JPH0717836B2 - Method for stabilizing organopolysiloxane emulsion containing alkyl ester group of phosphorus - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for stabilizing an organopolysiloxane emulsion containing an alkyl ester group of phosphorus.

[Prior Art] Conventionally, as an organopolysiloxane containing an alkyl ester group of phosphorus, one described in JP-A-54-48718 is known. Further, as a method for obtaining a stable emulsion of an organopolysiloxane containing an alkyl ester group of phosphorus, a method of emulsion polymerizing an organopolysiloxane and a phosphoric acid ester group-containing alkoxysilane in water (see JP-A-60-248732). )It has been known.

[Problems to be Solved by the Invention] However, the organopolysiloxane described in JP-A-54-48718 is used as an anionic surfactant and / or
Alternatively, when emulsified in water using a nonionic surfactant, the resulting organopolysiloxane emulsion has a drawback that it is inferior in various stability such as mechanical stability, dilution stability and storage stability. Further, the organopolysiloxane emulsion described in JP-A-60-248732 has a drawback that it requires a long time for emulsion polymerization and is inferior in productivity.

The present invention aims to eliminate the above-mentioned drawbacks, and easily and quickly provides organopolysiloxane emulsions containing alkyl ester groups of phosphorus with various stability such as mechanical stability, dilution stability, and storage stability. It provides a method of giving.

[Means for Solving Problems] The above-mentioned object is to provide at least one formula in one molecule. (In the formula, R is a monovalent hydrocarbon group or X, R ² is a monovalent hydrocarbon group, R ¹ is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is an alkoxy group having 1 to 4 carbon atoms. , A is 0 or 1, b
Is 1 or 2, c is 0 or 1, d is 0, 1 or 2, b
+ C is 2, provided that when a is 0, b is 2, and c is 0), an organopolysiloxane having a unit represented by the formula (1) is used in an anionic surfactant and / or a nonionic surfactant in water. Into an emulsion emulsified into
This can be achieved by a method for stabilizing an organopolysiloxane emulsion containing an alkyl ester group of phosphorus, which is characterized by adding a water-soluble alkaline substance to make the pH of the emulsion 6 or more.

To explain this, the organopolysiloxane which is the main component in the present invention has at least one formula in one molecule. It is an organopolysiloxane having a group represented by.
In the above formula, R is a monovalent hydrocarbon group or X,
The monovalent hydrocarbon group is an alkyl group such as a methyl group, an ethyl group, a propyl group, an octyl group, a vinyl group, an allyl group, an alkenyl group such as a propenyl group, a 2-phenylethyl group, a 2-phenylpropyl group, and a 3 group. Examples include substituted alkyl groups such as 3.3-trifluoropropyl group, aryl groups such as phenyl group and tolyl group, or substituted aryl groups. X is an alkoxy group having 1 to 4 carbon atoms, which includes a methoxy group, an ethoxy group, a propoxy group,
A methoxyethoxy group etc. are illustrated. R ¹ is an alkylene group having 2 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a butylene group. R ² is a monovalent hydrocarbon group, and examples thereof include those exemplified for the R monovalent hydrocarbon group. a is 0 or 1, b is 1 or 2,
c is 0 or 1, d is 0, 1 or 2, b + c is 2, provided that when a is 0, b is 2 and c is 0.

formula As a specific example of the unit shown by, There is.

The present organopolysiloxane may be composed of only an organosiloxane unit containing a phosphorus alkyl ester group, or may have another organosiloxane unit. Examples of the other organosiloxane units include monoorganosiloxane, diorganosiloxane and triorganosiloxane units. In these organosiloxane units, the organic group bonded to the silicon atom is a monovalent hydrocarbon group, and examples thereof include those exemplified for the R monovalent hydrocarbon group. Specific examples of the organosiloxane units _{(CH 3) 2 SiO, (} CH 3) 3 SiO 1/2, CH 3 SiO 3/2, CH 3 · CF 3 CH 2 CH 2 SiO, CH 3 · C 6 H ₅ SiO, is _{C 6 H 5 (CH 2)} 2 SiO 3/2.

The molecular structure of the organopolysiloxane is linear,
It may be branched or reticulated. Further, the terminal group is not particularly limited, a hydroxyl group, a trialkylsiloxy group,
Alkoxysiloxy group, also formula (In the formula, R, R ¹ , R ² , X, a, b, and c are the same as the above). The total number of siloxane units in the organopolysiloxane varies depending on the intended use and application of the emulsion and is not particularly limited, but is generally 3 to 5000.

The organopolysiloxane used in the present invention is obtained, for example, by hydrolyzing an alkoxysilane containing an alkyl ester group of phosphorus and polycondensing it with a cyclic or linear diorganopolysiloxane.

