JP2003003127A - Water repellent glazing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion-type water repellent glazing agent having excellent compounding stability, free from the occurrence of uneven coating, wiping unevenness, uneven luster and stickiness when applied on the surface of a base material, having durable excellent water repelling property and glazing effect, and further excellent in stability during high temperature storage and low temperature storage. SOLUTION: The emulsion-type water repellent glazing agent contains an O/W-type amino-functional silicone emulsion comprising (A) 100 pts.wt. of an amino-functional polyorganosiloxane, (B) 10-200 pts.wt. of a mixture of a nonionic surfactant and a carboxylic acid-type amphoteric surfactant and (C) 20-400 pts.wt. of water, as the main components. The ratio (weight ratio) of nonionic surfactant/carboxylic acid-type amphoteric surfactant of the mixture (B) is 1/0.1 to 1/20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion-type water-repellent polish, and in particular, it imparts an excellent glossy appearance to various base materials and excellent water-repellent properties, and at the time of storage at high temperature and at low temperature. The present invention relates to a water-repellent polish which is mainly composed of an amino-functional silicone emulsion excellent in storage stability.

[0002]

2. Description of the Related Art Conventionally, in an aqueous polish containing mainly wax, an emulsion of polydiorganosiloxane such as polydimethylsiloxane or polymethylphenylsiloxane has been added to improve the polish effect and workability. (Japanese Patent Laid-Open No. 52-141
493). Further, addition of a polyorganosiloxane microemulsion having an average particle diameter of 150 nm or less has also been carried out (see JP-A-63-301280).

However, JP-A-52-141493
The water-based polish shown in Japanese Patent Laid-Open Publication No. 2003-108242 is one in which a normal emulsion obtained by mechanically emulsifying a polyorganosiloxane oil with a surfactant and water is added, and the average particle diameter of the emulsion is very large (0.3 μm). Therefore, the stability as an aqueous polish is insufficient. That is, since the long-term storage stability and the compounding stability when used in combination with various additives such as abrasives are insufficient, the polyorganosiloxane oil is easily separated, and the emulsion separated as an oil is used as a polish. When it is used, there is a defect that unevenness of gloss, unevenness of unevenness, unevenness of wiping and / or stickiness occur on the substrate. Further, the oil-separated polish has a drawback in that the product value is remarkably reduced in appearance.

Further, the polyorganosiloxane microemulsion having an average particle size of 0.15 μm or less, which is disclosed in JP-A-63-301280, has alleviated the above-mentioned drawbacks, but has an amino group in the molecule of the polysiloxane. Since such a functional group does not exist, there is a drawback that the adhesion to the treated surface is poor and the water repellency and glossiness are not maintained well. Further, since the microemulsion is produced by an emulsion polymerization method, there is a restriction that it cannot be used in combination with various additives.

Therefore, the applicant of the present application filed Japanese Patent Application Laid-Open No. 9-530.
In Japanese Patent Laid-Open No. 50, a water-repellent polishing agent containing a microemulsion produced by a specific method as a main component was proposed. Although such a water-repellent polish has the drawbacks of the prior art solved and is excellent in glossiness, compounding stability, etc., it was found from the subsequent study that the stability at high temperature storage was the same as that of the conventional product. Poor turbidity may occur, or emulsifier coagulation may occur during storage at low temperatures, resulting in a phenomenon of thickening and whitening, resulting in inconvenience such as deterioration of properties.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to eliminate the above-mentioned drawbacks of existing water-repellent polishes, has excellent compounding stability, and is applied to the surface of a substrate. Emulsion-type emulsion that does not cause uneven coating, uneven wiping, uneven gloss, and stickiness, has excellent water repellency with excellent durability, and has a polishing effect, and has excellent stability during high-temperature storage and low-temperature storage. The purpose is to provide a water repellent polish.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has identified a nonionic surfactant and a carboxylic acid type amphoteric surfactant as a surfactant used for producing an emulsion. It was found that the combined use in a ratio is extremely effective, and the present invention has been completed.

