JPH08302197A - Silicone emulsion composition - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide an aqueous silicone emulsion composition suitable for use as a polish. [Structure] (1) A unit represented by the general formula R ¹ ₂ SiO _2/2 and a unit represented by the general formula R ² SiO _3/2 (R ¹ and R ² are each an unsubstituted or substituted 1 to 20 carbon atom) Aqueous silicone emulsion containing a polyvalent hydrocarbon group) as a constituent unit and having a viscosity at 25 ° C of 3 to 30 million cP at 25 ° C, and (2) the general formula R ³
A unit represented by ₂ SiO _2/2 and a unit represented by the general formula R ⁴ ₃ SiO _1/2 (R ³ and R ⁴ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms) are structural units. Viscosity at 25 ℃ is 1 to 10,000 cP
An aqueous silicone emulsion containing the organopolysiloxane of
Organopolysiloxane in (2) = 1/99 to 99/1
(Weight ratio) Aqueous silicone emulsion composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous silicone emulsion (emulsion) composition containing a high-viscosity organopolysiloxane and a medium to low-viscosity organopolysiloxane as main components, particularly a silicone suitable as a polish. It relates to an emulsion composition.

[0002]

2. Description of the Related Art It has already been disclosed that a silicone emulsion comprising a high-viscosity diorganopolysiloxane and a medium to low-viscosity diorganopolysiloxane is suitable as a polish (see Japanese Patent Publication No. 60-59942). surely,
According to this, there is little stickiness, and a polish composition excellent in extensibility and polishability is obtained.However, when a high-viscosity diorganopolysiloxane is produced by an emulsion polymerization method, it is necessary to increase the viscosity at a low temperature. Not only is it industrially disadvantageous because it requires a long polymerization step, but the viscosity obtained is limited to 3 million cP at 25 ° C, and the properties were insufficient. In addition, the production of this high-viscosity diorganopolysiloxane by the bulk polymerization method is extremely difficult to emulsify and is industrially disadvantageous. It is also possible to dissolve these two types of diorganopolysiloxane in a solvent and then make an emulsion, but this dissolving operation was also complicated.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned disadvantages and is an aqueous silicone emulsion mainly composed of a high-viscosity organopolysiloxane suitable for use as a polish and a medium to low-viscosity organopolysiloxane. It is intended to provide a liquid composition.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have achieved the object if a high-viscosity organopolysiloxane is contained as a constitutional unit of a monoorganosiloxane unit. The present invention has been accomplished by finding out what can be done. That is, the aqueous silicone emulsion composition of the present invention comprises (1) the general formula R ¹ ₂ S as the first component.
A unit represented by iO _2/2 and a unit represented by the general formula R ² SiO _3/2 (wherein R ¹ and R ² are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms) as constituent units. The viscosity at 25 ℃ is 3
Aqueous silicone emulsion containing 0,000,000 to 30,000,000 cP of organopolysiloxane, and (2) the unit represented by the general formula R ³ ₂ SiO _2/2 as the second component and the general formula R ⁴ ₃ SiO _1/2 Containing an organopolysiloxane having a viscosity at 25 ° C. of 1 to 10,000 cP as a constituent unit of a unit represented by (wherein R ³ and R ⁴ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms). An aqueous silicone emulsion is contained, and [first component organopolysiloxane] / [second component organopolysiloxane] = 1/99 to 99/1 (weight ratio).

The present invention will be described in more detail below. The first component constituting the silicone emulsion composition of the present invention comprises a unit represented by the general formula R ¹ ₂ SiO _2/2 and a general formula R ² SiO ^2.
It is an aqueous silicone emulsion containing a unit represented by _3/2 as a constitutional unit and containing an organopolysiloxane having a viscosity at 25 ° C. of 3,000,000 to 30,000,000 cP. R ¹ and R ² in the general formula are an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. As such R ¹ and R ² , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; alkenyl groups such as vinyl group, allyl group; aryl groups such as phenyl group, tolyl group; cyclopentyl group , A cycloalkyl group such as a cyclohexyl group or a cyclooctyl group; or a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom or an organic group containing an epoxy group, a carboxyl group, an amino group, etc. Examples thereof include monovalent hydrocarbon groups, and among them, a methyl group and a phenyl group are preferable.

