JP2000073013A - Glazing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject glazing agent capable of forming a protective film excellent in water repellency, etc., by coating and polishing finishing using a sponge, etc., by including a specific hydroxyl group-containing siloxane polymer, etc. SOLUTION: This glazing agent contains (A) a hydroxyl group-containing siloxane polymer obtained by copolymerization of (i) a siloxane macromonomer represented by formula I [R1 is a 1-10C alkyl; R2 is a 1-6C bivalent hydrocarbon; R3 is H or methyl; and (n) is 6-300] with (ii) a hydroxyl group-containing vinyl monomer and, as necessary, (iii) other unsaturated monomers copolymerizable therewith and having a hydroxyl value within the range of 50-290 mg KOH/g, (B) a polyisocyanate compound and (C) a reactional product, etc., prepared by previously reacting (iv) an epoxy-terminated siloxane polymer represented by formula II [the average value of (m) is 6-150; (l) is 0-6; and R4 is a 1-6C alkyl] with (v) a sulfonic acid compound in a ratio so as to provide (1/1) to (10/1) (equiv. ratio) of the epoxy groups/sulfonate groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a water-repellent, water-sliding,
The present invention also relates to a polishing agent which is excellent in its durability and can form a protective film having excellent weather resistance and scratch resistance. The polishing agent of the present invention can be applied so as to be spread with a cloth or a sponge like an ordinary wax, and can form a urethane crosslinked film.

[0002]

2. Description of the Related Art Automobiles, railway vehicles, airplanes,
The coating surface of various outer panels of buildings and the like gradually deteriorates with time due to water or ultraviolet rays, and is contaminated or damaged by dust, dust, exhaust gas, and the like.
2. Description of the Related Art For the purpose of maintaining aesthetic appearance, a surface protective agent such as a wax is applied. For automobiles, for example, car wax or the like obtained by mixing silicone oil with wax is used, and this is applied on a coating film of an automobile outer panel to form a water-repellent film. As it is not formed, it does not have sufficient scratch resistance, acid resistance, and weather resistance, and is inferior in sustainability as a water-repellent film. There was a problem of coming. In some cases, fluororesin particles or polyethylene particles are added to wax to impart water repellency to make it easier to remove dirt. However, water droplets hardly flow down on the resulting water-repellent coating and become stained with time.

[0003]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a specific hydroxyl-containing siloxane polymer and polyisocyanate compound, a specific amount of an epoxy-terminated siloxane polymer and a sulfonic acid By using the reaction product of the compound or the composition containing the silicone oil as a polishing agent, it can be applied using a sponge, flannel, cloth, etc. in the same manner as a normal wax.
The present inventors have found that a protective film excellent in water repellency, water slippage, weather resistance, scratch resistance, acid resistance, and the like can be formed by polishing and finishing, and have reached the present invention.

That is, the present invention relates to (A) (a)

[0005]

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Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom or a methyl group, n is 6
A siloxane macromonomer represented by the following formula: (b) a hydroxyl group-containing vinyl monomer, and (c) if necessary, a hydroxyl value obtained by copolymerization with another unsaturated monomer copolymerizable therewith, is 50 to 50. 290mg KOH
/ G of a hydroxyl-containing siloxane polymer in the range of
(B) a polyisocyanate compound, and (C) (d) the following formula (II)

[0007]

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(Wherein, the average number of m is from 6 to 150,
l is an integer of 0 to 6, and R ⁴ is an alkyl group having 1 to 6 carbon atoms) and the sulfonic acid compound (e) and the epoxy group in (d). The equivalent ratio of the sulfonic acid groups in (e) is 1/1 to 10
/ 1) and / or a silicone oil having a viscosity of 10,000 cSt (25 ° C.) or less, and the amount of (C) used is (A) and (B). 30 to 200 parts by weight per 100 parts by weight of resin solids
Parts (A), (B) and (C) in two parts or three parts
It is intended to provide a polishing agent characterized by being mixed and dispersed immediately before use as a liquid.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a hydroxyl group-containing siloxane polymer (A) comprises a siloxane macromonomer (a), a hydroxyl group-containing vinyl monomer (b) and, if necessary, another unsaturated monomer copolymerizable therewith (c). Is obtained by copolymerization of

The siloxane macromonomer (a) is
It imparts water repellency to the surface of the crosslinked coating film, and has the following formula (I)

[0011]

Embedded image

Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, and R ² represents an alkyl group having 1 to 10 carbon atoms.
6 represents a divalent hydrocarbon group, R ³ represents a hydrogen atom or a methyl group, and n represents an average degree of polymerization of dimethylsiloxane units, and is 6 to 300, preferably 6 to 300.
A number in the range of 0.

