JP2000212547A - Water repellent soilproof agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water repellent soilproof agent excellent in workability during application and capable of forming a film excellent in water repellency and soilproof properties. SOLUTION: This water repellent soilproof agent comprises a polytetrafluoroethylene having 1,000-100,000 molecular weight, a spherical organic powder made of a melamine-based synthetic resin, an acryl-based synthetic resin, a silicone resin or a polyethylene resin, a silicone oil, a hydrocarbon-based solvent and a wax. The said polytetrafluoroethylene and the spherical organic powder are dispersed in the said hydrocarbon-based solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent and antifouling agent, and more particularly to a water-repellent and antifouling agent for imparting water repellency and antifouling property to a painted surface. The present invention relates to a water-repellent and antifouling agent that imparts water repellency and antifouling properties to office furniture, painted surfaces of building exteriors, and the like over a long period of time.

[0002]

2. Description of the Related Art As a treatment agent for forming a protective film on a painted surface of a vehicle such as an automobile and imparting properties such as water repellency, luster, and pollution prevention effect,
Conventionally, car wax has been well known.

[0003] The compounding ingredients of car wax include the know-how of each company. However, a wax component including a polishing component that protects the painted surface and gives a gloss to the painted surface, and a silicone oil and the like as main components are used. In general, a car wax mixed with a dispersant such as hydrocarbon and water, a surfactant, an abrasive, and the like has been generally used.

However, since the car wax contains silicone oil as a main component, it has been extremely difficult for the car wax to achieve both water repellency and antifouling property on a painted surface. That is, in the conventional car wax, those having good water repellency are inferior in antifouling properties, and therefore, on the painted surface treated with such car wax,
It was difficult to remove dirt by washing with water. On the other hand, the painted surface treated with car wax having a good antifouling property could easily wash off dirt by washing with water, but tended to have poor water repellency.

On the other hand, car wax mainly containing a fluororesin such as polytetrafluoroethylene is disclosed in
-38480, JP-A-6-25609, and JP-A-9-235506
No. has been proposed.

Japanese Patent Application Laid-Open No. 64-38480 discloses a low molecular weight polytetrafluoroethylene having a molecular weight of 1,000 to 100,000 and a coating surface protective agent such as carnauba wax which imparts water repellency to the coated surface. A coating agent containing the low molecular weight polytetrafluoroethylene and a dispersion medium such as industrial naphtha for dispensing the coated surface protective agent into a predetermined dosage form has been proposed.

Japanese Patent Application Laid-Open No. 6-25609 proposes a protective water repellent for automotive coating containing polytetrafluoroethylene, silicone fine particles, polyethylene fine particles and the like dissolved or swelled in a solvent.

Japanese Patent Application Laid-Open No. 9-235506 proposes a coating surface coating composition containing polytetrafluoroethylene having an average molecular weight of 1,000 to 100,000 and a fluorosilicone compound.

When car wax is applied to the surface of an automobile body, the car wax is usually applied and then left for a while to dry the car wax layer. After the car wax has dried, the car body surface is wiped with a towel or the like to remove excess car wax. This step of wiping the body surface with a towel or the like is usually referred to as “wiping up”. Car wax is also required to be easily wiped.

However, the low-molecular-weight polytetrafluoroethylene contained in any of the above-mentioned coating agent, coating protective agent, and coating surface coating composition (hereinafter sometimes referred to as “the above-mentioned coating agent”). Fluoroethylene is excellent in waterproofness and antifouling properties, but cannot be easily wiped off when excessively adhered to a painted surface.

Therefore, in the case of a car wax containing a large amount of polytetrafluoroethylene, such as the above-mentioned coating agent, in order to improve wiping properties,
It has been common practice to blend large amounts of oil components such as silicone oil, fluorosilicone oil, and fluorine-based oil.

However, in general, when a large amount of the oil component is added to car wax, the water repellency and the antifouling property of the protective film formed on the surface of the coating film tend to decrease. Therefore, in many cases, the coating agent and the like do not sufficiently exhibit the waterproofness and antifouling properties, etc., characteristic of polytetrafluoroethylene.

The present invention is excellent in workability at the time of coating,
Furthermore, a coating film having excellent water repellency and excellent antifouling property, that is, antifouling property (difficulty of soiling, easy of soiling) over a long period of time by being applied to a painted surface such as an automobile body. It is an object of the present invention to provide a water-repellent and antifouling agent capable of forming a water repellent.

[0014]

The water-repellent and antifouling agent for solving the above-mentioned problems has a molecular weight of 1,000 to 1,000.
100,000 polytetrafluoroethylene;
Melamine-based synthetic resin, acrylic-based synthetic resin, silicone resin, and spherical organic powder containing one or more synthetic resins selected from polyethylene resin, silicone oil, hydrocarbon-based solvent, and waxes, The polytetrafluoroethylene and the spherical organic powder are dispersed in the hydrocarbon-based solvent.

Preferred embodiments of the water-repellent / soil-repellent treatment agent include, for example: a polytetrafluoroethylene content of 0.5 to 50;
A water-repellent antifouling agent having a content of spherical organic powder of 0.5 to 20% by weight; a water-repellent antifouling agent having a content of hydrocarbon solvent of 30 to 97% by weight. A soil repellent, a water-repellent antifouling agent having a silicone oil content of 0.1 to 5% by weight, and a water repellent antifouling agent having a wax content of 1.0 to 10% by weight. be able to.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Description of each component The polytetrafluoroethylene, spherical organic powder, hydrocarbon solvent, silicone oil, and wax used in the water-repellent and antifouling agent of the present invention will be described in detail below. Will be described.