As the surfactant for emulsifying the organopolysiloxane in water, an anionic surfactant and / or a nonionic surfactant is used.

As the anionic surfactant, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, alkylbenzenesulfonic acid 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 (C
H ₂ ) ₁₉ CH ₂ O (C ₂ H ₄ O) ₄ SO ₃ H, CH ₃ (CH ₂ ) ₈ CH ₂ C ₆ H ₄ O (C ₂ H
₄ ) Sulfuric acid ester of polyoxyethylene monoalkyl ether such as ₂ SO ₃ H and alkylnaphthyl sulfonic acid are exemplified, and one or more of these may be used.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, and diethylene glycol. You may use 1 type (s) or 2 or more types.

The amount of the surfactant used varies depending on the kind of the surfactant and is not particularly limited, but is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the organopolysiloxane.

The amount of water used is 50 to 500 parts by weight based on 100 parts by weight of organopolysiloxane.

The water-soluble alkaline substance used in the present invention is a component for easily and promptly improving the stability of the emulsion, which includes hydroxides of alkali metals such as sodium, potassium, rubidium and cesium. Or
Examples thereof include salts with weak acids such as carbonic acid, boric acid and molybdic acid; aliphatic amines such as diethanolamine and triethanolamine; aqueous ammonia. The amount of the emulsion used is such that the pH of the emulsion is 6.0 or more, preferably 6.5 to 9.
The amount is 0.

In the method of the present invention, the above-mentioned organopolysiloxane, anionic surfactant and / or nonionic surfactant and water are uniformly mixed, and an emulsion is prepared through an emulsifying machine such as a homogenizer, a colloid mill or a line mixer, A water-soluble alkaline substance may be added.

The emulsion obtained by the method of the present invention is an antiseptic agent; a protective colloid agent such as polyvinyl alcohol and carboxymethyl cellulose; a dye; a silane coupling agent, dimethyl polysiloxa oil, organic, to the extent that the object of the present invention is not impaired. An emulsion such as a modified diorganopolysiloxane may be added.

The emulsion obtained by the method of the present invention, as it is or diluted with water, a release agent, a release agent, a fiber treatment agent,
It is useful as a rinsing agent for hair, a polish, a paint additive, an antifoaming agent, and the like. Natural fibers such as hair, alpaca, mohair, angora, wool, silk, hemp, cotton, asbestos, regenerated fibers such as rayon and acetate, polyester, polyamide, vinylon, polyacrylonitrile, among others.
It is useful as synthetic fiber such as polyethylene, polypropylene, spandex, glass fiber, carbon fiber, silicone carbide fiber and thread, knitting, woven fabric, non-woven fabric, resin processed cloth of these fibers, lubricant and antistatic agent for these sewn products. is there.

[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.

Example 1 Formula with viscosity 150 centistokes 20 parts of the organopolysiloxane represented by, 5 parts of polyoxyalkylene nonylphenol ether (HLB11.5) and 3 parts of water were uniformly stirred. This was passed through a colloid mill, and 72 parts of water was added to prepare an emulsion (emulsion A). The pH of this emulsion is 4.8.
Met. A 10 wt% aqueous solution of sodium hydroxide was added to this to adjust the pH to 8.5 to stabilize the emulsion (emulsion B).

The emulsion B thus obtained was subjected to various tests as follows. Further, the same test was performed for the emulsion left at 50 ° C. for 7 days.

・ Centrifugation test: Process at 2500 rpm for 30 minutes and observe with the naked eye. ・ Dilution stability test: Dilute emulsion 20 times with water,
Observing with the naked eye-Transmittance measurement: The emulsion is diluted 100 times with water and the transmittance at 580 nm is measured by a colorimeter. The results are shown in Table 1.

Comparative Example 1 Emulsion A prepared in Example 1 to which no aqueous sodium hydroxide solution was added was subjected to various tests just after emulsification and left for 7 days at 50 ° C., and the results are shown in Table 1. It was shown to.

Example 2 Formula with viscosity 145 centistokes 15 parts of the organopolysiloxane represented by the formula, 3 parts of a 7 mol adduct of a higher alcohol with ethylene oxide (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: Softanol 70) and 4 parts of water were uniformly stirred. Pass this through a colloid mill,
Further, 78 parts of water was added to prepare an emulsion (emulsion C). The pH of this emulsion was 4.0. A 10 wt% aqueous solution of potassium hydroxide was added to this to adjust the pH to 8.5 to stabilize the emulsion (emulsion D).

The emulsion D thus obtained was subjected to various tests in the same manner as in Example 1. In addition, emulsion at 50 ℃
The same test was performed for the one left for 10 days. The results are shown in Table 2.