The siloxane macromonomer (a) is generally in the range of 300 to 30,000, preferably 500 to 20,000.
It can have a number average molecular weight in the range of 00.

The hydroxyl group-containing vinyl monomer (b) is
It has both a role as a cross-linking functional group with a cross-linking agent and a role to give a water-sliding property.
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth)
C2-C8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as acrylate; polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and (meth)
Monoesters with unsaturated carboxylic acids such as acrylic acid;
Hydroxyalkyl vinyl ether, allyl alcohol, hydroxyalkyl ester of (meth) acrylic acid, (poly) alkylene glycol mono (meth) acrylate and the like and lactones (for example, ε-caprolactone,
adduct with γ-valerolactone); monoethers of polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol with hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; A saturated carboxylic acid;
Adducts with monoepoxy compounds such as Cardura E10 (manufactured by Shell Chemical) or α-olefin epoxide; glycidyl (meth) acrylate and acetic acid, propionic acid,
adducts with monobasic acids such as pt-butylbenzoic acid and fatty acids; acid anhydride-containing unsaturated compounds such as maleic anhydride and itaconic anhydride; ethylene glycol;
Monoester or diester with glycols such as 6-hexanediol and neopentyl glycol; containing hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether and chlorine such as 3-chloro-2-hydroxypropyl (meth) acrylate. Examples thereof include a hydroxyl group-containing monomer and allyl alcohol.

The other unsaturated monomers (c) include:
For example, carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 5-carboxypentyl (meth) acrylate Containing unsaturated monomers;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate (n-,
i-, t-), hexyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, (meth) acrylic acid n
-Alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as octyl, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. C2 to C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxybutyl (meth) acrylate; ethyl vinyl ether, n-propyl vinyl ether; Isopropyl vinyl ether, butyl vinyl ether, t-
Chain alkyl vinyl ethers such as butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether and octyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and trivinyl phenyl ether;
Aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; allyl ethers such as allyl glycidyl ether and allyl ethyl ether; vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, and pivalin Vinyl esters such as vinyl acrylate, vinyl caprate and veova monomer (manufactured by Shell Chemical Co.); propenyl esters such as isopropenyl acetate and isopropenyl propionate; ethylene, propylene, butylene,
Olefinic compounds such as vinyl chloride; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) Acrylates, nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-
Methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-
Polymerizable amides such as butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; 2-vinyl Aromatic nitrogen-containing monomers such as pyridine, 1-vinyl-2-pyrrolidone and 4-vinylpyridine;
Polymerizable nitriles such as acrylonitrile and methacrylonitrile; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, vinyltriacetooxysilane, β- (Meth) acryloyloxyethyltrimethoxysilane, γ
A hydrolyzable alkoxysilyl group-containing monomer such as-(meth) acryloyloxypropyltriethoxysilane;
Polymerizable glycidyl compounds such as glycidyl (meth) acrylate and allyl glycidyl ether; allyl monomers such as diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate, pentaerythritol diallyl ether, and allyl glycidyl ether; Perfluoroalkyl (meth) acrylates such as fluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-
Butylene glycol di (meth) acrylate, 1,4-
Butanediol diacrylate, glycerin di (meth)
Acrylate, glycerin tri (meth) acrylate,
Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Hydroxyisocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, glycerol allyloxydi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate 1,1,1-tris (hydroxymethyl) ethanetri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate,
Examples thereof include (meth) acrylates of polyhydric alcohols such as diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, and divinylbenzene.

The proportion of the above monomers can be varied over a wide range depending on the desired physical properties of the hydroxyl-containing siloxane polymer (A) to be obtained, but the siloxane macromonomer may be changed based on the total amount of the monomer mixture. (A) is 2 to 40% by weight, preferably 3 to 25% by weight, hydroxyl group-containing vinyl monomer (b) is 5 to 98% by weight, preferably 10 to 70% by weight, and other unsaturated monomer (c) is 0%. ９３93% by weight, preferably 5-87% by weight.

