JPH0625609A - Protective water-repellent agent for automotive coating film - Google Patents

Abstract

PURPOSE:To obtain an agent which protects the appearance of a coating film of an automobile from natural staining or degradation by dissolving or swelling polytetrafluoroethylene in a solvent. CONSTITUTION:This agent is obtd. by dissolving or swelling polytetrafluoroethylene in a solvent in a concn. of 0.1-20wt.%. Polytetrafluoroethylene, having a low surface tension, imparts water repellency, lubricity, capability of preventing stickiness, and releasability to a coated surface and improves the stain resistance of a coating film. A concn. of polytetrafluoroethylene lower than 0.1wt.% gives a nonuniform film inferior in water repellency; one higher than 20wt.% makes the coating work and finishing difficult though no problem occurs in protective and water-repellent effects. A volatile, completely fluorinated fluorocarbon represented by the formula is the most derivable as the solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a coating film for automobiles, which is intended to protect the original aesthetic appearance of the coating film in a beautiful state, since the coating film of an automobile is deteriorated by rainwater and natural contaminants. It relates to an aqueous polish.

[0002]

BACKGROUND OF THE INVENTION In the natural environment, automobile coatings are usually dust, sand dust, dirt and mud, exhaust gas, tire mist, asphalt and pitch, factory exhaust, Mist scattered from construction sites and farms,
It is very easy to get dirty due to the components of acid rain.
And, these are firmly adhered so that it is difficult to remove them by washing with water or simple washing. Eventually, these not only spoil the aesthetics of the coating film, but also rainwater, hot water rays,
It is a major enemy of the coating film that promotes deterioration of the coating film along with oxygen and the like.

The conventional method used for recovering such a contaminated coating film state requires a considerable amount of labor for cleaning with a rubbing compound, a cleaner wax, a strong detergent, or the like. . For rubbing compounds and strong detergents that do not have the function of forming a protective film, the progress of contamination and deterioration cannot be stopped, but on the other hand, there are cleaner waxes that have the function of forming a protective film. The car waxes
Although it can be kept aesthetically beautiful for a period of time, it will not be able to maintain its beauty for a long time due to contamination or deterioration. And, the water-repellent function has already been lost on the coated surface which is in such a contaminated or deteriorated state.

In such a case, it is unavoidable to carry out cleaning again to recover. During this period, the limit is about 1 week to 1 month. Particularly for car waxes, the glossy coating that is formed consists of natural and synthetic wax components, oils and fats, and silicones with a high degree of polymerization, so on the contrary, it gives tackiness more than the original coating and accelerates the progress of contamination. There is also the adverse effect of being lost.

As means for solving the above-mentioned conventional drawbacks, means for forming a coating film containing tetrafluoroethylene resin powder, means for forming a polyolefin film having a high melting point and a hard polyolefin, or a fluorinated resin coating film. There is a means to try to form the, but these have been considerably improved, but not completely.

[0006] The present invention eliminates the contamination tendency as seen in the conventional car wax, and also maintains the water-repellent function for a long period of time to improve the appearance of the coating film from natural contamination and deterioration. It's something you want to protect.

[0007]

Means for Solving the Problems and Actions The present invention solves the above problems and is an automobile characterized in that polytetrafluoroethylene is dissolved or swollen in a solvent at a concentration of 0.1 to 20 wt%. It is a protective water repellent for coating films. In particular, it is a protective water repellent agent for automobile coating films, in which the solvent component is a volatile fluorocarbon represented by the general formula C _n F _{2n + 2} (where n is an integer of 5 to 15).

Polytetrafluoroethylene, which is an essential component of the present invention, needs to be dissolved or swollen in a solvent, and polytetrafluoroethylene which is not dissolved or swollen is generally in a dispersed state in the form of particles. However, there is a problem that it does not adhere to the coated surface and does not form a film by itself.

Polytetrafluoroethylene, which is dissolved in a solvent, and polytetrafluoroethylene, which is dissolved when heated and swells after cooling, can adhere to the coated surface to form a uniform glossy film. It is now possible to provide the most suitable protective water repellent for the coating film.

