JPH11302542A - Surface-protective polishing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polishing agent capable of protecting the surface of molded products such as of rubber from ultraviolet light and moisture and the like by including a both terminal hydroxyl group-blocked diorganopolysiloxane, a both terminal trisubstituted siloxy group-blocked diorganopolysiloxane and an organic solvent-soluble silicone resin and others. SOLUTION: This polishing agent is obtained by including (A) 10-70 wt.% of a silicone mixture comprising (i) 1-90 wt.% of a both terminal hydroxyl group-blocked biorganopolysiloxane of formula I (R1 , R<2> and R<3> are each a 1-20C monovalent organic group; (m) and (n) are each 10-2,000) with a viscosity of 0.01-1,000 Pa.s at 25 deg.C, (ii) 5-94 wt.% of a both terminal trisubstituted siloxy group-blocked diorganopolysiloxane of formula II with a viscosity of 0.01-1,000 Pa.s at 25 deg.C and (iii) 5-50 wt.% of an organic solvent-soluble silicone resin containing a total of >=80 mol.% of R<3> 3 SiO1/2 unit and SiO4/2 unit in the molar ratio of 0.5-1.5, (B) 1-10 wt.% of a nonionic surfactant, and (C) water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface protective polishing agent, and more particularly, to a molded article made of rubber, leather, plastic, or the like, which protects the surface of the molded article from ultraviolet rays, ozone, moisture, etc., to give an aesthetic appearance. The present invention relates to a surface protective polishing agent for performing

[0002]

2. Description of the Related Art Various molded articles made of rubber, leather, plastic, and the like are constantly exposed to ultraviolet rays, ozone, moisture, and the like, so that they are inevitably deteriorated with time and their aesthetic appearance is spoiled. Has disadvantages. Therefore, measures such as internal addition of antioxidants and ultraviolet absorbers have been taken at the time of their manufacture, but this alone cannot completely prevent discoloration and blooming over time. was there. In order to prevent this, paint is applied to the surface of the molded article, but in this case, the painted surface has an unnatural appearance, and removal of the old paint film at the time of repainting is required. There was an inconvenience of difficulty. There is also known a method of treating the surface of a molded article with a protective glaze containing dimethyl silicone oil as a main component (JP-A-60-382).
No. 05), in this method, the protective effect and the persistence of the effect are insufficient, and depending on the base material,
On the contrary, there is a disadvantage that stress cracks may be promoted.

[0003] As a protective glossing agent containing dimethyl silicone oil as a main component, conventionally, 10 to 20% by weight of a dimethyl silicone oil component is dissolved in an organic solvent such as a hydrocarbon solvent or a fluorocarbon solvent (fluorocarbon solvent). Solvent types have been used. However, the conventional solvent type has drawbacks in that the antioxidant and the plasticizer may be eluted from the molded product, and the rubber may swell to accelerate deterioration. Fluorocarbon solvents cause destruction of the ozone layer, while hydrocarbon solvents have been problematic in terms of flammability and toxicity. Therefore, in order to solve such a problem, an aqueous type has been proposed in recent years. As the aqueous type, a silicone oil emulsified in an oil-in-water type with a surfactant is generally used (Japanese Patent Publication No. 6-72240, Japanese Patent Application Laid-Open No. 6-80932). Although this product has good gloss and workability, it is not yet satisfactory in durability such as aesthetic appearance and water repellency. In addition, depending on the type of surfactant used, cracks may be generated on the surface of the molded product, and the weather resistance may be poor.

On the other hand, in order to improve the durability of a coating film, a method of blending colloidal silica or other resin powder dispersion with a high-viscosity silicone oil (JP-A-7-109440, JP-A-7-216229) JP, JP-A-7-310051, JP-A-8-601
No. 00) has been proposed, but none of these methods has a sufficient polishing effect. Further, silicone powders (JP-A-9-3407, JP-A-9-34)
No. 08), urethane resin (JP-A-62-81467).
JP, JP-A-5-98213, JP-A-2524160), polyvinyl ether resin (JP-A-7-242857), natural or synthetic wax (JP-A-6-65541, JP-A-8-855) −73
815, JP-A-8-199199, JP-A-8-199199
-239629), silicone varnish (Japanese Unexamined Patent Publication No.
-100836, JP-A-7-310055, JP-A-8-34970, JP-A-9-40915
No., Japanese Unexamined Patent Publication (Kokai) No. 2000-216, etc. have been proposed. However, although these methods have some effects on the gloss and durability of the surface, they have a drawback that they are poor in slip resistance due to the addition of slipperiness.