The copolymerization of the above monomer mixture is usually carried out by
In an organic solvent, in the presence of about 0.01 to about 8 parts by weight of polymerization initiator per 100 parts by weight of the total amount of monomers, about -2
At a temperature of 0 ° C. to about 150 ° C., at normal pressure or optionally about 3
The reaction can be carried out under a pressure of up to 0 kg / cm ² G.

The hydroxyl-containing siloxane polymer (A) thus obtained has a hydroxyl value of 50 to 290 mgKOH /
g, preferably in the range of 60 to 200 mg KOH / g. If the hydroxyl value is less than 50 mgKOH / g, the crosslinking is insufficient, the film strength is not obtained, and the durability is poor.

Further, the hydroxyl-containing siloxane polymer (A) has a number average molecular weight of 1,000 to 100,000.
0, preferably in the range of 3,000 to 50,000.

In the present invention, the polyisocyanate compound (B) includes, for example, tolylene diisocyanate,
Xylylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Aromatic, alicyclic or aliphatic polyisocyanate compounds such as neat, methylene diisocyanate and isophorone diisocyanate;
And isocyanurate and buret forms of these isocyanate compounds, ethylene glycol, propylene glycol, and the like in excess of these isocyanate compounds.
Examples thereof include a terminal isocyanate-containing compound obtained by reacting a low-molecular-weight active hydrogen-containing compound such as trimethylolpropane, hexanetriol, and castor oil, and lysine triisocyanate.

In the present invention, the component (C) comprises an epoxy-terminated siloxane polymer (d) and a sulfonic acid compound (e).
Reaction product (C-1) and / or silicone oil (C-2), which contributes to the improvement of the slipperiness and serves as a dispersion medium for the components (A) and (B). .
That is, since the component (C) is hardly compatible with the components (A) and (B), when the component (C) is stirred and mixed, the component (C) becomes cloudy as if the components (A) and (B) were emulsified. Is what you do. By the component (C), it is possible to spread with a sponge, flannel or the like in the same manner as a normal wax agent.

Epoxy-terminated siloxane polymer (d)
Is represented by the following general formula (II)

[0023]

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Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, preferably 1 to ⁴ carbon atoms;
Means the average degree of polymerization of dimethylsiloxane units, and 6 to
It is a number in the range of 300, preferably 6-100, and l is an integer of 0-6, preferably 1-5. The siloxane polymer (d) is generally used at 300 to 30,000.
It can have a number average molecular weight of 0, preferably in the range of 500 to 20,000.

The sulfonic acid compound (e) reacted with the siloxane polymer (d) has the following formula: R ⁵ —SO ₃ H (where R ⁵ is an organic residue, for example, an aliphatic hydrocarbon group,
Represents an aromatic hydrocarbon group or the like, the aliphatic hydrocarbon group,
The aromatic hydrocarbon group may be optionally substituted by a halogen atom or the like), specifically, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid,
Examples thereof include 2,4- or 2,5-dimethylbenzenesulfonic acid, naphthalene-α-sulfonic acid, and naphthalene-β-sulfonic acid. Of these, methanesulfonic acid is preferable.

The reaction product (C-1) is obtained by combining the siloxane polymer (d) and the sulfonic acid compound (e) with (d)
It can be obtained by reacting at a ratio such that the equivalent ratio of epoxy group in the sulfonic acid group in (e) becomes 0.5 / 1 to 10/1, preferably 1/1 to 8/1. Unreacted epoxy group-containing siloxane polymer (d) may be present in the reaction product (C-1). Unreacted sulfonic acid compound (e) in the reaction product (C-1)
May remain, but desirably does not substantially contain the unreacted sulfonic acid compound (e).

The reaction between the siloxane polymer (d) and the sulfonic acid compound (e) can be carried out, for example, by mixing the two at room temperature to 100 ° C. in the presence of an organic solvent, if necessary. Of course, both may be mixed and heated. Examples of the organic solvent include toluene, xylene, cyclohexane, petroleum ether, gasoline, kerosene, naphtha, chloroform, carbon tetrachloride, ethylene dichloride, 2-ethylhexanol, diethyl ether,
Examples include methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, butanol, dioxane, and mineral oil.

