JPH04149294A - Water-repelling protection agent for coating film of automobile - Google Patents

Abstract

PURPOSE:To obtain the subject water-repellent having luster, water-repellency and stain-proofing property durable over a long period by dissolving or dispersing a fluorine-modified wax, soluble in organic solvent in a solvent or water. CONSTITUTION:The objective water-repellent is produced by dissolving or dispersing (A) a waxy hydrocarbon compound having fluorine-containing organic group and soluble in organic solvent [preferably having a fluorine content of 5-70% (especially 10-50%)] in (B) water or a solvent such as industrial gasoline, mineral spirit, ester or alcohol at a concentration of 0.2-10.0wt.%. The component A is e.g. a compound produced by bonding a higher alcohol and a carboxylic acid having fluorine-containing organic group by esterification reaction or a compound produced by bonding an alpha-olefin and an organic silicon compound having fluorine-containing organic group and Si-H group by hydrosilylation reaction.

Description

[Detailed Description of the Invention] "Industrial Application Field" The present invention aims to preserve the original beauty of automobile paint films in a beautiful state, since the paint films of automobiles are deteriorated by rainwater and natural pollutants. This invention relates to a water-abrasive polishing agent that forms a film.

"Prior Art and Problems to be Solved by the Invention" Automotive paint films are normally exposed to dust, sand, dirt, mud, exhaust gas, tire wear mist, asphalt and pitch, factory smoke, etc. in the natural world. It is highly susceptible to contamination due to scattered mist from construction sites and farms, and components of acid rain. And these are difficult to remove with water or simple cleaning.
〈It is very firmly attached. These substances not only impair the beauty of the paint film, but also act as natural enemies of the paint film, accelerating the deterioration of the paint film along with rainwater, sunlight, oxygen, etc.

Conventional methods used to restore the contaminated paint film include cleaning with rubbing compounds, cleaner wax, and strong detergents.
It required a lot of hard labor. Rubbing compounds and strong detergents that do not have the function of forming a protective film cannot stop the progress of contamination and deterioration. Car waxes can maintain an aesthetically beautiful state for a while, but they will eventually become contaminated and deteriorate, making it impossible to maintain their beauty for a long period of time. The painted surface is contaminated and deteriorated in this way, and has already lost its ability to repel water.

If K occurs like this, cleaning must be performed again to recover. During this time, the limit is approximately one week to one month. This is especially true for car waxes, as the glossy film formed is made up of natural or synthetic wax components, oils and fats, and highly polymerized silicone, which gives the paint film its own tackiness and promotes the progression of contamination. The opposite effect can also be seen.

To overcome these conventional drawbacks, there are methods to form a film containing tetrafluoroethylene resin, a method to form a hard polyolefin film with a high melting point, or a method to form a film containing a fluorinated resin film. There are ways to create and try to do this, and although these have improved considerably, complete envy is far from acceptable.

This product eliminates the staining tendency seen in conventional car waxes, maintains its water repellent function for a long time, and protects the beauty of the paint film from natural pollution and deterioration. That is.

"Means and Effects for Solving the Problems" The present invention is a book that solves the above problems, and is based on the following: An organic solvent-soluble waxy hydrocarbon compound having a fluorine-containing organic group is added to a solvent or water at 0.00%.
This is a protective water repellent for automobile paint films, characterized in that it is dissolved or dispersed at a concentration of 2 to 10.0 wt%. The fluorine-modified wax of the present invention may be obtained by bonding a higher alcohol and a carboxylic acid having a fluorine-containing organic group through an esterification reaction, or by esterifying a higher fatty acid and an alcohol having a fluorine-containing organic group. Furthermore, it may be one in which an α-olefin and an organosilicon compound having a fluorine-containing organic group and a 5i-H group are bonded by a hydrosilylation reaction. 0.2 to 40 parts by weight of a waxy aliphatic hydrocarbon having a melting point of 80 to 160° C. may be dissolved or dispersed in 100 parts by weight of the above protective water repellent agent.

The higher alcohols, higher fatty acids, and α-olefins that are the raw materials for the fluorine-modified wax, which is an essential component of the components of the present invention, have water repellency and stain resistance because they each have polar groups of -OH, -COOH, and double bonds. However, by bonding fluorocarbon to this polar group moiety, the original functionality is removed), and it now shows the water repellent properties of hydrocarbons similar to the paraffin skeleton. Surface tension can further enhance the water repellency, and by dissolving or dispersing only this part in a solvent or water, it is now possible to form a uniform glossy film, making it ideal for automotive paint films. We are now able to provide a protective water repellent agent that is optimal for use.

