JPH05339560A - Water repellent for protecting coating film of automobile - Google Patents

Abstract

PURPOSE:To obtain the title repellent which is applied to the coated surface of an automobile to allow the surface to maintain its gloss, water repellency, and antifouling properties for a long term. CONSTITUTION:The title repellent is prepd. by dissolving or dispersing a fluorine modified composite resin in a solvent or water in a concn. of 0.2-10.0wt.%. The resin is obtd. by grafting a vinyl monomer having a 3-20C fluoroalkyl group and, if necessary, another vinyl monomer onto a cyclic hydrocarbon resin.

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 on automobiles is deteriorated by rainwater and contaminants in the natural world. It relates to an aqueous polish.

[0002]

BACKGROUND OF THE INVENTION In the natural world, automobile coatings are usually dust, sand dust, dirt and mud, exhaust gas, tire mist, asphalt and pitch, factory non-smoke, 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 they are difficult to be removed by washing with water or simple washing. Eventually, these not only spoil the appearance of the coating film, but also rainwater, sun rays,
It becomes a major enemy of the coating film which accelerates the deterioration of the coating film together with oxygen and the like.

The conventional method used for recovering such a contaminated coating film state requires a considerable amount of labor for rubbing compound, cleaner wax, cleaning with a strong detergent and 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 some pollution or deterioration. The water-repellent function has already been lost on the painted surface that has been contaminated or deteriorated in this way.

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. 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 high melting point, hard polyolefin coating, or a fluorinated resin coating film. There is a means to try to form, but these have been improved considerably, but not completely.

[0006] The present invention eliminates the tendency of contamination such as that found in the conventional car wax, maintains the water-repellent function for a long period of time, and improves 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 is to solve the above-mentioned problems. A cyclic hydrocarbon resin (a) has a vinyl compound (b1) having a fluorine-containing alkyl group having 3 to 20 carbon atoms. And other vinyl-based monomer (b
A protective water repellent for automobile coatings, characterized in that the fluorine-modified composite resin obtained by graft polymerization of 2) is dissolved or dispersed in a solvent or water at a concentration of 0.2 to 10.0 wt%.

The fluorine-modified composite resin of the present invention is, for example, a cyclic petroleum resin, a terpene resin, a saturated aliphatic hydrocarbon resin and a vinyl compound having a fluorine-containing alkyl group, and optionally other vinyl monomers. A graft polymer obtained by radical polymerization is mentioned. Further, 0.2 to 40 parts by weight of waxy aliphatic hydrocarbon having a melting point of 60 to 160 ° C. may be dissolved or dispersed in 100 parts by weight of the above Matata water repellent.

The cyclic hydrocarbon resin (a) which is a raw material of the fluorine-modified composite resin which is an essential component of the present invention includes cyclic petroleum resin, terpene resin and alicyclic saturated hydrocarbon resin. Since the resin having a double bond among the above resins has a double bond polar group for each, it was inferior in water repellency and antifouling property. However, by bonding a fluorocarbon to this polar group part, the original Loses sensuality,
The water-repellent property of hydrocarbon becomes similar to that of paraffin skeleton, and due to the low surface tension of fluorocarbon, the water-repellent function can be further enhanced.
Only by dissolving or dispersing this component in a solvent or water, a uniform glossy film can be formed, and it becomes possible to provide optimum protective water repellency for automobile coating films.

The fluorine content of the fluorine-modified composite resin of the present invention is calculated by the following formula. Fluorine content (%) = equivalent number of fluorine atoms contained in 100 g of fluorine-modified composite resin × 19 This fluorine content is 0.01-
50% is preferable, and 1 to 30% is more preferable.
If it is less than 0.01%, the water repellency and antifouling property will be insufficient. On the other hand, if it is more than 50%, the solubility in an organic solvent and the compatibility with other components in the composition are deteriorated, and the improvement of the properties is reduced although the expensive fluorine component is increased, which is uneconomical.

The fluorine-modified composite resin is obtained by chemically bonding an organic fluorine compound having a vinyl group and a cyclic hydrocarbon resin together with other vinyl compounds as required.