In order to improve gloss and water repellency, amino-modified silicones (JP-A-5-98215) and alkylaryl-modified silicones (JP-A-6-9927) have been proposed.
Publication), polyether-modified silicone (Japanese Patent Publication 6-6)
No. 692) has been proposed, but these methods also have problems such as poor slip resistance and insufficient gloss durability.
Furthermore, in order to improve gloss durability and slip resistance, a method is used in which a silicone resin having a large coefficient of friction and a silicone oil are used in combination (JP-A-60-179250,
Japanese Patent Application Laid-Open No. Sho 60-101162) has been proposed, but these methods can provide good durability, but sometimes have poor coating extensibility and ozone crack resistance.

[0006]

Under such circumstances, the present invention protects the surface of molded articles made of rubber, leather, plastic, etc., particularly rubber products such as tires, from ultraviolet rays, ozone, moisture and the like. It is an object of the present invention to provide a surface protective polishing agent capable of imparting good appearance, durability of gloss, good slip resistance and ozone crack resistance, and the like.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a surface protective polishing agent having the above-mentioned excellent functions, and as a result, have found that both ends of hydroxyl-blocked diorganopolysiloxane and both ends of triorganopolysiloxane can be used. By combining the substituted siloxy group-blocked diorganopolysiloxane and the organic solvent-soluble silicone resin in a predetermined ratio, the adhesion to the base material can be increased, the protective glazing property can be improved, and unfavorable slip property can be obtained. It has been found out that no ozone crack is generated and that the occurrence of ozone cracks can be reduced by blending a specific surfactant in a predetermined ratio. The present invention
It has been completed based on such knowledge. That is,
The present invention relates to (A) (A-1) an average structural formula (I)

[0008]

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(Wherein, R ¹ represents a monovalent organic group having 1 to 20 carbon atoms, and m represents a positive number of 10 to 2000.
A plurality of R ¹ may be the same or different. ) Having a viscosity at 25 ° C of 0.01 to 1000 Pascal second (Pa · s) at 1 to 90% by weight of a diorganopolysiloxane capped at both ends with hydroxyl groups, and (A-2) an average structural formula (II)

[0010]

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(Wherein, R ² represents a monovalent organic group having 1 to 20 carbon atoms, and n represents a positive number of 10 to 2000.
A plurality of R ² may be the same or different. ) And a viscosity at 25 ° C. of 0.01 to 1000 Pa · s
Both ends trisubstituted siloxy groups diorganopolysiloxane 5-94 wt% and _{^{(A-3) R 3 3}} SiO 1/2 units and SiO _4/2 units with containing in its total at least 80 mol% of, if R ³ ₂ SiO _2/2 units and / or R ³
Containing SiO _3/2 units, and R ³ ₃ SiO _1/2 units / S
The molar ratio of iO _4/2 units is 0.5 to 1.5 (where R
³ is a monovalent organic group having 1 to 20 carbon atoms, more R ³
May be the same or different. ) 10 to 70% by weight of a silicone mixture comprising 5 to 50% by weight of an organic solvent-soluble silicone resin, (B) nonionic surfactant 1 to 1
An object of the present invention is to provide a surface protective polishing agent characterized by comprising an emulsified composition comprising 10% by weight and (C) the balance of water as a main component.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The surface protective polishing agent of the present invention comprises:
(A) a silicone mixture, (B) a nonionic surfactant, and (C) an emulsion composition comprising water as a main component. The silicone mixture of the component (A) includes:
A mixture of (A-1) a diorganopolysiloxane capped with hydroxyl groups at both ends, (A-2) a diorganopolysiloxane capped with trisubstituted siloxy groups at both terminals, and (A-3) a silicone resin soluble in an organic solvent is used. In the silicone mixture of the component (A), R ¹ , R ² and R ³ in the component (A-1), the component (A-2) and the component (A-3) are each a monovalent compound having 1 to 20 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, and hexadecyl groups. Linear or branched alkyl groups such as octadecyl group, octadecyl group, eicosyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and linear or branched unsaturated alkyl groups such as vinyl group, allyl group and propenyl group Aryl groups such as phenyl, tolyl and xylyl groups, aralkyl groups such as benzyl group and phenethyl group, and some of these hydrogen atoms And a halogeno organic group substituted with a hydrogen atom.
One kind of these organic groups may be contained in one molecule, or two or more kinds may be contained in one molecule.
Those containing 0 mol% or more are preferred. (A-1)
The diorganopolysiloxane having hydroxyl groups blocked at both ends of the component is
Average structural formula (I)

