JP2000007998A - Luster agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a luster agent capable of giving an excellent repellency and slidableness of water by mixing a specific amount of a reaction product obtained by reacting a specific siloxane polymer having an epoxy terminal with a sulfonic acid compound in a specific ratio in a prior reaction, with wax. SOLUTION: A reaction product obtained by reacting a siloxane polymer having an epoxy terminal of the formula with a sulfonic acid compound in a ratio of 1/1-10/1 equivalent and which is obtained in a prior reaction is mixed in an amount of not more than 20 wt.% of the solid content of this luster agent. Wherein (m) is 6-150; (l) is 0-6; and R4 is a 1-6C alkyl. Wax is natural and/or synthetic ones, and a material substituted for wax may be concomitantly used. The sulfonic acid compound is represented by R2-SO3H (wherein R2 is an organic residue). The reaction of the siloxane polymer with the sulfonic acid compound, for example, is conducted by mixing both compounds at a room temperature optionally in the presence of organic solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polishing agent for imparting water repellency, water lubricity and the like to a coating surface of various kinds of outer plates of automobiles, railway vehicles, airplanes, buildings and the like.

[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, a 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. Further improvements in aqueous properties have been desired.

[0003]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific amount of a reaction product of an epoxy-terminated siloxane polymer and a sulfonic acid compound is mixed with a wax. Polishing agent has excellent water repellency,
The present inventors have found that water can be imparted, and have reached the present invention.

That is, the present invention relates to (A) wax,
(B) The following general formula (1)

[0005]

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(Wherein, the average number of m is from 6 to 150,
n is an integer of 0 to 6, and R ¹ is an alkyl group having 1 to 6 carbon atoms). The epoxy-terminated siloxane polymer (a) and the sulfonic acid compound (b) are The equivalent ratio of the epoxy group in the sulfonic acid group in (b) / 1 /
An object of the present invention is to provide a polishing agent obtained by mixing a reaction product obtained by previously reacting at a ratio of 1 to 10/1 by 20% by weight or less based on the solid content in the composition.

[0007]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, wax (A) is used.
Is a natural wax and / or a synthetic wax. Examples of the natural wax include vegetable waxes such as carnauba wax, candelilla wax, rice wax, palm wax, and wood wax; animal waxes such as beeswax, spermaceti, and tallow. Mineral waxes such as montan wax, ceresin wax and ozokerite; petroleum waxes such as paraffin, microcrystalline wax and petrolatum; and synthetic waxes such as polyethylene and polypropylene. These can be used alone or in combination of two or more. Further, dimethyl silicone oil (dimethyl siloxane), diethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, polysiloxane amino, carboxy, epoxy, polyester, phenol- Wax-based substances such as modified compounds such as oils, other silicone-based compounds such as modified silicone oil, petroleum resin, terpene resin, rosin gum, acrylic resin, silicone resin, and resin varnish such as ethylene tetrafluoride resin. it can.

[0008] In the present invention, the reaction product (B) of the epoxy-terminated siloxane polymer (a) and the sulfonic acid compound (b) contributes to the improvement of the slipperiness.

Epoxy-terminated siloxane polymer (a)
Is the following general formula (1)

[0010]

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Wherein m represents the average degree of polymerization of the dimethylsiloxane unit, and 6 to 15
0, preferably a number in the range of 6 to 70, n is an integer of 0 to 6, preferably 1 to 5, and R ¹ is an alkyl group of 1 to 6, preferably 1 to 4 carbon atoms. It is.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and hexyl. Among them, methyl group, n-
Butyl groups are preferred.

The siloxane polymer (a) generally comprises 53
It may have a number average molecular weight in the range of 0 to 11,400, preferably 540 to 5,500.

The sulfonic acid compound (b) reacted with the siloxane polymer (a) has the following formula: R ² —SO ₃ H (where R ² is an organic residue, for example, an aliphatic hydrocarbon group,
An aliphatic hydrocarbon group or the like, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be optionally substituted by a halogen atom or the like). , 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 (B) is obtained by mixing the siloxane polymer (a) and the sulfonic acid compound (b) at an equivalent ratio of epoxy group in (a) / sulfonic acid group in (b) of 1 /. 1
To 10/1, preferably 1.5 / 1 to 8/1. This compounding ratio is a ratio in which the epoxy group is equivalent to or a large excess with respect to the sulfonic acid group, and in the reaction product (B),
Unreacted epoxy group-containing siloxane polymer (a) may be present. Although the unreacted sulfonic acid compound (b) may remain in the reaction product (B), it is preferable that the unreacted sulfonic acid compound (b) is not substantially contained.

The reaction between the siloxane polymer (a) and the sulfonic acid compound (b) can be carried out, for example, by mixing the two at room temperature 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,
-Ethylhexanol, diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, butanol, dioxane, mineral oil and the like.

The reaction product (B) is substantially an adduct of a siloxane polymer (a) and a sulfonic acid compound (b),
It can be composed of unreacted epoxy group-containing siloxane polymer (a).

Examples of the adduct of the siloxane polymer (a) and the sulfonic acid compound (b) include an epoxy group in the siloxane polymer (a) and a sulfonic acid in the sulfonic acid compound (b). Adducts obtained by equimolar reaction with a group are mentioned.

