JPH0368676A - Liquid stainproofing composition for coated surface - Google Patents

Abstract

PURPOSE:To enable a colorless, transparent, durable coating film with excellent stainproofness to be formed on an automobile coated surface by compounding a specific moisture-curable organopolysiloxane, an organotin compd. and/or a metal chelate, and a volatile dimethylpolysiloxane. CONSTITUTION:The title composition comprises 0.5-10.0 pts.wt. moisture-curable organopolysiloxane of the formula wherein R<1> and R<2> are each an optionally subted. monovalent hydrocarbon group; a is a mean value, being 0.40-1.70; b is a value at which the content of OR<2> group attached to Si is 5wt.% or higher; and q is 3 or higher; 0.005-1.0 pt.wt. controlling agent of stainproof coating film formation comprising an organotin compd. (dibutyltin diacetate) and/or a metal chelate [e.g. aluminum tris(acetylacetone)]; and 89.0-99.0 pts.wt. carrier comprising a volatile dimethylpolysiloxane boiling at 100-250 deg.C, the total compsn. being 100 pts.wt.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a liquid composition for preventing stains on painted surfaces, and particularly for forming a colorless, transparent, durable film with excellent stain resistance on painted surfaces of automobiles. be.

``Prior art'' The painted surface of a car is constantly exposed to rain, soot, dust, etc., so dirt easily invades the strongly adhered B1 painted surface and is difficult to remove by washing with water. The aesthetic appearance is seriously impaired.

Therefore, as a method of imparting antifouling properties, various polishing agents such as wax, silicone oil, and solvent are mainly used, and other methods include metal alkoxides such as S i , T and Zr (Japanese Patent Application Laid-open No. 1-113475). , moisture-curable organic polymer (JP-A No. 63-213575), silicone face, etc. Alternatively, it has been proposed to dilute it with a solvent and apply it to form a film.

``Problem to be solved by the invention'' However, in the method according to ■, since the coating component consists of Fuchs, silicone oil, etc., the coating becomes sticky and easily absorbs dirt, making it less durable on the adhesion surface of the casing. It's dim. Furthermore, as the surface temperature of the painted surface increases, the film itself tends to soften, trapping and retaining dust and oil-based dirt, which can seriously impair the appearance of the car.

Therefore, in order to improve the stain resistance and durability, method (2) above has been proposed, in which metal alkoxide, silicone face, and moisture-curing organic polymer are diluted with 11 or a solvent. There are many difficulties in forming this film, and a satisfactory film has not been obtained.

In other words, with the method of applying a cured film-forming component in one groove, it is difficult to apply it thinly and uniformly, and the thicker the film, the longer the curing time. The appearance of the painted surface is spoiled due to optical phenomena that occur. On the other hand, if the coating is softened, dust and dirt will be trapped.
b1 becomes easily damaged and the original stain resistance and durability cannot be achieved.

In addition, the method of diluting the moisture-curing film components with a solvent (hereinafter referred to as solvent dilution type) does not have the effect of cleaning the painted surface, so it must be applied to a pre-cleaned painted surface, or the film-forming components must be diluted with a solvent. Ingredients with a cleaner effect must be added and applied. The painted surface is dirty! When applied to the casing, the appearance is poor and the film has poor adhesion.

Even if a cleaner component is added and applied, the cleaner component and dirt remain in the film after application, and the desired antifouling film cannot be obtained at all.

In general, therefore, the painted surface is washed with water or detergent, and any remaining stains are removed with automobile cleaner wax, and then a solvent diluted type is applied to the painted surface. However, in this method, a small amount of silicone oil and solvent contained in the cleaner wax always remain, causing phenomena such as smearing and sagging, and the film-forming components are not evenly fixed on the painted surface, making it difficult to obtain a uniform film. Even with the method of applying the cured film-forming component 11, if silicone oil remains on the painted surface, the original structure of the film will be damaged and the antifouling performance will not be exhibited.

