JPH0749567B2 - Additive for aqueous polish - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aqueous polish additive.

[Prior Art] Conventionally, in a water-based polish based on wax,
In order to improve the polishing effect and workability, an emulsion of a diorganopolysiloxane such as dimethylpolysiloxane or methylphenylpolysiloxane has been added (see JP-A-52-141493).

[Problems to be Solved by the Invention] However, such an aqueous polishing agent is one in which a normal emulsion obtained by mechanically emulsifying an organopolysiloxane with a surfactant and water is added, and the average particle size is very large (0.3 .mu.m or more) and the stability as an aqueous polish is insufficient.

That is, since the long-term storage stability and the compounding stability when various additives such as abrasives are used in combination are insufficient, the organopolysiloxane easily separates oil, and when used as a polishing agent with the oil separated, In addition, there are drawbacks such as uneven gloss, uneven stretch, uneven wiping, and stickiness.

In addition, the oil-separated polish has a drawback in that the product value is remarkably reduced in appearance.

The present invention is intended to eliminate the above-mentioned drawbacks, has excellent long-term storage stability in an aqueous polish, compounding stability, with respect to the substrate, uneven stretch, wiping unevenness, tackiness, It is an object of the present invention to provide an additive capable of imparting an excellent gloss effect without causing uneven gloss.

[Means for Solving Problems and Actions Thereof] (Wherein R is a monovalent hydrocarbon group, n is an integer of 3 to 10) while adding a crude emulsion consisting of a cyclic diorganopolysiloxane, a surfactant and water to the aqueous solution containing the emulsion polymerization catalyst. This is achieved by an additive for an aqueous polish, which comprises an organopolysiloxane microemulsion having an average particle size of 0.15 μm or less obtained by emulsion polymerization as a main component.

To explain this, the organopolysiloxane microemulsion used in the present invention is required to have an average particle size of 0.15 μm or less, preferably 0.12 μm or less. This has an average particle size of 0.15μ
When it is larger than m, the long-term storage stability and the compounding stability become insufficient, and the organopolysiloxane easily separates. Therefore, when used as a polish, uneven gloss on the substrate,
This is because uneven stretching, uneven wiping, and stickiness occur.

General formula The cyclic diorganopolysiloxane represented by is a raw material in the crude emulsion.

In the above formula, R is a monovalent hydrocarbon group, which includes
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-phenylethyl group, 2-phenylpropyl group, substituted alkyl groups such as 3.3.3-trifluoropropyl group, vinyl group, propenyl group Examples of such an alkenyl group, a phenyl group, an aryl group such as a tolyl group, or a substituted aryl group, and Rs in the molecule may be the same or different. n is an integer of 3-10.
The cyclic organopolysiloxane may be one kind, and
It may be a combination of two or more species.

The organopolysiloxane requires a surfactant in order to form a crude emulsion, which includes anionic surfactants, cationic surfactants and nonionic surfactants.

Anionic surfactants include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, alkylbenzenesulfonic acids such as myristylbenzenesulfonic acid, CH ₃ (CH ₂ ) ₆ CH ₂ O (C ₂ H ₄ O) ₂ SO ₃ H CH ₃ (CH ₂ ) ₈ CH ₂ O (C ₂ H ₄ O) ₈ SO ₃ H CH ₃ (CH ₂ ) ₁₉ CH ₂ O (C ₂ H ₄ O) ₂ SO ₃ H CH ₃ (CH ₂ ) ₈ CH ₂ C ₆ H ₄ O (C ₂ H ₄ O) ₂ SO ₃ H, such as sulfuric acid ester of polyoxyethylene monoalkyl ether, alkylnaphthyl sulfonic acid It is illustrated.

As the cationic surfactant, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow trimethyl. Examples are ammonium hydroxide, quaternary ammonium hydroxides such as coconut oil trimethylammonium hydroxide, and salts thereof.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl ester, polyethylene glycol, polypropylene glycol, and diethylene glycol.

As the surfactant, one kind may be used, or two or more kinds excluding a combination of an anionic surfactant and a cationic surfactant may be used. That is, one or more combinations of anionic surfactants, one or more combinations of nonionic surfactants, one or more combinations of cationic surfactants, anionic interfaces A combination of two or more kinds of the active agent and the nonionic surfactant, and a combination of two or more kinds of the cationic surfactant and the nonionic surfactant may be used.

