 12 carbon atoms such as dodecyl group, alkenyl group such as vinyl group and allyl group, and aryl group such as phenyl group, tolyl group and xylyl group , An aralkyl group such as a β-phenylethyl group and a β-phenylpropyl group, N- (β-aminoethyl) -γ
An aminoalkyl group such as an aminopropyl group, an epoxy group-containing group such as a γ-glycidoxypropyl group, a 3,4-epoxycyclohexyl group, a (meth) acryl group-containing group such as a γ-methacryloxypropyl group, γ- Examples include mercaptoalkyl groups such as mercaptopropyl groups, cyanoalkyl groups such as cyanoethyl groups, chloroalkyl groups such as β-chloroethyl groups and γ-chloroethyl groups, and fluoroalkyl groups such as 3,3,3-trifluoropropyl groups. Is done. Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of easy availability and curing speed. X in the component (A) represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an alkenyloxy group, and a halogen atom. A hydroxyl group and an alkoxy group having 1 to 4 carbon atoms are preferred because a by-product generated during the curing reaction has a low odor and excellent curability and film properties, and a hydroxyl group, a methoxy group or an ethoxy group is particularly preferred. In the component (A), a and b must be numbers having the following relationship. If 0.8 ≦ a <21.3 ≦ b <2a is less than 0.8, the cured film becomes brittle, and if it is 2 or more, a favorable cured film cannot be obtained and the film becomes sticky, which is not preferable. On the other hand, if b is less than 1.3, the curing speed is too slow to be suitable for practical use, and if b is 2 or more, the cured film becomes brittle, which is not suitable for the purpose of the present invention.

The curable liquid silicone resin of the component (A) is
It can be easily obtained by a known method. That is, methyl trialkoxysilane, dimethyldialkoxysilane,
Alkoxysilanes such as tetraalkoxysilane, phenyltrialkoxysilane, diphenyldialkoxysilane, methylphenyldialkoxysilane and the alkyl group of alkylalkoxysilane are converted to ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, Alkyl groups having 1 to 12 carbon atoms such as decyl group and dodecyl group; alkenyl groups such as vinyl group and allyl group; monovalent hydrocarbon groups such as aryl groups such as tolyl group and xylyl group One or a mixture thereof selected from the organosilicon compounds substituted with, can be obtained by hydrolysis or partial hydrolysis in the presence of a catalyst. Examples of the catalyst for synthesizing the resin include organic acids such as acetic anhydride, glacial acetic acid, propionic acid, benzoic acid, formic acid, acetic acid, and oxalic acid; titanates such as tetrabutoxytitanate and tetraisopropoxytitanate; Examples thereof include chlorosilanes such as trichlorosilane and dimethyldichlorosilane; inorganic bases such as aqueous ammonia; and organic bases such as ethylenediamine and triethanolamine. Also, (A)
As a component, one or more curable polyorganosiloxanes obtained as described above and having different properties may be mixed and used.

The component (B) used in the coating composition of the present invention comprises R ¹ _m SiO _{(4-m) / 2} units 50 to 99 mol% and R ² ₃ SiO _1/2 units 1 to 5
0% by mole (wherein R ¹ and R ² represent a substituted or unsubstituted monovalent hydrocarbon group, and m is a number satisfying 0 <m <2). In the coating agent composition, it is a component related to the shielding property, water repellency, weather resistance, and film strength at the time of film formation. Here, as R ¹ and R ² , alkyl groups such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group and xylyl group A cycloalkyl group such as a cyclohexyl group or a cyclooctyl group; or a group in which a hydrogen atom bonded to a carbon atom of such a group is substituted with a halogen atom, a cyano group, an amino group, or the like, for example, a chloromethyl group, 3,3, Examples thereof include a 3-trifluoropropyl group. Of these, a methyl group and an ethyl group are preferable because they are easily available. Also, R ² ₃ SiO
_{The 1/2} unit is required to be 1 to 50 mol%, and particularly preferably 5 to 20 mol%, of the total of R ¹ _m SiO _{(4-m) / 2} units. If the R ² ₃ SiO _1/2 unit is less than 1 mol%, the effects of the present invention cannot be obtained, and if it is more than 50 mol%, it becomes difficult to synthesize a resin. (B) component of the silicone resin, with respect to R ² ₃ SiO _1/2 silanol group-containing organopolysilsesquioxane 100 parts by weight consisting of units, in _{^{(R 2 3 Si) e Z}} ( wherein, e is 1
Or 2; Z represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group when e is 1, and when c is 2, -O-, -N (Y)-,-
Represents S-. Wherein Y is obtained by reacting a hydrogen atom, a monovalent organic silicon compound 5-100 parts by weight represented by the hydrocarbon represents a group or R ² ₃ Si-) of 1 to 4 carbon atoms.