The first component can be produced by emulsion polymerization in water. That is, as a raw material for introducing the R ¹ ₂ SiO _2/2 unit, the following formulas [1] to [3]
The compound shown by the following formula [4] or a hydrolyzate thereof may be used as a raw material for introducing the R ² SiO _3/2 unit by using the compound shown by [4].

Embedded image ^{_{HO (R 1 2 SiO) b}} H (b = 1~1,000) [2] R 6 O (R 1 2 SiO) c R 6 (c = 1~1,000, R 6 is a monovalent hydrocarbon having 1 to 6 carbon atoms Hydrogen group) [3] R ² Si (OR ⁷ ) ₃ (R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) [4] The emulsion polymerization may be carried out according to a conventionally known method. ,
That is, the above raw materials may be emulsified and dispersed in water using an emulsifier using a known device, and then a catalyst may be added thereto for polymerization, and the catalyst may be deactivated after completion of the polymerization.

The emulsifier used in this emulsion polymerization is not particularly limited, and examples thereof include cationic emulsifiers such as quaternary ammonium salts and alkylamine salts; zwitterionic emulsifiers such as alkyl betaines; polyoxyethylene alkyl. Nonionic emulsifiers such as ethers, polyoxyethylene alkylphenyl ethers, sorbitan fatty acid esters, glycerin fatty acid esters; acidic anionic emulsifiers such as organic sulfonic acids, higher alcohol sulfates, higher alkyl ether sulfates, etc. One or more of these can be used for emulsion polymerization.

When a cationic emulsifier, a zwitterionic emulsifier, or a nonionic emulsifier is used as the catalyst, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, ammonia, tetrahydrochloride is used. Examples thereof include alkali compounds such as methylammonium hydroxide, triethylamine and triethanolamine, but acidic anionic emulsifiers such as organic sulfonic acids, higher alcohol sulfates and higher alkyl ether sulfates have a catalytic action as they are. For the deactivation of this catalyst, in the case of an alkaline compound, a method of neutralizing with an acid such as acetic acid, phosphoric acid, hydrochloric acid or citric acid can be mentioned. When an acidic anionic emulsifier is used as a catalyst, it is neutralized with an alkaline compound such as potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methylate, ammonia, tetramethylammonium hydroxide, triethylamine, triethanolamine. There is a method of doing.

If the concentration of the active ingredient in the aqueous emulsion produced in this manner is less than 1% by weight, it becomes uneconomical because the amount of the active ingredient to be blended must be increased, and it becomes 70% by weight. If it exceeds, the viscosity of the first component becomes high and handling becomes difficult. Therefore, the range is 1 to 70% by weight, and the preferable range is 10 to 60% by weight.

The viscosity of the organopolysiloxane itself contained in the aqueous emulsion obtained by this emulsion polymerization is required to be 3 to 30 million cP at 25 ° C. If this viscosity is lower than 3 million cP, the dry film of the finally obtained silicone emulsion composition will be sticky and lack in smoothness, and if higher than 30 million cP, the dry film will be uneven. This is because the gloss will be poor. To obtain an organopolysiloxane having the above viscosity range and excellent characteristics, R ¹ ₂ SiO _2/2 unit / R ² Si
It is preferable to mix the raw materials so that the O _3/2 unit (molar ratio) is 2,000 / 1 to 100/1. This has a molar ratio of 2,000 / 1
If it is larger than 100, it is difficult to obtain an organopolysiloxane having a viscosity of 3 million cP or more, and if it is smaller than 100/1, the finally obtained film becomes highly sticky.