(1-1) Polytetrafluoroethylene As the polytetrafluoroethylene used in the present invention, a polymer obtained by polymerizing ethylene tetrafluoride according to a conventionally known method, and a polymer mainly containing ethylene tetrafluoride And a polymer obtained by polymerizing the monomer composition according to a conventionally known method.

The monomers other than ethylene tetrafluoride in the monomer composition include fluorine-containing monomers such as perfluoropropylene, perfluorovinyl ether, monochlorotrifluoroethylene and vinylidene fluoride, and fluorine-containing monomers such as ethylene. Copolymerization monomers can be mentioned. The content of the copolymerized monomer is preferably 10% by weight or less based on the entire monomer composition. When two or more copolymerizable monomers are contained, the total content of the copolymerizable monomers is preferably 10% by weight or less based on the entire monomer composition.

The molecular weight of the polytetrafluoroethylene is in the range of 1,000 to 100,000, preferably in the range of 1,000 to 25,000. Polytetrafluoroethylene having a molecular weight of less than 1,000 is
Since polytetrafluoroethylene may be sublimable and volatile, long-lasting water repellency and stain resistance may not be obtained when polytetrafluoroethylene is used. On the other hand, polytetrafluoroethylene having a molecular weight exceeding 100,000 does not adhere to the painted surface because of insufficient adhesion to the painted surface, and thus may not be fixed on the painted surface. The effect of adding polytetrafluoroethylene to the treating agent may not be obtained.

The above-mentioned polytetrafluoroethylene is usually used in the preparation of the water-repellent and antifouling agent of the present invention in the form of a dispersion dispersed in an appropriate dispersion medium. It can also be used for the preparation of a water stain control agent.

When the polytetrafluoroethylene is used in the form of a dispersion in the preparation of the water-repellent and antifouling agent of the present invention, the polytetrafluoroethylene dispersion may be, for example, a fluorocarbon solvent or kerosene. A dispersion or the like in which polytetrafluoroethylene powder is dispersed can be used.

Examples of the polytetrafluoroethylene powder include polytetrafluoroethylene particles having an average particle size of 0.1 to 100 μm or less. However, it is preferable that the particle diameter of the polytetrafluoroethylene particles does not exceed 100 μm from the viewpoint of dispersibility in the fluorocarbon solvent and a hydrocarbon solvent described below.

As the chlorofluorocarbon-based solvent, chlorofluorocarbon R-1
13 (HCFC-141b), Freon R-11, HCF
Examples thereof include halogenated aliphatic hydrocarbon compounds having at least one of a chlorine atom and a bromine atom and a fluorine atom, such as C-225 and Freon R-112. However, a solvent that dissolves or swells polytetrafluoroethylene, such as perfluorocarbon having a structure in which all hydrogen atoms of an aliphatic hydrocarbon are replaced by fluorine atoms, is not preferable.

The concentration of the polytetrafluoroethylene powder in the polytetrafluoroethylene dispersion is as follows:
It is usually 10 to 30% by weight based on the entire dispersion,
Preferably it is 10 to 25% by weight.

Examples of the polytetrafluoroethylene dispersion include "AG Lu" manufactured by Asahi Glass Co., Ltd.
b ”(trade name),“ KRYTOX D ”manufactured by DuPont
F "(trade name)," VYDAX fluorotelomer "(trade name)," Vidax AR "(trade name), and" Lubron "(trade name) manufactured by Daikin Industries, Ltd.

When the polytetrafluoroethylene is used in the form of a powder or a dispersion in the preparation of the water-repellent / soil-repellent treatment agent of the present invention, the polytetrafluoroethylene powder may be the polytetrafluoroethylene. Powders similar to the polytetrafluoroethylene powder described for the ethylene dispersion can be used. (1-2) Spherical organic powder The spherical organic powder in the water-repellent and antifouling treatment agent of the present invention includes:
It contains at least one synthetic resin selected from a melamine synthetic resin, an acrylic synthetic resin, a silicone resin, and a polyethylene resin. The content of the synthetic resin in the spherical organic powder is usually 80% by weight or more, preferably 90% by weight, and particularly preferably 95% by weight or more.

Examples of the melamine-based synthetic resin include melamine-lower aldehyde resins obtained by polycondensing melamines and lower aldehydes.

Examples of the melamines include melamine, acetoguanamine, and benzoguanamine.

The lower aldehydes include formaldehyde, acetaldehyde, paraformaldehyde,
Examples include paraacetaldehyde and trioxane.

Specific examples of the melamine / lower aldehyde resin include melamine formaldehyde resin, acetoguanamine formaldehyde resin, and benzoguanamine formaldehyde resin.

Examples of the acrylic synthetic resin include a functional acrylic resin which is an acrylic resin having a functional group such as a (meth) acrylic acid ester polymer, a hydroxy group, an amino group, and a carboxyl group; A crosslinked acrylic resin obtained by crosslinking an acrylic resin can be used. In addition, in this specification, "(meth) acryl" means both methacryl and acryl.

The (meth) acrylate polymers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Homopolymers and copolymers of (meth) acrylates selected from hexyl (meth) acrylate, ethylhexyl (meth) acrylate and the like can be mentioned.

Examples of the functional acrylic resin include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, (meth) acrylamide, and glycidyl (meth) acrylate. A polymer of a functional acrylic monomer having a group, a copolymer of the functional acrylic monomer and a (meth) acrylate, a copolymer of the functional acrylic monomer and styrene, and a polymer of the functional acrylic monomer ( A copolymer of (meth) acrylic acid ester and styrene can be exemplified.

