JPH0753922A - Water-repellent lustering composition requiring no wiping - Google Patents

Abstract

PURPOSE:To obtain the compsn. which is excellent in lustering capability, water repellency, prevention of incrustation, and durability and has a good workability by compounding a combination of specific silicone resins with a specified amt. of wax. CONSTITUTION:The compsn. is prepd. by dissolving, in a hydrocarbon solvent, 100 pts.wt. wax, 10-25 pts.wt. mixture comprising an org.-solvent-sol. organopolysiloxane consisting of units of formulas I and II (wherein R1 is a hydrocarbon group) in a molar ratio of (1:0.4)-(1:1) and a diorganopolysiloxane having a viscosity at 25 deg.C of 10-100,000cSt in a wt. ratio of the former polysiloxane to the latter of (100:20)-(100:1,000), 20-140 pts.wt. above-mentioned diorganopolysiloxane [wherein the molar ratio of units of formula I to units of formula II is (1:1)-(1:99)], and 5-40 pts.wt. long-alkyl-modified organopolysiloxane of formula III (wherein R<3> is methyl or hydroxyl; X is 10-30C alkyl; a>=0; and b>=1) in such amts. that the total amt. of all the ingredients dissolved accounts for 0.5-5wt.% of the compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent polish composition, and more specifically, a composition used for surface treatment of a painted surface of an automobile, which has excellent water-repellency and polishability without requiring wiping. It is about things.

[0002]

2. Description of the Related Art Conventional water-repellent polishes used for painted surfaces of automobiles include natural or synthetic waxes such as carnauba wax, montan wax, paraffin wax, microcrystalline wax and polyethylene wax, and silicone oils. It is well known that there are a solution type obtained by dissolving or dispersing the above in a solvent, or an emulsion type obtained by further emulsifying the above components with an emulsifier and water. As a means for suppressing the influence of the added silicone oil (sliding property), a technique for suppressing the slip property by adding a resin component composed of R ₃ SiO _1/2 units and SiO ₂ units as in JP-A-4-337378. On the other hand, JP-A-60
As disclosed in JP-A-101162 and JP-A-4-363375, a technique for obtaining a surface treating agent having excellent water repellency by adding a long chain alkyl group-modified silicone oil as a silicone oil is disclosed. However, although these techniques improve the non-slip properties and water repellency of the coating film, they are not an essential solution to durability, workability, etc., and the treatment is easy and durable. A polish was desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and is excellent in glossiness, water repellency, water stain resistance, durability, and workability. It is intended to provide an agent composition.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor has found that by combining a specific silicone resin with a wax, glossiness, water repellency, and water stain adhesion can be obtained. We have succeeded in obtaining a water-repellent polish composition having excellent preventive properties and durability and good workability, and completed the present invention.

That is, according to the present invention, (A) 100 parts by weight of wax and (B) (i) R ¹ ₃ SiO per 1 mol of SiO ₂ unit.
_1/2 unit (provided that R ^1's are the same or different from each other and represent a substituted or unsubstituted monovalent hydrocarbon group) 0.4 to 1.0
Organic solvent-soluble organopolysiloxane ¹ essentially consisting of SiO ₂ units and R ¹ ₃ SiO _1/2 units in a molar ratio 1
00 parts by weight and (ii) the viscosity at 25 ° C is 10 to 10
20,000 cSt diorganopolysiloxane 20
A mixture 10 to 25 parts by weight of a 1,000 parts by weight, R ² SiO against (C) R ² ₃ SiO _1/2 units to 1 mol
_3/2 unit 1.0 to 99.0 mol (however, R ² is the above R ¹
Is synonymous with. ) In an amount of 70 to 140 parts by weight of an organic solvent-soluble organopolysiloxane consisting essentially of R ² ₃ SiO _1/2 units and R ² SiO _3/2 units, and (D) a general formula:

[Chemical 2] (In the formula, R ³ is a methyl group or a hydroxyl group, and X is a carbon number of 10 to 10.
It represents an alkyl group of 30, and a ≧ 0 and b ≧ 1. ) Long-chain alkyl group-modified organopolysiloxane 2
5 to 40 parts by weight in the hydrocarbon solvent (E), and the total amount of (A), (B), (C) and (D) is (A), (B), (C) and (D). ) And (E) are dissolved in a total amount of 0.5 to 5.0% by weight to obtain a water-repellent polish composition.

