JPH0598215A - Protective lustering agent composition for tire - Google Patents

Abstract

PURPOSE:To obtain a protective lustering agent composition for a tire which attains a well-balanced combination of a high degree of water repellency, luster, blackness, and long-lasting water repellency and is completely free from the drawback of discoloration of conventional aminosilicone. CONSTITUTION:The title composition is an aqueous emulsion of a silicone oil composition comprising 5-30wt.% organopolysiloxane and 95-70wt.% dimethylpolysiloxane having a viscosity at 25 deg.C of 100-10,000cSt. The organopolysiloxane is one obtained by reacting an organopolysiloxane having two or more primary and/or secondary amino groups per molecule on the average with an organic acid or an anhydride or chloride thereof to thereby acylate part or the whole of the amino groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a protective glazing agent which is applied to a rubber surface of an automobile tire or the like with a hand spray, a gas filling spray, a sponge or the like to impart a highly durable and water-repellent and glossy finish. It is a thing.

[0002]

2. Description of the Related Art Conventionally, a glazing agent for rubber products has a solvent type of dimethylpolysiloxane (hereinafter referred to as dimethyl silicone) as a main component and 10 to 20% by weight of the dimethyl silicone component diluted with a chlorofluorocarbon solvent or an interface. An aqueous type has been used in which an activator is used and an emulsion of 10 to 20% by weight of a dimethyl silicone component is used.

[0003]

However, although the solvent type is superior in blackness and gloss to the aqueous type, it is inferior in easiness of coating and is likely to cause spots, and is contained in rubber. To elute anti-aging agents,
Swells rubber to accelerate deterioration. In addition, a chlorofluorocarbon-based solvent in which dimethyl silicone is dissolved is the mainstream, and it has become an environmental problem that the volatilized solvent destroys the ozone layer. On the other hand, the water-based type has good workability, but is still insufficient in gloss and gloss durability, water repellency and water repellency. Therefore, an amino group-containing organopolysiloxane (hereinafter referred to as aminosilicone), which is effective for water repellency, water repellency durability, and gloss durability, has come to be used. However, when aminosilicone is used, a reddish brown discoloration is observed, so that there is a drawback that the original function as a polishing agent is lost, such that the tire loses gloss and becomes reddish. An object of the present invention is to provide a protective glazing agent for tires in which the above drawbacks are eliminated.

[0004]

In order to solve the above problems, the inventors of the present invention have studied the improvement of conventionally used amino group-containing organopolysiloxane emulsions, and as a result, have found that The present invention was completed by achieving the initial purpose by acylating the amino group, which is considered to be caused by a group, and attention is paid to the fact that the drawbacks are prevented by modifying the amino group and only the advantages remain. ..

That is, according to the present invention, an organopolysiloxane having an average of two or more primary and / or secondary amino groups in one molecule is reacted with an organic acid, an organic acid anhydride or an organic acid chloride. At least a part or all of the amino group obtained is at most acylated organopolysiloxane 5
30% by weight and a viscosity at 25 ° C of 100 to 1000
The present invention provides a protective polish for tires, characterized in that a silicone oil composition consisting of 0 to 95% by weight of dimethylpolysiloxane is emulsified and dispersed in water.

Amino group-containing organopolysiloxane (aminosilicone oil) used in the polish of the present invention
As the compound, those having an average of two or more primary and / or secondary amino groups per molecule are used. This may be a straight chain or a branched chain,
Further, the terminal may be blocked with triorganopolysiloxane or may be blocked with other one.

The viscosity of the aminosilicone oil used in the polishing agent of the present invention may be in the range of 100,000 to 100,000 cs (25 ° C.), preferably 1,000 to 300.
Those having 0 cs (25 ° C.) can be preferably used. Examples of such amino silicone oil include KF867 (produced by Shin-Etsu Chemical Co., Ltd.) and TSF47.
01 (manufactured by Toshiba Silicone Co., Ltd.), BY-16850
Commercially available products such as (manufactured by Toray Dow Corning Silicone Co., Ltd.) can be preferably used.

For the acylation of the amino group of the aminosilicone oil used in the present invention, an organic acid, an organic acid anhydride or an organic acid chloride can be used. These organic acids are not particularly limited as long as they can be acylated and do not exclude the formation of an emulsifier, but preferably a lower fatty acid, a fatty acid anhydride or an acid having a linear alkyl group having 1 to 8 carbon atoms. Chloride can be used. In particular,
Acylation using an anhydride of a lower fatty acid is preferable from the viewpoint of ease of the acylation step.