[0019]

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As an example of an adduct of the siloxane polymer (a) and the sulfonic acid compound (b), the adduct obtained by the equimolar reaction shown below was further added with the siloxane polymer (a). Adduct (siloxane polymer
(A) An adduct of 2 mol and a sulfonic acid compound (b) 1 mol).

[0021]

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Further, as an example of an adduct of the siloxane polymer (a) and the sulfonic acid compound (b), the adduct of the adduct of the siloxane polymer (a) with 2 mol and the sulfonic acid compound (b) with 1 mol is exemplified. An adduct obtained by further adding a siloxane polymer (a) to a hydroxyl group (siloxane polymer).
(An adduct of (a) 3 mol and a sulfonic acid compound (b) 1 mol) is conceivable.

According to the study of the present inventors, the adduct of the siloxane polymer (a) and the sulfonic acid compound (b) is
Depending on the raw materials used, the gel
From the results of the measurement by the mu- sion chromatography, the equimolar adduct of the siloxane polymer (a) and the sulfonic acid compound (b) and, in some cases, a mixture of the equimolar adduct and 2 mol to 1 mol adduct are usually obtained. is there.

In the present invention, the above reaction product (B) is contained in an amount of not more than 20% by weight, preferably 5 to 15% by weight in terms of solid content in the composition. If the content exceeds 20% by weight, tackiness is undesirably caused.

The polishing agent of the present invention mainly contains the above (A) and (B), and if necessary, an organic solvent, fine powder such as pigment or resin powder, a thickener, an antioxidant, and the like. The additives can be appropriately selected from additives commonly used in ordinary polishes such as ultraviolet absorbers.

The form of the polishing agent of the present invention may be liquid, solid, or soft paste.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

Epoxy-terminated siloxane polymer and sulfo
Production of Reaction Product with Acidic 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, and “Silaprene FM-0511” (Chisso 98.8 parts by weight of a polydimethylsiloxane having an epoxy group at one end and R ⁴ of the formula (II) having a methyl group and a molecular weight of 1,000 (manufactured by Sharp Corporation) were added and stirred to dissolve.
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 solution having a nonvolatile content of 83%.

Example 1 10 parts by weight of carnauba wax and mineral spirit 90
The mixture was heated to 80 ° C. to disperse the wax component, and after the temperature was cooled to 40 ° C., 2 parts by weight of the reaction product solution obtained above was mixed with stirring to prepare a polishing agent.

Example 2 A polishing agent was prepared in the same manner as in Example 1 except that the amount of the reaction product solution was changed to 1 part by weight.

Example 3 A polishing agent was prepared in the same manner as in Example 1 except that the same amount of polyethylene wax (manufactured by Petrolite, USA) was used instead of carnauba wax.

Example 4 "Ion Coat" (manufactured by Taiho Industries, Inc., car wax,
5 parts by weight of the reaction product solution were mixed with 100 parts by weight of the trade name solution while stirring to prepare a polishing agent.

Comparative Examples 1 and 3 Polishing agents of Comparative Examples 1 and 3 were obtained by removing the reaction product solution in Examples 1 and 3.

Comparative Example 2 A polishing agent was prepared in the same manner as in Example 1 except that the amount of the reaction product solution was changed to 5 parts by weight.

(Performance test) "Magiclon TC-71 Clear" (manufactured by Kansai Paint Co., Ltd.), which is used for coating an automobile outer panel, is applied to a glass plate and dried to form a clear coating film. Each of the polishing agents prepared in the above Examples and Comparative Examples was applied with a urethane sponge and dried at room temperature for 15 minutes. After drying, excess polishing agent was wiped off with a flannel to obtain each polishing agent coated plate for performance test. These were subjected to the following performance tests. The results are shown in the table.

(1) Finish appearance: The gloss and unevenness of each glazing agent coating surface were visually evaluated.

：: Both gloss and unevenness are good. △: 〃 is slightly inferior. ×: か な り is considerably inferior. (2) Water repellency: A certain amount of water is dropped on the surface of each glazing agent film, and after 30 seconds, the film and water Was measured.

：: Contact angle of 90 ° or more △: 〃80 ° or more and less than 90 ° X: 未 満 less than 80 ° (3) Water-sliding property: After leveling each glazing-coated plate, and dropping water drops on it The plate was inclined at a constant speed, and the inclination angle at the time when water droplets began to slide was investigated.

：: Water droplets began to slide when the inclination angle was less than 40 degrees.

[0040]

When the polishing agent of the present invention is applied to a painted surface such as an outer panel of an automobile or a railroad vehicle, a wax component and a reaction product of an epoxy-terminated siloxane polymer and a sulfonic acid compound act. Excellent stain resistance as well as good water-repellency and water-sliding properties, as well as good gloss on the coating surface, so that contaminants hardly accumulate on the coating surface and even if accumulated, they can be easily removed by washing with water. It can form a protective film.

[0041]

[Table 1]

Claims (1)

[Claims] (A) a wax; (B) a compound represented by the following general formula (1): (Wherein, the average number of m is 6 to 150, n is an integer of 0 to 6, and R ¹ is an alkyl group having 1 to 6 carbon atoms). a)
And the sulfonic acid compound (b) with an equivalent ratio of epoxy group in (a) / sulfonic acid group in (b) of 1/1 to 10/1.
A polishing agent obtained by mixing a reaction product previously reacted at a ratio of 20% by weight or less based on the solid content in the composition.