The fluorine content of the fluorine-modified wax of the present invention is calculated by the following formula.

Fluorine content (chi)=Number of fluorine atoms contained in 100 y of wax X19 This fluorine content is preferably 5 to 70 y, more preferably 10 to 50 y. If it is less than 5%, water repellency, stain resistance, etc. will be insufficient. On the other hand, if the amount exceeds 70%, the solubility in organic solvents and compatibility with other components in the composition will deteriorate, and the improvement in 4 properties will be small even though the expensive fluorine component increases, which is uneconomical. .

Fluorine-modified wax is a chemical bond of an organic fluorine compound having a reactive group and a waxy hydrocarbon compound having a reactive group.

Examples of the organic fluorine group include a polyfluoroalkyl group, a polyfluoroether group, a polyfluoroalkenyl group, etc. This organic fluorine group is preferably a linear or branched chain having 3 to 20 carbon atoms. It is an organic fluorine group. Furthermore, although it is not essential for these organic fluorine groups to have fluorine atoms bonded to all carbon atoms in them,
Generally speaking, the more fluorine atoms bonded to carbon atoms, the better.

In particular, the proportion 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%, and more preferably 100%, i.e. perfluoroalkylethyl group, perfluoroalkyl group. group, perfluoroether group, perfluoroalkenyl group, etc.

Preferred organic fluorine groups in the present invention can be found in known books, including, for example, the following, but are not limited to these.

As the polyfluoroalkyl group, linear CF3 (C
F2)2-, CF, (CF2)3. CF3 (CF
2), -CF, ('CF2), -,CF3(CF,),
−, CF3(CF2)0, (CF,,CF) −, −(
CF2CF2)4- is exemplified.

+22 Polyfluoroether groups include CF, CF2CF20CF-, CF3CF2CF20C
FCF20CF-CF30F CF3 is exemplified.

Examples of the fluoroalkenyl group (1) include. These organic fluorine groups are bonded to the waxy hydrocarbon compound via, for example, ester bonds, ether bonds, amide bonds, siloxane bonds, and lyle ester bonds.

Here, the waxy hydrocarbon compound having a reactive group is a hydrocarbon compound having, for example, a hydroxyl group, a carboxyl group, an amino group, an unsaturated group, etc. as a reactive group and having a melting point of 30 to 200°C.

The higher alcohol, which is a typical example of a waxy hydrocarbon compound having a hydroxyl group, is preferably a saturated aliphatic alcohol having a melting point of 45° C. or higher. Representative examples of such higher alcohols include cetanol, stearyl alcohol, behenyl alcohol, and Unilin Alcohol (a synthetic high-molecular saturated alcohol manufactured by Toyo Betcolite Co., Ltd.), which can be used alone or in combination.

The characteristics of these representative examples are as follows.

Cetyl Alcohol Stearyl Alcohol 7 Gyl Alcohol Beheny. alcohol carnabil alcohol seryl alcohol coryanyl alcohol myricyl alcohol Nori/! L・AI Shiko! Relaf Seryl Alcohol Seronori Nru Alcohol Tetratriaconta, Norheptatriacontanol Tetratetracontanol Unilin Alcohol-A4:425 Uni1]n Alcohol A4550 Unilin Alcoholken 00 XVi Freezing Point 242.49 270.55 298.61 326.67 354.73 382.79 410.85 4.38.91 452.94 466.86 495.03 509.06 635.19 Average 425 Average 550 Average 700 58.0 65.5 70.5 75.5 79.3 82.5 86.5 \' 86.5 88.5 × 88.5 91.0 × 91, O Also, as a substitute for this, it has a 10H group and is generally used as a polishing agent. The following wax-like substances can be mentioned.

(1) Hydrogenated oils and fats containing OH groups, such as hydrogenated coconut oil (2) Oxidized wax with OH groups x 1 Shin Nippon Rika Seisaku x 2 Nippon Seiro Seisaku On the other hand, wax-like carbonization with carboxylic groups The higher fatty acid as a hydrogen compound is preferably a saturated fatty acid with a melting point of 50°C or higher, or esters or oxidized type waxes may be used instead.