The acylation reaction of aminosilicone with an organic acid, organic acid anhydride or acid chloride may be carried out by an ordinary method. For example, the reaction of aminosilicone and acid anhydride is carried out by mixing the two at room temperature, The mixture is heated and heated under a nitrogen gas stream to react in the range of about 50 ° C to 110 ° C. At this time, a reaction solvent and a catalyst are not particularly required, which is convenient. The acylation rate of the acylated aminosilicone used in the present invention can be appropriately selected depending on the amount of organic acids. Normally,
Acylation is carried out by adding an organic acid in an amount equivalent to that of the amino group contained therein, but the acylation is usually carried out at an acylation rate of 20 to 100%.

The polish of the present invention contains 5 to 30% by weight of the above acylated aminosilicone and a viscosity of 100 to 1 at 25 ° C.
It consists of an emulsion obtained by emulsifying and dispersing an oily composition in which 95 to 70 wt% of 0000 cs dimethyl silicone is mixed with a surfactant. The amount of the oily composition in the emulsion of the present invention can be appropriately selected from the viewpoint of convenience of use, but normally, a content of 10 to 30% by weight relative to the total amount of the emulsion is preferably used. it can. For emulsifying the oily composition, one or more kinds of cationic surfactants, anionic surfactants and nonionic surfactants are used and emulsified by a usual method. The amount of the surfactant used is generally 10 to 40% by weight based on the oil composition. Examples of the cationic surfactant used in the present invention include primary amine acetate or hydrochloride, alkyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride, higher amine ethylene oxide adduct and the like.

Examples of the anionic surfactant used in the present invention include higher fatty acid alkali salts, higher fatty acid amine salts, higher alcohol sulfuric acid ester salts, alkyl ether sulfuric acid ester salts and the like. Examples of the nonionic surfactant used in the present invention include polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, and fatty acid monoglyceride. However, the surfactant is not limited to the above, and various surfactants can be appropriately used by blending them so as to be suitable for the required HLB of silicone oil.

When the amount of the acylated aminosilicone compounded in the oil composition of the polishing agent of the present invention is less than 5% by weight, the effects of water repellency and durability cannot be sufficiently obtained, and when it exceeds 30% by weight, uneven coating is caused. Occurs. Particularly, a blending ratio of 8 to 20% by weight is preferable. Further, the concentration of the silicone oil composition component in the emulsion when applied to the tire is 10 to 30.
% Is preferable, and if it is less than 10% by weight, glossiness is insufficient and durability is poor. If it exceeds 30% by weight, uneven coating tends to occur. The content of the surfactant is preferably 10 to 40% by weight with respect to the silicone oil composition, and if it is less than 10% by weight, emulsification becomes difficult, and if it exceeds 40% by weight, gloss becomes dull. It is preferably 15 to 30% by weight.

[0013]

EXAMPLES The present invention will be described in more detail with reference to specific examples. Example 1 Viscosity at 25 ° C. is 1200 cs, Aminosilicone SF
Charge 9817 parts by weight of 8417 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and 2 parts by weight of acetic anhydride into a reaction vessel, and raise the temperature in nitrogen gas to about 1 at a temperature of 100 to 110C.
The reaction was carried out for a time to obtain an acylated reaction product A. After completion of the reaction, the reaction mixture is cooled, and 4 parts by weight of the acylation reaction product A is added to obtain a viscosity of 1000
16 parts by weight of dimethyl silicone of s, 5 parts by weight of a nonylphenol ethylene oxide adduct, and 100 parts by weight of water were added to obtain an emulsion.

Example 2 Aminosilicone BY having a viscosity of 1100 cs at 25 ° C.
96 parts by weight of -16 850 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and 4 parts by weight of acetic anhydride were placed in a reaction vessel and reacted in the same manner as in Example 1 to obtain an acylation reaction product B. Acylation reaction product B is 4 parts by weight and the viscosity is 100.
16 parts by weight of 0 cs dimethyl silicone, 5 parts by weight of a higher alcohol ethylene oxide adduct, and 100 parts by weight of water were added, and the whole was stirred to obtain an emulsion.

Example 3 Aminosilicone SF8 acylated as in Example 1
417 (acylation reaction product A), 7 parts by weight, viscosity of 350
18 parts by weight of cs dimethyl silicone, 5 parts by weight of higher alcohol ethylene oxide adduct, and 100 parts by weight of water were added to stir to obtain an emulsion.

Example 4 Aminosilicone BY having a viscosity of 1100 cs at 25 ° C.
100 parts by weight of -16 850 and 6 parts by weight of NAA60 (manufactured by Nippon Oil & Fats Co., Ltd.) were charged into a reaction vessel, heated in nitrogen gas and reacted at a temperature of 160 to 170 ° C for about 3 hours (reactant C). .. After completion of the reaction, the reaction product is cooled and acylated reaction product C
Got 6 parts by weight of acylation reaction product C, viscosity 1000
14 parts by weight of cs dimethyl silicone, 5 parts by weight of nonylphenol ethylene oxide adduct, water was added to make 100 parts by weight, and the whole was stirred to obtain an emulsion.