"Means for Solving the Problem" As a result of research in order to solve the above-mentioned drawbacks, the inventors found that by adding an antifouling film-forming regulator and a specific volatile dimethylpolysiloxane to moisture-curable organopolysiloxane. The inventors have discovered that a thin, uniform film can be formed on a painted surface treated with silicone oil or the like, exhibiting an excellent antifouling effect, and have arrived at the present invention.

That is, the present invention provides (A)-Momona [I] (wherein R and R are substituted or unsubstituted monovalent hydrocarbons, a
is a value whose average value is within the range of 0.40 to 1.70, and b is the O bonded to the silicon atom (general formula CI)
(B) Formation of antifouling film ~1.0 parts by weight of an organotin compound, a metal chelate, or a mixture thereof as a regulator; and (C) 89.0 to 99.0 parts by weight of a volatile dimethylpolysiloxane with a boiling point of 100 to 250°C as a carrier;
This is a liquid composition for preventing stains on painted surfaces, in which the above components α) to (0) are added in a total amount of 100 parts by weight.

In the present invention, in addition to the above components (A) to (C), , C is a value whose average value is within the range of 0.80 to 1.80, d
is a value at which the ratio of hydroxyl groups bonded to the silicon atoms in the general formula [■] is 0.011 parts by weight, and p is an integer of 3 or more. 0.1 to 5.0 parts by weight of resin and (2)-Momona (III) In the formula C, R represents a substituted or unsubstituted monovalent hydrocarbon group, R5 represents a substituted or unsubstituted alkyl group, and 6 represents a substituted or unsubstituted alkyl group. Alkoxysilane 0.1 to 5, each represented by an integer of 0 to 2)
．． 0 parts by weight, 0.7≦[α)+)+(E)] component≦
This is a liquid composition for preventing stains on painted surfaces, in which 15.0 parts by weight and a total of 100 parts by weight of components (A) to (2) are added.

In the composition of the present invention, the curable organopolysiloxane as component (1) has the above general formula (m), where R and R are, for example, a methyl group, an ethyl group, a globyl group, 3,3
．． 3-) Examples include substituted or unsubstituted monovalent hydrocarbon groups such as lifluoropropyl, butyl, hexyl, and phenyl groups, especially when R1 is a methyl group and R is a methyl group or an ethyl group. is preferable from an industrial point of view.

It is preferable that the ratio of OR groups in the housing is 5 weight φ or more, and if it is smaller than that, a solvent-resistant product cannot be obtained.

The content of component (4) in the composition of the present invention is from 0.5 to
It is 10.0 parts by weight. If it is less than 0.5 parts by weight, no lasting antifouling effect can be obtained, and if it exceeds 10.0 parts by weight, the coating film becomes thick, has poor workability, and has poor curability.

In the composition of the present invention, the antifouling film formation regulator (B) includes an organic tin compound, a metal chelate, or a mixture thereof, which adjusts the moisture curing speed of the component (A). To enable general consumers to easily work in an environment similar to that in which an automobile polish is used. These include, for example, organotin compounds such as diptyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, aluminum tris (acetylacetone), aluminum tris (acetoacetate ethyl), aluminum diisopropoxy (acetoacetate ethyl), zirconium (acetylacetone). , zirconium tris (acetylacetone), titanium tetrakis (ethylene glycol monomethyl ether), titanium tetrakis (ethylene glycol monoethyl ether), titanium tetrakis (ethylene glycol monomethyl ether), zirconium tetrakis (ethylene glycol monomethyl ether), zirconium tetrakis (ethylene Examples include metal chelates such as glycol monoethyl ether) and zirconium tetrakis (ethylene glycol monobutyl ether).

These can be used alone or in combination.

The content of component (B) in the composition of the present invention is 0.00
The amount is 5 to 1.0 parts by weight, preferably 0.01 to 0.5 parts by weight. If the amount is less than 1.0 parts by weight, the film formation rate will be too slow, and if it exceeds 1.0 parts by weight, the rate will be too fast and the work will be difficult.

In the composition of the present invention, the carrier which is component (C) is a volatile dimethylpolysiloxane having a boiling point of 100 to 250°C, for example, a linear dimethylpolysiloxane having a boiling point of 100 to 250°C with a viscosity, cts to Examples include carriers having a diameter of about 3.0 cm and tri- to hexamer cyclic dimethylpolysiloxanes having a boiling point of 100 to 250''C. These carriers can be used alone or in combination.