The reaction product (C-1) obtained as described above
Can be used as it is or by appropriately diluting or partially removing the solvent with an organic solvent to adjust the solid content concentration, and removing unreacted sulfonic acid compounds.

As the silicone oil (C-2), conventionally known various oils can be used. Specific examples thereof include polysiloxane type such as dimethylpolysiloxane, methylhydrogenpolysiloxane and methylphenylpolysiloxane. Silicone modified oils; alkyl-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, higher fatty acid-modified silicone oil, epoxy-modified silicone oil, vinyl-modified silicone oil, carbinol-modified silicone oil, Alcohol-modified silicone oil, polyether-modified silicone oil, alkyl-polyether-modified silicone oil, fluorine-modified silicone oil, and the like.
Among them, those containing a hydroxyl group, an amino group, an alkoxy group and the like can be suitably used. These commercial products include:
For example, "X-22-160AS", "KF-600
1 "," X-22-170DX "," X-22-176 "
“DX”, “KF-857” (all manufactured by Shin-Etsu Silicone), “TSF4770”, “TSF4702” (all manufactured by Toshiba Silicone), “SF8417”, “SF”
8427 "and" SF8428 "(both manufactured by Tre Silicone).

The silicone oil (C-2) has a viscosity of 10,000 cSt (25 ° C.) or less, preferably 3,0 cSt (25 ° C.).
00 cSt (25 ° C.) or less. The viscosity is 10,000
If it exceeds 0 cSt, it becomes difficult to spread and wipe it, which is not desirable.

In the present invention, the component (C) is used in an amount of 30 to 30 parts by weight based on 100 parts by weight of the resin solids in the composition.
200 parts by weight, preferably 50 to 150 parts by weight. If the content is less than 30 parts by weight, it is difficult to spread the composition as a polishing agent, while if it exceeds 200 parts by weight, there is no difference in the effect obtained.

In the present invention, the above-mentioned components (A), (B) and (C) may be used as a base liquid, a curing agent and a waxing agent, respectively, or as the base liquid (A). , The component (C) and the curing agent are stored as two components, the component (B), and mixed and dispersed immediately before use for use. In that case, the isocyanate group contained in the component (B) is 0.3 to 2.5 mol, preferably 0.5 to 2. mol per 1 mol of the active hydrogen group contained in the component (A). It is appropriate to mix and mix so as to be 0 mol.

The base liquid may optionally contain colloidal silica (D). The colloidal silica (D) is blended in order to improve the hardness, the abrasion resistance, and the slipperiness of the film, and is a dispersion in which ultrafine particles of silicic anhydride are dispersed in a solvent. The particle size of the silica particles is about 5 to 200 nm, and methano-
Alcohols such as toluene, ethanol, propanol and ethylene glycol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate; ethers such as diisopropyl ether. And mixtures thereof. As such colloidal silica, commercially available products include, for example, "Sno-Tex" series (manufactured by Nissan Chemical Industries, Ltd.) and "Oscar" (manufactured by Catalysis Chemical Industry). The above-mentioned colloidal silica may be partially reacted with an organosilicate.

The amount of the colloidal silica (D) used is
10 to 10 parts by weight of the total resin solids in the composition
100 parts by weight, preferably in the range of 20 to 50 parts by weight, is suitable.

In the present invention, an active hydrogen group-containing fluororesin or a fine powder wax can be added to the base liquid, if necessary. The active hydrogen group-containing fluororesin includes a hydroxyl group, a trialkylsilyloxy group, an amino group,
It is a resin soluble in an organic solvent containing an active hydrogen group such as a carboxyl group, and mainly contains a hydroxyl group. The hydroxyl group-containing fluorine-based resin is obtained, for example, by copolymerizing a monomer mixture containing fluoroolefin and hydroxyalkyl vinyl ether as main components and optionally other monomers such as alkyl vinyl ether. Perfluoroalkyl group-containing (meth) acrylic monomers, hydroxyl group-containing monomers and monomers containing other monomers copolymerizable therewith.
An acrylic copolymer obtained by copolymerizing a mixture is exemplified. The addition amount of the active hydrogen group-containing fluororesin is suitably not more than 50 parts by weight, preferably about 1 to 20 parts by weight, based on 100 parts by weight of the total resin solids in the composition.