As the cross-linkable acrylic resin, for example, an appropriate cross-linking agent such as phosgene, a diisocyanate compound, maleic acid, fumaric acid, phthalic acid, itaconic acid, citraconic acid, and divinylbenzene may be used. Examples of the resin include a resin crosslinked by at least one of means such as heat, electron beam, visible light, ultraviolet light, and radiation.

Examples of the spherical organic powder containing the silicone resin include silicone rubber powder, which is a fine powder of silicone rubber having a crosslinked linear dimethylpolysiloxane, and a structure in which siloxane bonds are crosslinked in a three-dimensional network. Resin powder which is a powder of a cured polyorganosilsesquioxane having a silicone resin, silicone composite powder which is a spherical powder in which the surface of a silicone rubber powder is coated with a silicone resin, and hydrophobicizing the surface of a spherical amorphous silica with silicone Hydrophobic silica powder, which is a treated silica fine powder, may be mentioned.

Examples of the spherical organic powder containing the polyethylene resin include fine powders obtained by treating the polyethylene resin by a method such as a fluid immersion method, a powder rotational molding method, and a chemical pulverization method. .

The average particle size of the spherical organic powder is usually in the range of 1 to 20 μm, preferably in the range of 1 to 11 μm. By using a spherical organic powder having an average particle size in the above range, to the water-repellent antifouling treatment agent of the present invention,
Particularly good workability and long-lasting water repellency and antifouling properties can be imparted.

The spherical organic powder in the water-repellent and antifouling agent of the present invention includes, in addition to particles having a true spherical shape, particles having a substantially spherical shape. Here, the “substantially spherical shape” means a shape that is almost spherical to such an extent that it is observed to be substantially spherical when the shape is observed using a magnifying observation means such as an electron microscope and an optical microscope. As the "substantially spherical shape", specifically, a spheroid, oval, nearly spherical to the extent that it is observed to be substantially spherical when observing the shape using the magnifying observation means And a shape of a rotating body such as a pear type.

Specific examples of the spherical organic powder include "Eposter" (melamine formaldehyde resin and benzoguanamine formaldehyde resin) manufactured by Nippon Shokubai Co., Ltd., and "Eposter" manufactured by Soken Chemical Co., Ltd. MR series "(crosslinked acrylic resin), Toshiba Silicone Co., Ltd. product name" Tospearl "(silicone resin),
Toray Dow Corning Silicone Co., Ltd. product name "Trefil" (silicone resin), Shin-Etsu Silicone Co., Ltd. product name "KMP series" (silicone resin, silicone rubber), and Sumitomo Seika Co., Ltd. product name "Flow beads" (polyethylene resin) and the like can be mentioned.

(1-3) Hydrocarbon Solvent In the water repellent / fouling / treating agent of the present invention, the hydrocarbon solvent is
It has a function as a dispersion medium in which the polytetrafluoroethylene and the spherical organic powder are dispersed.

Therefore, a hydrocarbon solvent which does not substantially dissolve or swell the polytetrafluoroethylene and the spherical organic powder can be used as the hydrocarbon solvent in the water-repellent and antifouling agent of the present invention. .
Here, the phrase "does not substantially dissolve or swell"
When the polytetrafluoroethylene and the spherical organic powder are dispersed in the hydrocarbon-based solvent, the polytetrafluoroethylene and the spherical organic powder do not dissolve in the hydrocarbon-based solvent. And does not swell with the hydrocarbon-based solvent to the extent that it can be confirmed by observation with an observation means such as a microscope.

Examples of the hydrocarbon solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and petroleum solvents.

Examples of the aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, isooctane,
Linear aliphatic hydrocarbons such as nonane, decane, undecane, and dodecane, 2-methylbutane, 2-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2,2,3-trimethylpentane, and 2, 2,5
-Branched aliphatic hydrocarbons such as trimethylhexane, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, methylcyclopentane, ethylcyclohexane, p-menthane, and decalin.

Examples of the aromatic hydrocarbon solvent include:
Benzene, toluene, p-xylene, o-xylene, m
-Xylene, ethylbenzene, cumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, p-cymene, mesitylene, tetralin, cyclohexylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, pentylbenzene,
Examples thereof include dipentylbenzene and dodecylbenzene.

As the petroleum solvent, for example, 30 to 3
Petroleum solvents having a boiling point in the range of 00 ° C. can be mentioned, and specific examples thereof include petroleum ether, petroleum benzene, petroleum naphtha, ligroin, industrial gasoline, kerosene, and solvent naphtha.

As the hydrocarbon solvent, the petroleum solvent is preferable because it is inexpensive, has low odor and toxicity, and further dissolves well the silicone oils and waxes described later. Particularly, petroleum ether, petroleum benzine, petroleum naphtha, ligroin, and solvent naphtha are preferable.

(1-4) Silicone Oil Examples of the silicone oil include liquid silicone which is liquid at room temperature, and specifically, 0.65 to 1,000,000 cSt at room temperature (for example, 25 ° C.). A liquid silicone having a viscosity can be used.

Examples of the liquid silicone include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, and modified silicone oil.

As the modified silicone oil, at least a part of the methyl groups of the dimethyl silicone oil is
For example, polyoxyalkylene group, long chain alkyl group, fluoroalkyl group, chlorophenyl group, amino group, amino group-containing alkyl group, epoxy group, epoxy group-containing alkyl group, mercapto group, mercapto-containing alkyl group, carboxyl group, carboxyl group-containing And a silicone oil substituted by at least one group selected from the group consisting of a group, a higher fatty acid residue, and a vinyl group.