The content of component (C) in the composition of the present invention is 89.0
~99.0 parts by weight. If it is less than 8,960 parts by weight, the film formation rate will be too fast, the film will be thick, and workability will be poor;
If it exceeds 9.0 parts by weight, the formation of a film will be insufficient and the antifouling effect will not last long.

In the present invention, in addition to the above components (A) to (c), a hydroxyl group-containing organopolysiloxane resin (represented by general formula (II)) and an alkoxy moiety (excitation component) represented by general formula (II) are added. Silanes can be added to form liquid compositions that prevent stains on painted surfaces.

The hydroxyl group-containing organopolysiloxane resin which is component (D) is based on the above general formula [■], and R3 is, for example, methyl, ethyl, propyl, t-butyl, 2-ethylhexyl, dodecyl, 1-inbutyl-3,5 , -alkyl groups such as dimethylhexyl and octadecyl, vinyl,
Alkenyl groups such as allyl and decenyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, cycloalkenyl groups such as cyclopentenyl, cyclohexenyl and cyclo-2,4-hexagenyl, aralkyl groups such as benzyl, phenylethyl and xylyl, phenyl and tolyl. , dimethylphenyl, naphthyl, etc., 3
,3.3-)lifluoropropyl,2,2゜2-)
! jFluorotolyl, α, β, β-trifluoro α-
Examples include those representing a substituted or unsubstituted monovalent hydrocarbon group such as a halogenated hydrocarbon group such as chlorocyclobutyl.

■) The content of the component in the composition of the present invention is 0.1 to 5.
．． It is 0 parts by weight. If it is less than 0.1 parts by weight, it will not be possible to impart desirable water repellency to the surface of the coating, and if it exceeds 5.0 parts by weight, curing properties will be poor and workability will be poor.

Examples of the alkoxysilane which is the component ω) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltri(methoxyethoxy)silane, dimethyldimethoxysilane, diethyljethoxysilane, and ethylpropyldimethoxy. Silane, propylmethyldimethoxysilane, dimethyldi(methoxyethoxy)silane, vinyltrimethoxysilane, 3,3.3-)lifluoropropyltrimethoxysilane, 3,3.3-)lifluoropropylmethyldimethoxysilane, methyl Examples include orthosilicate, methyl orthosilicate, hexyl orthosilicate, and the like. These alkoxysilanes impart storage stability to the compositions of this invention.

The amount of component (E) added to the composition of the present invention is from 0.1 to
It is 5.0 parts by weight. If it is less than 0.1 parts by weight, the storage stability will be poor, and if it exceeds 5.0 parts by weight, the curability of the coating will be poor.

19 When the composition of the present invention consists of components (A) to (E), the amount of component C(A) 10) + (E)) added is 0.
．． 7 to 15.0 parts by weight is preferred. If it is less than 0.7 parts by weight, the durability of the antifouling effect will be poor, and if it exceeds 15.0 parts by weight, curing properties and workability will be poor.

The composition of the present invention may optionally contain perfluoroalkylsilane to enhance water and oil repellency and improve antifouling effect, and T-aminopropyltrimethoxysilane as an adhesion improver to the painted surface. , γ-aminopropyltriethoxysilane, γ-(aminoethyl)-aminopropyltrimethoxysilane, methyl-γ-aminopropyldimethoxysilane, methyl-γ-(aminoethyl)-aminopropyldimethoxysilane, γ-dimethylal Aminoalkylalkoxysilane such as minnowpropyltrimethoxysilane and dimethylpolysiloxane having a viscosity of 3.0 to 500 cs can be added to provide ease of wiping the painted surface.

Furthermore, ultraviolet absorbers, antioxidants, colorants, fragrances, etc. can be optionally added.

"Function" The antifouling liquid composition of the present invention has the following features.

(1) Can be applied uniformly without being affected by trace amounts of protective components such as automotive cleaner wax remaining on the painted surface of the vehicle.

(2) A film can be easily formed under the same environment and using the same working time and method as automobile polishes conventionally used by general consumers.