The second component constituting the silicone emulsion composition of the present invention comprises a unit represented by the general formula R ³ ₂ SiO _2/2 and a unit represented by the general formula R ⁴ ₃ SiO _1/2. Is an aqueous silicone emulsion containing an organopolysiloxane having a viscosity at 25 ° C. of 1 to 10,000 cP. R ³ in the general formula
And R ⁴ are selected from the group of unsubstituted or substituted monovalent hydrocarbon groups similar to the above-mentioned R ¹ and R ^2, and among them, a methyl group and a phenyl group are preferable. This 2nd component can be manufactured by carrying out emulsion polymerization in water like the 1st component. That is, as the raw material for introducing the R ³ ₂ SiO _2/2 unit, the compounds represented by the following formulas [5] to [7] are used, and the raw material for introducing the R ⁴ ₃ SiO _1/2 unit is used. For example, compounds represented by the following formulas [8] to [9] may be used.

Embedded image HO (R ³ ₂ SiO) _e H (e = 1 to 1,000) [6] R ⁸ O (R ³ ₂ SiO) _f R ⁸ (f = 1 to 1,000, R ⁸ is a monovalent carbon having 1 to 6 carbon atoms) Hydrogen group) [7] R ⁴ ₃ SiO (R ³ ₂ SiO) _g SiR ⁴ ₃ (g = 0 to 100) [8] R ⁴ ₃ SiOR ⁹ (R ⁹ is hydrogen atom or monovalent with 1 to 6 carbon atoms (Hydrocarbon group) [9] Then, as the emulsion polymerization method, the same method as described above for the first component may be used.

The second component, the aqueous silicone emulsion, is represented by the following formula [10] R ⁴ ₃ SiO (R ³ ₂ SiO) _h SiR ⁴ ₃ (h = 1 to 1,000) [10] It can also be obtained by emulsifying an organopolysiloxane having a viscosity at 1 ° C. of 1 to 10,000 cP with a nonionic emulsifier, an anionic emulsifier, a cationic emulsifier, a zwitterionic emulsifier and the like.

Examples of the nonionic emulsifier used here include polyoxyethylene higher alcohol ether, polyoxyethylene alkylphenyl ether, sorbitan monoalkylate, sorbitanial chelate, polyoxyethylene sorbitan monoalkylate and polyoxyethylene sorbitanial. Chelate, polyoxyethylene sorbitan tetraalkylate, glycerol monoalkylate, etc. are exemplified, and these can be used alone or in combination of two or more kinds, and in addition to these general nonionic emulsifiers, fluorine can be used. A system emulsifier or a silicone nonionic emulsifier can also be used. The nonionic emulsifier may have an HLB in the range of 1.5 to 20, but it is preferably in the range of 7.0 to 19.0.

The ionic emulsifiers include anionic, cationic and zwitterionic ones, and the anionic emulsifiers include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate and sodium dialkylsulfosuccinate. , Potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc., as the cationic emulsifier, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl Trimethylammonium chloride, stearylamine hydrochloride, coconut amine hydrochloride, coconut amine Acetate, stearylamine acetate, and alkyl benzene dimethyl ammonium chloride and the like. As the zwitterionic emulsifier, N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N'-
Examples thereof include dimethyl-N′-β-hydroxypropylammoniobetaine.

For this emulsification, a conventionally known emulsifying machine may be used. Examples of the emulsifier include a homomixer, a high-pressure homogenizer, a colloid mill, and an ajihomomixer. Whichever method is used, the organopolysiloxane in the second component has a viscosity of 1 cP at 25 ° C.
If it is lower, the film obtained will be less smooth and glossy, and if it is higher than 10,000 cP, the film obtained will be poor in smoothness and sticky, so 1 to 10,000 cP is required. . It is preferably 10 to 1,000 cP. If the concentration of the active ingredient in the aqueous emulsion of the second component produced in this way is less than 1% by weight, it becomes uneconomical because the amount of the ingredient to be added must be increased.
When the content is more than 10% by weight, the viscosity of the second component becomes high and the handling becomes difficult. Therefore, the range may be 1 to 70% by weight, but the preferred range is 10 to 60% by weight.