The amount of these surfactants used in the crude emulsion may be such an amount that an emulsion can be formed, and it varies depending on the type of the surfactant and is not particularly limited, but preferably 2 to 50% by weight. Is.

The amount of water used in the crude emulsion is preferably such that the concentration of organopolysiloxane is 10 to 60% by weight.

The crude emulsion is the aforementioned organopolysiloxane,
Mix evenly the surfactant and water, homogenizer,
Prepare through an emulsifying machine such as a colloid mill or line mixer.

In addition, when preparing a crude emulsion, a small amount of diorganopolysiloxane with both end hydroxyl groups blocked, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
Silanes having hydrolyzable groups such as trimethoxyvinylsilane and γ-glycidoxypropyltrimethoxysilane may be added. Hexaorganodisiloxane may be added as a viscosity adjusting end-capping agent.

In the present invention, the microemulsion used is
It is obtained by emulsion polymerization while adding the crude emulsion to a separately prepared aqueous solution containing an emulsion polymerization catalyst.

The emulsion polymerization catalyst includes an anion catalyst and a cation catalyst, and the anion catalyst includes a mineral acid such as hydrochloric acid or sulfuric acid, or an alkylbenzene sulfonic acid or polyoxyethylene monoalkyl ether exemplified as a surfactant. Illustrative are sulfuric acid esters and alkylnaphthyl sulfonic acids. As the cation-based catalyst, potassium hydroxide, alkali metal hydroxide such as sodium hydroxide,
In addition, the quaternary ammonium hydroxides and salts thereof exemplified as the surfactant are exemplified. However, since the quaternary ammonium salt has a low catalytic action, it is used in combination with an alkali metal hydroxide and activated.

From the relationship between the ionicity of the surfactant and the catalyst, when the anionic surfactant is used in the crude emulsion, the anion-based catalyst is used for producing the microemulsion. Further, when a cationic surfactant is used in the crude emulsion, the catalyst used for producing the microemulsion is cationic. When a nonionic surfactant is used in the crude emulsion, an anionic or cationic catalyst is used for producing the microemulsion.

The amount of the emulsion polymerization catalyst used varies depending on the type of the catalyst and is not particularly limited, but in the case of a mineral acid or an alkali metal catalyst,
With respect to 100 parts by weight of the organopolysiloxane in the crude emulsion, 0.2 to 5.0 parts by weight is preferable, and more preferably 0.
5 to 3.0 parts by weight. In the case of alkylbenzene sulfonic acid, sulfuric acid ester of polyoxyethylene monoalkyl ether and alkylnaphthyl sulfonic acid, quaternary ammonium hydroxide and its salt, 0.5 parts by weight per 100 parts by weight of organopolysiloxane in the crude emulsion are used.
-50 parts by weight is preferable, and 1.0-30 parts by weight is more preferable. Here, in order to improve the stability during emulsion polymerization, a nonionic surfactant exemplified as the surfactant used in the crude emulsion may be further added.

The temperature of the aqueous catalyst solution during the addition of the crude emulsion was 40-95.
C is preferred. The addition rate depends on the type of catalyst, the temperature, and the temperature of the aqueous catalyst solution. When the temperature of the catalyst is high or the temperature of the aqueous solution of the catalyst is high, it can be added early, but it is generally preferable to add it over 30 minutes from the viewpoint of producing a microemulsion having a smaller particle size. After the addition, emulsion polymerization is further carried out at a temperature of 0 to 90 ° C. until a desired viscosity is reached, whereby a microemulsion having an average particle size of 0.15 μm or less can be obtained. After emulsion polymerization, when an anionic polymerization catalyst is used, it is preferable to neutralize the polymerization catalyst with an acid. The concentration of the organopolysiloxane used in emulsion polymerization is not particularly limited, but may be 5 to 50.
Weight percent is preferred.

The viscosity of the organopolysiloxane in the microemulsion is not particularly limited, but the viscosity at 25 ° C is 20 to 100,000.
Centistokes are preferred, and 20-500000 centistokes are more preferred. Further, two or more kinds of microemulsions of organopolysiloxanes having different viscosities (for example, a microemulsion of organopolysiloxane having a viscosity of 200 centistokes and an organopolysiloxane microemulsion having a viscosity of 100000 centistokes) may be used in combination.