Here, the hydrolyzable group of Z includes alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group; alkenyloxy groups such as propenoxy group; acetoxy group and benzoxy group. Examples include an acyloxy group; an organooxime group such as an acetone oxime group and a butanone oxime group; and an organoamide group such as a dimethylamino group, a diethylamino group, and a cyclohexylamino group. Of these, an alkoxy group is preferable because of easy availability of raw materials, and a methoxy group and an ethoxy group are particularly preferable. Polysilsesquioxane represented by R ¹ _m SiO _{(4-m) / 2} can be synthesized by a known method, for example, by subjecting organotrichlorosilane or organotrialkoxysilane to hydrolysis / condensation reaction with excess water. can get. (R ² ₃ Si) organic silicon compound represented by _e Z is for silylation of _{^{R 1 m SiO (4-m}} ) / 2 component silanol groups. Components represented by (R ² ₃ Si) _e Z include hydrogen silanes such as trimethylsilane and triethylsilane; trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, CF ₃ (CH ₂ )
₂ Si (CH ₃₎ chlorosilane such as ₂ Cl; trimethylsilanolate; trimethyl silane, alkoxysilane such as trimethyl _{silane; (CH 3) 3 SiNHCH 3} , (CH 3) 3
_{SiNHC 2 H 5, (CH 3} ) 3 SiN (CH 3) 2, (CH 3) 3 SiN (C 2 H 5) acyloxy and the like; hexamethyldisilazane, 1,3 - divinyl tetramethyl disilazane and [(CH ₃ ) ₃ S
_i] silazane such as ₃ N is illustrated. Among these, silazanes and chlorosilanes are preferable because the reaction can be easily controlled and unreacted substances can be easily removed. R ¹ _m SiO
Reaction with _{(4-m) / 2} component and R ² ₃ SiO _1/2 component can be carried out by known methods for silylating silanols.
The amount of the silicone resin (B) to be added is 5 to 20 parts by weight, preferably 7 to 12 parts by weight, per 100 parts by weight of the component (A). If the amount is less than 5 parts by weight, the strength of the film is inferior. If the amount is more than 20 parts by weight, the toughness of the film is reduced, which causes cracks and insufficient shielding properties, which is not preferable.

The polydiorganosiloxane of the component (C) used in the present invention has a hydroxyl group or a hydrolyzable group and is represented by the following general formula (I).

[0014]

Embedded image

Here, R ³ represents a monovalent organic group, such as methyl, ethyl, propyl, butyl, hexyl, octyl,
Alkyl groups such as decyl and dodecyl, cyclohexyl,
Examples thereof include a cycloalkyl group such as cyclooctyl, an aryl group such as phenyl and tolyl, and an alkenyl group such as vinyl, allyl and propenyl. Among these,
An alkyl group and an aryl group are preferable, and a methyl group and a phenyl group are particularly preferable because raw materials are easily available. Y
Represents a hydroxyl group or a hydrolyzable group. As the hydrolyzable group, those similar to X shown in the component (A) are exemplified, and the hydroxyl group is preferable because the curability of the composition is good, and the gloss of the film becomes good. , A methoxy group or an ethoxy group is preferred. Also, c
Is an integer satisfying 0 ≦ c ≦ 5000, and is preferably an integer satisfying 10 ≦ c ≦ 200, particularly preferably satisfying 20 ≦ c ≦ 100, since good antifouling property is obtained. If c exceeds 5,000, the film becomes sticky, which is not preferable. The compounding amount of the polydiorganosiloxane of the component (C) is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, particularly preferably 100 parts by weight of the curable liquid silicone resin of the component (A).
15 to 30 parts by weight. If the amount is less than 5 parts by weight, good antifouling properties cannot be obtained, and the protective film becomes brittle.
If the amount is more than the weight part, the film becomes sticky and the antifouling property is reduced.