Examples of the organic fluorine group include a polyfluoroalkyl group, a polyfluoroether group and a polyfluoroalkenyl group. This organic fluorine group is a linear or branched organic fluorine group having 3 or more carbon atoms, preferably 3 to 20 carbon atoms. Further, it is not essential that these organic fluorine groups have fluorine atoms bonded to all carbon atoms, but it is more preferable that more fluorine atoms bond to carbon atoms on average. Particularly, the ratio of fluorine atoms to the total number of fluorine atoms and hydrogen atoms bonded to carbon atoms is at least 50.
%, Preferably at least 80% or more, more preferably 100%, that is, a perfluoroalkylethyl group, a perfluoroalkyl group, a perfluoroether group, a perfluoroalkenyl group and the like. Known organic fluorine groups can be used in the invention, and specific examples thereof include the following, but are not limited thereto.

As the polyfluoroalkyl group, linear CF ₃ (CF ₂ ) ₂ −, CF ₃ (CF ₂ ) ₃ −, C are used.
F ₃ (CF ₂ ) ₅ −, CF ₃ (CF ₂ ) ₇ −, CF
₃ (CF ₂ ) ₉ −, CF ₃ (CF ₂ ) ₁₁ −, CF
_{3 (CF 2) 7 CH 2} CH 2 -, branched _(CF 3)
_{2 CF -, (CF 3)} 2 CF (CF 2) 4 -, (C
F ₃ ) ₂ CF (CF ₂ ) ₃ −, divalent — (CF ₂ C
_{F 2) 2 -, - (} CF 2 CF 2) 4 - and the like. Examples of the polyfluoroether group include CF ₃ CF ₂ CF ₂ O
CF (CF ₃ )-, CF ₃ -CF ₂ CF ₂ OCF (CF
_{3) CF 2 OCF (CF 3} ) -, CF 3 CF 2 CF 2 O
_{(CF (CF 3) CF 2} O) 3 CF (CF 3) -, (C
_{F 3) 2 CFO (CF 2} ) 5 - and the like. As the polyfluoroalkenyl group, (CF ₃ ) ₂ C═C (CF _{2
CF 3) -, (CF 3} ) 2 CF-CF = C (CF 3)
_{-, ((CF 3) 2} CF) 2 C = C (CF 3) -, CF
_{3 CF 2 CF 2 C (CF} 3) = C (CF (CF 3) 2)
-Is illustrated. These vinyl compounds having an organic fluorine group are bonded to the cyclic hydrocarbon resin together with other vinyl compounds, if necessary, by radical polymerization through graft polymerization.

The cyclic hydrocarbon resin has a melting point of 3
It is a hydrocarbon compound of 0 to 200 ° C.

Examples of the cyclic hydrocarbon resin (a) used for the fluorine-modified composite resin include cyclic petroleum resin, terpene resin, and alicyclic saturated hydrocarbon resin.

Examples of such cyclic petroleum-based resins include Hilets, Petrozine, Tack Ace manufactured by Mitsui Petrochemical Co., Ltd., Adtack, Picodyne, Pecoper, Picotack, Hercotack, Pico, Picomer, and Nippon Zeon manufactured by Rika Hercules Co., Ltd. Quinton, manufactured by Nippon Petrochemical Co., Ltd., Nisseki Neo Resin, Nisseki Neo Polymer, Toho High Resin, manufactured by Toho Chemical Industry Co., Ltd.
Representative examples include Marukarez manufactured by Maruzen Petrochemical Co., Ltd. and Eskoletz manufactured by Tonex Co., Ltd.

As the terpene resin, YS resin PX, YS resin PXN, YS manufactured by Yasuhara Chemical Co., Ltd.
S resin TO, Clearon P, Clearon M, Clearon K, YS resin A, YS resin PF, YS resin Z,
Representative examples include picolite manufactured by Rika Hercules Co., Ltd.

Examples of the alicyclic saturated hydrocarbon resin include Alcon manufactured by Arakawa Chemical Industry Co., Ltd. The characteristics of these representative examples are as shown in Table 1-1 to Table 1-5. The above is an example of a typical cyclic hydrocarbon resin, and the present invention is not limited to these.