Examples of the component (A) wax used in the present invention include petroleum waxes such as microcrystalline wax and paraffin wax; mineral waxes such as montan wax and ceresin wax; carnauba wax, candelilla wax, and rice. Plant waxes such as waxes; animal waxes such as beeswax, wool wax, insect wax, whale wax; Fischer-Tropsch wax,
Synthetic waxes such as polyethylene wax may be mentioned, and these waxes may be used alone or in combination of two or more kinds.

The organic solvent-soluble organopolysiloxane of the component (i) constituting the component (B) is substantially SiO ₂
It is composed of a unit and an R ¹ ₃ SiO _1/2 unit (provided that R ¹ has the same meaning as described above), and has a relatively low molecular weight. R
^{As the} monovalent hydrocarbon group represented by 1, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, an alkyl group having 1 to 20 carbon atoms such as a decyl group, Vinyl group, alkenyl group having 2 to 10 carbon atoms such as allyl group, benzyl group, aralkyl group such as β-phenylethyl group, aryl group such as phenyl group, and some or all of these hydrogen atoms are chlorine atoms, Examples thereof include those substituted with a fluorine atom, a nitrile group or the like, but from the viewpoint of ease of synthesis, it is preferable that 90 mol% or more of R ¹ is a methyl group. The amount of R ¹ ₃ SiO _1/2 units needs to be in the range of 0.4 to 1.0 mol per 1 mol of SiO ₂ units, and the amount of R ¹ ₃ SiO _1/2 units is. If it is less than 0.4 mol, gelation tends to occur during synthesis to form an insoluble and infusible polymer. If the amount of R ¹ ₃ SiO ^_1/2 units is more than 1.0 mol, it is impossible to impart sufficient durability to the resulting composition.

The diorganopolysiloxane of the component (ii) constituting the component (B) has a substantially chained siloxane skeleton and has a viscosity at 25 ° C. of 10 to 100,000 c.
St St is used. When the viscosity is less than 10 cSt, when treated with the obtained polish, the gloss has no depth, and when it exceeds 100,000 cSt, the treated surface becomes sticky. The diorganopolysiloxane is not particularly limited as long as it has a substantially chain-like siloxane skeleton and has a viscosity at 25 ° C. of 10 to 100,000 cSt. For example, JP-A-4-337378.
General formula described in the publication:

[Chemical 3] (In the formula, R ⁴ is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ^4
5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms,
m represents an integer of 5 to 2,000. ) Diorganopolysiloxane represented by Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ⁴ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, octyloxy group, and R ⁴
Or, as the C 1-20 monovalent hydrocarbon group represented by R ⁵ , for example, a methyl group, an ethyl group, a propyl group,
Butyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, alkyl group such as octadecyl group, vinyl group, alkenyl group such as allyl group, cyclohexyl group,
Cycloalkyl group such as cycloheptyl group, benzyl group,
aralkyl group such as β-phenylethyl group, phenyl group,
An aryl group such as a naphthyl group can be mentioned. In the alkoxy group and the hydrocarbon group, some or all of these hydrogen atoms may be substituted with a chlorine atom, a halogen atom such as a fluorine atom, a nitrile group, or an arbitrary organic group. R ⁴ and R ⁵ are preferably methyl groups.

The mixing ratio of the component (i) and the component (ii) in the component (B) is (ii) based on 100 parts by weight of the component (i).
20 to 1,000 parts by weight of the component. When the amount of the component (ii) is more than 1,000 parts by weight, the resulting polishing composition has poor durability, cleaning resistance and non-slippery effect, and when the amount is less than 20 parts by weight, the composition is less than 20 parts by weight. Gloss is reduced, and workability is deteriorated.

The blending amount of the component (B) with respect to the component (A) is 10 to 10 parts by weight of the component (B).
25 parts by weight. When the amount of the component (B) is more than 25 parts by weight, water stain is easily attached, and when it is less than 10 parts by weight, the composition has poor durability.

The component (C) is an essential component which imparts durability and water redness preventive property to the composition of the present invention, and is substantially R.
It is composed of ² ₃ SiO _1/2 units and R ² SiO _3/2 units (provided that R ² has the same _{meaning as the} above R ¹ ). As the monovalent hydrocarbon group represented by R ² , those similar to R ¹ can be exemplified, but a methyl group and a phenyl group are preferable from the viewpoint of easiness of synthesis and availability of raw materials. R ² SiO _3/2
The amount of the unit is 1.0 with respect to 1 mol of R ² ₃ SiO _1/2 unit.
Is required to be within the range of ˜99.0 mol, and R ²
If the amount of SiO _3/2 units is less than 1.0 mol, the synthesis becomes difficult, and if the amount of R ² SiO _3/2 units is more than 99.0 mol, gelation occurs during the synthesis and the insoluble and infusible weight increases. Easy to unite.