Examples of the fine powder wax include fine powders of low molecular weight fluorinated ethylene resin, polyethylene wax, carnauba wax, bisamide wax, synthetic wax, mixed wax, silicone resin and the like. The fine powder wax has a particle diameter of 5 μm or less, preferably 2 μm or less. If the particle diameter exceeds 5 μm, it is not preferable because the wax is detached during wiping work or the finish is poor. The addition amount of the fine powder wax is 10% of the total resin solid content in the composition.
About 0.1 to 5 parts by weight to 0 parts by weight is appropriate.

In the present invention, if necessary, a curing catalyst, an ultraviolet absorber, a light stabilizer, an organic solvent, fine powders such as resin powders, additives such as a viscosity modifier and an antioxidant may be added to a base solution. Alternatively, it can be blended with any of the curing agents. As the curing catalyst, conventionally known curing catalysts can be used without any particular limitation. For example, amine catalysts such as triethylamine, tripropylamine, tributylamine, diethanolamine and triethanolamine; organic acids such as phosphoric acid and sulfonic acid; Esters: Organic metal compounds such as dibutyltin dilaurate, dibutyltin oxide, tin octylate, lead naphthenate, and cobalt naphthenate can be used, and among these, organic metal compounds are particularly preferable.

The polishing agent of the present invention is applied and spread by a sponge, cloth, or the like on a surface of various materials or a surface of a cured coating film formed thereon as a wax agent. Is wiped off with a flannel or cloth to form a thin protective film. The material surface includes, for example, glass, metal, plastic, ceramic, and the like, and the cured coating surface includes, for example, the coating surface of various outer plates such as automobiles, railway vehicles, airplanes, and buildings.

[0039]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Note that “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

Hydroxyl-containing siloxane polymer (A) solution
In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping device, 53.8 parts of xylene and 28 parts of methyl isobutyl ketone were charged, heated under stirring, and maintained at 115 ° C. Then, at the same temperature, “Silaprene FM-072
1 "(manufactured by Chisso Corporation, methacryl group-containing siloxane macromonomer, molecular weight: about 5,000) 5 parts, 2-hydroxyethyl methacrylate 35 parts, styrene 15 parts, n-butyl methacrylate 14 parts, i A mixture consisting of 30 parts of -butyl methacrylate, 1 part of acrylic acid and 4.2 parts of azobisisobutyronitrile was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was aged at 115 ° C. for 2 hours to obtain a nonvolatile content of 55%.
Hydroxyl value 151 mgKOH / g, number average molecular weight 12.0
A solution of the hydroxyl-containing siloxane polymer of No. 00 was prepared.

As a hydroxyl group-containing siloxane polymer solution, commercially available Reseda GSX-1015 (manufactured by Toa Gosei Chemical Co., Ltd., nonvolatile content: 45%, hydroxyl value: 120 mg)
KOH / g).

Epoxy-terminated siloxane polymer and sulfo
Production of reaction product (C-1) with acid compound 100 parts by weight of toluene are added to a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping device, into which "Silaprene FM" is added. 98.8 parts by weight of “-0511” (manufactured by Chisso Corporation, one-terminal epoxy group-containing polydimethylsiloxane, R ⁴ of the formula (II) is a methyl group, molecular weight 1,000), and the mixture was stirred and dissolved. Acid 1.
Two parts by weight were mixed at room temperature, and the mixture was stirred and reacted for about 1 hour. Further, toluene was removed to obtain a reaction product (C-1) solution having a nonvolatile content of 83%. Polishes Creating Example 1 above prepared as the hydroxyl group-containing siloxane polymer - solution 100g to dibutyl tin dilaurate - was vinegar - DOO 0.01 g, base and mixed and stirred compounding acetate n- butyl 10g. Immediately before use, "Duranate TPA-90E" (a polyisocyanate manufactured by Asahi Kasei Corporation) was added to the base solution immediately before use.
90%, nonvolatile content 90%, isocyanate group content: 21
%) Was mixed and stirred and mixed, and then 49 g of the reaction product (C-1) solution produced above was mixed with the mixture as a waxing agent, followed by stirring and mixing to prepare a milky white polishing agent. .