That is, the present invention relates to a mixture of 100 parts by weight of (A) amino-functional polyorganosiloxane, (B) a nonionic surfactant and a carboxylic acid type amphoteric surfactant.
00 parts by weight, 20 to 400 parts by weight of (C) water, and the mixture (B) has a nonionic surfactant / carboxylic acid type amphoteric surfactant ratio (weight ratio) of 1 / 0.1 to 1: 1. / 20
Is a water-repellent polish which contains an oil-in-water amino-functional silicone emulsion as a main agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The (A) amino-functional polyorganosiloxane used in the present invention typically comprises the following siloxane units (a) and (b): (a) R _a Q _b SiO _{(4-ab) / 2} units; b) R _c SiO _{(4-c) / 2} unit [in the formula, R may be the same or different, and a monovalent substituted or unsubstituted hydrocarbon having 1 to 6 carbon atoms (provided that , And Q may be a silicon-functional group, and Q is a general formula —R ¹ NZ ₂ (wherein R ¹ is an ether bond, a thioether bond, an ester bond in the chain). Or a divalent hydrocarbon group in which a carbonyl thioether bond may be present; Z may be the same or different, and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 2-amino. Represents an ethyl group), and a represents 0 to 2 By and; b is a number from 1 to 3, provided that a + b is a number from 1 to 3; c is 1 to 3
Of the amino acid number], which is an amino-functional polyorganosiloxane in which a silicon functional group may be present.

R of the above-mentioned (a) unit and (b) unit is methyl, ethyl, propyl, butyl, amyl,
Alkyl groups such as hexyl; alkenyl groups such as vinyl and allyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; phenyl groups; 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl , Halogenated hydrocarbon groups such as chlorophenyl and bromophenyl; and mercaptohydrocarbon groups such as 3-mercaptopropyl, 6-mercaptohexyl and mercaptophenyl. Further, a part of R is a hydroxyl group; or methoxy,
It may be an alkoxy group such as ethoxy and propoxy. As R, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is most preferable. In addition, since a fine microemulsion can be obtained, R
It is preferable that a part of the above is a silicon functional group.

In the amino functional group Q of the unit (a),
R bonded to the silicon atom of¹ As methylene, tri
Methylene, 2-methyltrimethylene, tetramethylene,
Alkylene groups such as hexamethylene and decamethylene;
Phenylene, biphenylene, bis (phenylene-4-i)
Ru) methylene, arylene groups such as naphthylene;
(CH₂)₃ OCH2-,-(CH₂)₃ O (CH₂)₂ -,
-(CH₂)₃ S (CH₂) ₂ -Like ether linkages in the chain
Divalent hydrocarbon group having a compound or a thioether bond;
-(CH₂)₃ C (O) OCH₂ -,-(CH₂)₃ C
(O) O (CH₂)₂ -,-(CH₂)₃ C (O) S (CH
₂)₂ -Such as an ester bond or a carbonyl group in the chain
Examples of the divalent hydrocarbon group having an ether bond,
The trimethylene group is the most suitable because it is easy to synthesize and stable.
preferable.

As mentioned above, Z is a hydrogen atom or an alkyl group such as methyl, ethyl, propyl or butyl;
Most preferably, it is a 2-aminoethyl group, and at least one of the two Z is a 2-aminoethyl group.

That is, the amino functional group Q is most preferably an N- (2-aminoethyl) -3-aminopropyl group having two amino groups.

The amino group content of the amino-functional polyorganosiloxane is preferably 0.02 to 3.0 meq / g, more preferably 0.3 to 1.5 meq / g,
Most preferred is 0.6 to 1.0 meq / g.

To obtain such an amino group content,
The molar ratio of the (a) unit to the (b) unit is 1: 2 to 1:13.
The range of 00 is preferable, 1: 5 to 1:65 is more preferable, and 1:15 to 1:20 is the most preferable.