[0013]

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(Wherein, R ¹ represents a monovalent organic group having 1 to 20 carbon atoms, and m represents a positive number of 10 to 2000.
A plurality of R ¹ may be the same or different. ). Specific examples of R ¹ in the general formula (I) are as described above. This (A
-1) The diorganopolysiloxane having hydroxyl groups blocked at both ends as a component has a viscosity at 25 ° C of 0.01 to 1000 Pa · s.
Must be in the range of This viscosity is 0.01 Pa
If the value is less than s, the obtained emulsified composition may not have a long-lasting protective glossing effect over a long period of time, and may elute an antioxidant or a plasticizer from a molded product, and may cause cracks. On the other hand, if it exceeds 1000 Pa · s, the obtained emulsified composition will have poor coating extensibility. In consideration of the durability of the protective glossing effect, the prevention of crack generation, and the application extensibility, the preferred viscosity is in the range of 0.1 to 100 Pa · s, and particularly preferably in the range of 0.5 to 50 Pa · s. .
This (A-) in the silicone mixture as the component (A)
The content of the diorganopolysiloxane having hydroxyl groups blocked at both ends of the component (1) is selected in the range of 1 to 90% by weight. If the content is out of the above range, a durable protective glossing effect may not be exhibited. From the viewpoint of the effect, the preferred content of the component (A-1) is in the range of 5 to 80% by weight, and more preferably 10 to 70% by weight. Next, the diorganopolysiloxane capped with a trisubstituted siloxy group at both ends of the component (A-2) has an average structural formula (II)

[0015]

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(Wherein, R ² represents a monovalent organic group having 1 to 20 carbon atoms, and n represents a positive number of 10 to 2000.
A plurality of R ² may be the same or different. ). In the general formula (II), OSiR ² ₃ represents the tri-substituted siloxy group, R ²
Depending on the type, there are various groups such as a trialkylsiloxy group, a triarylsiloxy group, a tricycloalkylsiloxy group, a dialkylmonoarylsiloxy group, and a dialkylmonoalkenylsiloxy group. Specific examples of R ² are as described above. The diorganopolysiloxane having a tri-substituted siloxy group at both ends of the component (A-2) has a viscosity of 0 at 25 ° C. for the same reason as the diorganopolysiloxane having a hydroxyl group at both ends of the component (A-1). It is necessary to be in the range of 0.01 to 1000 Pa · s, preferably 0.1 to 100 Pa · s, particularly preferably 0.5 to 50 Pa · s. The content of the diorganopolysiloxane blocked with a trisubstituted siloxy group at both ends of the component (A-2) in the silicone mixture as the component (A) is selected in the range of 5 to 94% by weight. If the content is less than 5% by weight, the surface gloss becomes inferior,
If it exceeds 94% by weight, the durability will be poor. From the viewpoint of balance between surface gloss and durability, this (A-2)
The preferred content of the components is in the range of 15 to 80% by weight, and particularly preferably in the range of 20 to 70% by weight.