The component (D) used in the coating composition of the present invention is a silane mixture having two hydrolyzable groups represented by the following general formula and is used for imparting strength and adhesion to the film. Is an important ingredient. R ⁴ in ₂ Si (OR ⁵⁾ ₂ Formula, R ⁴ represents a hydrocarbon group or a substituted or unsubstituted monovalent 1-8 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, amyl group , Hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclohexyl group, cycloalkyl group such as cyclooctyl group, phenyl group, aryl group such as tolyl group, vinyl group, allyl group, propenyl group and the like An alkenyl group and the like can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of easy availability and easy balance of reactivity with each component.
R ⁵ is an alkyl group having 1 to 4 carbon atoms, and this component is a mixture of silanes having two hydrolyzable groups. Examples of these silanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like. Among these, dimethyldiethoxysilane, Diphenyldiethoxysilane is particularly preferred. The mixture of the silane as the component (D) is blended in an amount of 5 to 100 parts by weight, preferably 20 to 50 parts by weight, per 100 parts by weight of the curable liquid silicone resin as the component (A). When the amount is less than 5 parts by weight, the adhesiveness is reduced, and when the amount is more than 100 parts by weight, the reactivity at the time of forming the film is deteriorated, so that the citron skin phenomenon may occur and the film may become cloudy, which is not preferable.

The component (E) used in the coating composition of the present invention is dimethyl silicone oil represented by the following general formula (II) and having a viscosity at 25 ° C. of 50 to 200,000 cP. It is a component for improving the properties. If the viscosity is less than 50 cP, interference fringes will be generated when the film is formed, and components will precipitate over time, which is not preferable.If the viscosity exceeds 200,000 cP, the coating will not be smoothed when applying the coating agent, and workability will not be improved. Malfunctions.

[0018]

Embedded image

Wherein d is the dimethyl silicone oil
(Indicates an arbitrary integer whose viscosity at 25 ° C. is 50 to 200,000 cP.)
The amount is preferably from 0.2 to 5 parts by weight, particularly preferably from 0.8 to 2 parts by weight, per 100 parts by weight of the component (A). If the amount is less than 0.2 parts by weight, the slipperiness decreases and the workability deteriorates. Also,
If the amount exceeds 5 parts by weight, interference fringes occur when a film is formed, which is not preferable.

(F)
The component is a hydrocarbon solvent, a volatile silicone or a mixture thereof, and the volatile silicone is preferably represented by the following general formula (III) or (IV).

[0021]

Embedded image

In the volatile polydimethylsiloxane as described above, p is 0 to 0 whose terminal is blocked with a trimethylsilyl group.
9 is a cyclic polydimethylsiloxane or q is a cyclic polydimethylsiloxane having 3 to 8;
Either a linear or cyclic polydimethylsiloxane or a mixture thereof is used in consideration of the solubility of the component and the catalyst component. Among them, it is preferable to use a linear polydimethylsiloxane in which p is 2 to 7 or a cyclic polydimethylsiloxane in which q is 4 or 5. Here, "volatile" means having a vapor pressure that can be measured at room temperature, and the component (F) preferably has a boiling point of 99 to 260 ° C. Component (F) is used in an amount of 800 to 1500 parts by weight, preferably 1000 to 1500 parts by weight, per 100 parts by weight of component (A). If the amount is less than 800 parts by weight, the smoothness of the film surface becomes insufficient, and if it is more than 1500 parts by weight, it becomes difficult to form a film having properties such as sufficient gloss and shielding properties.