Such higher fatty acids include palmitic acid, stear 1
J acid, behenic acid, montanic acid, Hoechstwax S (
Hoechst's acid wax), Hoechst wax KFO (
Hoechst's ester wax), Ceramer 67 (Valeco's emulsifying wax), Sasol Wax Alt' South America Sasol Corporation's oxidized Fischer-Tropsch wax) h4.

They are listed as a table and can be used alone or in combination.

The characteristics of these representative examples are as follows.

×2 Emulsifying wax manufactured by Valeco A representative example of the α-olefin used in the production of fluorine-modified wax is Dialene 30 manufactured by Mitsubishi Chemical Industries, Ltd., which is a linear type with a melting point of 50°C or higher. is preferred. Dialene 30 has a carbon number of 30 or more and a melting point of 80°C.

The fluorine-modified wax of the present invention has a content of 0.2 to 10% in the product (solution or dispersion) of the present invention. Owtchi, preferably 1.0~
6. If it is less than 0.2wt, a uniform film cannot be obtained and the clear water effect will be poor. 10.
If the coating exceeds 70%, there will be no problem in terms of the protective effect, but it will make the coating process difficult and the finish will be difficult, which is wasteful.

The solvent used in the present invention may be any solvent as long as it can dissolve or disperse fluorine-modified wax and waxy hydrocarbons, but solvents that are generally used as automotive polishes and which are said to be safe for paint films may be used. Preferably. For example, industrial gasoline, kerosene, mineral spirits, Stodart solvent, normal paraffinic, isoparaffinic, naphthenic, odorless aliphatic solvents, chlorinated solvents, fluorinated solvents, aromatic solvents, ester solvents, ethers, etc. These solvents can include solvents such as ketone-based solvents, alcohol-based solvents, silicone-based solvents, and other solvents that do not adversely affect the finely-finished surface, as well as water, and even if one or more solvents are mixed and used. good.

The product of the present invention is an aliphatic solvent or a silicone solvent (such as a cyclic or linear volatile low molecular weight dimethyl polysiloxane).
It is most preferable to use it dissolved or dispersed in water, but it can also be emulsified in water and used in either the emulsified state of 0/W emulsion or W10 emulsion.

In the case of emulsions, higher fatty acids such as oleic acid and Hoechstwax S, natural or synthetic ester waxes with an acid value, Ng such as alkylbenzene sulfone, alkyl sulfate, polyoxyalkyl sulfate, and alkanesulfone e are used as emulsifiers. s K
%L 1% Anionic surfactants represented by ammonia, morpholine, alkanolamine salts, etc., polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene rubber fatty acid ester, polyoxyethylene rubber fatty acid ester, Hydrolic alcohol fatty 9 ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene algylamine, polyoxyethylene fatty acid ester, oxyethylene/oxypropylene block polymer, fatty acid alkanolamide, amine oxide, other polyoxyethylene derivatives, etc. Nonionic surfactants represented by
Cationic surfactants such as alkylamine salts and quaternary ammonium salts, zwitterionic surfactants such as alkylbetaine, and substitutes for hydrocarbons that form the oily part of the above hydrocarbon surfactants. Fluorine-based surfactants containing fluoroalkyl groups, silicone-based surfactants containing dimethylpolysiloxane instead of the above hydrocarbons, and those that have pore-forming, solubilization, and dispersibility. Examples include commonly used surfactants.

These are less than 10wt in the products of the present invention, especially 7wt
S or more, 0.1 wt S or more, especially 0.2 wt- or more is preferable. If it exceeds 10 wt%, there is a danger that it will have a negative effect on the painted surface of the car, remain in the film, weaken the lever film, impair its water repellency and stain resistance, and make the application process heavier. There is. Further, if the amount is less than o, 1 Wts, it becomes difficult to uniformly emulsify and mix the fluorine-modified wax of the present invention.

The main component of the present invention is fluorine-modified wax with a melting point of 80 to 160°C.
A mixture of waxy aliphatic hydrocarbons can be used.

Examples of such hydrocarbons include natural or synthetic hydrocarbon waxes that do not have polar groups, such as osikerite, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax.

These hydrocarbons can be used as diluting and bulking agents for fluorine-modified waxes, and can also adjust the workability during coating work and can adjust the shape. It is possible to use 0.2 to 40 parts by weight, preferably 0.5 to 30 parts by weight.

The product of the present invention can be in solid form, soft paste form, liquid form, or aerosol form.