The polytetrafluoroethylene used in the present invention can be easily produced by polymerizing by a conventionally known method, and the low surface tension of polytetrafluoroethylene causes water repellency, lubricity and adhesion to the coated surface. Prevention performance,
It exerts release performance and contributes to the improvement of the stain resistance of the coating film.

The polytetrafluoroethylene of the present invention is
0.1 to 20 wt% in the product of the present invention, preferably 0.2 to 1
5 wt% is sufficient, and if it is less than 0.1 wt%, a uniform film cannot be obtained and the water repellency effect is poor. 20 wt%
There is no problem in the protective water repellent effect if it exceeds
The coating work is heavy and the finish is difficult, which is wasteful.

Any solvent can be used in the present invention as long as it can dissolve or swell polytetrafluoroethylene, but a fluorine-based solvent is preferable, and among them, a completely fluorinated solvent represented by the general formula C _n F _{2n + 2} is particularly preferable. Most preferred is the use of volatile fluorocarbons.

Fluorocarbon is capable of dissolving or swelling polytetrafluoroethylene, and those using this solvent have strong adhesion to the coating film, the polishing effect is further enhanced, and the coating film has excellent appearance and durability. Is obtained.

It is most preferable to use a volatile solvent for the fluorocarbon which naturally dries and evaporates after being used on the coated surface. If you use a solvent that is almost non-volatile,
It remains in the coating film formed on the coated surface, and the coating film is soft and deteriorates water repellency and stain resistance, which is not preferable.

Further, in the product of the present invention, a volatile solvent which is generally used for a polish for automobiles, which is regarded as a safe coating film, can be partially used. For example, industrial gasoline, kerosene, mineral spirits, Stodt solvent, normal paraffins, isoparaffins, naphthenes, odorless and other aliphatic solvents, chlorine solvents, fluorine solvents, aromatic solvents, ester solvents, ethers. System solvent,
Ketone solvent, alcohol solvent, silicone solvent,
Other solvents and water that do not adversely affect the coated surface can be used, and one or more solvents may be mixed and used.

The product of the present invention is most preferably used in a state of being dissolved or swollen in a solvent. However, water is added to a product of polytetrafluoroethylene dissolved or swollen to obtain an O / W type emulsion or It can be used in any emulsified state of W / O type emulsion.

The product of the present invention can also be used in a state in which a solution or swelling of polytetrafluoroethylene is dispersed in a solvent that cannot dissolve or swell.

Higher fatty acids such as oleic acid and Hoechst wax S, and natural or synthetic ester waxes having an acid value, alkylbenzenes as surfactants when water is added to form an emulsion or dispersed in a solvent. Na such as sulfonic acid, alkyl sulfate ester, polyoxyalkyl sulfate ester, alkane sulfonic acid,
Anionic surfactants represented by K, Li, ammonia, morpholine, alkanolamine salts, etc., polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyhydric alcohols Non-typified by fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid ester, oxyethylene / oxypropylene block polymer, fatty acid alkanolamide, amine oxide and other polyoxyethylene derivatives. Ionic surfactants, cationic amines represented by alkylamine salts, quaternary ammonium salts, etc., amphoteric surfactants represented by alkyl betaines, Fluorine-based surfactants containing fluoroalkyl groups in place of the hydrocarbons that form the oily part of the above hydrocarbon-based surfactants, fluorocarbon-based compounds, and dimethylpolysiloxane in place of the above hydrocarbons. Examples thereof include the silicone-based surfactants contained therein, and other surfactants which are emulsified, solubilized, and dispersible and which are commonly used. These are 10w in the product of the present invention
It is preferably t% or less, particularly 7 wt% or less, 0.1 wt% or more, and particularly 0.2 wt% or more. If it exceeds 10 wt%,
There is a risk that it may adversely affect the painted surface of the car, may remain in the coating to weaken the coating, impairing water repellency and stain resistance, or make the coating operation heavy. Also, 0.1 wt%
When it is less, it becomes difficult to uniformly emulsify and mix the product of the present invention.