If necessary, various curing catalyst components may be added to the coating composition of the present invention. As the catalyst components, those known as polyorganosiloxane curing catalysts can be used. is there. Specific examples include tin dioctylate, dibutyltin dilaurate, dibutyltin dioctoate, organic tin compounds such as dioctyltin dilaurate; and organosilicone quaternary ammonium salts. Among these, curability and liquid stability are exemplified. From the viewpoint, dibutyltin dilaurate and dioctyltin dilaurate are particularly preferred. The amount of the catalyst component is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the component (A).
If the amount is less than 0.001 part by weight, the curing speed of the film is slow and may not be suitable for practical use, and if it exceeds 1 part by weight, there is no particular effect on the film formation, but rather the stability of the coating composition is deteriorated. There is.

The viscosity of the composition at 25 ° C. is 1 to 1000 cP.
And particularly preferably 5 to 100 cP. If the viscosity is less than 1 cP, the coatability on the substrate is poor and liquid dripping occurs, which is not preferable. If it exceeds 1000 cP, uneven coating is generated, which is not preferable.

The coating composition of the present invention may further contain, if necessary, an ultraviolet absorber, an antibacterial agent, a leveling agent and an antioxidant.

The method for applying the rust-proof and stain-resistant protective coating composition of the present invention to the surface of a substrate includes brush coating,
Methods such as spray coating, roller coating, and float coating can be used.

[0027]

According to the present invention, the surface of a metal material typified by aluminum, alumite, etc. has an excellent rust-preventive effect and water resistance against inorganic materials such as stone and mortar used in contact with the metal material. It is possible to impart properties and a protective effect, and it is possible to prevent a change in the appearance of the substrate due to the generation of rust, a decrease in substrate strength, and a decrease in commercial value. Moreover, since the coating composition of the present invention can be easily applied even at room temperature and high temperature, it can be applied to a substrate having no heat resistance and can be applied at a work site where heat is not applied. The industrial value is extremely high.

[0028]

The present invention will be described below with reference to examples. Unless otherwise specified, parts in Examples are parts by weight,
% Indicates% by weight, and viscosity indicates a value at 25 ° C. Synthesis Example 1 Methyltrimethoxysilane 1360 was added to a flask equipped with a stirrer, heating jacket, reflux condenser and dropping funnel.
g (10 mol), 200 g of methanol and methyltrichlorosilane were charged so that the hydrochloric acid content became 50 ppm, and 171 g (0.95 mol) of water was gradually dropped with a dropping funnel while stirring. The mixture was kept at a reflux temperature (about 68 to 72 ° C.) for 4 hours to carry out hydrolysis and condensation reactions. After distilling off volatiles under the conditions of normal pressure and 100 ° C, the pressure was gradually reduced to 40 mmHg, 1
Volatile components are further distilled off under reduced pressure at 50 ° C to give a viscosity of 20 cP
630 g (A-1) of silicone was obtained.

Synthesis Example 2 Methyltriethoxysilane was placed in a flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel.
2g (0.9mol), dimethyldimethoxysilane 12g (0.1mo
l), 200 g of methanol and 5 g of acetic acid were charged, and 171 g (0.95 mol) of water was gradually added dropwise using a dropping funnel while stirring. Hold at reflux temperature (about 68-72 ° C) for 4 hours,
Hydrolysis and condensation reactions were performed. After removing volatile components under normal pressure and 100 ° C, gradually reduce the pressure to 40 mmHg,
The volatiles were further distilled off under reduced pressure at 150 ° C to give a viscosity of 20
630 g (A-2) of silicone of cP was obtained.