When making the product of the present invention into a solid or soft paste form, it is often difficult to maintain a sufficiently stable form using fluorine-modified wax and hydrocarbon wax. Natural or synthetic waxes can be used in combination. These include, for example, natural waxes 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, Acid waxes and ester waxes based on oxidized microcrystalline wax, castor wax, montan wax and their derivatives, lanolin derivatives, petroleum-based olefin-based olefins, waxes consisting of maleic anhydride or acrylic acid, or vinyl acetate, synthetic fatty acids. There are wax-like substances such as esters, synthetic waxes such as synthetic glycerides, metal soaps, oils and fats, higher fatty acids, higher alcohols, hydrogenated oils, fatty acid amides, and polyethers, which can be used alone or in combination. Can be used.

The content of such wax in the product of the present invention is 15 wt% or less, especially 1
It is preferably 0 wt% or less. If the amount of such wax is too large, there is a risk that the fluorine-modified wax coating will become non-uniform and the original water-repellent and stain-proofing effect will be impaired, so it is preferable to use as little as possible.

Further, such a wax can be used to adjust the stability and viscosity of a liquid or an aerosol.

In addition, when the product of the present invention is made into an aerosol, commonly used carrier gases include P, G, fluorocarbon gas, and D.
ME, charcoal gas, liquid nitrogen, etc. can be sprayed using 1 to 300 parts by weight per 100 parts by weight of the product of the present invention.

In addition, the product of the present invention is generally used as a polishing agent.

Inorganic or organic fine powder commonly used for cleaners or for wiping to create a uniform film7.
It can be used as Such fine powders include, for example, kaolin, talc, crushed stone, diatomaceous earth, perlite, calcium carbonate, zeolite, alumina, hydrated silica, 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 sulfate, diamond, glass, ceramic, polyolefin powder, cellulose powder, tetrafluoroethylene resin powder, tetrafluoroethylene resin powder Propylene hexafluoride copolymer resin powder, vinylidene fluoride resin powder, higher fatty acid bisamide, higher fatty acid metal soap, amino acid powder silicone powder, other synthetic resin powders such as nylon, natural or synthetic inorganic or organic powders similar to these. These can be used alone or in combination to contain up to 25 wt%, particularly 20 wt%, in the product of the present invention.
It can be used below. In addition, in the product of the present invention, a lubricating oil commonly used as a polishing agent can be used for wiping off to create a uniform film.

Such lubricating oils include dimethylpolysiloxane and modified products thereof, perfluoroalkyl polyethers, trifluorochloroethylene polymerized oils, liquid paraffin, spindle oils, machine oils, ester synthetic oils with fatty 1111 alcohols, and acrylic dispersion polymerized oils. Oils, polyoxyolefins and their copolymers and their derivatives, polyhydric alcohols such as glycerin and their derivatives, and other oil-based and water-based ones can be mentioned, and these can be used alone or in combination,
It can be used in the product of the present invention in an amount of 15vt or less, particularly 10wt% or less.

Furthermore, polyhydric alcohols such as ethylene glycol and propylene glycol, alcohols such as ethanol and isopropyl alcohol, and other substances having an antifreeze effect are commonly used to prevent freezing in the case of emulsified mixtures of the products of the present invention. 10w in the product of the present invention by replacing some of the liquid with water.
It can be used in an amount of 1% or less, particularly 5wt% or less.

In addition, Viscous I, which is commonly used as a polishing agent,
fy4 regulator, pH adjuster, antioxidant, ultraviolet absorber,
Components such as preservatives, rust preventives, fragrances, colorants, and agents to enhance adhesion to resin-based coatings may be added as necessary.

By applying the product of the present invention to the paint film of an automobile, the water repellency and antifouling properties of the paint film can be maintained for a long period of time, and the beautiful appearance of the car can be maintained for a long period of time. That is, the fluorine moiety of the fluorine-modified wax provides a sustained water repellency effect and non-staining effect, and the hydrocarbon moiety provides a polishing effect and a sustained gloss.

Since the product of the present invention does not contain any components that would damage the paint film, it will not cause any damage to the paint film even if the new paint 11c is applied any number of times.

As described above, the product of the present invention has extremely excellent water repellency and stain prevention properties, and has an excellent effect that is not found in conventional automotive polishes in that it can maintain the beauty of the paint film for a long time. It is.

"Examples and Comparative Examples" The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

The fluorine-modified waxes used are listed below.