The microemulsion thus obtained is used as it is or further diluted with water, and for example, a predetermined amount of carnauba wax emulsified with a surfactant is added to the emulsion to give a water-based polish which does not cause uneven glossiness, uneven wiping, or stickiness. Is obtained.

The amount of the aqueous polish additive of the present invention added to the aqueous polish is preferably at least 0.001% by weight, more preferably 0.005 to 50% by weight, as an organopolysiloxane component.

Examples of the water-based polish to which the additive for a water-based polish of the present invention is added include those obtained by emulsifying a wax, a solvent, a thickening agent, an abrasive, a coloring agent, an aromatic and the like with a surfactant.

Examples of the above-mentioned waxes include animal waxes such as beeswax, wool wax, whale wax, carnauba wax, cotton wax,
Plant waxes such as showa, montan wax, celite wax,
Synthetic wax such as ceresin wax and paraffin wax, toluene as solvent, xylene, kerosene, MVP naphtha, naphtha mineral spirit, etc. as thickeners, aluminum silicate, diatomaceous earth, bentonite, silica, hydrated silica. Calcium acid, magnesium oxide, iron oxide, tin oxide, etc., as the surfactant, alkyl sulfate, alkyl sulfonate, sodium polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan monoester , Benzyl ammonium salt and the like.

The water-based polish of the present invention to which the additive for a water-based polish is added is useful for polishing various base materials such as automobiles, furniture, glass, and leather.

[Examples] Next, the present invention will be described with reference to Examples. In the examples, "parts" means "parts by weight", and the viscosity is a value at 25 ° C.

850 parts of water, 10 parts of dodecylbenzenesulfonic acid and 600 parts of cyclic dimethyl siloxane tetramer were put into the beaker of Example 12 and stirred uniformly. This mixture was passed through a homogenizer emulsifier at a pressure of 400 kg / cm ² four times to obtain a crude emulsion. Next, 1300 parts of water and 130 parts of dodecylbenzenesulfonic acid were put into another four-necked flask of No. 5 and dissolved therein, and the mixture was maintained at a liquid temperature of 85 ° C. with slow stirring. The crude emulsion prepared previously was gradually added dropwise to the dodecylbenzenesulfonic acid aqueous solution over 2 hours. After dropping, the mixture was cooled, and further held at 60 ° C. for 1 hour for emulsion polymerization. After polymerization, with a 50% by weight aqueous solution of sodium hydroxide,
The pH was adjusted to 7.0 to obtain a transparent emulsion. The average particle size of the obtained emulsion is calculated by QUNDSIELAT
IC LIGHTSCATTERING MODEL M2000 (MALVER: USA)
It was 0.05 μm when measured using (Emulsion A). When the microemulsion was destroyed with methanol and the oil was extracted, it was confirmed to be dimethylpolysiloxane with a viscosity of 6000 centistokes blocked at both ends by hydroxyl groups. When the transmittance was measured at 580 nm, it was 96%.

Then, 8 parts of carnauba wax, 6 parts of beeswax, 6 parts of solid paraffin and 3 parts of oleic acid were heated and melted at 120 ° C., and 3 parts of morpholine was added to obtain a wax mixture, which was heated to 95 ° C.
Was added to 74 parts of water, emulsified using a homogenizer, and allowed to cool to room temperature (emulsion wax B).

Next, 10 parts of emulsion A, 40 parts of emulsion wax B and 50 parts of water were uniformly mixed to prepare an aqueous polish.

After applying this polish to a black-painted panel (40 cm x 40 cm) and polishing it, there was no unevenness of stretch, uneven wiping or stickiness, and a black glossy and even gloss was obtained.

Moreover, the present polish was stable without oil separation of the organopolysiloxane even after being left at 40 ° C. for 3 months.
Further, when it was applied and polished in the same manner using a black painted panel, its gloss and workability did not change at all.

Comparative Example 1 80 parts of dimethylpolysiloxane blocked with trimethylsiloxy groups at both ends (viscosity 6000 centistokes), 8 parts of polyoxyethylene lauryl ether (HLB: 11.5) and 12 parts of water were uniformly mixed, and then emulsified using a homogenizer. Then
Disperse this evenly in 300 parts of water, average particle size 1.2μ
A mechanical emulsion of m (Emulsion C) was obtained.

Next, 10 parts of emulsion C, 40 parts of emulsion wax B prepared in Example 1 and 50 parts of water were uniformly mixed to prepare an aqueous polish.