Further, a waxy aliphatic hydrocarbon having a melting point of 60 to 160 ° C. can be added to the product of the present invention.
Examples of such hydrocarbons include natural or synthetic hydrocarbon waxes having no polar group such as ozokerite, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax. These hydrocarbons can be used as a diluent extender and can adjust workability during coating work, and can be adjusted in form, but should be used as little as possible. Preferably, 0.2 to 40 parts by weight, preferably 0.5 to 30 parts by weight, can be used per 100 parts by weight of the product of the present invention.

The product of the present invention may be in the form of solid, soft paste, liquid or aerosol, or may be used by impregnating sponge, non-woven fabric, paper, cloth or the like. When the product of the present invention is made into a solid or soft paste, natural or synthetic waxes commonly used for polishes can be used in combination. These are, for example, carnauba wax, candelilla wax, montan wax, ceresin, paraffin, microcrystalline wax, and other natural waxes, α-olefin wax, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, paraffin oxide, Oxidized microcrystalline wax, castor wax, acid wax and ester wax and their derivatives based on montan wax,
Lanolin derivatives, waxes consisting of petroleum-based olefin-based olefins and maleic anhydride or acrylic acid, or vinyl acetate, synthetic waxes represented by synthetic fatty acid esters, synthetic glycerides, metal soaps, fats and oils, higher fatty acids, higher alcohols, There are wax-like substances represented by hydrogenated oil, fatty acid amide, polyether and the like, and they can be used alone or in combination. Such wax is contained in the product of the present invention in an amount of 15 wt% or less, particularly 10 wt%.
% Or less is preferable. If the amount of such wax is too large, there is a risk that the coating film formed on the coating film becomes non-uniform and the original water repellent and antifouling effect is impaired. Further, such a wax can be used for controlling the stability or viscosity of a liquid or a liquid when it is made into an aerosol. Further, when the product of the present invention is aerosolized, LPG, CFC gas, which is commonly used as a carrier gas,
DME, carbon dioxide gas, liquid nitrogen, etc. can be sprayed by using 1 to 300 parts by weight with respect to 100 parts by weight of the product of the present invention.

In addition, in the product of the present invention, an inorganic or organic fine powder, which is generally used for a polish, can be used for a cleaner or for a wiping operation for forming a uniform film. Examples of such fine powders include kaolin, talc, silica, diatomaceous earth, perlite, calcium carbonate, zeolite, alumina, aluminum hydroxide, hydrous silicic acid, chromium oxide, titanium oxide, zinc oxide,
Iron oxide, zirconium oxide, silicon oxide, cerium oxide, magnesium oxide, calcium fluoride, bentonite, montmorillonite, silas balloon, mica, mica, calcium silicate, zirconium silicate, diamond, glass, ceramic, polyolefin powder, cellulose powder, Tetrafluoroethylene resin powder, tetrafluoroethylene hexafluoropropylene copolymer resin powder, vinylidene fluoride resin powder, higher fatty acid bisamide, higher fatty acid metal soap, amino acid powder, silicone powder, other synthetic resin powder such as nylon, etc. The natural or synthetic inorganic or organic powders similar to the above can be mentioned, and it is preferable to use them alone or in combination and to use as little as possible. It is possible to have. In addition, in the product of the present invention, a lubricating oil generally used for a polish can be used for wiping work for forming a uniform film. Examples of such lubricating oil include dimethyl polysiloxane and its modified products, perfluoroalkyl polyether, trifluorochloroethylene polymerized oil, liquid paraffin, spindle oil, machine oil, ester synthetic oil of fatty acid and alcohol, acrylic acid-based polymerization. Oils and aqueous ones such as oils, polyoxyolefins and their copolymers and their derivatives, polyhydric alcohols such as glycerin and their derivatives, etc. can be mentioned, and these can be used alone or in combination and used as little as possible. Preferably, it can be used in the present invention in an amount of 15 wt% or less, particularly 10 wt% or less. Further, as antifreezing in the case of the emulsion mixture of the product of the present invention, polyhydric alcohols such as ethylene glycol and propylene glycol, alcohols such as ethanol and isopropyl alcohol, and others having an antifreezing effect are commonly used. Instead of a part of water, it can be used in an amount of 10 wt% or less, particularly 5 wt% or less in the product of the present invention. In addition, if necessary, components such as a viscosity adjusting agent, a pH adjusting agent, an antioxidant, an ultraviolet absorber, an antiseptic, a rust preventive, a fragrance, and a coloring agent, which are commonly used for a polish, are blended. It doesn't matter.