Meanwhile, (A-3) component organic solvent-soluble silicone resin of the R ³ ₃ SiO _1/2 units and SiO _4/2 units as essential components, and optionally R ³ ₂ SiO _2/2 units and /
Or R ³ SiO _3/2 units, wherein R ³ ₃
The total content of SiO _1/2 units and SiO _4/2 units is 80
Mol% or more, preferably 90 mol% or more. If the total content is less than 80 mol%, the durability of the protective glossing effect will be insufficient. The molar ratio of R ³ ₃ SiO _1/2 units / SiO _4/2 unit is required to be in the range of 0.5 to 1.5. When the molar ratio is less than 0.5, it is difficult to obtain a composition having an industrially stable composition, and when it exceeds 1.5, the durability of the protective glossing effect is reduced. From the viewpoint of the stability of the composition and the durability of the protective glossing effect, the preferred range of the molar ratio is 0.6 to 1.2. Note that a specific example of R ³ is
As described above. The method for producing the organic solvent-soluble silicone resin of the component (A-3) is not particularly limited, and a conventionally known method can be used. For example,
R ³ ₃ SiCl, chlorosilanes such as R ³ ₂ SiCl ₂ and R ³ SiCl ₃ for use according to SiCl ₄ and necessary or _{^{R 3 3 Si (OCH 3)}} ,, Si (OCH 3) 4
And optionally used in _{^{R 3 2 Si (OCH 3)}} 2 and R
It can be produced by co-hydrolyzing a predetermined amount of an alkoxysilane such as ³ Si (OCH ₃ ) _{3 in} the presence of a solvent, and further performing polycondensation in the presence of an acid catalyst or an alkali catalyst.

The content of the organic solvent-soluble silicone resin of the component (A-3) in the silicone mixture as the component (A) is selected from the range of 5 to 50% by weight. When the content is less than 5% by weight, the obtained protective coating has poor durability and is provided with slipperiness. For example, when the protective coating is applied to a rubber tire, there is a possibility that the braking may be hindered. On the other hand, if it exceeds 50% by weight, the coating extensibility of the emulsified composition is reduced. Considering the durability, slip resistance, coating extensibility and the like of the protective coating, the preferred content of the component (A-3) is in the range of 10 to 40% by weight. In the present invention,
The silicone mixture used as the component (A) may be prepared by simply mixing the components (A-1), (A-2) and (A-3), or after mixing. Alternatively, the treatment can be performed using an acid or an alkali catalyst. Examples of the acid catalyst used at this time include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid and trifluoromethanesulfonic acid. On the other hand, examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide and siliconates thereof, and inorganic alkalis and organic alkalis such as tetrabutylphosphonium hydroxide and tetramethylammonium hydroxide.

In the surface protective glaze of the present invention, the content of the component (A) in the emulsion composition is from 10 to 70% by weight.
Is selected in the range. If the content is less than 10% by weight, the stability will be poor, and if it exceeds 70% by weight, the viscosity will be too high and the coating extensibility will decrease. Considering the stability and the coating extensibility, the preferred content of the component (A) is 20
〜60% by weight. In addition, the component (A) may contain, if desired, as long as the object of the present invention is not impaired.
Other polar organic group-containing organopolysiloxanes can be added as appropriate. Examples of the polar organic group include an amino group, an epoxy group, an acryloxy group, a methacryloxy group, a mercapto group, and a carboxyl group.

The nonionic surfactant of component (B) in the emulsion composition according to the present invention is DAVIS HL.
At least one selected from polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers having a B value in the range of 3 to 9 and sorbitan fatty acid esters having a DAVIS HLB value in the range of 7 to 16 is preferably used. If the DAVIS HLB value of the polyoxyethylene alkyl ether or polyoxyethylene alkyl phenyl ether is less than 3, the stability of the emulsified composition may be inferior. If it exceeds 9, the weather resistance of the molded article is likely to be reduced. Considering the stability of the emulsified composition and the weather resistance of the molded article, the more preferable DAVIS of the polyoxyethylene alkyl ether and the polyoxyethylene alkyl phenyl ether is preferable.
HLB values are in the range of 4-8. On the other hand, if the DAVIS HLB value of the sorbitan fatty acid ester is less than 7, the stability of the emulsified composition may be poor, and if it exceeds 16, the weather resistance of the molded article is likely to be reduced. Considering the stability of the emulsified composition and the weather resistance of the molded article, the more preferable DA of this sorbitan fatty acid ester
VIS HLB values range from 8-15.