Example 3 In Example 2, a 10 wt% aqueous solution of sodium carbonate was used in place of the potassium hydroxide aqueous solution to prepare an emulsion.
Emulsions were prepared in exactly the same manner except that the pH was adjusted to 8.0, and various tests were carried out immediately after emulsification and left at 50 ° C. for 10 days, and the results are shown in Table 2.

Example 4 An emulsion was prepared in the same manner as in Example 2 except that the pH of the emulsion was adjusted to 7.5 using a 10% by weight aqueous solution of sodium hydrogencarbonate instead of the potassium hydroxide aqueous solution. Various tests were conducted on the samples left for 10 days, and the results are shown in Table 2.

Example 5 An emulsion was prepared in the same manner as in Example 2 except that the pH of the emulsion was adjusted to 8.5 by using a 10% by weight aqueous solution of triethanolamine instead of the aqueous potassium hydroxide solution. Various tests were conducted on the samples left for 10 days, and the results are shown in Table 2.

Comparative Example 2 The emulsion C prepared in Example 2 to which no aqueous potassium hydroxide solution was added was subjected to various tests just after emulsification and left at 50 ° C. for 10 days, and the results are shown in Table 2. It was shown to.

Example 6 Formula with viscosity 158 centistokes 15 parts of an organopolysiloxane represented by the formula, 3 parts of a 7-mol ethylene oxide adduct of a higher alcohol (trade name: Softanol 70 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) and 4 parts of water were uniformly stirred. Pass this through a colloid mill,
Further, 78 parts of water was added to prepare an emulsion (emulsion E). The pH of this emulsion was 2.8. A 10% by weight aqueous solution of potassium hydroxide was added to this to adjust the pH to 8.5 to stabilize the emulsion (emulsion F).

The emulsion F thus obtained was subjected to various tests in the same manner as in Example 1. In addition, emulsion at 50 ℃
The same test was performed for the one left for 10 days. The results are shown in Table 2.

Example 7 In Example 6, a 10 wt% aqueous solution of sodium carbonate was used in place of the potassium hydroxide aqueous solution to prepare an emulsion.
An emulsion was prepared in exactly the same manner except that the pH was adjusted to 8.3, and various tests were carried out on the emulsion immediately after emulsification and at 50 ° C. for 10 days, and the results are shown in Table 2.

Example 8 An emulsion was prepared in the same manner as in Example 6 except that the pH of the emulsion was adjusted to 7.5 by using a 10 wt% aqueous solution of sodium hydrogencarbonate instead of the potassium hydroxide aqueous solution, and the emulsion was prepared immediately after emulsification and at 50 ° C. Various tests were conducted on the samples left for 10 days, and the results are shown in Table 2.

Example 9 An emulsion was prepared in the same manner as in Example 6 except that the pH of the emulsion was adjusted to 8.0 by using a 10% by weight aqueous solution of triethanolamine instead of the aqueous potassium hydroxide solution. Various tests were conducted on the samples left for 10 days, and the results are shown in Table 2.

Comparative Example 3 The emulsion E prepared in Example 6, to which the aqueous potassium hydroxide solution was not added, was subjected to various tests in the same manner as in Example 1 immediately after emulsification and left at 50 ° C. for 10 days, and the results are shown in Table 2. It was shown to.

Example 10 Formula with viscosity 165 centistokes 15 parts of the organopolysiloxane represented by the formula, 3 parts of a 7 mol adduct of a higher alcohol with ethylene oxide (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: Softanol 70) and 4 parts of water were uniformly stirred. Pass this through a colloid mill,
Further, 78 parts of water was added to prepare an emulsion (emulsion G). A 10 wt% aqueous solution of sodium hydroxide was added to this to adjust the pH to 8.5 to stabilize the emulsion (emulsion H).

The emulsion H thus obtained was subjected to various tests in the same manner as in Example 1. In addition, emulsion at 50 ℃
The same test was performed for the one left for 10 days. The results are shown in Table 2.

Example 11 In Example 10, a 10 wt% aqueous solution of sodium carbonate was used instead of the potassium hydroxide aqueous solution to prepare an emulsion.
Emulsions were prepared in exactly the same manner except that the pH was adjusted to 8.5, and various tests were carried out immediately after emulsification and left at 50 ° C. for 10 days, and the results are shown in Table 2.

Example 12 In Example 10, 10% by weight of sodium hydrogen carbonate was used in place of the aqueous potassium hydroxide solution to adjust the pH of the emulsion.
Except that the emulsion was adjusted to 7.3, emulsions were prepared in exactly the same manner, and various tests were carried out immediately after emulsification and left at 50 ° C. for 10 days, and the results are shown in Table 2.

Example 13 An emulsion was prepared in the same manner as in Example 10 except that the pH of the emulsion was adjusted to 8.0 using a 10 wt% aqueous solution of triethanolamine instead of the aqueous potassium hydroxide solution, and the emulsion was prepared just after emulsification and at 50 ° C. Various tests were conducted on the samples left for 10 days, and the results are shown in Table 2.