The component (A) is, for example, when R ¹ is a trimethylene group, an amino group represented by the general formula: CH ₂ ═CHCH ₂ NZ ₂ (wherein Z is as described above) in the polyorganohydrogensiloxane. Containing unsaturated compounds,
It can be synthesized by reacting in the presence of a hydrosilylation catalyst.

Component (A) is, for example, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-.
Obtained by ring-opening polymerization of a low-molecular weight cyclic polydiorganosiloxane such as octamethylcyclotetrasiloxane in the presence of an amino group-containing alkoxysilane such as (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. You can

In this case, an amino-functional polyorganosiloxane having an alkoxy group such as methoxy or ethoxy and a silicon functional group such as a hydroxyl group formed by hydrolysis of the alkoxy group at the molecular end and in some cases in the molecule is obtained. To be In order to form a microemulsion having a fine oily phase, those having such a silicon functional group are preferable. Depending on the purpose, this may be treated with a silylating agent such as hexamethyldisilazane and substituted with a trimethylsilyl group before use.

Preferred amino-functional polyorganosiloxanes have the general formula (I):

[0020]

[Chemical 1]

(Wherein Z is as described above, preferably — (CH ₂ ) ₂ NH ₂ ; R ² is a methyl group, R ³ or the following formula:

[0022]

[Chemical 2]

Is a side chain represented by the formula;
³ is a methyl group, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group; x is a number from 1 to 20, y and z are each a number from 0 to 1500, provided that y and z
Has 20 to 1500 dimethylsiloxy groups in the molecule.
Is an oily polyorganosiloxane. x is preferably 5-10, most preferably 8. The above formula (I) represents the number of siloxane units, and does not mean a block copolymer.

In the present invention, as the surfactant as the component (B),
It is characterized by using a mixture of a nonionic surfactant and a carboxylic acid type amphoteric surfactant.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene isocetyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, and polyoxyethylene stearyl ether. Polyoxyethylene alkyl ether-based surfactants such as oxyethylene oleyl ether and polyoxyethylene behenyl ether; polyoxyethylene alkyl such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and polyoxyethylene dodecyl phenyl ether Aryl ether type surfactant; polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid Ether, polyoxyethylene fatty acid esters, polyoxyethylene hardened castor oil, glycerin fatty acid esters, polyglycerol fatty acid esters, sorbitan fatty acid esters, and ester-based surfactants such as sucrose fatty acid esters.

Particularly preferred are polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether. These nonionic surfactants may be used alone or in combination of two or more.

On the other hand, examples of the carboxylic acid type amphoteric surfactant include betaine type coconut oil fatty acid amide propyl betaine, lauric acid amide propyl betaine lauryl dimethylaminoacetic acid betaine, coconut oil alkyl betaine, and the like, and particularly coconut oil fatty acid. Amidopropyl betaine is preferred. These betaine-type amphoteric surfactants are 1
The seeds may be used alone or in combination of two or more.

The amount of the surfactant (B) used is preferably 10 to 200 parts by weight, more preferably 30 to 180 parts by weight, based on 100 parts by weight of the component (A). If it is less than 10 parts by weight, a good microemulsion cannot be obtained, and 2
If it is used in an amount of more than 00 parts by weight, an excessive amount of the surfactant will hinder the adhesion of the amino-functional polyorganosiloxane to the fiber, or the viscosity of the resulting composition will increase, resulting in poor fluidity and This makes it difficult to process.

In the present invention, the ratio (weight ratio) of the nonionic surfactant / carboxylic amphoteric surfactant in the mixture (B) is 1 / 0.1 to 1/20, preferably 1
It is necessary to be in the range of / 1 to 1/10.