Example 2 0.01 g of dibutyltin dilaurate, 10 g of n-butyl acetate were added to 100 g of a siloxane polymer solution containing a hydroxyl group.
49 g of the reaction product (C-1) solution produced above was blended and mixed with stirring to obtain a milky white base solution. Immediately before use, "Duranate TPA-9", a curing agent, was added to the base solution.
0E "was mixed and stirred and mixed to prepare a polishing agent.

Examples 3 to 8 and Comparative Examples 1 to 3 In the same manner as in Example 1, except that the composition of the base liquid, the curing agent and the waxing agent was as shown in Table 1, Each polish was made. (Note 1) to (Note 9) in Table 1 are as follows.

(Note 1) "Snow-Tex MIBK-S"
T ": Nissan Chemical Industries, organic solvent type colloidal silica, non-volatile content 30% (Note 2)" Reseda GF-2000 ": Toa Gosei Chemical Co., Ltd., hydroxyl group-containing fluororesin, non-volatile content 60%, hydroxyl value 97 mg KOH / G (Note 3) "Tospar 105": Toshiba Silicone Co., Ltd.
Silicone resin fine particles, average particle size 0.5 μm (Note 4) “TSF-451”: Toshiba Silicone Co., Ltd., dimethylpolysiloxysan type silicone oil, viscosity 1,000 cSt (25 ° C.) (Note 5) ) "XF3905": dimethylpolysiloxysan type silicone oil, manufactured by Toshiba Silicone Co., Ltd., viscosity 70
0cSt (25 ° C) (Note 6) “TSF-4750”: manufactured by Toshiba Silicon Corporation
Alcohol-modified silicone oil, viscosity 170 cSt
(25 ° C) (Note 7) “YF3807”: dimethylpolysiloxysan-type silicone oil, manufactured by Toshiba Silicone Co., Ltd., viscosity 2
8,000 cSt (25 ° C.) (Note 8) “X-22-170DX”: a hydroxyl group-containing dimethylpolysiloxane type silicone oil manufactured by Shin-Etsu Silicone Co., Ltd., viscosity 75 cSt (25 ° C.) (Note 9) Commercial car Wax: Car wax mainly composed of carnauba wax

[0046]

[Table 1]

Performance test # 400 "Rethane PG-80 No400 Black" (two-part acrylic urethane paint, manufactured by Kansai Paint Co., Ltd.) was dried to a thickness of 50 .mu.m on a mild steel plate whose surface was polished by sandpaper. And spray dried at 60 ° C. for 30 minutes to obtain a test material plate.
× 400 × 0.8mm size, 70 × 1 for test plate II
The size was 50 × 0.8 mm. The glass plate whose surface was degreased was used as Test Plate III. Each test plate was subjected to the following performance tests. Table 2 shows the results.

(* 1) Coating workability: Each of the polishes obtained above was applied to test plate I using a commercially available sponge for car wax. The spreadability was evaluated according to the following criteria. ：: good △: slightly difficult to spread ×: fairly difficult to spread (* 2) Wiping workability: after the application work of (* 1) above
It was left at 25 ° C. for 15 minutes, and then wiped while polishing the coated surface with a flannel. The ease of wiping was evaluated according to the following criteria.

：: good Δ: slightly difficult to wipe ×: considerably difficult to wipe (* 3) glossiness: The test plate after the above-mentioned (* 2) wiping operation was visually evaluated.

○: good △: some gloss / unevenness ×: considerable gloss / unevenness (* 4) Scratch resistance: Each of the polishes obtained above was coated on test plate II with a car wax. It was applied using a commercially available sponge, allowed to stand at 25 ° C. for 15 minutes, and then wiped off while polishing the coated surface with a flannel to obtain each test plate.