By applying the product of the present invention to the coating film of an automobile, the glossiness, water repellency and antifouling property of the coating film can be maintained for a long time, and the appearance of the vehicle can be maintained for a long time. That is, the effect of maintaining the water repellency and non-contaminating property by the fluorine portion of polytetrafluoroethylene, and the effect of the glossing effect and the durability of the gloss by the dense structure of the formed film can be obtained. Since the product of the present invention does not contain a component that damages the coating film, the coating film is not damaged even if it is applied to the renewed coating film any number of times.

As described above, the product of the present invention is extremely excellent in glossiness, water repellency and antifouling property, and is superior to conventional polishes in that it can maintain the aesthetic appearance of the coating film for a long period of time. It has an action.

[0024]

EXAMPLES, COMPARATIVE EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The components used are listed below. Bydax AR (DuPont), a solid component of polytetrafluoroethylene 20 wt% is dispersed in trichlorotrifluoroethane. The solid component polytetrafluoroethylene has a melting point of 300 ° C. and an average molecular weight of 37.
00. Lubron LD-1 (Daikin Industries), polytetrafluoroethylene 6 wt% solid component dispersed in trichlorotrifluoroethane. The solid component polytetrafluoroethylene has a melting point of about 320 ° C. and an average molecular weight of 8
It is 000. -AG Lub-G (Asahi Glass), a solid component of polytetrafluoroethylene 10 wt% is dispersed in trichlorotrifluoroethane. Polytetrafluoroethylene as a solid component has a melting point of 300 ° C. and an average molecular weight of 3500.
Is. -HOSTAFLON TF-9202 (Hoechst), melting point 324-327 [deg.] C., average particle size about 2.5 [mu] m.
Is a white powder of polytetrafluoroethylene. Megafac F178 (Dainippon Ink and Chemicals), a nonionic fluorine-based surfactant containing 30 wt% of the active ingredient.・ PF5070 (Sumitomo 3M), molecular formula C
It is a fluorocarbon solvent having ₇ F ₁₆ , a boiling point of 80 ° C., and a specific gravity of 1.73 (25 ° C.).・ PF5080 (Sumitomo 3M), molecular formula C
It is a fluorocarbon solvent having ₈ F ₁₈ , a boiling point of 102 ° C., and a specific gravity of 1.76 (25 ° C.).・ Pegasol 3040 (mobile oil), distillation range 15
It is an aliphatic solvent having a temperature of 5 to 197 ° C and an aniline point of 56 ° C.・ Shell Sol 71 (Shell Chemistry), distillation range 174-2
It is an isoparaffinic solvent having a temperature of 07 ° C and an aniline point of 84 ° C. -Carnauba wax (Yoko Kato), a natural vegetable ester wax with a melting point of 83 ° C. -Polywax 655 (Valeco), melting point 102 ° C, average molecular weight 700, homopolymer of ethylene, which is a hard aliphatic hydrocarbon. -Polywax 1000 (Valeco), melting point 112 ° C,
It is a homopolymer of ethylene with an average molecular weight of 1,000 and is a hard aliphatic hydrocarbon. PW powder 2010 (Toyo Petrolite), a polyethylene fine powder having an average particle size of 5.9 μm, a melting point of 125 ° C., and an average molecular weight of 2000.・ Tospearl 120 (Toshiba Silicone), average particle size 2.
It is a white fine powder of 0 μm, spherical silicone resin.・ Silicone KF96-350cs (Shin-Etsu Chemical Co., Ltd.),
Viscosity 350 ± 17 cs (25 ° C), specific gravity 0.965-
It is a silicone oil having a dimethylpolysiloxane structure of 0.975 (25 ° C).・ Silicone KF96-1000cs (Shin-Etsu Chemical Co., Ltd.), viscosity 1000 ± 50cs (25 ° C), specific gravity 0.9
It is a silicone oil having a dimethylpolysiloxane structure of 65 to 0.975 (25 ° C). Alumina AM-22 (Sumitomo Aluminum Smelting Co., Ltd.), an insoluble alumina fine powder having an average particle size of 4.5 μm. -Hoechst wax S (Hoechst), dropping points 81 to 87
It is a higher fatty acid having an acid value of 130 to 150 at ℃. -Emazole S-10 (Kao), sorbitan monostearate, a nonionic surfactant of HLB 4.7.