Here, the DAVIS HLB value refers to the H set for each atomic group of the hydrophilic group and the hydrophobic group of the surfactant.
It is a value calculated from the number of LB groups by the following formula ["New surfactant" by Hiroshi Horiguchi, Sankyo Publishing Co., Ltd.]. HLB = {(number of hydrophilic groups) +} (number of hydrophobic groups) +7 Examples of the polyoxyethylene alkyl ether include polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, and polyoxyethylene. Examples include cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of polyoxyethylene alkylphenyl ether include polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. On the other hand, examples of the sorbitan fatty acid ester include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate,
And polyoxyethylene sorbitan trioleate. These may be used alone or in combination of two or more.

In the surface protective glaze of the present invention, the content of the component (B) in the emulsion composition is from 1 to 10% by weight.
Is selected in the range. If the content is less than 1% by weight, the stability of the emulsified composition will be insufficient, and if it exceeds 10% by weight, the coating extensibility will be reduced. Considering the stability of the emulsified composition and the spreadability of the coating composition, the preferred content of the component (B) is in the range of 3 to 8% by weight. The method for preparing the emulsion composition according to the present invention is not particularly limited, and a conventionally known method can be used. For example, an O / W type is obtained by adding a nonionic surfactant of the component (B) to the silicone mixture of the component (A) and further adding water of the component (C) to perform phase inversion and dilution. Can be obtained as an emulsified composition. Various additives such as preservatives, pigments, and ultraviolet absorbers can be added to the emulsified composition according to the present invention, if desired, as long as the object of the present invention is not impaired. The surface protective glaze of the present invention is based on the emulsified composition thus obtained, and there is no particular limitation on the method of use, for example, as it is, or appropriately diluted with water. After that, it is applied to the surface of various molded products, especially natural or synthetic rubber products, natural or synthetic leather products, various thermoplastic resin products, thermosetting resin products, wood products, etc. by brush coating, spray coating, dipping, etc. Then, it may be dried. The protective film thus formed has an excellent polishing effect and serves as a protective film against ozone, ultraviolet rays, oxygen, nitrogen oxides, etc., so that a durable protective polishing effect can be imparted to the surface to be treated. .

[0023]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the emulsified composition obtained in each example was diluted with ion-exchanged water to 5 times the weight to prepare a test solution, and its properties were evaluated as described below. (1) Appearance (a) Initial luster After washing the actual car tire with water, spray the test liquid to the side wall area of 500 cm ^{2 on} the tire surface in an area of 500 cm ² using a spray and apply the appearance after natural drying. The state was visually observed and evaluated according to the following criteria. ：: glossy, glossy, and deep black. Δ: Slightly glossy and glossy. ×: There is no gloss (substantially the same as the uncoated portion). (B) Gloss after outdoor exposure After leaving the automobile tire coated with the test liquid prepared in (a) above outdoors for 30 days, the surface dust was wiped off, and the appearance was visually observed. Evaluation was made based on the same criteria.

(C) Gloss after washing with water A car tire coated with the test solution in the same manner as in (a) above was washed with a household detergent ("Mama Lemon", manufactured by Lion Corporation).
Immersed in a 1% by weight aqueous solution of
After rubbing 0 times, the bubbles were washed off with tap water, the appearance of the coating film was visually observed, and evaluated according to the same criteria as in (a) above. (2) Ozone crack resistance The tire test piece coated with the test liquid obtained in (1) (a) above was subjected to static ozone 50 pphm × 40 ° C. × 24.
A static ozone test was performed with a 40% stretch in time. The number of cracks was evaluated according to the following criteria. ：: The occurrence of cracks is small. Δ: Many cracks occurred. ×: Infinite number of cracks (substantially equivalent to uncoated tires).

(3) Slip resistance SBR test piece (10 cm × 15 cm × thickness 0.2c)
m) is spray-coated with a test solution and dried at 25 ° C. for 24 hours.
The coefficient of kinetic friction was measured (for aluminum plate, load 1k
g, tensile speed 100 mm / min). The larger the value of the dynamic friction coefficient, the better the slip resistance. The dynamic friction coefficient of the test piece (blank) not coated with the surface protective agent was 1.6. As the component (A-1) in Examples and Comparative Examples, those shown in Table 1 were replaced with (A-
2) The components shown in Table 2 were used.