Synthesis Example 3 A flask equipped with a stirrer, a heating jacket, a reflux condenser and a dropping funnel was charged with 220 g (1 mol) of methyltriisopropoxysilane and 150 g of toluene, and 108 g of a 1% aqueous hydrochloric acid solution was taken for 20 minutes. , And the methyltriisopropoxysilane was hydrolyzed. After stirring for 40 minutes, the stirring was stopped. After liquid separation, the organic layer was washed with water to remove hydrochloric acid, and toluene was further removed under reduced pressure to give a molecular weight of 12000, a softening point of 115 ° C.,
Methyl polysilsesquioxane P-1 having a silanol group content of 1.2% was prepared. Next, 100 g of methylpolysilsesquioxane P-1, 200 g of toluene, 10 g of trimethylchlorosilane and 50 g of hexamethyldisilazane were charged into a flask, and heated and stirred. After heating and stirring at the reflux temperature of toluene for 2 hours, ammonia, hydrochloric acid or salts thereof produced by the reaction were removed by washing with water, and further, toluene was distilled off under reduced pressure to obtain a trimethylsilylated silicone resin having a softening point of 80 ° C (B). -1) was obtained.
Incidentally, the silanol group content of B-1 was 0.3% by weight. Here, the softening point was measured according to the ring and ball type softening point measurement method of JIS C 2104. The molecular weight is determined by GPC (HLC-
The molecular weight (in terms of polystyrene) was measured using 802 U (manufactured by Tosoh Corporation). In the measurement of the molecular weight, the molecular weights of the methyl polysilsesquioxane P-1 and the trimethylsilylated silicone resin (B-1) showed almost the same value. The silanol group content is calculated by the following formula by measuring the amount of water generated when the silicone resin is heated at 300 ° C. for 2 hours using a coulometric titration type moisture meter CA-06 (manufactured by Mitsubishi Kasei Corporation). did. Silanol group content (%) = ｛(moisture generated × 34/1
8) {Silicone resin weight} × 100 In the examples, the following polydiorganosiloxane was used as the component (C).

[0031]

Embedded image

In the examples, the following silane was used as the component (D). D-1 Me ₂ Si (OEt) ₂ D-2 Ph ₂ Si (OEt) _{2 In the} examples, the following dimethyl silicone oil as the component (E) was used. E-1 Dimethyl silicone oil having a viscosity of 100 cP at 25 ° C. E-2 Dimethyl silicone oil having a viscosity of 100,000 cP at 25 ° C. Reference Example 1 50 parts of carnauba wax, 25 parts of liquid paraffin, 9 parts of polyoxyethylene (10) stearate in a container Then, 9 parts of polyoxyethylene (40) stearate and 12 parts of polyoxyethylene (10) octyl phenyl ether were taken, dissolved gradually by heating, and stirred while heating at 90 ° C.
The mixture was stirred for 1 hour while gradually adding 380 parts of warm water heated to ℃, and then cooled and stirred, and cooled to 25 ° C to obtain a comparative emulsion composition (X-1).

Reference Example 2 In the same manner as in Reference Example 1, a comparative aqueous dispersion (X-2) containing 33% of liquid paraffin and 12% of propylene glycol monostearate was obtained.

Reference Example 3 In the same manner as in Reference Example 1, a comparative aqueous dispersion (X-3) containing 20% of carnapalow and 5% of glycerin monolaurate was obtained.