[0019]

[Table 1-1]

[0020]

[Table 1-2]

[0021]

[Table 1-3]

[0022]

[Table 1-4]

[0023]

[Table 1-5]

In the present invention, the other vinyl-based monomer (b2) optionally used together with the vinyl-based compound (b1) having a fluorine-containing alkyl group having 3 to 20 carbon atoms includes:
Methyl (meth) acrylate, butyl (meth) acrylate, styrene, glycidyl (meth) acrylate, (meth) acrylic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Representative examples thereof include (methylol) acrylamide. The amount when (b2) is used in combination is (b
1) Usually, 1500 parts by weight or less is preferable with respect to 100 parts by weight.

The fluorine-modified composite resin of the present invention may be 0.2 to 10.0 wt% in the product (solution or dispersion) of the present invention, preferably 1.0 to 6.0 wt%, 0.2 wt%
If the amount is less, a uniform film cannot be obtained and the water repellency effect is poor. If it exceeds 10.0 wt%, there is no problem in the protective water repellent effect, but the workability for coating is heavy and the finish becomes difficult, which is a waste.

The solvent used in the present invention may be any solvent as long as it can dissolve or disperse the fluorine-modified composite resin and the hydrocarbon wax, but it is generally used as a polish for automobiles, which is supposed to be safe for the coating film. What has been described is preferable. For example, industrial gasoline, kerosene, mineral spirits, Stodart solvent, normal paraffin,
Isoparaffin-based, naphthene-based, odorless and other aliphatic solvents, chlorine-based solvents, fluorine-based solvents, aromatic-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, alcohol-based solvents, silicone-based solvents, and other coated surfaces Solvents and water that do not adversely affect the above can be used, and one or more solvents may be mixed and used.

The product of the present invention is most preferably used after being dissolved or dispersed in a resin group solvent or a silicone solvent (a volatile low molecular weight dimethylpolysiloxane cyclic or linear product, etc.). O / W type emulsion or W /
It can be used in any emulsified state of the O-type emulsion.

In the case of an emulsion, higher fatty acids such as oleic acid and Hoechst wax S are used as emulsifiers,
N such as natural or synthetic ester wax having acid value, alkylbenzene sulfonic acid, alkyl sulfuric acid ester, polyoxyalkyl sulfuric acid ester, alkane sulfonic acid, etc.
a, K, Li, anionic surfactant represented by ammonia, morpholine, alkanolamine salt, etc., polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, sorbitan fatty acid ester,
Polyoxyethylene sorbitan fatty acid ester, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid ester, oxyethylene / oxypropylene block polymer, fatty acid alkanolamide, amine oxide, etc. Nonionic surfactants represented by polyoxyethylene derivatives, cationic amines represented by alkylamine salts, quaternary ammonium salts, and zwitterionic surfactants represented by alkylbetaines. Fluorine-based surfactants containing fluoroalkyl groups instead of the hydrocarbons that form the oily part of the hydrocarbon-based surfactants, and silicone-based surfactants containing dimethylpolysiloxane instead of the above hydrocarbons. , So Other emulsifying or solubilizing, etc. may be mentioned a surfactant which is commonly used generally in some of the dispersibility. These are 10 wt% or less, especially 7 wt% in the product of the present invention.
% Or less, 0.1 wt% or more, particularly preferably 0.2 wt% or more. If it exceeds 10% by weight, there is a risk that it may adversely affect the painted surface of the car, may remain in the coating and weaken the coating to deteriorate water repellency and stain resistance, or may make the coating operation heavy. is there. On the other hand, if it is less than 0.1 wt%, it becomes difficult to uniformly emulsify and mix the fluorine-modified composite resin of the present invention.

The main component fluorine-modified composite resin of the present invention has a melting point of 6
A waxy aliphatic hydrocarbon at 0 to 160 ° C. can be mixed and used. 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 for a fluorine-modified composite resin, can adjust workability during coating work, and can be adjusted in form. 0.2 to 40 parts by weight, preferably 0.5 to 30 parts by weight, can be used with respect to 100 parts by weight.