The blending amount of the component (C) with respect to the component (A) is 70 to 70 parts by weight of the component (A).
It is 140 parts by weight. When the amount of the component (C) is more than 140 parts by weight, the gloss effect of the composition is deteriorated, and 70
When the amount is less than the weight part, the composition has poor durability.

The component (D) is an essential component that imparts excellent water repellency to the composition of the present invention, and has the general formula:

[Chemical 4] (In the formula, R ³ is a methyl group or a hydroxyl group, and X is a carbon number of 10 to 10.
It represents an alkyl group of 30, and a ≧ 0 and b ≧ 1. ) Is a long-chain alkyl group-modified organopolysiloxane. Examples of the alkyl group having 10 to 30 carbon atoms represented by X include a decyl group, a dodecyl group, a tetradecyl group,
Examples thereof include a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, and a triacontyl group. These alkyl groups may be linear or branched.

The blending amount of the component (D) with respect to the component (A) is 25 to 25 parts by weight of the component (D) with respect to 100 parts by weight of the component (A).
40 parts by weight. If the amount of component (D) is greater than 40 parts by weight, the gloss effect of the composition will be reduced, and if it is less than 25 parts by weight, sufficient water repellency cannot be imparted.

The hydrocarbon solvent as the component (E) is indispensable for dissolving the components (A), (B), (C) and (D) of the present invention and forming a uniform film on the coated surface. A volatile component having a boiling point within the range of 100 to 370 ° C. is preferable as the component. Examples of such a hydrocarbon solvent include hexane, heptane, octane, decane, ligroin, mineral spirits, kerosene, isoparaffin, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, industrial gasoline, toluene, xylene, benzene, etc. However, it is preferable to use kerosene or isoparaffin.

The total amount of the (A) component, the (B) component, the (C) component and the (D) component is the (A) component, the (B) component, the (C) component, the (D) component and the (E) component. 0.5 of the total amount of ingredients
~ 5.0 wt%. When the total amount of the components (A) to (D) is more than 5.0% by weight, the oil film becomes thick and coating unevenness occurs when the composition is applied and the solvent is volatilized.
If it is less than 0.5% by weight, a sufficient water repellent effect cannot be exhibited.

[0017]

EXAMPLES The present invention will be described in more detail below with reference to Preparation Examples, Examples and Comparative Examples, but these do not limit the scope of the present invention. In the following,
Parts represent parts by weight, and% represents% by weight. The viscosity represents the value at 25 ° C.

[0018] (Preparation Example 1) SiO ₂ units 1 (CH ₃₎ moles ₃ SiO _1/2 units and substantially SiO ₂ units in a ratio of 0.75 mole (CH _{3) 3} SiO _1/2 100 parts of a xylene-soluble organopolysiloxane consisting of units and a molecular chain end blocked with a trimethylsilyl group, 2
150 parts of dimethylpolysiloxane having a viscosity of 1,000 cSt at 5 ° C. was mixed by an ordinary method to obtain colorless and transparent organopolysiloxane B-1.

(Preparation Example 2) Organopolyene having a softening point of 80 ° C. was synthesized by a conventional method so that 1 mol of (CH ₃ ) ₃ SiO _1/2 unit was mixed with 11 mol of CH ₃ SiO _3/2 unit. Siloxane resin C-1 was obtained.

Preparation Example 3 A polysiloxane having 20 dimethylsiloxane units and 40 methylhydrogensiloxy units in one molecule was subjected to an addition reaction with a C ₃₀ H ₆₀ 1-alkene by a conventional method. A waxy organopolysiloxane D-1 having a melting point of 60 ° C. was obtained.

(Examples 1 to 3) The components shown in Table 1 were mixed, heated to 80 to 90 ° C to dissolve until transparent, and then cooled with stirring to obtain a uniform polish composition. Obtained.

(Comparative Examples 1 to 3) The components shown in Table 1 were mixed to obtain uniform polish compositions in the same manner as in Examples 1 to 3.