Comparative Example 1 Aminosilicone BY- having a viscosity of 1100 cs at 25 ° C.
16 850 without acylation, amino silicone BY-
16850 parts by weight, 16 parts by weight of dimethyl silicone having a viscosity of 1000 cs, 5 parts by weight of nonylphenol ethylene oxide adduct, and water to add 100 parts by weight.
This was made into a weight part, and this was stirred to obtain an emulsion.

Comparative Example 2 20 parts by weight of dimethyl silicone having a viscosity of 200 cs at 25 ° C., 5 parts by weight of higher fatty acid amine salt and water were added to make 100 parts by weight, and the whole was stirred to obtain an emulsion.

Comparative Example 3 Dimethyl silicone 20 having a viscosity of 1000 cs at 25 ° C.
By weight, 5 parts by weight of polyoxyethylene higher alcohol ether and water were added to make 100 parts by weight, and the whole was stirred to obtain an emulsion.

Comparative Example 4 Dimethyl silicone 20 having a viscosity of 5000 cs at 25 ° C.
By weight, 5 parts by weight of nonylphenol ethylene oxide adduct and water were added to make 100 parts by weight, and the whole was stirred to obtain an emulsion.

Comparative Example 5 Aminosilicone BY- having a viscosity of 1200 cs at 25 ° C.
20 parts by weight of 16850, 5 parts by weight of a higher alcohol ethylene oxide adduct, and 100 parts by weight of water were added to the whole to obtain an emulsion. The above was applied to an actual automobile tire and a comparative test was conducted. The results are shown in Table 1.

[0022]

[Table 1]

Test method After washing an actual automobile tire, the above emulsions were sprayed as undiluted solution onto an area of 500 cm ² of tire side wall 4 times using a hand spray (applied about 2 ml), and gloss was applied. , Blackness, uneven coating, water repellency, durable water repellency and the presence or absence of discoloration were evaluated by visual comparison with an uncoated blank portion provided next to the coated portion.

Performance Evaluation Method 1. Glossiness The presence or absence of gloss is evaluated with the naked eye. ○: There is luster. △: There is luster. Clearness of blackness Evaluation of blackness with the naked eye ○: Blackness with depth Δ: Black ×: Dull blackness (equivalent to blank part) 3. Coating unevenness Evaluation of coating unevenness immediately after coating ○: There is no unevenness Δ: There is some unevenness ×: There is unevenness

4. 4. Water repellency After application, water was sprayed 50 times with a hand spray to evaluate the repelling of water. ○: Water droplets are small and repelled. △: Water droplets are a little large. ×: Wet (same as blank portion). Durable water repellency After the tire subjected to the water repellency test after application is left at room temperature for 1 week, the portion subjected to the water repellency test is washed with water, dried and then sprayed with water in the same manner as in the above water repellency test to evaluate the water repellency. : Repels water well △: Repels water slightly ×: Wet (equivalent to blank part)

From the above examples and comparative examples, the following can be seen. From Table 1, Examples 1 to 4 of the present invention show gloss, blackness,
The water repellency and durable water repellency were also good. Furthermore, there was no discoloration due to the amino group. Comparative Example 1 was good in terms of gloss and durable water repellency, but discoloration due to amino groups of aminosilicone was observed. Comparative Examples 2 to 4 were performed only with dimethyl silicones having different viscosities, but the gloss,
It can be seen that any of blackness, uneven coating, water repellency and durable water repellency is inferior. Comparative Example 5 was carried out only with aminosilicone, but with aminosilicone alone, gloss and uneven coating were poor, and further discoloration was observed.

[0027]

EFFECT OF THE INVENTION The protective glazing composition for tires of the present invention is capable of obtaining a high degree of water repellency, gloss, blackness, and durable water repellency in a well-balanced manner, and has a good performance in addition to conventional amino silicones. The drawback of discoloration that was present has been completely eliminated.

Claims (1)

[Claims] 1. Obtained by reacting an organopolysiloxane having an average of two or more primary and / or secondary amino groups in one molecule with an organic acid, an organic acid anhydride or an organic acid chloride. , 5 to 30% by weight of organopolysiloxane in which a part or all of the amino group is acylated, and 25 ° C.
A protective polish for tires, characterized in that a silicone oil composition consisting of 95 to 70% by weight of dimethylpolysiloxane having a viscosity of 100 to 10,000 cs is emulsified and dispersed in water.