The product of the present invention may be in the form of solid, soft paste, liquid or aerosol. 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
Natural wax represented by carnauba wax, candelilla wax, montan wax, ceresin, paraffin, microcrystalline wax, etc., α-olefin wax, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, oxidized paraffin, oxidized microcrystalline wax , Castor wax, acid wax based on montan wax and ester wax and its derivatives, lanolin derivative, wax containing petroleum-based olefin-based olefin and maleic anhydride or acrylic acid, or vinyl acetate, synthetic fatty acid ester, synthetic glyceride Substitute for synthetic wax, metal soap, oil and fat, higher fatty acid, higher alcohol, hardened oil, fatty acid amide, polyether, etc. Is the have a wax-like substance may be used in separately or in combination. The content of such wax in the product of the present invention is preferably 15 wt% or less, particularly 10 wt% or less. If the amount of the wax is too large, there is a risk that the fluorine-modified composite resin 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. In addition, when the product of the present invention is aerosolized, LPG, chlorofluorocarbon, DM, which are commonly used as a carrier gas, are used.
E, carbon dioxide, liquid nitrogen, etc. can be made into a spray form 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, shirasu balloon, mica, mica, calcium silicate, zirconium silicate, diamond, glass, ceramic, polyolefin powder, cellulose powder, Tetrafluoride ethylene resin powder, tetrafluoroethylene hexafluoropropylene copolymer resin powder, pinylidene 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 these can be used alone or in combination in the product of the present invention at 25 wt% or less, particularly 20 wt% or less. In addition, in the product of the present invention, a lubricating oil commonly used as a polish may be used for wiping work for forming a uniform film. Examples of such lubricating oil include dimethylpolysiloxane and its modified products,
Perfluoroalkyl polyether, trifluoroethylene chloride polymer oil, liquid paraffin, spindle oil, machine oil,
Synthetic oils of fatty acids and alcohols, acrylic acid-based polymerized oils, polyoxyolefins and their copolymers and their derivatives, oily and aqueous ones such as polyhydric alcohols such as glycerin and their derivatives and the like can be mentioned. These may be used alone or in combination in the product of the present invention.
It can be used in an amount of 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. 1 in the product of the present invention instead of a part of water
It can be used in an amount of 0 wt% or less, particularly 5 wt% or less. In addition, viscosity adjusting agents, pH adjusting agents, antioxidants, ultraviolet absorbers, which are generally used for polishes,
Ingredients such as antiseptics, rust preventives, fragrances, and coloring agents may be added as necessary.

By applying the product of the present invention to the coating film of an automobile, the 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 the fluorine-modified composite resin, and the effect of polishing the hydrocarbon portion and maintaining the luster can be obtained. Since the product of the present invention does not contain a component that damages the coating film, even if the product is applied to the renewed coating film any number of times, the coating film is not damaged at all.

As described above, the product of the present invention is extremely excellent in water repellency and antifouling property, and has an excellent effect that the appearance of the coating film can be maintained for a long time, which is not found in the conventional polishes for automobiles. Is to have.

[0034]

EXAMPLES, COMPARATIVE EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The fluorine-modified composite resins used are listed below. Parts and% in Synthesis Examples, Examples and Comparative Examples are on a weight basis.

Synthetic Example 1 180 parts of xylene to Kolben, 90 of Alcon P-125 (aliphatic saturated hydrocarbon resin, manufactured by Arakawa Chemical Industry Co., Ltd.)
Part, perfluoroalkyl ethylene (Fluowet
V3196-612 Hoechst Co., Ltd. 22 parts and methyl methacrylate 2 parts were put. 140 this mixture
The temperature was raised to ℃, under a nitrogen atmosphere and stirring conditions, di-t-
After 25 parts of butyl oxide was added dropwise over 10 minutes, the reaction was continued for 1 hour under the same conditions. Further, 5 parts of di-t-butyl oxide was added dropwise for 10 minutes, and then the reaction was continued for 1 hour under the same conditions. The solvent was removed from the reaction product to obtain the fluorine-modified composite resin A1 of the present invention. The IR (infrared absorption spectrum) of A1 shows 1648 cm ⁻¹ due to the carbon-carbon double bond.
Was never absorbed.