Example 1 Bydax AR 25.0 PF5080 75.0 100.0 wt% Bydax AR was added to PF5080 and heated to about 70 ° C. to evaporate trichlorotrifluoroethane in Bydax AR. Polytetrafluoroethylene P
Dissolve in F5080 and cool to room temperature to obtain a liquid.

Example 2 Lubron LD-1 40.0 PF5070 40.0 Megafac F178 2.0 Pegazole 3040 18.0 100.0 wt% Lubron LD-1 was added to PF5070 and heated to about 70 ° C. to Lubron. Trichlorotrifluoroethane in LD-1 was evaporated to convert polytetrafluoroethylene to P
After being dissolved in F5070 and cooled to room temperature, Megafac F178 and pegazole 3040 are added to obtain a liquid substance.

Example 3 AG Lub-G 30.0 PF5070 15.0 PF5080 20.0 Megafac F178 2.0 Pegazole 3040 33.0 100.0 wt% PF5070 and PF5080 were added with AG Lub-G to obtain about 70. The mixture was heated to ℃ to evaporate trichlorotrifluoroethane in AG Lub-G to dissolve polytetrafluoroethylene in PF5070 and PF5080,
After cooling to room temperature, Megafac F178 and Pegasol 3040 are added to obtain a liquid substance.

Example 4 Bydax AR 25.0 PF5080 30.0 Polywax 1000 3.0 Pegazole 3040 25.0 Megafac F178 2.0 HOSTAFLON TF-9202 5.0 PW Powder 2010 5.0 Tospearl 120 5. 0 100.0wt% PF5080 was added with Vidax AR and heated to about 70 ° C. to evaporate trichlorotrifluoroethane in the Vidax AR and polytetrafluoroethylene to PF
Melted in 5080 and cooled to room temperature, and polywax 1000 was heated and dissolved in pegazole 3040 at 120 ° C. and cooled, and wax liquid and Megafac F17 were melted and cooled.
8 was added, and finally HOSTAFLON TF-9202
The PW powder 2010 and the Tospearl 120 are dispersed to obtain a liquid substance.

Comparative Example 1 (Dispersion type of polytetrafluoroethylene fine powder) Lubron LD-1 15.0 Shell Sol 71 85.0 100.0 wt% Lubron LD-1 was added to Shell Sol 71 to disperse it to obtain a liquid substance.

Comparative Example 2 (Dispersion type of polytetrafluoroethylene fine powder) HOSTAFLON TF-9202 20.0 Pegazole 3040 80.0 Pegasol 3040 HOSTAFLON TF-92
02 is added and dispersed to obtain a liquid substance.

Comparative Example 3 (type in which fine powder of polytetrafluoroethylene is dispersed in wax) AG Lub-G 10.0 Polywax 1000 10.0 10.0 Pegasol 3040 75.0 Silicone KF96-350cs 5.0 100. Add polywax 1000 to 0 wt% pegazole 3040,
After heating and melting at 120 ° C and cooling to room temperature, AG Lub-
A liquid is obtained by adding G and silicone KF96-350cs.

Comparative Example 4 (JIS K2236 Solid Wax Wax for Polishing Wax) Carnauba wax 15.0 Polywax 655 5.0 Silicone KF96-1000cs 10.0 Pegazole 3040 70.0 100.0 wt% Carnauba wax Add Polywax 655 and Silicone KF96-1000cs,
It is melted by heating at 100 ° C. and cooled to room temperature to obtain a solid paste material.