(3) The formed film has a uniform and dense structure that adheres to the base, keeping out external contaminants (soot, rain, dust, oily and water-based stains), and is a transparent hardened thin film with excellent weather resistance. It is.

(4) Excellent storage stability.

(5) Does not damage paint films like those used in automotive polishes.

(6)j! & It is possible to form a hardened film on the surface that maintains stain resistance for a long period of time.

"Examples, Comparative Examples" The present invention will be explained below with reference to Examples, where "parts" in each example indicate parts by weight, and "parts" indicate parts by weight.

Production of moisture-curable organopolysiloxane A A mixture consisting of 108.8 parts of methyltrimethoxysilane, 18.0 parts of dimethyldimethoxysilane, 2.2 parts of diphenyldimethoxysilane and 12.0 parts of water was hydrolyzed, and then The produced methanol was distilled off under reduced pressure to obtain organopolysiloxane A, component (A).

Production of hydroxyl group-containing organopolysiloxane B Dimethyldichlorota2F20 methylchlorosilane 80 mol st By cohydrolyzing in the presence of toluene, the hydroxyl group-containing component (■) with a silicon-bonded hydroxyl group content of 0.9φ A 50% toluene solution of organopolysiloxane B was obtained.

Examples 1 to 5 and Comparative Example 1 Moisture-curable organopolycloxane A, component (A), and hydroxyl-containing organopolysiloxane B, component (2), obtained as described above, were blended together with other components and uniformly heated at room temperature. 1 to obtain the antifouling liquid composition of the present invention and the composition of Comparative Example 1 shown in Table 1.

Margin below Each method in Table 1 means the following:

(Note 1) Manufactured by Nihon Kagaku Sangyo Co., Ltd.: Zirconium acetylacetonate (Note 2) Manufactured by Toray Silicone Co., Ltd.: Octamethylcyclotetrasiloxane (Note 3) Manufactured by Toray Silicone Co., Ltd. #! : Volatile linear dimethylpolysiloxane (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Perfluoroalkylsilane (Note 5) Manufactured by Toray Silicone Co., Ltd.: γ-(2-aminoethyl)aminopropyltrimethoxysilane (Note 6) Toray Silicone Two-linear dimethylpolysiloxane (Note 7) manufactured by Mobil Oil Company: Aliphatic hydrocarbon solvent (boiling point 155-197°C) Test example 1 White painted steel plate for automobile exterior panels (using melamine alkyd type baking paint) ), each blended composition of Examples 1 to 5 and Comparative Example 1 was applied. In the case of each blended composition, the blended liquid was soaked onto a cotton towel and then applied, and after the surface had dried to a white color, it was wiped off. Further, as Comparative Example 2, a commercially available solid polishing wax for automobiles was used, and after applying it to a sponge according to the instructions in the instruction manual, it was applied thinly, and after the surface had dried to a white color, it was wiped off.

The test board coated with each compounded composition was left outdoors exposed to direct sunlight, wind and rain, soot, dust, etc., and after 2 weeks, 1 month, 2 months, and 3 months, it was washed with water with a sponge and the moisture was wiped off with a rag. After cleaning, the stain resistance of the surface coating state,
Water repellency and whiteness were evaluated by the following methods.

Test method for anti-fouling properties of coated surfaces The whiteness of the untreated test plate was visually observed as the standard for evaluation.

○ mark: The visual whiteness is almost the same as the standard test plate.

Δ mark: Slight staining occurred on the whole compared to the standard test plate.

× mark: Partially severely soiled.

XX mark: Severely soiled throughout.

Water repellency test method: The test plate was tilted at 30 degrees, and a constant amount of water was poured onto the test plate for 1 minute.After the water flow was stopped, the time at which there was no water on the test plate was measured. In this case, a test was conducted immediately after applying solid wax, which has excellent water repellency as an automobile polishing wax, to a test plate, and the time at which the water was removed was used as a standard for evaluation.

○: Same or shorter than standard time.

Δ mark: Slightly inferior to standard time.

×: Significantly inferior to standard time.