Synthesis Example 2 100 parts of xylene in Kolben and Nisseki Neo Resin EP-
90 parts of 110 (dicyclopentadiene-based hydrocarbon resin, manufactured by Nippon Petrochemical Co., Ltd.) was added and the temperature was raised to 140 ° C. Perfluoroalkyl methacrylate (NOXGUARD
FAMAC-M, manufactured by Nippon Mektron Ltd., 22 parts,
80 parts of xylene and 30 parts of di-t-butyl oxide are mixed, and the mixture is mixed with 6 parts under a nitrogen atmosphere and stirring conditions.
It was dripped in 0 minutes. Further, 3 parts of di-t-butyl oxide was added dropwise over 10 minutes, and then the reaction was continued for 1 hour under the same conditions. The solvent was removed from the reaction product to obtain the fluorine-modified composite resin A2 of the present invention. IR of A2 (infrared absorption spectrum)
Has no absorption at 1648 cm ⁻¹ by the carbon-carbon double bond.

Synthesis Example 3 180 parts of Pegasol 3040 (mineral terpene, manufactured by Mobil Oil Co., Ltd.) in Kolben, YS RESIN T
100 parts of O-125 (aromatic modified terpene resin, manufactured by Yasuhara Chemical Co., Ltd.), 22 parts of perfluoroalkyl methacrylate (NOXGUARD FAMAC-M, manufactured by Nippon Mektron Co., Ltd.) and 5 parts of glycidyl methacrylate were added. This mixture was heated to 140 ° C., and di-t-butyl oxide 20 was added under a nitrogen atmosphere and stirring conditions.
After 10 minutes of dropwise addition, the reaction was continued for 1 hour under the same conditions. Further, 5 parts of di-t-butyl oxide was added dropwise over 10 minutes, and then the reaction was continued for 1 hour under the same conditions. The solvent was removed from the reaction product to obtain the fluorine-modified composite resin A3 of the present invention. In the IR (infrared absorption spectrum) of A3, there was no absorption at 1648 cm ⁻¹ due to the carbon-carbon double bond.

The components used other than the fluorine-modified composite resin are as follows. -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.・ KF994 (Shin-Etsu Chemical Co., Ltd.), viscosity 2.3 cs (25
℃), specific gravity 0.96 (25 ℃), flash point 55 ℃, boiling point 1
Volatile cyclic polydimethylsiloxane at 75 ° C, used as a solvent.・ Swazol 1000 (Maruzen Petrochemical), distillation range 16
It is an aromatic solvent having a mixed aniline point of 12.5 ° C. at 1.0 to 179.0 ° C. Hoechst wax S (Hoechst), acid number 35-15
It is a higher fatty acid of 5. Sazol wax A1 (South Africa Sazol Corporation), an oxidation type ester wax having an acid value of 25 to 30. -Emazole S-10 (Kao Atlas), sorbitan monostearate, a nonionic surfactant of HLB 4.7. ． Sazol wax H1 (South Africa Sazol Corporation), a freezing point of 97 to 98 ° C., an average molecular weight of 814, and a hard paraffin wax by Fischer-Tropsch. -Polywax 655 (Valeco), melting point 102 ° C, average molecular weight 700, homopolymer of ethylene, which is a hard aliphatic hydrocarbon. -Carnauba wax (Kato Hiroyuki), a natural vegetable ester wax with a melting point of 83 ° C. -V wax (BASF Corporation), a polyvinyl ether wax having a melting point of 45 to 48 ° C. Alumina AM-22 (Sumitomo Aluminum Smelting Co., Ltd.), an insoluble alumina fine powder having an average particle size of 4.5 µ. PW powder 2010 (Toyo Petrolite), a polyethylene fine powder having an average particle size of 5.9 μ, a melting point of 125 ° C., and an average molecular weight of 2,000.・ KF96-350cs (Shin-Etsu Chemical Co., Ltd.), viscosity 350
± 17 cs (25 ° C), specific gravity 0.965 to 0.975
It is a silicone oil having a dimethylpolysiloxane structure (25 ° C.).・ Dianal BR Resin 105 (Mitsubishi Rayon), T
It is a thermoplastic acrylic resin that is soluble in an aliphatic solvent at g50 ° C. Lubron L-2 (Daikin Industries), melting point about 329 ° C,
It is a polytetrafluoroethylene white fine powder having an average particle diameter of 0.3 μm. -Polywax 2000 (Valeco), melting point 125 ° C,
It is a homopolymer of ethylene with an average molecular weight of 2,000 and is a hard aliphatic hydrocarbon.