When this blackener was applied to a black-painted panel and polished, there was no unevenness in spreading or wiping, but there were slight unevenness in stickiness and gloss.

In addition, when this polish was left for 3 months at 40 ° C., organopolysiloxane was separated in the upper layer and an oil film was formed. Further, when a black painted panel was used to apply and polish the upper part of the oil film, unevenness occurred in stretching and wiping, and a large amount of the oil film was partially adhered and sticky. Also, many uneven glosses were seen.

Example 2 After uniformly mixing 400 parts of cyclic dimethyl siloxane tetramer, 10 parts of hexamethyldisiloxane, 560 parts of water and 30 parts of an ethylene oxide 45 mol adduct of octylphenol,
Using a homogenizer emulsifying machine under a pressure of 450 kg / cm ² ,
Three passes were made to obtain a crude emulsion. Then another 3
Into a four-necked flask of No. 1 was added 130 parts of dodecylbenzenesulfonic acid and 870 parts of water to dissolve, and the mixture was maintained at a liquid temperature of 80 ° C. with slow stirring. The crude emulsion prepared above was gradually added dropwise to this aqueous dodecylbenzenesulfonic acid solution over 2 hours.

After the completion of dropping, the mixture was cooled and kept at the same temperature for 3 hours for emulsion polymerization. After the polymerization, the pH was adjusted to 7.0 with a 10% by weight aqueous solution of sodium hydroxide. The obtained product was a transparent microemulsion having an average particle size of 0.08 μm and a transmittance (580 nm) of 91% (emulsion D). When this microemulsion was broken with methanol,
It was confirmed that the extracted oil was a dimethylpolysiloxane having a viscosity of 280 centistokes and blocked at both ends with trimethylsilyl groups.

Next, 25 parts mineral spirits, 9 parts carnauba wax,
A mixture of 3 parts of a surfactant (trade name: Esomin C-10, manufactured by Lion Armor Co., Ltd.) heated at 95 ° C. and dissolved in water 40
The part was emulsified using a homogenizer and allowed to cool to room temperature (emulsion wax E).

Next, 50 parts of emulsion D and emulsion wax E
39 parts were uniformly mixed, 12 parts of celite powder having an average particle diameter of 5 microns was further added, and mixed with a stirrer for 2 hours to prepare a polish. No oil separation of the resulting polish polyorganosiloxane was observed.

Next, using a polish, a black painted panel (40cmX40c
When it was applied to m) and polished, excellent gloss without unevenness was obtained. Also, it was excellent in stretching and wiping, and was not sticky.

Comparative Example 2 80 parts of dimethylpolysiloxane (viscosity 280 centistokes) blocked with trimethylsiloxy agents at both ends, 8 parts of polyoxyethylene lauryl ether (HLB: 11.5) and 12 parts of water were uniformly mixed, and then emulsified using a homogenizer. Then
Disperse this evenly in 300 parts of water, the average particle size 1.1μ
A mechanical emulsion of m (Emulsion F) was obtained.

Next, 50 parts of Emulsion F and 39 parts of Emulsion Wax E prepared in Example 2 were uniformly mixed, and Celite powder having an average particle size of 5 microns was further added and mixed with a stirrer for 2 hours to prepare a polish. .

In the obtained polish, oil separation of organopolysiloxane was observed. Next, when this blackening agent was applied to a black panel and polished, unevenness occurred in stretching and wiping and unevenness in gloss. Also, a lot of stickiness occurred.

[Effect of the invention] The aqueous polish additive of the present invention has an average particle diameter of 0, which is obtained by emulsion polymerization of a crude emulsion comprising a cyclic diorganopolysiloxane, a surfactant and water.
Since the main component is an organopolysiloxane microemulsion having a size of 15 μm or less, the water-based polish containing the same has excellent long-term storage stability, and has uneven spread, uneven wiping, uneven gloss on the substrate. It is characterized by having no stickiness and having an excellent polishing effect and workability.

Claims (1)

[Claims] 1. A general formula (Wherein R is a monovalent hydrocarbon group, n is an integer of 3 to 10) while adding a crude emulsion consisting of a cyclic diorganopolysiloxane, a surfactant and water to the aqueous solution containing the emulsion polymerization catalyst. An additive for an aqueous polish, which comprises an organopolysiloxane microemulsion having an average particle size of 0.15 μm or less obtained by emulsion polymerization as a main component.