Examples 1 to 8 and Comparative Examples 1 to 9 Coating compositions were prepared according to the formulations shown in Tables 1 and 2, and the rust-proofing properties, shielding properties, weather resistance, water resistance and stain resistance were determined as follows. The method was evaluated. [Preparation of Specimen] Specimen 1 An aluminum panel having a size of 15 × 15 cm was rubbed lightly with sandpaper to scratch. The coating composition was applied thereto using a sponge and air-dried for one day to form a film, which was used as a test piece. -Specimen 2 An aluminum panel having a size of 15 x 15 cm was lightly rubbed with sandpaper to scratch. The coating agent composition was applied thereto using a spray, wiped off with a dry waste, and dried at 60 ° C. for 30 minutes to form a film, which was used as a test piece. [Rust prevention] Put a test piece in a glass petri dish and add 5% NaCl aqueous solution
After 50 g was sprayed and sealed, and allowed to stand at 35 ° C. for 2 days, the occurrence of rust was visually observed and evaluated according to the following four grades. ◎: No rust occurred. : Discolored on the surface (less than 5% of the substrate surface). Δ: White or brown discoloration on the surface (less than 50% of the substrate surface). ×: Rust is formed on the entire surface. [Shielding Property] The appearance of the test piece was visually observed and evaluated according to the following four grades. ◎: The abrasion part is well shielded and the transparency of the film is good. ：: A part of the scratches is exposed, but the transparency of the film is good. Δ: A part of the abrasion was exposed, and the transparency of the film was slightly poor. ×: Insufficient shielding effect and no transparency of the film. [Weather resistance] 500 using sunshine weatherometer
After exposure for a period of time, the appearance was visually observed and evaluated according to the following four grades. ◎: The abrasion part is well shielded and the transparency of the film is good. ：: A part of the scratches is exposed, but the transparency of the film is good. Δ: A part of the abrasion was exposed, and the transparency of the film was slightly poor. ×: Insufficient shielding effect and no transparency of the film. [Water resistance] After running tap water on the test piece for 24 hours, the appearance was visually observed and evaluated according to the following four grades. ◎: The abrasion part is well shielded and the transparency of the film is good. ：: A part of the scratches is exposed, but the transparency of the film is good. Δ: A part of the abrasion was exposed, and the transparency of the film was slightly poor. ×: Insufficient shielding effect and no transparency of the film. [Anti-fouling property] Sesame oil was applied as a contaminant to a test piece with a brush, and easiness of wiping off with a cloth after leaving for 1 hour was evaluated on the following four scales. ◎: No contaminant material left, good wiping. ：: No contaminated material remains, but some stains remain. Δ: The contaminant on the surface can be removed, but contaminants remain in the details of the scratch. ×: Contaminants remain throughout.

[0036]

[Table 1]

[0037]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4H020 BA32 BA33 4J038 DL051 DL052 DL071 DL072 DL081 DL082 DL091 GA03 JA01 JC32 KA03 KA06 MA15 NA01 NA03 NA05 NA07 NA11 PB07 PC02 PC04 4K062 AA01 BC16 BC19 BC26 CA04 GA10 FA06 GA06

Claims (1)

[Claims] (A) a compound represented by the general formula: R _a SiX _b O _{(4- (a + b)) / 2} (where R is a substituted or unsubstituted monovalent hydrocarbon group, X
Represents a hydroxyl group or a hydrolyzable group, a and
b is a number that has the following relationship: 0.8 ≦ a <2 1.3 ≦ b <2) curable liquid silicone resin 100 parts by weight represented by ^{_{(B) R 1 m SiO (}} 4-m) / 2 units 50 to 99 mol% and R ² ₃ SiO _{1 / 2 to} 1 mol% (wherein R ¹ and R ^{2 each} represent a substituted or unsubstituted monovalent hydrocarbon group, and m is a number of 0 <m <2). 20 parts by weight (C) Polydiorganosiloxane represented by the general formula (I)
5-100 parts by weight (Wherein, R ³ represents a monovalent organic group, Y represents a hydroxyl group or a hydrolyzable group, c is an integer satisfying 0 ≦ c ≦ 5000.) ( D) formula R ⁴ ₂ Si (OR ⁵ ) ₂ (wherein, R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms). 5 to 100 parts by weight of a silane mixture having two hydrolyzable groups having a viscosity of 50 to 2000 at 25 ° C. represented by the general formula (II)
00cP dimethyl silicone oil 0.2 to 5 parts by weight (In the formula, d represents an arbitrary integer such that the viscosity of dimethyl silicone oil at 25 ° C. is 50 to 200,000 cP.) (F) One kind of hydrocarbon solvent and / or volatile silicone and / or a mixture thereof 800 to It contains 1500 parts by weight and has a viscosity of 1 to 1000 cP at 25 ° C.
A stain-resistant protective coating composition.