Example 1 A1 1.0 shell sol 71 99.0 100.0 wt% A1 is added to the shell sol 71 and dissolved to obtain a liquid dispersion liquid.

Example 2 A2 3.0 Pegasol 3040 90.0 Swazol 1000 5.0 5.0 Sazol wax H1 2.0 100.0 wt% A2 and Sazol wax H1 were added to Pegasol 3040 mixed with Swasol 1000. About 120 ℃
It is heated to dissolve and then cooled to room temperature to obtain a liquid dispersion.

Example 3 A3 3.0 Shell Sol 71 45.4 Water 25.0 Hoechst Wax S 2.0 Sazol Wax A1 1.0 Morpholine 0.6 Polywax 655 3.0 Alumina AM-22 5.0 PW Powder 2010 10.0 Glycerine 5.0 100.0 wt% A3, Hoechst wax S, and Sazol wax A1 are added to shell sol 71 and heated to about 90 ° C. to dissolve. This is melted with glycerin and morpholine and poured into water heated to about 80 ° C. with stirring to emulsify. After that, alumina AM-22 and Pw powder 2010 are dispersed and allowed to stand to room temperature to obtain a soft paste.

Example 4 A1 2.0 Pegasol 3040 46.7 KF994 8.0 Water 31.0 Emazol S-10 0.3 Alumina AM-22 8.0 Ethylene glycol 4.0 100.0 wt% KF994 on Pegasol 3040 In the melted
1. Add Emazole S-10 and heat to about 90 ° C. to dissolve. Water with ethylene glycol dissolved in it,
Inject under stirring to make a W / O emulsion. Alumina AM-22 is uniformly dispersed in this and cooled to room temperature to obtain a liquid emulsion.

Example 5 A2 5.0 Pegasol 3040 62.0 KF994 10.0 Polywax 655 15.0 Carnauba wax 5.0 KF96-350cs 3.0 100.0 wt% A2, KF994, Polywax 655 on Pegasol 3040 , Carnauba wax and KF96-350cs are added and heated to about 100 ° C. to melt, and cooled to room temperature to obtain a solid form.

Example 6 A3 2.0 Shell Sol 71 60.8 Poly Wax 655 2.0 V Wax 1.0 PW Powder 2010 4.0 Diinal BR Resin 105 0.2 LPG 30.0 100.0 wt% Shell Sol 71 Add A3, poly wax 655, V wax, and Dynar BR resin 105 to about 100
Melt by heating to ℃, and cool to room temperature. PW powder 2010 is uniformly dispersed in this to obtain a liquid dispersion liquid. An aerosol can is filled with this dispersion and LPG to obtain an aerosol product having a pressure of 3.0 Kg / cm ² .

Example 7 A2 0.2 Sazol Wax H1 2.0 Shell Sol 71 97.8 100.0 wt% A2 and Sazol Wax H1 were added to Cielsol 71 and dissolved by heating to about 120 ° C. To obtain a liquid dispersion.

Example 8 A1 1.0 A3 1.0 Pegasol 3040 52.7 Water 35.0 Sazol wax A1 5.0 Morpholine 0.3 PW powder 2010 5.0 100.0 wt% A1 and A3 in Pegasol 3040 , Sazol Wax A
Add 1 and heat to about 90 ° C. to melt. This was poured into warm water of about 80 ° C. to which morpholine was added while stirring to give O /
Make a W-type emulsion. PW powder 20 in this
10 is uniformly dispersed and cooled to room temperature to obtain a liquid emulsion.

Example 9 A2 3.0 Pegasol 3040 71.0 KF994 7.0 Polywax 655 4.0 Carnauba wax 10.0 KF96-350cs 5.0 100.0 wt% A2, KF994, Polywax 655 on Pegasol 3040 , Carnauba wax, and KF96-350cs are added, and the mixture is heated to about 120 ° C to melt it, and allowed to stand at room temperature to obtain a solid state.