(1) Set a stirrer, a thermometer, a nitrogen gas inlet tube, and an ester adapter in a 108 P 200-liter four-tube flask, and add 50 y of perfluorononanoic acid, 700 y of dinyline alcohol (Toyo Petrolite Co., Ltd.), and 60 y of toluene. Preparation 11
Heated to 0°C. After uniformly dissolving, 0.2y of dibutyltin dilaurate was added, the temperature was further raised, and the mixture was reacted under refluxing toluene. After the generation of condensed water was no longer observed, the mixture was further heated for 1 hour. Next, toluene and excess perfluorononane were removed and vacuum stripping was carried out at 100'C and 10 mmHg for 3 hours. When the residual liquid was cooled to room temperature and crushed into thin pieces, a pale yellow solid was obtained. Melting point: ”19
The temperature was 3-95°C.

(2) 108 R Bar 7 fiv, Kuchi Dairyan 23y, Unilin Alcohol Lua 00 10! ', other than toluene 6oy (1)
The same operation was performed. The product obtained has a melting point of 93-9
It was a pale yellow solid substance at 5°C.

(3) 13. Set a stirrer, thermometer, nitrogen gas inlet tube, and ester adapter in an OF 200d four-way flask, and add 46y of perfluorooctyl ethanol.

Montanic acid wax (manufactured by CBASF) 382 and 50 tons of toluene were added and heated to 110°C.

After uniformly dissolving, 22 hours of para-toluenesulfonic acid was added, the temperature was further raised, and the mixture was reacted under refluxing toluene. After the generation of condensed water was no longer observed, the mixture was further heated for 1 hour. Next, to remove toluene and excess C, F, and 7CH2CH20H, the temperature was 100°C and 10 rnr.

The tube was vacuum-stripped with Hg for 3 hours. When the residual liquid was cooled to room temperature and crushed into thin pieces, a pale gray-green solid was obtained. The sand temperature was 67-68°C.

(4) Set a stirrer, thermometer, dropping funnel, and Dimroth cooling tube in a 108N 200-Yoturo flask, and put Dyallen 30 (Mitsubishi Chemical Industries, Ltd. In65y1 Etsumi Toluene 30y) into the flask.
and then add the following fluorine-modified silicone compound 35? to the dropping funnel. was charged and heated to 105°C.

After homogeneously dissolving the platinum catalyst (toluene solution of platinum complex,
A PT content of 0.5f (0.317) was added, and the above fluorine-modified silicone compound was added dropwise over 30 minutes. 2 more
After heating for an hour, to remove toluene and unreacted substances,
Vacuum stripping was carried out at 00° C. and 3 mmHg for 2 hours. When the residual liquid was cooled to room temperature, a white solid was obtained.

The melting point was 58-60°C.

(5) 130 B Carboxylic acid 53 of the following formula? , Unilin Alcohol 425
CF, CF
2CF20CFCOoH F3 went. The six products obtained were pale yellow solids with a melting point of 61-63°C.

The components used other than the fluorine-modified wax are as follows.

・Vegasol 3040 (Mobil Oil) Distillation range 15
It is an aliphatic solvent with a temperature of 5 to 197°C and an aniline point of 56°C.

・Rusol 71 (Shell Chemical Co., Ltd.) This is an isoparaffinic solvent with a distillation range of 174 to 207°C and an aniline point of 84°C.

・KF994 (Shin-Etsu Chemical) Viscosity 2.3c @ (25℃), Specific gravity 0.96 (25℃)
, a volatile cyclic polydimethylsiloxane with a flash point of 55°C and a boiling point of 175°C, used as a solvent.

・Swazol 1000 (Maruzen Petrochemical) Distillation range 16L
It is an aromatic solvent with a mixed aniline point of 12.5°C.

・Bechstwax S morpholine completely neutralized at a ratio of 0.25 parts by weight of morpholine to 1 part by weight of Hoechstwax S (Hoechst), a high-grade fat with a dropping point of 81 to 87°C and a strength of 135 to 155. This soap is obtained through a neutralization reaction at the same time as the sample is prepared.

・Sasol Wax A1 Morpholine Salt: 0.05 parts by weight of morpholine per 1 part by weight of Sasol Wax A1 (South Africa Sasol Corporation), which is a fermented type ester wax with a salt melting point of 96.5°C and an acid value of 25 to 30. This soap is completely neutralized in proportion, and is obtained through a neutralization reaction at the same time as the preparation of the sample.

・Emazol S-10 (Kao Atlas) is a nonionic surfactant with an HLB of 4.7.