The above-described mixing of the first component and the second component is easily carried out by using a conventionally known mixing stirrer having a stirring blade such as a paddle type or anchor type, or by using a shaker. Can be used after homogenization. When this is used as an additive, the first component and the second component may be separately added to the additive and then uniformly mixed. Further, these mixtures may be diluted with water as necessary to adjust the concentration to an appropriate level. The mixing ratio of the first component and the second component is [first
[Organopolysiloxane of component] / [Organopolysiloxane of second component] = 1/99 to 99/1 (weight ratio), which means that if this weight ratio is less than 1/99, the film obtained is smooth. This is because the film has poor properties, and when it is greater than 99/1, the film obtained has poor smoothness and gloss. A preferred range is 10/90 to 90/10.

[0017]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. [Preparation Example 1: Preparation of first component-1] Octamethylcyclotetrasiloxane 350 g, phenyltriethoxysilane 1.
After charging 3 g into a 1 liter glass beaker and stirring and mixing with a homomixer at 2,000 rpm, 35 g of 10% sodium lauryl sulfate aqueous solution and 35 g of 10% aqueous dodecylbenzenesulfonic acid solution were added, and stirring was continued at 6,000 rpm. , Phase inversion occurred and thickening was observed, but 280 g of water was added while stirring at 2,000 rpm, and then 30
An aqueous emulsion was obtained by passing through a high pressure homogenizer at 0 kg / cm ² . Next, the aqueous emulsion was anchored with a stirring blade, a thermometer,
Transfer to a 1-liter glass flask equipped with a reflux condenser, carry out polymerization reaction at 50 ° C for 12 hours, then leave at 25 ° C for 24 hours, then neutralize with 10% sodium carbonate aqueous solution to obtain an aqueous emulsion. (First component-1) was obtained. Isopropyl alcohol was added to this to destroy the emulsified state, and then the organopolysiloxane was taken out, dried, and the viscosity was measured by Rheopexy Analyzer RPX-705 (manufactured by Iwamoto Seisakusho) to find that it was 12 million cP.

[Preparation Example 2: Preparation of first component-2] An aqueous emulsion (first component) was prepared in the same manner as in Preparation Example 1, except that 1.3 g of phenyltriethoxysilane was changed to 1.1 g of methyltrimethoxysilane. -2) was obtained. Organopolysiloxane was taken out from this aqueous emulsion in the same manner as in Preparation Example 1, dried and measured for a viscosity of 19 million cP.
Met.

[Preparation Example 3: Preparation of first component-3] An aqueous emulsion (first component-3) was obtained in exactly the same manner as in Preparation Example 1, except that phenyltriethoxysilane was not added. The organopolysiloxane was taken out from this aqueous emulsion in the same manner as in Preparation Example 1, dried and measured for a viscosity of 2 million cP.

[Preparation Example 4: Preparation of first component-4] An aqueous emulsion (first component) was prepared in the same manner as in Preparation Example 1, except that 1.3 g of phenyltriethoxysilane was changed to 6.8 g of methyltrimethoxysilane. -4) was obtained. Organopolysiloxane was taken out of this aqueous emulsion in the same manner as in Preparation Example 1, dried and measured for a viscosity of 36 million cP.
Met.

[Preparation Example 5: Preparation of Second Component-1] An aqueous emulsion (second component) was prepared in the same manner as in Preparation Example 1, except that 1.3 g of phenyltriethoxysilane was changed to 5.0 g of hexamethyldisiloxane. -1) was obtained. Isopropyl alcohol was added to this to destroy the emulsified state, the organopolysiloxane was taken out, dried and the viscosity was measured with an EM type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) to find 320 cP.

[Preparation Example 6: Preparation of Second Component-2] The viscosity represented by the following average formula [11] (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₄₂ Si (CH ₃ ) ₃ [11] Polyoxyethylene nonylphenyl ether (HLB = 13) 4 in 300 g of organopolysiloxane with 50 cP
When 0 g and 3 g of a 30% aqueous solution of sodium polyoxyethylene octyl phenyl ether sulfate were mixed, 100 g of water was added, and the mixture was stirred at 6,000 rpm with a homomixer, phase inversion occurred and thickening was observed, but further stirring Was continued for 20 minutes to homogenize. After that, turn the homomixer rotation speed to 2,
While stirring at 000 rpm, 557 g of water was added and mixed. Further, this was passed through a high pressure homogenizer at 300 kg / cm ² to obtain an aqueous emulsion (second component-2).