COMPARATIVE EXAMPLE 5 (JIS K2236 Automotive waxy wax type) Hoechst wax S 2.5 Silicone KF96-350cs 7.0 Polywax 655 3.0 Pegasol 3040 50.0 Alumina AM-22 10.0 Water 27.0 Morpholine 0.5 100.0 wt% To pegazole 3040, Hoechst wax S, polywax 655 and silicone KF96-350cs are added and dissolved by heating at about 90 ° C. This is poured into warm water of about 80 ° C. to which morpholine is added with stirring to prepare an O / W type emulsion. Alumina AM-22 was dispersed in this and allowed to cool to room temperature to obtain a soft paste.

Comparative Example 6 (JIS K2236 Liquid Wax Type of Polishing Wax for Automobile) Polywax 655 5.0 Silicone KF96-350cs 3.0 Pegasol 3040 36.0 PW Powder 2010 5.0 Alumina AM-22 5.0 Emazole S-10 1.0 ethylene glycol 5.0 water 40.0 100.0 wt% polywax 655, silicone KF96-350cs, and Emerazole S-10 were added to pegazole 3040,
Melt by heating to about 90 ° C. Water and ethylene glycol are poured into this under stirring to form a W / O type emulsion. Finally PW powder 2010 and alumina AM
-22 is dispersed and cooled to room temperature to obtain a liquid substance.

Test Method The roof of a Mitsubishi Galant white paint car of the 1989 model year is used for testing. First, a car is washed, then a cleaner wax is applied to remove dirt, and the remaining wax coating components are removed with an aliphatic solvent to prepare a test surface. This test surface is divided into 11 sections, and each sample is applied to each section. Leave only one segment uncoated for blank testing. First, collect an appropriate amount of the sample on a urethane sponge and
Spread over one test category. After air-drying for about 15 minutes, brush up with a clean cotton towel to form a test film. The test car is parked outdoors. The unit is one week, and during that time, the vehicle travels on the road for about 100 km or more. The unit is washed once with water. The following test items are tested according to this test procedure. The test period is 3
Conduct the test continuously for one month and evaluate the gloss, water repellency, and stain resistance after one month and three months. The test results are shown in Table 1.

Gloss lasting effect Gloss lasting: Gloss is visually judged by comparison with blank test. Gloss evaluation ◎: Very good gloss. ◯: There is gloss. Δ: There is a little gloss. X: Almost no gloss

Continuation effect of water repellency Concerning the persistence of water repellency: After washing with water, water is applied to the coating film, and the state of polka dots on the surface of the coating film is visually judged. Water repellency evaluation ⊚: Water droplets with a small diameter are formed and water repellency is good. ◯: The diameter of the water droplet is slightly large, but the water repellency is sufficient. Δ: Water repellency is inferior because there are some parts that do not repel water. X: Almost no water repellent and no water repellency.

Contamination effect of antifouling property Regarding the continuation of antifouling property: After being washed with water, the contamination state after wiping off water is visually judged. Antifouling evaluation ◎: Almost no dirt is attached. ○: A little dirt is attached. Δ: A lot of dirt is attached. X: Dirt is attached to the entire surface.

[0040]

[Table 1] As shown in Table 1, all of the examples maintained their initial performances even after 1 month or 3 months, and were extremely excellent as protective polishes for automobiles.

[0041]

EFFECT OF THE INVENTION The composition of the present invention has the above-mentioned constitution, and in particular, when it is used on the coating surface of an automobile, its glossiness, water repellent property and antifouling property are maintained for a long period of time. Therefore, it is suitable as a protective water repellent for automobile coating films.

Claims (2)

[Claims] 1. A protective water-repellent agent for automobile coating films, which is obtained by dissolving or swelling polytetrafluoroethylene in a solvent at a concentration of 0.1 to 20 wt%. 2. The solvent component according to claim 1 has the general formula C _n F
_The protective water repellent agent for a coating film of an automobile according to claim 1, which is a volatile fluorocarbon represented by _{2n + 2} (wherein n represents an integer of 5 to 15).