(1-5) Waxes The waxes used in the water-repellent and antifouling material of the present invention include:
Vegetable waxes, animal waxes, mineral waxes, synthetic waxes, and wax-like substances can be exemplified.

Examples of the vegetable wax include carnauba wax, candelilla wax, rice wax, and wood wax.

Examples of the animal wax include beeswax, spermaceti, lanolin, lanolin derivatives, tallow and lard.

Examples of the mineral wax include paraffin, vaseline, ozokerite, ceresin, and microcrystalline wax.

Examples of the synthetic wax include polyethylene wax, polypropylene wax, α-olefin wax, ester of synthetic fatty acid and higher alcohol, synthetic fatty acid glyceride, paraffin oxide, microcrystalline oxide wax, olefin, maleic anhydride, acrylic Copolymers with one or more monomers selected from the group consisting of acids and vinyl acetate can be mentioned.

Examples of the wax-like substance include higher fatty acids, synthetic fatty acids, higher alcohols, hardened oils, fatty acid amides, metal soaps, and polyethers.

(2) Compounding Amount of Each Component The compounding amounts of polytetrafluoroethylene, spherical organic powder, hydrocarbon solvent, silicone oil, and wax are as follows.

The blending amount of polytetrafluoroethylene is
Usually 0.5 to 50% by weight based on the total weight of the water repellent / antifouling agent
And preferably in the range of 1 to 30% by weight.

When the compounding amount of polytetrafluoroethylene in the water-repellent / soil-repelling agent of the present invention is within the above range, it is easy to wipe off after application and a film having high water repellency and antifouling property is provided. A water-repellent and stain-proofing agent is obtained.

When the polytetrafluoroethylene is blended in the form of a dispersion, the dispersion should be blended so that the amount of the polytetrafluoroethylene powder with respect to the entire water-repellent and antifouling agent is in the above-mentioned ratio. Is preferred.

The compounding amount of the spherical organic powder is usually in the range of 0.5 to 20% by weight, preferably in the range of 1 to 15% by weight, based on the whole water-repellent and antifouling agent. When the compounding amount of the spherical organic powder is within the above range, a water-repellent and antifouling agent which imparts water repellency and antifouling property that is particularly long-lasting can be obtained. Further, when the compounding ratio of the spherical organic powder is within the above range, the workability at the time of applying and wiping the water repellent / soil repellent is greatly improved.

The amount of the hydrocarbon solvent is usually in the range of 30 to 97% by weight, preferably 50 to 85% by weight, based on the total amount of the water-repellent and antifouling agent.

The content of silicone oil is usually 0.1
-5% by weight, preferably 0.5-4% by weight. The content of the wax is usually 1 to 10% by weight, preferably 2 to 7% by weight. The water-repellent and antifouling agent containing the silicone oil and the wax in the above-mentioned ranges is preferable in that it imparts a very beautiful luster to a painted surface of an automobile or the like and has good elongation.

(3) Other Components In addition to the polytetrafluoroethylene, the spherical organic powder, the hydrocarbon-based solvent, the silicone oil, and the waxes, the water-repellent and stain-proofing agent of the present invention includes a luster. At least one of a dispensing agent, a resin, a surfactant, an abrasive, and a thickener can be blended.

Examples of the resin include petroleum resin, methacrylic resin, resin varnish, terpene resin, rosin gum, copal and the like.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a fluorine-based surfactant. When the surfactant is blended in the water-repellent antifouling agent of the present invention, a water-repellent antifouling agent having an emulsion form is prepared by further mixing water in addition to the surfactant. be able to.

Examples of the abrasive include silica, kaolin, diatomaceous earth, zeolite, calcium carbonate, alumina, aluminum hydroxide, cerium oxide, and magnesium oxide.

Examples of the powder include an inorganic powder and a synthetic resin powder. Examples of the inorganic powder include fine powder silica and fine powder alumina, and examples of the synthetic resin powder include polyolefin powder, polytetrafluoroethylene powder, and silicone resin powder. Incidentally, the powder may be in an irregular shape.

Examples of the thickener include an inorganic thickener, a cellulose derivative thickener, a starch derivative thickener, a synthetic thickener, a vegetable thickener, and an animal thickener. it can.

Examples of the inorganic thickener include clay minerals such as bentonite, montmorillonite, and mica.

The cellulose derivative-based thickeners include:
Examples thereof include carboxymethyl cellulose, methyl cellulose, and ethyl cellulose.

Examples of the starch derivative-based thickener include soluble starch, carboxymethyl starch, and dialdehyde starch.

Examples of the synthetic thickener include polyvinyl alcohol, polyacrylate, and a water-soluble polyacryl copolymer.

Examples of the vegetable thickener include galactan, tragacanth gum, gum arabic, karaya gum, xanthan gum, locust bean gum, tara gum, tamarind gum, quince seed gum, pectic polysaccharide, agar, carrageenan, sodium alginate, and cyclodextrin. And the like, and secretions of plants, extracts from seeds, and thickeners derived from seaweed and the like.

Examples of animal thickeners include thickeners derived from animal muscle, skeleton, exoskeleton and the like, such as gelatin, casein, collagen, chitin, and chitosan.

The types and amounts of the above-mentioned polishes, resins, surfactants, abrasives, powders, thickeners and the like (hereinafter sometimes referred to as “other components”) are determined, for example, by the water-repellent protection. It is freely selected according to the form of the soil treatment agent and the performance required of the water-repellent and soil-resistant treatment agent. However, if the other components are excessively mixed, there is a possibility that a film having high water repellency and antifouling property may not be obtained, so the amount of the other components is based on the entire water repellent and antifouling agent. It is preferable that the total amount does not exceed 20% by weight, and particularly a range of 10% by weight or less.