[Preparation Example 7: Preparation of Second Component-3] 60 g of polyoxyethylene lauryl ether (HLB = 14) and 1 g of a 20% aqueous solution of sodium polyoxyethylene lauryl ether sulfate were dissolved in 539 g of water with stirring. Then, while stirring at 6,000 rpm with a homomixer, 400 g of organopolysiloxane having a viscosity of 0.8 cP represented by the following formula [12] (CH ₃ ) ₃ SiO (CH ₃ ) ₂ SiOSi (CH ₃ ) ₃ [12]
Was added to emulsify. Further, this product was passed through a high pressure homogenizer at 300 kg / cm ² to obtain an aqueous emulsion (second component-
3) was obtained.

[Preparation Example 8: Preparation of Second Component-4] An aqueous emulsion (second component) was prepared in the same manner as in Preparation Example 1 except that 1.3 g of phenyltriethoxysilane was changed to 0.8 g of hexamethyldisiloxane. -4) was obtained. Isopropyl alcohol was added to this to destroy the emulsified state, and then the organopolysiloxane was taken out, dried, and the viscosity was measured with an EM type rotational viscometer (described above) to be 15,000 cP.

Table 1 summarizes the first and second components obtained in Preparation Examples 1 to 8 above.

[Table 1]

[Examples 1-9, Comparative Examples 1-6] Preparation Example 1
The first and second components obtained in 8 to 8 were mixed by stirring with the composition (% by weight) shown in Table 2, and further diluted with water to a concentration of 5% by weight of organopolysiloxane to obtain a silicone emulsion. A liquid composition was obtained. 5 parts of tanned cowhide (30 mm x 150 mm, thickness 2 mm) were added to the obtained silicone emulsion composition.
It was soaked for a minute, and then left in the air at room temperature for 16 hours to be dried. The treated tanned cowhide obtained in this way was observed for the glossiness of the surface (surface gloss), and the presence or absence of stickiness due to finger touch was confirmed (surface stickiness). Furthermore, an autograph (Shimadzu Corporation) was used. And attached untreated tanned cowhide (25mm x 35mm, thickness 2mm) to the bottom.
Place 200 g of weight on the surface of the above-treated tanned cowhide to 0.3 m
The coefficient of kinetic friction when moved at a speed of / min was measured (surface smoothness). The results of examining these characteristics are shown in Table 2. The surface gloss is indicated by ○: glossy, ×: non-glossy, and surface tackiness is indicated by ○: non-sticky, Δ: slightly sticky, x: sticky.

[0027]

[Table 2]

[0028]

The present invention provides a novel aqueous silicone emulsion composition containing a high-viscosity organopolysiloxane and a medium to low-viscosity organopolysiloxane as a main component, which is particularly suitable for use as a polish. . Use of the emulsion of the present invention provides a treated surface having good gloss, no stickiness, and excellent smoothness, which is extremely advantageous in practice.

Claims (1)

[Claims] 1. A general formula R ¹ ₂ SiO _2/2 as a first component
And a unit represented by the general formula R ² SiO _3/2 (wherein R ¹ and R ² are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms) as a constituent unit at 25 ° C. Viscosity is 3 million ~
Aqueous silicone emulsion containing 30 million cP organopolysiloxane and (2) general formula R ³ ₂ S as second component
A unit represented by iO _2/2 and a unit represented by the general formula R ⁴ ₃ SiO _1/2 (wherein R ³ and R ⁴ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms) are structural units. Containing an aqueous silicone emulsion containing an organopolysiloxane having a viscosity at 25 ° C. of 1 to 10,000 cP, [first component organopolysiloxane] / [second component organopolysiloxane]
= 1/99 to 99/1 (weight ratio), an aqueous silicone emulsion composition.