Polishing powder (Dharma cleanser) and water:
2 to make an abrasive, dyeing fastness friction tester FR-
II (manufactured by Suga Test Instruments Co., Ltd.) was used. The abrasive was applied to the flannel and a load of 500 g was applied, and the coated surface of each test plate was reciprocated 20 times.
I rubbed it. Thereafter, the coated surface was washed with running water, and after natural drying, the 20-degree specular reflectance (20 ° G value) of the coated surface was measured, and the gloss retention rate relative to the 20 ° G value before the test was evaluated as follows. .

○: 20 ° G gloss retention of 40% or more Δ: Δ 20% or more and less than 40% ×: Δ less than 20% (* 5) Stain resistance: carbon black as a contaminant;
This was adhered to a flannel and rubbed lightly on the coated surface of the test plate as in the above (* 4). After leaving this in a constant temperature and humidity room at 20 ° C. and 75% RH for 24 hours, the coated surface is washed with running water,
The degree of contamination of the coating film was visually evaluated.

○: good Δ: a little stain remains ×: considerable stain remains (* 6) Accelerated weathering resistance: A test plate similar to the above (* 4) was tested for 1000 hours using a sunshine weather ometer. The state of the painted surface was visually evaluated.

：: There is almost no change in the coated surface. X: Water mark is observed on the coated surface, and the gloss is greatly reduced. (* 7) Gasoline resistance: The same test plate as in the above (* 4) was fixed horizontally. Gauze folded in four (50 x 50m
m) was impregnated with about 5 cc of regular type gasoline and left as it was for 3 minutes. Thereafter, the gauze was removed and the state of the coated surface after the gasoline was wiped off with another gauze was observed.

：: No abnormality Δ: Decrease in gloss of coated surface ×: Decrease in gloss and softening of coated surface (* 8) Water resistance: A test plate similar to (* 4) above was prepared at 20 ° C.
Was immersed in tap water for 7 days to examine the state of the coated surface.

：: No abnormality ×: Swelling, whitening occurred (* 9) Water slippage: Each glazing agent obtained above was applied on a test plate III using a commercially available sponge for car wax,
After standing at 25 ° C. for 15 minutes, the coated surface was wiped off while being polished with a flannel to obtain each test plate. After 20 μl of water was dropped on these test plates, each test coated plate was tilted at a constant speed, and the inclination angle at the time when water droplets flowed out was examined.

(* 10) Contact angle: A fixed amount (3 μl) of water was dropped on the same test plate as in (* 4), and the contact angle was measured after 30 seconds.

[0058]

According to the present invention, a resin solution containing the components (A) and (B) capable of forming a crosslinked film is prepared in a specific amount (C).
By mixing and dispersing in the components, an organic solvent-diluted resin solution that normally requires means such as spray coating to form a uniform film is dispersed, and the component (C) is used as a protective / lubricating agent. It acts as a layer to facilitate the application of the composition. After applying the polishing agent of the present invention, the component (C) is localized in the surface layer in the process of forming a crosslinked film, and is polished by wiping it with a flannel or a cloth.
Small scratches can be filled, and a protective film having excellent water repellency, water slippage, weather resistance, scratch resistance, acid resistance, etc. can be formed. Further, the protective coating is excellent in gloss and excellent in durability, and further enhances the depth when applied to a coating surface using a glittering material.

[0059]

[Table 2]

Claims (1)

[Claims] (A) (a) a compound represented by the following formula (I): (Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms;
R ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, R ³
Represents a hydrogen atom or a methyl group, and n is a number of 6 to 300);
A hydroxyl group-containing vinyl monomer, and if necessary, (c) a hydroxyl group-containing siloxane polymer having a hydroxyl value in the range of 50 to 290 mgKOH / g obtained by copolymerization of another unsaturated monomer copolymerizable therewith, (B) polyisocyanate And (C) (d) the following formula (II): (Wherein the average number of m is 6 to 150, 1 is an integer of 0 to 6, and R ⁴ is an alkyl group having 1 to 6 carbon atoms). e) the sulfonic acid compound and the epoxy group in (d)
(E) a reaction product obtained by preliminarily reacting the sulfonic acid groups in a ratio of 1/1 to 10/1 and / or a silicone oil having a viscosity of 10,000 cSt (25 ° C.) or less; (C) is used in an amount of 30 to 200 parts by weight based on 100 parts by weight of the resin solid content of (A) and (B). A polishing agent characterized by being mixed and dispersed immediately before use as three liquids.