(4) Method for Preparing Water-Repellent / Soil-Repellent Treatment Agent of the Present Invention In preparing the water-repellent / soil-repellent treatment agent of the present invention, polytetrafluoroethylene, spherical organic powder, hydrocarbon solvent
There are no particular restrictions on the order in which the silicone oil and waxes are compounded.

The polytetrafluoroethylene may be blended in the form of a dispersion as described above.
You may mix | blend in the form of a powder.

The method for preparing the water-repellent / soil-repellent treatment agent containing the above-mentioned polytetrafluoroethylene in the form of a dispersion liquid is as follows.
For example, a wax is dissolved in the hydrocarbon solvent,
A method of blending the obtained solution with the dispersion of polytetrafluoroethylene, the spherical organic powder, and the silicone oil can be used.

In the above method, there is no particular limitation on the order in which the dispersion of polytetrafluoroethylene, the spherical organic powder, and the silicone oil are mixed with the solution in which the wax is dissolved in the hydrocarbon solvent. Therefore, a dispersion of polytetrafluoroethylene, a spherical organic powder, and a silicone oil may be simultaneously blended into the solution, and a tetrafluoroethylene dispersion is blended into the solution first, and then a spherical organic powder is blended. And
Finally, silicone oil may be blended.

As a method for preparing a water-repellent / soil-repellent treating agent in which polytetrafluoroethylene is blended in the form of a dispersion, other than the above, a dispersion of polytetrafluoroethylene, a spherical organic powder, a hydrocarbon solvent, A method in which silicone oil and waxes are mixed at the same time can be used.

On the other hand, as a method for preparing a water-repellent / fouling-treating agent containing the polytetrafluoroethylene in the form of a powder, for example, the waxes are first dissolved in the hydrocarbon-based solvent, and the resulting solution is added to the solution. And a method of blending the polytetrafluoroethylene powder, the spherical organic powder, and the silicone oil.

In the above method, there is no particular limitation on the order in which the polytetrafluoroethylene powder, the spherical organic powder, and the silicone oil are mixed with the solution in which the wax is dissolved in the hydrocarbon solvent. In the solution, the polytetrafluoroethylene powder, the spherical organic powder, and the silicone oil may be simultaneously compounded.In the solution, the polytetrafluoroethylene powder is first suspended, and then the The spherical organic powder may be suspended, and finally, the silicone oil may be blended.

As a method for preparing a water-repellent / fouling / treating agent containing polytetrafluoroethylene in the form of powder,
A method of first dispersing polytetrafluoroethylene powder in the hydrocarbon-based solvent, then dispersing the spherical organic powder, and then blending silicone oil and waxes can be mentioned.

As a method for preparing a water-repellent / soil-repelling agent containing the above-mentioned polytetrafluoroethylene in the form of a powder, a polytetrafluoroethylene powder and a spherical organic powder were further mixed in advance in a dry state. Dispersing the mixture in a hydrocarbon solvent, a method of blending silicone oil and waxes in the resulting dispersion, and first dispersing the spherical organic powder in the hydrocarbon solvent, then the polytetrafluoroethylene Dispersion and a method of blending silicone oil and wax with the obtained dispersion can be mentioned.

When the above-mentioned other components are added to the water-repellent / antifouling agent, the other components may be added at any time.

Therefore, when a powder or dispersion of polytetrafluoroethylene, a spherical organic powder, and silicone oil are simultaneously added to a solution in which waxes are dissolved in a hydrocarbon solvent, the above-mentioned other components are used. To
The respective components can be simultaneously added to the solution at the same time.

On the other hand, when a powder or dispersion of polytetrafluoroethylene, a spherical organic powder, and silicone oil are mixed in this order in a solution in which waxes are dissolved in a hydrocarbon solvent, May be blended before or after blending the polytetrafluoroethylene powder or dispersion, may be blended after blending the spherical organic powder, or after blending the silicone oil, that is, finally You may mix.

The preparation of the water-repellent / soil-repellent treating agent may be carried out at normal temperature or under heating. Here, "perform at room temperature"
Means that the water-repellent and antifouling agent is prepared without heating the system. However, even when the preparation of the water-repellent and antifouling agent is performed “at room temperature”, when the waxes are previously dissolved in a hydrocarbon solvent and the remaining components are blended, the wax is heated to the melting point of the waxes. The waxes are dissolved in a hydrocarbon solvent, the resulting solution is cooled to room temperature, and the remaining components can be added to the solution.

(5) Method of Using the Water-Repellent / Soil-Repellent Treatment Agent of the Present Invention The water-repellent / soil-repellent treatment agent of the present invention can be used in accordance with the same procedure as that for applying a conventional car wax.

For example, when the water-repellent and stain-proofing agent of the present invention is applied to the body of an automobile, the water-repellent and stain-proofing agent is attached to a sponge or a cloth, and the sponge or the cloth is used to paint the surface of an automobile or the like. By lightly rubbing, the water-repellent and antifouling agent can be applied. Then, the applied water-repellent and antifouling agent is naturally dried, and finally, the body surface is wiped up and excess water-repellent and antifouling agent is wiped off, whereby a film having excellent water-repellent and antifouling properties is formed on the body surface. It is formed.

[0091]

The water-repellent and antifouling agent of the present invention contains a spherical organic powder in addition to polytetrafluoroethylene. Therefore, in the water-repellent and antifouling agent, the amount of the oil component such as a polishing agent can be greatly reduced as compared with the conventional car wax, and in some cases, the oil component becomes unnecessary. Therefore, the coating film formed on the painted surface by the water-repellent / antifouling agent has high antifouling properties.