Of the component (B), the nonionic surfactant is
It mainly functions to disperse the amino-functional polyorganosiloxane of the component (A) in water. Further, since the carboxylic acid type amphoteric surfactant also has a function as a storage stabilizer of the composition in addition to a function as an emulsifier, if the ratio is too small, the storage stability is deteriorated and is too large. It becomes difficult to obtain a good emulsion because the composition is extremely discolored. The water of the component (C) is 10 parts of the component (A).
20 to 400 parts by weight is used with respect to 0 parts by weight.

The silicone emulsion of the present invention can be produced by a conventionally known method. That is, the step of adding an acid such as acetic acid to convert at least a part of the amino-functional polyorganosiloxane in the system into a salt at the end of the emulsion production step, and adding a water-soluble polyhydric alcohol such as glycerin are included. However, it is well known that it is permissible to add an effective amount of the preservative as necessary.

Examples of the emulsifying machine used include a homomixer, a homogenizer and a colloid mill.

The microemulsion thus obtained may be used as it is as a water-repellent polish.
Alternatively, two or more kinds may be mixed and used. Alternatively, it may be further diluted with water before use, or may be used in combination with a conventional silicone oil emulsion and / or wax emulsion.

The silicone oil emulsion used together with the microemulsion of the present invention includes dimethyl silicone emulsion, methylphenyl silicone emulsion, alkyl modified silicone emulsion, fatty acid modified silicone emulsion, carboxyl modified silicone emulsion, alcohol modified silicone emulsion, polyether modified. Examples thereof include silicone emulsion and trifluoropropyl modified silicone emulsion.

Similarly, examples of the wax emulsion used in combination with the microemulsion of the present invention include emulsions of natural or synthetic waxes such as carnauba wax, beeswax, montan wax, paraffin wax, microcrystalline wax and polyethylene wax. .

Further, as additives to be added to the microemulsion of the present invention, there may be mentioned solvents, thickeners, rust preventives, abrasives, colorants, ultraviolet absorbers, fragrances and the like.
These may be contained in a silicone oil emulsion or a wax emulsion to be emulsified, or those emulsified with various emulsifiers may be added. Further, a water-soluble substance may be added as it is to the microemulsion of the present invention. As the solvent, toluene, xylene, kerosene,
Examples include thickeners such as naphtha and mineral spirits; examples of thickeners include silica, diatomaceous earth, bentonite, aluminum silicate, hydrated calcium silicate, magnesium oxide, iron oxide and tin oxide.

[0037]

EFFECT OF THE INVENTION The water-repellent polish of the present invention has excellent storage stability and compounding stability, is excellent in stability by simple work, and has uneven stretch, uneven wiping, and uneven gloss on the surface of a substrate. It is also non-greasy and can impart a long-lasting luster effect and water repellency.This water repellent polish has poor stability during storage at high temperatures and causes turbidity, and emulsifier coagulation during storage at low temperatures. It has excellent high and low temperature stability, and does not cause inconveniences such as the generation of substances and the phenomenon of thickening and whitening.