- Sasol Wax H1 (South African Sasol Corporation) A hard paraffin wax with a freezing point of 97-98°C and an average molecular weight of 814, manufactured by Fischer-Tropsch.

-Polywax 655 (Valeco) A homopolymer of ethylene with a melting point of 102°C and an average molecular weight of 7001, and is a hard aliphatic hydrocarbon.

・Carnauba wax (Kase Yoko) It is a natural plant-based ester wax with a melting point of 83°C.

- V wax (BASF) A polyvinyl ether wax with a melting point of 45 to 48°C.

- Alumina AM-22 (Sumitomo Aluminum Smelting) Insoluble alumina fine powder with an average particle size of 4.5μ.

- PW Powder 2010 (Toyo Betrolite) A fine polyethylene powder with an average particle size of 5.9μ, a melting point of 125°C, and an average molecular weight of 2.000.

・KF 96 350es (Shin-Etsu Chemical) Viscosity 35
0±17es (25℃), specific gravity 0.965-0.975
(25°C) silicone oil with a dimethylpolysiloxane structure.

・Dianal BR Resin] 05 (Mitsubishi Rayon) 7g
It is a thermoplastic acrylic resin that is soluble in aliphatic solvents at 50°C.

- Lublon L-2 (Daikin Industries) A polytetrafluoroethylene white fine powder with a melting point of about 329°C and an average particle size of 0.3μ.

・Polywax 2000 (Valeco) Melting point 125℃,
It is an ethylene homopolymer with an average molecular weight of 2,000, and is a hard aliphatic hydrocarbon.

- Asahi Guard AQ-710 (Asahi Glass) A 18 wt% 'IIkK nonionic aqueous emulsion of a fluororesin having perfluoroalkyl groups, used for water and oil repellent finishing.

Example 1 108 P 5.0100.0
vrt% Add 108P to shell run 71, heat to about 120°C to dissolve, cool to room temperature, and obtain a liquid dispersion.

Example 2 108 N 3.0 Vegasol 3040 92.0 Swasol 1000
2.0100, add 108N and Sasol Wax H1 to a mixture of Owt Tibegasol 3040 and Swasol 1000, and make about 12
The mixture is heated to 0° C. to dissolve and cooled to room temperature to obtain a liquid dispersion.

Example 3 108 R3,0 Schier Tsurua 1 42.6 water
25.0 Hoechst Wax 81.0 Sasol Wax A 1 3.0 Morpholine
0.4 poly wax 655
5.0 Alumina AM-225,0 PW Powder 2010 10.0 Glycerin
5.0 Add 108R, Hoechstwax S, and Sasolwax AI to El Sol 71 and heat to about 90°C to melt. Dissolve this in glycerin and morpholine and add about 80%
Emulsify by pouring into water heated to ℃ while stirring. Thereafter, alumina AM-22 and PW powder 2010 are dispersed and left to stand at room temperature to obtain a soft paste.

Example 4 130 F 6.0 Vegasol 3040 38.7KF994
10.0 water
35.0 Emazol 5-10 0.3
Alumina AM 22 7.0+00.0
wt% In KF994 dissolved in Veganol 3040, 13
0F, add Emazol 5-10 and heat to about 90C to melt. Water in which ethylene glycol was dissolved was injected into this while stirring to form a W10 type emulsion. Alumina AM-22 is uniformly dispersed in this and cooled to room temperature to obtain a liquid emulsion.

Example 5 108 N 5.0 Vegasol 3040 65.0KF994
5.0 poly wax 655
20.0 carnauba wax
2. OKF 96350cs 3.01
00.0vtS Vegasol 3040, 108N, KF994, Polywax 655, Carnauba wax, KF 96350e
Add s, heat to about 100°C to melt, and cool to room temperature to obtain a solid.

Example 6 130 B 2.0 Shell Vine 71 59.8 Polywax 655
2.0■Wax 2.0
PW Powder 2010 4.0 Dianal BR Resin 105 0.21 00, Owt * Shell Tsuru 71, 130 B, Polywax 655,
■Add wax and Diamondal BR Resin 105,
Heat to about 100°C to melt and cool to room temperature. PW powder 2010 is uniformly dispersed in this to obtain a liquid dispersion. This dispersion and LPG are filled into an aerosol can to obtain an aerosol product with a pressure of 3.0 Kq/cIi.

Example 7 108P 2.0130F
2.0108N
2.0 Ciel Tsurua 1
92.0100.0wt% 108P, 130F, 108N, and Sasol Wax H1 are added to Scherzl 71, heated to about 120°C to dissolve, and cooled to room temperature to obtain a liquid dispersion.