When the coating of the water-repellent and antifouling agent is dried,
The spherical organic powder in the water-repellent and antifouling agent is incorporated into the polytetrafluoroethylene coating. Therefore, it is considered that the spherical organic powder rolls like a ball bearing in the polytetrafluoroethylene coating during the wiping operation. Therefore, in the water-repellent and antifouling treatment agent of the present invention, the wiping operation after drying is extremely easy and the cleanliness is high even though the amount of the oil component is small or contains little or no oil component. It is possible to remove an excessive layer of the water-repellent and antifouling agent by wiping it once with a simple towel.

In addition, in the water-repellent and antifouling agent of the present invention, as described above, since a film having a structure in which the spherical organic powder is incorporated into the film of polytetrafluoroethylene is formed, polytetrafluoroethylene alone is used. It is considered that a higher degree of water repellency and antifouling effect can be obtained than in the case of

Further, the water-repellent and antifouling agent of the present invention contains a silicone oil and a wax. Therefore, this water-repellent antifouling agent is applied to a painted surface of an automobile or the like,
When wiped up, fine scratches on the painted surface are filled with the silicone oil and waxes, so the painted surface is considered to be a smooth glossy surface. Therefore, it is considered that this water-repellent and stain-proofing agent imparts an extremely beautiful luster to a painted surface of an automobile or the like.

[0095]

The present invention will be described more specifically below with reference to examples. Hereinafter, "%" means% by weight.

<1. Preparation of water-repellent and antifouling agent> (Example 1) Carnauba wax (manufactured by Kato Yoko Co., Ltd.)
5% by weight of Naphtha No. 1 was heated to the same temperature as the melting point of the carnauba wax. 5 (manufactured by Exxon Chemical Co., Ltd., boiling point: 154 to 197 ° C.). The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After the carnauba wax solution was cooled to room temperature, TS solution was added to the solution as silicone oil.
F451 (manufactured by Toshiba Silicone Co., Ltd., dimethyl silicone oil, viscosity 2 cSt) 2%, as a spherical organic powder, Eposter S-12 (trade name) (manufactured by Nippon Shokubai Co., Ltd.
Spherical melamine formaldehyde condensate, average particle size 1.2
μm) 10%, and KRYTOX DF (trade name) as a polytetrafluoroethylene (manufactured by DuPont, HCF such that the molecular weight is 3,300 and the solid content is 15% by weight).
30% by weight (dispersed in C-141b) and stirred at room temperature to prepare a water-repellent and stain-proofing agent. The resulting water-repellent and antifouling agent was a uniform dispersion.

(Example 2) Naphtha No. 33% by weight was prepared by heating 5% by weight of the carnauba wax to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, the solution contained 2% TSF451, 10% Eposter S-12, and 50% KRYTOX DF.
% By weight and stirred at room temperature to prepare a water-repellent and antifouling agent. The resulting water-repellent and antifouling agent was a uniform dispersion.

(Example 3) Carnauba wax 5% by weight
Was heated to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring.
After cooling the carnauba wax solution to room temperature,
The TSF451 (viscosity of 1,000 cS) was added to this solution.
t) is 1%, the eposter S-12 is 10%, the K
RYTOX DF was added at 30% by weight, and stirred at room temperature to prepare a water-repellent and antifouling agent. The water-repellent and antifouling agent was a uniform dispersion.

(Example 4) Carnauba wax 5% by weight
Was heated to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring.
After cooling the carnauba wax solution to room temperature,
TSF451 (viscosity 2 cS)
t) of 2%, 10% of MR-7G (trade name) (manufactured by Soken Chemical Co., Ltd., spherical crosslinked acrylic resin, average particle size of 3 to 10 μm) as spherical organic powder, and AG Lub-G as polytetrafluoroethylene. (Trade name) (manufactured by Asahi Glass Co., Ltd., molecular weight 4,000, solid content 11%, HCFC
(Dispersed in -225) and stirred at room temperature to prepare a water-repellent and antifouling agent. The resulting water-repellent and antifouling agent was a uniform dispersion.

Example 5 5% by weight of the carnauba wax was heated to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, 2% of the TSF451 was added to this solution, and Trefil E-605 (Dow Corning Toray Silicone Co., Ltd.) was used.
And spherical silicon rubber (average particle size: 2 μm), 10%, and 41% by weight of the AG Lub-G were added to prepare a uniform dispersion liquid water-repellent and antifouling agent.

Example 6 38% by weight of naphtha No. 1 obtained by heating 5% by weight of the carnauba wax to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, 2% of the TSF451 was added to the solution, and KMP-5 was added.
90 (Shin-Etsu Silicon Co., Ltd., spherical silicone resin, average particle size 2 μm) 10%, and Lubron LDE-3 (Daikin Industries, Ltd., polytetrafluoroethylene, molecular weight 10,000, solid content 10%) Kerosene and HCFC
(Dispersed in -141b) to prepare a uniformly dispersed liquid water-repellent and stain-proofing agent.

(Example 7) 38% by weight of naphtha No. 1 obtained by heating 5% by weight of the carnauba wax to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, 2% of the TSF451 and flow beads LE-1080 (manufactured by Sumitomo Seika Co., Ltd., spherical low-density polyethylene, average particle size 6 ± 1 μm) were added to the solution. 10% and 45% by weight of the above-mentioned Lubron LDE-3 were added to prepare a uniform dispersion liquid repellent / waterproofing agent.