Example 10 A1 3.0 Pegasol 3040 43.0 Swazol 1000 6.0 Water 28.5 Hoechst Wax S 2.0 Morpholine 0.5 Polywax 655 3.5 V Wax 1.5 Alumina AM-22 12 to .0 100.0wt% Pegasol 3040 in plus Swasol 1000, A1, Hoechst wax S, POLYWAX 655,
Add V wax and heat to about 90 ° C. to melt. This is poured into warm water of about 80 ° C. to which morpholine is added with stirring to make an O / W type emulsion. Alumina A in this
M-22 is dispersed and allowed to stand to room temperature to obtain a soft paste.

Example 11 A3 3.0 Pegasol 3040 90.0 Swazol 1000 5.0 Sazol wax H1 2.0 100.0 wt% A3 and Sazol wax H1 were added to Pegasol 3040 mixed with Swazol 1000. About 120 ℃
It is heated to dissolve and then cooled to room temperature to obtain a liquid dispersion.

Example 12 A1 and Sazol wax H1 are added to the shell sol 71, heated to about 120 ° C. to dissolve, and cooled to room temperature to obtain a liquid dispersion liquid.

Example 13 A2 3.0 Vegasol 3040 42.7 KF994 8.0 Water 34.0 Emazole S-10 0.3 Alumina AM-22 8.0 Ethylene Glycol 4.0 100.0 wt% KF994 on Pegasol 3040. In the melted
2. Add Emazole S-10 and heat to about 90 ° C. to dissolve. Water with ethylene glycol dissolved in it,
Inject under stirring to make a W / O emulsion. Alumina AM-22 is uniformly dispersed in this and cooled to room temperature to obtain a liquid emulsion.

Comparative Example 1 Pegasol 3040 95.0 Swazol 1000 2.0 Sazol Wax H1 3.0 100.0 wt% Sazol Wax H1 was added to Pegasol 3040 in which Swazol 1000 was dissolved and heated to about 100.degree. Dissolved and cooled to room temperature to obtain a liquid dispersion.

Comparative Example 2 Pegasol 3040 70.0 KF994 5.0 Polywax 655 20.0 Carnauba wax 2.0 KF96-350cs 3.0 100.0wt% Pegasol 3040 KF994, KF96-350c
Polywax 655 and carnauba wax are added to the s melted, heated to about 100 ° C. to melt, and allowed to stand at room temperature to obtain a solid form.

Comparative Example 3 Pegasol 3040 40.0 Swazol 1000 3.0 Water 28.7 Hoechst Wax S 5.0 Morpholine 1.3 Polywax 655 4.0 V Wax 3.0 Alumina AM-22 10.0 Glycerin 5 to .0 100.0wt% Pegasol 3040 in plus Swasol 1000, Hoechst wax S, POLYWAX 655, the V wax added and dissolved by heating to about 90 ° C.. This is poured into warm water of about 80 ° C. to which morpholine and glycerin have been added, with stirring to make an O / W type emulsion. Alumina AM-22 is dispersed in this and allowed to stand to room temperature to obtain a soft paste.

Comparative Example 4 Shell Sol 71 50.0 Water 39.7 Sazol Wax A1 5.0 Morpholine 0.3 PW Powder 2010 5.0 5.0 100.0 wt% Sazol Wax A1 was added to Shell Sol 71 to give about 9
Dissolve by heating to 0 ° C. This is poured into warm water of about 80 ° C. to which morpholine is added with stirring to make an O / W emulsion. PW powder 2010 is dispersed in this and cooled to room temperature to obtain a liquid emulsion.

Comparative Example 5 Pegasol 3040 44.7 KF994 10.0 Water 35.0 Emazol S-10 0.3 Alumina AM-22 7.0 Ethylene glycol 3.0 100.0 wt% KF994 dissolved in Pegasol 3040 Then, Emazol S-10 is added and heated to about 60 ° C. to dissolve.
Water to which ethylene glycol was added was poured into this under stirring to obtain a W / O type emulsion. Alumina AM-22 is dispersed in this and cooled to room temperature to obtain a liquid emulsion.