(Evaluation Test) Examples 1 to 3 and Comparative Examples 1 to 1
A small amount of composition 3 was dropped on a black-painted steel sheet coated in the same manner as in an actual car, and wiped with a cotton cloth to give a test piece.

As Comparative Example 4, an untreated plate was added.

The coating film physical properties of the test pieces were evaluated by the following methods. 1) Water repellency: Water was sprayed on the coating film in a shower to observe water repellency. ◯: Water repellency is excellent, and water droplets are fine. Δ: Water repellent, but large water droplets. X: Poor in water repellency, resulting in a wet state. 2) Water repellency: Washing was performed with a beaker brush using a 2% aqueous solution of a commercially available car wash detergent, and the water repellency after washing was repeatedly observed every 5 times. 3) Luster: The gloss of the coating film was visually observed. ○: Good gloss X: The gloss is not good.

[0026]

[Table 1]

(Examples 4 to 6) The components shown in Tables 3 and 4 were mixed to obtain uniform polish compositions in the same manner as in Examples 1 to 3. In Tables 3 and 4, the components (A) and (E) used had the same melting points as those shown in Table 1.

(Comparative Examples 5 to 8) As comparative examples, four commercially available polishes were used.

The coated plate was treated in the same manner as in the evaluation test of Examples 1 to 3, and the treated surface was evaluated as follows. However, the commercially available products were processed according to the specifications. 4) Workability: Judged the ease of processing the coated plate. ◯: Easy ×: Difficult 5) Contact angle ... The contact angle of water droplets on the treated surface was measured. 6) Water resistance glossiness ... Measured according to JIS K2236. 7) Gloss increase ... Measured according to JIS K2236. 8) Weather resistance ... Evaluated by the sunshine carbon arc lamp test according to JIS B7753. 18 test hours
The time was 0 hours, and the operating conditions were in accordance with the conditions shown in Table 2. The evaluation items were gloss retention, water repellency persistence, and color difference change.

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

(Coated Plate Test) Using the same coated plates as those used in the evaluation test for Examples 1 to 3, the compositions of Examples 1 and 4 and the commercially available Comparative Examples 5 to 8 were used. The following tests were carried out on the products.

The composition and a commercially available brightening agent were applied thickly on a coated plate, and the coated surface was observed after leaving it as it was for 4 hours in an atmosphere of 80 ° C. and 25% RH. As a result, all of the compositions other than the composition of the present invention swelled on the coated surface and caused adverse effects such as discoloration.

[0035]

The polish composition of the present invention is effective as a water-repellent polish for automobiles and does not adversely affect the painted surface such as swelling or discoloration, and is a conventional solid wax, wax wax or liquid wax. Compared with, it does not require wiping and has excellent workability, and has excellent water repellency, durability, and water stain resistance.

Claims (1)

[Claims] 1. (A) 100 parts by weight of wax, and (B) (i) R ¹ ₃ SiO per 1 mol of SiO ₂ unit.
_1/2 unit (provided that R ^1's are the same or different from each other and represent a substituted or unsubstituted monovalent hydrocarbon group) 0.4 to 1.0
Organic solvent-soluble organopolysiloxane ¹ essentially consisting of SiO ₂ units and R ¹ ₃ SiO _1/2 units in a molar ratio 1
00 parts by weight and (ii) the viscosity at 25 ° C is 10 to 10
20,000 cSt diorganopolysiloxane 20
A mixture 10 to 25 parts by weight of a 1,000 parts by weight, R ² SiO against (C) R ² ₃ SiO _1/2 units to 1 mol
_3/2 unit 1.0 to 99.0 mol (however, R ² is the above R ¹
Is synonymous with. 70% to 140 parts by weight of an organic solvent-soluble organopolysiloxane consisting essentially of R ² ₃ SiO _1/2 units and R ² SiO _3/2 units in a ratio of (D), and (D) a general formula: (In the formula, R ³ is a methyl group or a hydroxyl group, and X is a carbon number of 10 to 10.
It represents an alkyl group of 30, and a ≧ 0 and b ≧ 1. ) Long-chain alkyl group-modified organopolysiloxane 2
5 to 40 parts by weight in the hydrocarbon solvent (E), and the total amount of (A), (B), (C) and (D) is (A), (B), (C) and (D). ) And (E), the water-repellent polish composition obtained by dissolving so as to be 0.5 to 5.0% by weight of the total amount.