Example 8 108 R3,0 130B 3.0 Vegasol 3
040 43.7 Water 40.0 Sasol Wax AI 5.0 Morpholine 0.3 100.0 wt% Add 108R, 130B and Sasol Wax AI to Veganur 3040 and melt by heating in a trench at about 90°C. This is poured into warm water at about 80°C to which morpholine has been added, under stirring, to produce an O/W type emuldigon. PW in this
Powder 2010 is uniformly dispersed and cooled to room temperature to obtain a liquid emulsion.

Example 9 130 B 5.0 Vegasol 3040 70.0KF994
5.0 Polywax 655 5.0
Carnauba wax 10.0XOO, Owt
Chipegasol 3040, 130B, KF994, Polywax 655, Carnauba wax, KF96350cs
Add it, heat it to about 90℃ and let it stand until room temperature.
Obtain solid form.

Example 10 130 F 3.0 Veganur 3040 45.0 Swazol 1000
3.0 water
29.5 Hoechstwax S2.0 Morpholine 0.5 Polywax 6
55 4.0 ■ Wax
3.0100.0wt% Vegasol 3040 plus Swasol 1000, 130F, Vextowax S1 Polywax 655
Heat the V-wax to about 90°C and melt it.

This was poured into warm water at about 80° C. to which morpholine had been added, while stirring, to prepare an OLW-type emulginone. Alumina AM-22 is dispersed in this and left to stand until room temperature to obtain a soft paste.

Comparative example 1 Beganur 3040 95.0 Swazol 1
000 2.0 Sasol Wax I (13
,0 100, OwtSazol Wax H1 is added to a solution of Vegasol 3040 and Swasol 1000, heated to about 100°C to melt, and cooled to room temperature to obtain a liquid dispersion.

Comparative example 2 Peganur 3040 70.0KF994
5.0 poly wax 655
20.0 Carnauba wax 2.0
KF 96350cs 3,0100,
Owt Tibega Sol 3040, KF994, KF96350c-
Polywax 655 and carnauba wax are added to the melted mixture, heated to about 100°C to melt, and left to stand at room temperature to obtain a solid form.

Comparative example 3 Vegasol 3040 40.0 Swasol 1
000 3.0 water
28.7 Hoechst Wax S5.
0 Morpholine 1.3 Polywax 6
55 4.0 ■ Wax
3.0 Alumina AM-2210,0 Glycerin 5,0 100, Owt Vegasol 3040 to Swasol 1000tJI], u
Inside, Bextowax S1 Polywax 655,■
Add the wax and heat to approximately 90″C to melt.

This is poured into warm water at about 80° C. to which morpholine and glycerin have been added while stirring to prepare a 0/W type emulsion. Alumina AM-22 is dispersed in this and left to stand at room temperature to obtain a soft paste.

Comparative example 4 Scherzuru 71 50.0 water
39.7 Sasol Wax A 1 5.0 Morpholine
0.3PW powder 2010 5.0
100, add Sasol Wax A1 to Owt Chichel Tsuru 71, about 9
Heat to 0°C to dissolve. This is poured into warm water at about 80° C. to which morpholine has been added, under stirring, to produce a 0/W emuldigon. PW powder 2010 is dispersed in this and cooled to room temperature to obtain a liquid emulsion.

Comparative example 5 Vegasol 3040 44.7KF994
10.0 water
35,0 emazol 5-10
0.3 Alumina AM-227,0 Ethylene Glycol 3.0100. Owt
Add Emazol 5-10 to the melted Peganur 3040VCKF994 and heat to about 60°C to dissolve. Water to which ethylene glycol has been added is injected into this with a stirrer to obtain a W10 type emulsion. Alumina AM-22 was dispersed in this [7] and cooled to room temperature to obtain a liquid emulsion.

Comparative example 6 Beganur 3040 86.0 Polywax 655 2.0 ■ Wax
2.0 Alumina AM-225.0 LeBlon L -25.0 100.0wt% Add polywax 655, ■wax to Vegasol 3040, and heat to melt at about 90"C.
Alumina AM-22 and Leburon L-2 are dispersed and cooled at room temperature to obtain a liquid dispersion.