[0026]

[Table 1]

[0027]

[Table 2]

Example 1 190 g of a dimethylpolysiloxane (A-1-1) having a hydroxyl group-terminated at 25 ° C. having a viscosity of 4.8 Pa · s and a viscosity of 25 ° C. of 5.
In a mixture of 190 g of dimethylpolysiloxane (A-2-1) capped with a trimethylsiloxy terminal group at 0 Pa · s, M
The molar ratio of e ₃ SiO _1/2 units / SiO _4/2 units is 0.70
Then, 160 g of a silicone resin (A-3-1) having a total content of those units of 100 mol% was added thereto, and the mixture was stirred at 100 ° C. for 3 hours to prepare a uniform mixed solution.
Here, Me represents a methyl group. To this mixed solution, polyoxyethylene lauryl ether (B-1, ethylene oxide addition mole number 5 mol, DAVIS HLB 6.2)
After adding and mixing 60 g, 80 g of deionized water was added, and high-speed stirring was performed with a homomixer at 5000 rpm for 15 minutes to perform phase inversion and kneading. Further, add 320 g of deionized water and use a homomixer at 2000 rpm.
The resulting mixture was stirred for 15 minutes at m for dilution to prepare a target milky white emulsion composition. This emulsified composition was excellent in stability such that no separation was observed even after standing at 25 ° C. for one month. The characteristics of this
It is shown in the table.

Examples 2 to 7 Milk white emulsion compositions were prepared in the same manner as in Example 1 except that the components and types shown in Table 3 were used. The obtained emulsified composition was excellent in stability such that no separation was observed even after standing at 25 ° C. for one month. Table 4 shows the characteristics of these emulsified compositions. Comparative Example 1 270 g of the above (A-1-1) and 270 g of (A-2-1)
Was mixed with 60 g of (B-1), and 80 g of deionized water was added, followed by high-speed stirring at 5000 rpm for 15 minutes using a homomixer to perform phase inversion and kneading. Further, 320 g of deionized water was added, and the mixture was stirred for 15 minutes at 2000 rpm with a homomixer to perform dilution, thereby preparing a milky white emulsion composition of interest. The properties are shown in Table 4. Comparative Example 2 (A-3-1) 160 in 380 g of the above (A-2-1)
g, and stirred at 100 ° C. for 3 hours to prepare a uniform mixed solution. 60 g of (B-1) was added to this mixture.
Was added and mixed, and then 80 g of deionized water was added, followed by high-speed stirring at 5000 rpm for 16 minutes with a homomixer to perform phase inversion and kneading. Further, 320 g of deionized water is added, and the mixture is mixed at 2000 rpm with a homomixer.
The mixture was diluted by stirring for 5 minutes to prepare a target milky white emulsion composition. The characteristics of this
It is shown in the table.

Comparative Example 3 (A-3-1) 160 in 380 g of the above (A-1-1)
g, and the mixture was stirred at 100 ° C. for 3 hours to prepare a uniform mixed solution. 60 g of (B-1) was added to this mixture.
Was added and mixed, and then 80 g of deionized water was added, and the mixture was stirred at a high speed of 5000 rpm for 15 minutes with a homomixer to perform phase inversion and kneading. Further, 320 g of deionized water is added, and the mixture is mixed at 2000 rpm with a homomixer.
The mixture was diluted by stirring for 5 minutes to prepare a target milky white emulsion composition. The characteristics of this
It is shown in the table. Comparative Example 4 In Example 1, instead of B-1, the surfactant was sodium polyoxyethylene nonylphenyl ether sulfate (B-7, 3 moles of ethylene oxide added, DAVIS HLB) instead of B-1. Value 4
A milky white emulsion composition was prepared in the same manner as in Example 1 except that 3.1) was used. The properties are shown in Table 4.