Comparative Example 6 Pegasol 3040 86.0 Polywax 655 2.0 V wax 2.0 Alumina AM-22 5.0 Lubron L-2 5.0 100.0 wt% Pegasol 3040, polywax 655 and V wax Is added and the mixture is heated to about 90 ° C. to dissolve, alumina AM-22 and Lubron L-2 are dispersed in this, and cooled to room temperature to obtain a liquid dispersion.

Comparative Example 7 Shellsol 71 40.0 KF994 6.7 Water 40.0 Sazole Wax A1 5.0 Morpholine 0.3 Alumina AM-22 5.0 Polywax 2000 3.0 100.0 wt% Shellsol 71 In addition to KF994, add Sazol wax A1 and polywax 2000, and add about 120
Dissolve by heating to ℃. After cooling this to about 70 ° C., warm water at about 70 ° C. to which morpholine was added,
Injection under stirring gives a W / O emulsion. Alumina AM-22 is dispersed in this and cooled to room temperature to obtain a viscous emulsion.

Comparative Example 8 Pegasol 3040 59.9 Water 18.7 Hoechst Wax S 5.0 Morpholine 1.3 Alumina AM-22 5.0 PW Powder 2010 10.0 A1 0.1 100.0 wt% Pegasol 3040 Hoechst Add wax S and heat to about 90 ° C. to melt. This is poured into warm water of about 80 ° C. to which morpholine and A1 are added under stirring to prepare an O / W type emulsion. Alumina AM-22 and PW powder 2010 are dispersed in this and allowed to stand to room temperature to obtain a soft paste.

Comparative Example 9 A2 0.1 Pegasol 3040 99.9 100.0 wt%

Comparative Example 10 A3 12.0 Pegasol 3040 88.0 100.0 wt% As to the preparation of Comparative Examples 9 and 10, A2 or A3 was added to Pegasol 3040 and dissolved to obtain a liquid dispersion liquid.

Test Method The roof portion of a 57-year-old Toyota Corolla white-painted car is used for testing. First, a car is washed, and then a cleaner wax is applied to remove stains, and the remaining wax coating components are removed with an aliphatic solvent to prepare a test surface.
This test surface is divided into 24 sections, and each sample is applied to each section. Leave only one segment uncoated for blank testing. First, an appropriate amount of a sample is sampled on a urethane sponge, and this is spread over one test section. After air-drying for about 15 minutes, brush up with a clean cotton towel to form a wax film for testing. The test car is parked outdoors. 1
The unit is a week, and during that time, the vehicle runs for about 100 km or more. Washing with water is performed once per 1 unit. The following test items are tested according to this test procedure. The test period will continue for 2 months. The test results are shown in Table 2.

Gloss lasting effect Regarding the gloss lasting, the glossiness after 2 months was visually judged and compared with the blank test. Gloss ◎ Same as initial ○ Almost good △ Slightly deteriorated × Almost none

Sustaining effect of water repellency Regarding the sustaining of water repellency, after washing with water after 2 months,
The state of the polka dots was visually determined. Water repellent polka dot shape ◎ Same as initial ○ Almost good △ Slightly deteriorated × Almost none

Contamination resistance of antifouling property Regarding continuation of antifouling property, after washing with water after 2 months,
After the water repellency test was completed, water was wiped off, and the state of contamination was visually determined. Antifouling ◎ Same as the initial stage ○ Slightly contaminated △ Slightly contaminated × Considerable contamination

[0066]

[Table 2]

[0067]

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

Claims (3)

[Claims] 1. The cyclic hydrocarbon resin (a) contains 3 carbon atoms.
To 20 vinyl compounds having fluorine-containing alkyl groups (b
1) and a fluorine-modified composite resin obtained by graft-polymerizing another vinyl-based monomer (b2) if necessary, are dissolved or dispersed in a solvent or water at a concentration of 0.2 to 10.0 wt%. A protective water repellent for automobile coatings. 2. The protective water repellent for a coating film according to claim 1, wherein the cyclic hydrocarbon resin (a) is a resin selected from cyclic petroleum resins, terpene resins, and alicyclic saturated hydrocarbon resins. 3. A protective water repellent 100 for a coating film according to claim 1.
A protective water-repellent agent for automobile coating films, in which 0.2 to 40 parts by weight of a hydrocarbon wax having a melting point of 60 to 160 ° C. is dissolved or dispersed in parts by weight.