Comparative Example 7 Ciel Sol 71 40.0KF994
6.7 Wednesday
40.0 Sasol Wax A 1
5.0 Morpholine 0.3 Alumina AM-225.0 100, KF994 was added to Owt Shell Rune 71, and Sasol Wax A1 and Polywax 2000 were added to it, about 120
Heat to ℃ to dissolve. After cooling this at about 70"ct, warm water of about 70°C to which morpholine has been added is injected into it with a stirrer to obtain a W10 type emulsion.Alumina AM-22 is dispersed in this. Cool at room temperature to obtain a viscous emulsion.

Comparative Example 8 Peganur 3040 50.0 water
18.7 Hoechstwax S 5.0 Morpholine
1.3 Alumina AM-225.0 pw powder 2010 10.0 Asahi Guard AC-71010.0 100.0wt% Add Hoechstwax S to Vegasol 3040 and melt by heating to about 90°C. This is poured into warm water at about 80°C to which morpholine and Asahi Guard AG-710 have been added, using a stirrer to prepare an O/W emulsion. Alumina AM-22 and PW powder 2010 are dispersed in this and left to stand at room temperature to obtain a soft paste.

Comparative Example 9 108 P 0.1100, O
wt arrogant comparative example 10 108 R 12,0 Pegasol 3040 88.0100.0vt
S Comparative Example 9, how to make 108P or 10
Add 8R to Pegasol 3040, heat to about 120°C to melt, and cool in a room temperature trench to obtain a liquid dispersion.

Test method: The roof of a 1957 Toyota Corolla white painted car is used for testing. First, the car is washed, then a cleaner wax is applied to remove dirt, and the remaining wax coating components are removed using an aliphatic solvent to prepare a test surface.

This test surface is divided into 21 sections, and each sample is applied to each section. One section is left uncoated for use as an empty test soap.

First, take an appropriate amount of the sample onto a urethane sponge and spread it over one test section. After air drying for about 15 minutes, buff with a clean cotton towel to form a test wax film. The test vehicle is parked outdoors. Each week is a unit of time, during which time more than 1,100 km will be traveled on the road. Washing with water is performed at a rate of 1 VC per unit. The following test items will be tested using this test procedure. The test period will continue for four months.

(1) Sustaining effect of glossiness The persistence of glossiness is visually compared with a blank test, and the period until glossiness disappears is evaluated in weeks.

(2) Continuing effect of water repellency Regarding the continuation of water repellency, after washing with water, the water clarity when showering on the roof was visually compared with a blank test. 1. Evaluate on a weekly basis.If water repellency persists throughout the test period, the degree of water clarity will be visually determined at the final evaluation.

(3) Continuing effect of stain resistance Regarding the sustainability of stain resistance, after washing with water, completing a water repellency test, and wiping off the water, we conducted a blank test to check the contamination state and removed some of the stain with cleaner wax. The period until obvious contamination occurs is evaluated in weeks by visual judgment while comparing with the surface that has been contaminated. If the stain resistance is still maintained during the test period, the degree of stain resistance will be visually judged at the final evaluation. The test results are shown in Table-1.

Margin below ``Effects of the Invention'' The product of the present invention has the structure described above, and in particular, when used on painted surfaces of automobiles, the gloss, water repellency, and stain resistance last long. , suitable as a protective water-repellent polish for automotive paint films.

Claims (1)

Scope of Claims: (1) An organic solvent-soluble waxy hydrocarbon compound having a fluorine-containing organic group (hereinafter referred to as fluorine-modified wax) is dissolved in a solvent or water at a concentration of 0.2 to 10.0 wt%, or A protective water repellent for automobile paint films characterized by being dispersed. (2) The protective water repellent for automobile paint films according to claim (1), wherein the fluorine-modified wax is a product obtained by bonding a higher alcohol and a carboxylic acid having a fluorine-containing organic group through an esterification reaction. (2) The protective water repellent for automobile paint films according to claim (1), wherein the fluorine-modified wax is a product in which a higher fatty acid and an alcohol having a fluorine-containing organic group are bonded by an esterification reaction. (4) Claim (1) wherein the fluorine-modified wax is obtained by bonding an α-olefin with an organosilicon compound having a fluorine-containing organic group and an Si-H group through a hydrosilylation reaction.
Protective water repellent for automotive paint films as described. (5) Automotive coating in which 0.2 to 40 parts by weight of a waxy aliphatic hydrocarbon having a melting point of 80 to 160°C is dissolved or dispersed in 100 parts by weight of the protective water repellent for paint films according to claim (1). Protective water repellent for membranes.