[0031]

[Table 3]

[0032]

[Table 4]

[Note] A-3-1: Me ₃ SiO _1/2 unit / SiO _4/2 unit molar ratio = 0.70, their total content = 100 mol% A-3-2: Me ₃ SiO _1/2 unit / SiO _4/2 unit molar ratio = 0.65, their total content = 100 mol% A-3-3: Me ₃ SiO _1/2 unit / SiO _4/2 unit molar ratio = 1. 20, their total content = 100 mol% A-3-4: Me ₃ SiO _1/2 unit / SiO _4/2 unit molar ratio = 1.10, their total content = 100 mol% B-1: Polyoxyethylene lauryl ether, 5 moles of ethylene oxide added, DAVIS HLB value
6.2 B-2: Polyoxyethylene sorbitan monolaurate, 8 moles of ethylene oxide added, DAVIS
HLB value 14.4 B-3: polyoxyethylene tridecyl ether, 6 moles of ethylene oxide added, DAVIS HLB
Value 6.0 B-4: polyoxyethylene nonylphenyl ether, ethylene oxide addition mole number 10 mol, DAVIS
HLB value 6.4 B-5: Sorbitan monolaurate, DAVIS H
LB value 8.2 B-6: polyoxyethylene oleyl ether, ethylene oxide addition mole number 5 mol, DAVIS HLB value
6.6 B-7: Sodium polyoxyethylene nonyl phenyl ether sulfate, ethylene oxide added 3 mol,
DAVIS HLB value 43.1

[0034]

[Table 5]

In Comparative Example 1, since the component (A-3) is not blended, the durability of gloss is not good, the coefficient of dynamic friction is small, and there is a possibility that slip properties may be obtained. Comparative Example 2
Comparative Example 1 did not contain the component (A-1).
As in the above case, the durability of the gloss is poor, the coefficient of kinetic friction is small, and there is slip property. In Comparative Example 3, since the component (A-2) was not blended, the gloss was insufficient. In Comparative Example 4, since an anionic surfactant having a very large DAVIS HLB value is used as the component (B), the tire has a high erosion property and weather resistance (ozone crack resistance).
Is declining.

[0036]

The surface protective glaze of the present invention protects the surface of molded articles made of rubber, leather, plastic, etc., especially rubber products such as tires, from ultraviolet rays, ozone, moisture, etc. Gloss durability, good slip resistance and ozone crack resistance can be imparted.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kohei Hasegawa 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Satoshi Kuwata Matsuida-machi, Usui-gun, Gunma Prefecture Hitomi 1-10, Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (2)

[Claims] (A) (A-1) Average structural formula (I) (Wherein, R ¹ represents a monovalent organic group having 1 to 20 carbon atoms,
m shows a positive number of 10 to 2000. However, a plurality of R ¹ may be the same or different. ) At 25 ° C
At a viscosity of 0.01 to 1000 Pascal second (Pa.
s) diorganopolysiloxane 1 having hydroxyl groups blocked at both ends
90% by weight, (A-2) average structural formula (II) (Wherein, R ² represents a monovalent organic group having 1 to 20 carbon atoms,
n shows a positive number of 10 to 2000. However, a plurality of R ² may be the same or different. ) At 25 ° C
At end of tri-substituted siloxy group-blocked diorganopolysiloxane having a viscosity of 0.01 to 1000 Pa · s.
Wt% and _{^{(A-3) R 3 3}} SiO 1/2 units and SiO _4/2
Together containing at the sum more than 80 mole% of units, optionally containing R ³ ₂ SiO _2/2 units and / or R ³ SiO _3/2 units, and R ³ ₃ SiO _1/2 units / SiO _{4 /} The molar ratio of the _two units is 0.5 to 1.5 (where R ³ is
A 20 monovalent organic group, the plurality of R ³ may be the same or different. A) a silicone mixture 10-70 consisting of 5-50% by weight of an organic solvent-soluble silicone resin
% By weight, (B) 1 to 10% by weight of a nonionic surfactant,
And (C) a surface protective glazing agent comprising an emulsified composition comprising water as the main component. 2. The nonionic surfactant (B),
The surface protective gloss according to claim 1, which is at least one selected from polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers having a DAVIS HLB value of 3 to 9 and sorbitan fatty acid esters having a DAVIS HLB value of 7 to 16. Dispensing agent.