Whiteness test method For the above-mentioned untested coated plate, measure the whiteness at three predetermined points with a colorimeter (manufactured by Tokyo Denki Co., Ltd., trade name TC-1 type), with the average of b1 as 100, and then measure the whiteness of the treated test plate over time. The deterioration rate (%) of whiteness was investigated.

The above results are shown in Table 2.

Margin Test Example 2 The stain prevention properties and water repellency of the paint were evaluated using a car that runs between Kansai and Yen every day. The surface treatment of the painted surface is Test Example 1
I did the same thing.

Test method for preventing stains on painted surfaces: The entire car was washed, and a commercially available cleaner wax was used to thoroughly and evenly remove stains from the entire surface, restoring the original color and shine of the car's paint. This state was used as a standard and evaluated by visual observation.

○ mark: The appearance is almost the same as the standard state.

Δ mark: The whole has become slightly dirty.

× mark: Partially severely soiled.

XX mark: Severely soiled throughout.

This evaluation was performed on each part of the top plate and hood of the car.

Carbohydrate Test Method Water was sprayed onto the painted surface of a car in the form of a shower, and the condition of the water droplets remaining on the painted surface was visually observed.Evaluation was performed as follows.

○ mark: The water droplets are spherical or slightly flattened to the same extent as the water droplets of commercially available solid wax immediately after treatment.

Δ mark: The surface is partially wet.

×: The entire surface is wet.

This evaluation was performed on each part of the top plate and hood of the car.

The above results are shown in Table 3.

Table 3 "Effects of the Invention" As is clear from the results in Tables 2 and 3, when the antifouling liquid composition of the present invention is applied to a painted surface, it forms an excellent antifouling film on the painted surface. It is clear that the protective effect of the paint film is maintained over a long period of time.

Claims (2)

[Claims] (1) (A) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^1 and R^2 are substituted or unsubstituted monovalent hydrocarbon groups, and a is the The average value is within the range of 0.40 to 1.70, b is the value such that the ratio of OR^2 groups bonded to silicon atoms in general formula [I] is 5% by weight or more, and q is 0.5 to 10.0 parts by weight of a moisture-curable organopolysiloxane (each representing an integer of 3 or more); (B) 0.005 parts of an organotin compound, metal chelate, or a mixture thereof as a stain-preventing film formation regulator; ~1.0 parts by weight and (C) 89.0 to 99.0 parts by weight of volatile dimethylpolysiloxane with a boiling point of 100 to 250°C as a carrier,
A liquid composition for preventing stains on painted surfaces, in which the above components (A) to (C) are added in a total amount of 100 parts by weight. (2) (A) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^1 and R^2 are substituted or unsubstituted monovalent hydrocarbon groups, and a is the The average value is within the range of 0.40 to 1.70, b is the value such that the ratio of OR^2 groups bonded to silicon atoms in general formula [I] is 5% by weight or more, and q is 0.5 to 10.0 parts by weight of a moisture-curable organopolysiloxane (each representing an integer of 3 or more); (B) 0.005 parts of an organotin compound, metal chelate, or a mixture thereof as a stain-preventing film formation regulator; ~1.0 parts by weight, (C) 84.0 to 99.0 parts by weight of volatile dimethylpolysiloxane with a boiling point of 100 to 250°C as a carrier, (D) General formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼[II] (In the formula, R^3 represents a substituted or unsubstituted monovalent hydrocarbon group, c
is a value whose average value is within the range of 0.80 to 1.80, d is a value such that the ratio of hydroxyl groups bonded to silicon atoms in general formula [II] is 0.01% by weight or more, p 0.1 to 5.0 parts by weight of a hydroxyl group-containing organopolysiloxane resin (indicates an integer of 3 or more) and (E) general formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] ( In the formula, R^4 represents a substituted or unsubstituted monovalent hydrocarbon group;
^5 represents a substituted or unsubstituted alkyl group, and e represents an integer of 0 to 2.
1 to 5.0 parts by weight, 0.7≦[(A)+(D)+(E
)] A liquid composition for preventing stains on a painted surface, which contains components≦15.0 parts by weight and the total amount of components (A) to (E) is 100 parts by weight.