(Comparative Example 1) 5% by weight of the carnauba wax was heated to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, 2 wt% of the TSF451 (viscosity 2 cSt) was added to this solution instead of the spherical organic powder in the present invention,
10% by weight of amorphous polyethylene fine powder PW2010 (manufactured by Toyo Petrolite Co., Ltd., average particle size of 5.9 μm) and 30% by weight of the KRYTOXDF were added, and the mixture was stirred at room temperature to perform water-repellent and stain-proof treatment. An agent was prepared. The resulting water-repellent and antifouling agent was a uniform dispersion.

(Comparative Example 2) Naphtha No. of 63% by weight was prepared by heating 5% by weight of the carnauba wax to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, 2% by weight of the TSF451 (viscosity: 2 cSt) and 30% by weight of the KRYTOX DF were added to the solution, and the mixture was stirred at room temperature and stirred at room temperature. Was prepared. The resulting water-repellent and antifouling agent was a uniform dispersion.

(Comparative Example 3) 5% by weight of the carnauba wax was heated to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, the solution was added to the TSF451 (viscosity of 1,000 c).
8% by weight of St) and 30 of the KRYTOX DF
% By weight and stirred at room temperature to prepare a water-repellent and antifouling agent. The resulting water-repellent and antifouling agent was a uniform dispersion.

(Comparative Example 4) 5% by weight of the carnauba wax was heated to the same temperature as the melting point of the carnauba wax. 5 with stirring. The naphtha no. After dissolving carnauba wax in 5, the solution was cooled to room temperature while stirring. After cooling the carnauba wax solution to room temperature, 8 wt% of the TSF451 (viscosity: 2 cSt) and 30 wt% of the KRYTOX DF are added to the solution, and the mixture is stirred at room temperature and stirred at room temperature. Was prepared. The resulting water-repellent and antifouling agent was a uniform dispersion.

<2. Evaluation of water-repellent and antifouling agent> The water-repellent and antifouling agent of Examples 1 to 7 and Comparative Examples 1 to 4 were evaluated for water-repellent performance and antifouling performance according to the following methods.

2-1 Test Method Nissan AD van of 1994, Nissan Sunny of 1991,
And the car hood and roof of the 1995 Mitsubishi FTO. After washing the car, iron powder and the like remaining on the painted surfaces of the three automobiles were removed using trap clay, and scales remaining on the painted surfaces were removed using a cleaner wax and a buff. Further, the bonnet part and the roof part are designated by Naphtha No. 5 and the wax remaining on the painted surface was removed.

The hood portion and the roof portion of each of the three automobiles were divided into nine sections by using a masking tape, and one of the nine sections was left for a blank test, and the remaining eight sections were used in the first embodiment. To 7 and Comparative Examples 1 to 4 were applied in the same manner as ordinary waxing. Note that different water-repellent and stain-proofing agents were applied to different sections. After applying the water-repellent and stain-proofing agent to the eight sections, each section was wiped off, and the workability of each of the water-repellent and stain-proofing agents was evaluated according to the criteria described later.

After wiping the nine compartments of the hood and roof of each of the three automobiles, the masking tapes of the three automobiles were peeled off, and the three automobiles were parked outdoors.

One and three months after the application of the water-repellent and antifouling agent, the three automobiles were washed, and nine compartments in each of the three automobiles were subjected to water washing after washing. The water pulling property, the water repellency after car washing, and the contamination rate after car washing were evaluated.

2-2 Evaluation Method and Evaluation Criteria (a) Workability The selected clean towel was folded in three, and the wax was wiped off in each of the nine sections. For each of the compartments, one side of a trifolded towel was used. Workability, that is, wiping property was evaluated according to the following criteria.

：: The dried water-repellent and antifouling agent can be wiped off by wiping with a towel once or twice. Δ: Dry wax can be wiped off by wiping with a towel three to five times. X: The dried wax cannot be removed unless it is wiped with a towel five or more times.

(B) Water drainage after car washing One month and three months later, the bonnet and roof of the three automobiles were washed with sponge and tap water, and then the water-repellent and stain-proofing agent on the bonnet and roof was removed. Tap water was applied to the application surface, and the degree of water withdrawal on the surface was visually observed to evaluate the water drawability. The evaluation of water drawability was performed based on the following criteria.

A: Water does not get on the painted surface. ：: Water is drawn from the painted surface in about 1 to 2 seconds. Δ: Water is pulled from the painted surface in about 5 seconds. ×: Water does not drain from the painted surface.

(C) Water repellency after car washing After one month and three months after car washing, water remaining on the painted surface was wiped off with a clean towel, and water was sprayed on the painted surface by a trigger pump. The state of water droplets was observed to evaluate the water repellency after car washing. The evaluation of water repellency was performed according to the following criteria.

A: Water droplets are spherical and roll on the painted surface. ：: Water droplets are spherical. Δ: Water droplet is elliptical. ×: Water droplets are amoebic.

(D) Pollution rate after car washing After washing one month and three months later, each section of the three cars was analyzed by a color analyzer TC-1800 (Tokyo Denshoku Co., Ltd.). The whiteness was measured. The whiteness of the three cars before the application of the water-repellent and antifouling agent after descaling was as follows.

Nissan AD Van: 47.4 Nissan Sunny: 57.8 Mitsubishi FTO: 60.4

The contamination rate is calculated by the following equation.

[Equation 1] [100− (whiteness after car washing / whiteness immediately after descaling)] × 100. The pollution rate is an average of the pollution rates measured for the three vehicles.

The degree of contamination was evaluated according to the following criteria.

◎: 0 ≦ contamination rate <2.0 ... No dirt is visible to the naked eye. ：: 2.0 ≦ contamination rate <10.0 ... Slightly dirty. Δ: 10.0 ≦ contamination rate <15.0: Stained. ×: 15.0 ≦ contamination rate: Very dirty.