The silicone emulsion water-repellent polish of the present invention is useful for polishing various base materials such as automobiles, furniture, glass, leather, rubber and plastics, and is particularly useful when used outdoors or in water. , Excellent in water repellency and long lasting gloss effect. Example 1 Polydimethylsiloxane containing 2-aminoethyl-3-aminopropyl group with a terminal trimethylsilyl group blocked (viscosity of 1.00
0 cSt, amino content 0.6 meq / g, silicone (i) 100 parts, polyoxyethylene (7) cetyl ether 16 parts, polyoxyethylene (13) cetyl ether 16 parts,
And 40 parts of glycerin were added, and the mixture was heated with stirring at 50 ° C. for about 10 minutes. Next, 1.6 parts of acetic acid and 50 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution) were added and stirred to form a viscous gel, and further 270 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution), and Add 6 parts of purified water and stir uniformly, silicone content 20%, average particle size 25n
m silicone emulsion composition (emulsion-
1) was obtained. Example 2 Polydimethylsiloxane containing 2-aminoethyl-3-aminopropyl group having a terminal trimethylsilyl group blocked (viscosity 70,0
00cSt, amino content 0.02 meq / g, silicone (i
i)) 100 parts by weight of polyoxyethylene (7) cetyl ether 1
0 parts, 10 parts of polyoxyethylene (13) cetyl ether, and 40 parts of glycerin were added, and the mixture was heated with stirring at 50 ° C. for about 10 minutes. Next, 1.6 parts of acetic acid and 50 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution) were added and stirred to form a viscous gel, and further 350 parts of coconut oil fatty acid amide propyl betaine (30% aqueous solution) was added. Add and stir evenly,
A silicone emulsion composition (emulsion-2) having a silicone content of 17.8% and an average particle size of 275 nm was obtained. Comparative Example 1 2-Aminoethyl-3-aminopropyl Group-Containing Polydimethylsiloxane Blocking Terminal Trimethylsilyl Group
0 cSt, amino content 0.6 meq / g, silicone (i) 100 parts, polyoxyethylene (7) cetyl ether 16 parts, polyoxyethylene (13) cetyl ether 16 parts,
And 40 parts of glycerin were added, and the mixture was heated with stirring at 50 ° C. for about 10 minutes. Then, 1.6 parts of acetic acid and 50 parts of purified water are added and stirred to form a viscous gel, and then 276 parts of purified water is added and uniformly stirred to give a silicone content of 20% and an average particle size.
A 20 nm silicone emulsion composition (Emulsion-3) was obtained.

Water repellent polishes 1 to 3 were prepared by uniformly mixing 5.0 parts of these emulsions 1 to 3 with 5.0 parts of emulsion M for compounding described below and 90.0 parts of water to prepare water repellent polishes 1 to 3. The state change in the case of holding (50 ° C., 4 weeks) and low temperature holding (10 ° C., 4 weeks) was visually evaluated. (Preparation of emulsion M for compounding) 50 parts of polydimethylsiloxane having a viscosity of 500 cSt at 25 ° C. was mixed with 18 parts of carnauba wax, 3 parts of montan wax and 125 parts of paraffin wax 125P, and further 10 parts of sorbitan monolaurate and poly. Oxyethylene (3
2) 10 parts of monostearate was added, heated to 120 ° C. to completely dissolve it, and then cooled to 90 ° C. To this, 200 parts of water at 90 ° C. was added, emulsified using a homogenizer, and allowed to cool to room temperature to prepare an emulsion M for compounding.

Further, the performance of the obtained water-repellent polish was evaluated. That is, the surface of a test piece having a size of 75 mm × 100 mm × 1.5 mm obtained by cutting from a body-painted plate of an automobile (manufactured by Toyota Motor Corp., Mark II new car) was treated with tissue paper to obtain each of the above. After uniformly applying the water repellent polish at low temperature (5 ° C) and leaving it at 25 ° C for 5 minutes,
After soaking in water for 24 hours and gently wiping off the water with a tissue paper, visually the appearance (○; no uneven coating,
Δ: slight uneven coating, ×: uneven coating) and gloss (∘: good gloss, ×: little gloss) were evaluated. The results are shown in Table 1.

[0041]

[Table 1]

Claims (2)

[Claims] 1. 100 parts by weight of (A) an amino-functional polyorganosiloxane, 10 to 200 parts by weight of a mixture of (B) a nonionic surfactant and a carboxylic acid type amphoteric surfactant,
(C) Contains 20 to 400 parts by weight of water, and the mixture (B) has a nonionic surfactant / carboxylic acid type amphoteric surfactant ratio (weight ratio) of 1 / 0.1 to 1/20. A water-repellent polish which contains an oil-in-water type amino-functional silicone emulsion as a main agent. 2. The water-repellent polish according to claim 1, wherein the nonionic surfactant of the component (B) is polyoxyethylene alkyl ether, and the carboxylic acid type amphoteric surfactant is a betaine type amphoteric surfactant.