<3. Results> For the water-repellent and antifouling agents of Examples 1 to 7 and Comparative Examples 1 to 4, the evaluation results of workability, water-repellency, water-repellency, and contamination rate after car washing are shown in Tables 1 and 2 below. Show.

[0124]

[Table 1]

[0125]

[Table 2]

As shown in Tables 1 and 2,
On the painted surfaces coated with the water-repellent and stain-proofing agents of Examples 1 to 7, the water-repellent and stain-proofing agents could be wiped off only by rubbing with a towel once or twice after drying. Therefore, it was found that each of the water-repellent and stain-proofing agents of Examples 1 to 7 had good workability.

Among the water-repellent and antifouling agents of Examples 1 to 7, the water-repellent and antifouling agents of Examples 1 to 3 using melamine formaldehyde resin as the spherical organic powder were coated one month after application. The surface shows a high water-drawing property so that the tap water can be drawn in 1-2 seconds even after the car wash, and is extremely high enough that the tap water sprayed on the painted surface after the car wash rolls down in a spherical shape It showed water repellency.

The coated surface shows the same high water-repellency even after 3 months from the application as the coated surface one month after the application, and has a high water repellency such that the tap water becomes spherical. Indicated.

Examples 4 to 5 relating to a water-repellent and antifouling treatment agent using a spherical powder of a crosslinked acrylic resin, a silicone resin or a polyethylene resin instead of the spherical powder of melamine formaldehyde resin in Examples 1 to 3 as the spherical organic powder. In No. 7, the painted surface showed even higher water-drawing and water-repellent properties. That is, when the water-repellent treatment agents of Examples 4 to 7 were used, the painted surface after car washing had a high water-drawing property such that water immediately drained and sprayed, both at one month and three months after application. The water thus obtained became spherical and showed high water repellency enough to start rolling immediately.

Regarding the difficulty of soiling the painted surface, that is, the antifouling property,
Regarding the painted surface to which any of the water-repellent and antifouling treatment agents of Examples 1 to 7 was applied, the contamination rate after 1 month and 3 months after application was 2% or less, and the painted surface after car washing. No dirt could be recognized with the naked eye. From this, it was found that the coated surfaces to which the water repellent and antifouling agents of Examples 1 to 7 were applied had high antifouling properties over a long period of time.

On the other hand, in the water-repellent and stain-proofing agent of Comparative Example 1 in which PW powder which is an amorphous polyethylene powder was blended in place of the spherical organic powder, 3 to 10
The water-repellent and antifouling agent could not be completely wiped off unless rubbed five times. Further, in the water-repellent and stain-proofing agent of Comparative Example 2 in which neither the spherical organic powder nor the PW powder was blended, the water-repellent and stain-proofing agent on the painted surface could be wiped off even if the painted surface was rubbed with a towel five times or more. Did not.

The coated surfaces coated with the water-repellent and stain-proofing agents of Comparative Examples 1 to 4 were significantly deteriorated in water drainage and water repellency even one month after the application. Further, the water-repellent and soil-repellent treatment agent of Comparative Example 1 in which irregular particles such as the PW powder were blended, and the water-repellent and soil-repellent agent of Comparative Example 3 in which a high-viscosity silicone oil having a viscosity of 1000 cSt was blended in a large amount of 8% by weight. In the case of the treating agent, it was found that the painted surface was significantly stained three months after the application, and it was difficult to remove the stain only with a car wash using tap water and sponge.

[0133]

According to the present invention, there is provided a water-repellent and antifouling agent which forms a film having high workability and excellent water repellency and antifouling properties over a long period of time.

According to the present invention, it can be easily applied to the painted surface of metal products such as automobiles, office furniture, and aircraft, and the surface of wooden furniture and the like. The present invention provides a water-repellent and antifouling agent which imparts water repellency, water-repellency, and antifouling properties that last for a long period of time.

According to the present invention, furthermore, it is excellent in elongation at the time of application, and has a very beautiful and deep gloss on the painted surface of metal products such as automobiles, office furniture and aircraft, and the surface of wooden furniture. Is provided.

Continued on the front page F term (reference) 4H020 BA02 BA06 BA12 BA32 4J038 BA212 CB021 CD121 CG141 DA161 DL031 DL032 KA06 MA02 MA07 MA10 MA14 NA05 NA07

Claims (6)

[Claims] (1) a molecular weight of 1,000 to 100,000;
And polytetrafluoroethylene, a melamine-based synthetic resin, an acrylic-based synthetic resin, a silicone resin, and a spherical organic powder containing one or more synthetic resins selected from polyethylene resins, a silicone oil, and a hydrocarbon-based solvent. And a wax, and wherein the polytetrafluoroethylene and the spherical organic powder are dispersed in the petroleum-based solvent. 2. The water-repellent and antifouling agent according to claim 1, wherein the content of polytetrafluoroethylene in the above item 1 is 0.5 to 50% by weight. 3. The method according to claim 1, wherein the content of the spherical organic powder is 0.5 to 20% by weight.
3. The water-repellent and antifouling agent according to 1. 4. The water-repellent and stain-proofing agent according to claim 1, wherein the content of the hydrocarbon solvent in the above item 1 is 30 to 97% by weight. 5. The water-repellent and antifouling agent according to claim 1, wherein the content of the silicone oil in the above item 1 is 0.1 to 5% by weight. 6. The water-repellent and antifouling agent according to claim 1, wherein the content of the wax in the above item 1 is 1 to 10% by weight.