Comparative Example 4 Various tests were performed in the same manner as in Example 1 on the emulsion G prepared in Example 10 to which an aqueous potassium hydroxide solution was not added and immediately after emulsification and left at 50 ° C. for 10 days, and the results are shown in Table 2. It was shown to.

Example 14 Formula with viscosity 138 centistokes 20 parts of organopolysiloxane represented by the formula, 4 parts of ethylene oxide 7 mol adduct of higher alcohol (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: Softanol 70), formula 4 parts of an anionic surfactant represented by and 15 parts of water were uniformly stirred. Pass it through a colloid mill and add water 57
Parts were added to make an emulsion (emulsion H). The pH of this emulsion was 4.0. To this, add a 10 wt% aqueous solution of diethanolamine, and add PH
Was adjusted to 7.5 to stabilize the emulsion (Emulsion I).

The emulsion I thus obtained was subjected to various tests in the same manner as in Example 1, and the results are shown in Table 3.
Further, the same test was conducted for the emulsion I left at 50 ° C. for 10 days, and the results are shown in Table 3.

Comparative Example 5 The emulsion H prepared in Example 14, to which the aqueous dienolamine solution was not added, was used immediately after emulsification and at 50 ° C. for 10 minutes.
Various tests were carried out in the same manner as in Example 1 for those left for a day, and the results are shown in Table 3.

Example 15 Formula with viscosity 92 centistokes 15 parts of an organopolysiloxane represented by the formula, 5 parts of an ethylene oxide 7 mol adduct of a higher alcohol (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: Softanol 70)
10 parts were stirred uniformly. This was passed through a colloid mill and 70 parts of water was added to prepare an emulsion (emulsion J). The pH of this emulsion was 3.0. To this, add a 10 wt% aqueous ammonia solution to remove PH.
The emulsion was stabilized by adjusting to 7.5 (emulsion K).

The emulsion K thus obtained was subjected to various tests in the same manner as in Example 1, and the results are shown in Table 4.
Further, the same test was carried out for the emulsion K left at 50 ° C. for 10 days, and the results are shown in Table 4.

Comparative Example 6 Various tests were carried out in the same manner as in Example 1 on the emulsion J prepared in Example 15, to which the aqueous ammonia solution was not added, immediately after emulsification and left at 50 ° C. for 10 days.
The results are shown in Table 4.

Example 16 Formula with viscosity 1260 centistokes 15 parts of organopolysiloxane represented by the formula, 5 parts of nonylphenol ethylene oxide 9 mol adduct, formula C ₉ H
Anionic surfactant 3 represented by ₁₈ O (C ₂ H ₄ O) ₄ SO ₃ Na
Parts and 15 parts of water were stirred uniformly. This was passed through a colloid mill, and 62 parts of water was added to prepare an emulsion (emulsion L). In addition, PH4.5 of this emulsion
Was 10% by weight of dimethylformamide
The pH was adjusted to 7.0 by adding an aqueous solution to stabilize the emulsion (emulsion M).

The emulsion M thus obtained was subjected to various tests in the same manner as in Example 1, and the results are shown in Table 5. Further, the same test was conducted for the emulsion M left at 50 ° C. for 10 days, and the results are shown in Table 5.

Comparative Example 7 The emulsion L prepared in Example 16 to which the dimethylformamide aqueous solution was not added was used immediately after emulsification and at 50
Various tests were carried out in the same manner as in Example 1 for those left at 10 ° C. for 10 days, and the results are shown in Table 5.

[Effects of the Invention] A method for stabilizing an organopolysiloxane emulsion containing a phosphorus alkyl ester group of the present invention is to emulsify the organopolysiloxane in water using an anionic surfactant and / or a nonionic surfactant. Since the pH of the emulsion is adjusted to 6 or more by adding a water-soluble alkaline substance to the resulting emulsion, various stability such as mechanical stability, dilution stability and storage stability can be easily and quickly imparted. It has features and is extremely useful in industry.

Claims (2)

[Claims] 1. At least one formula per molecule (In the formula, R is a monovalent hydrocarbon group or X, R ² is a monovalent hydrocarbon group, R ¹ is a divalent hydrocarbon group having 2 to 6 carbon atoms, and X is an alkoxy group having 1 to 4 carbon atoms. , A is 0 or 1, b
Is 1 or 2, c is 0 or 1, d is 0, 1 or 2, b
+ C is 2, provided that when a is 0, b is 2, and c is 0), an organopolysiloxane having a unit represented by the formula (1) is used in an anionic surfactant and / or a nonionic surfactant in water. Into an emulsion emulsified into
A method for stabilizing an organopolysiloxane emulsion containing an alkyl ester group of phosphorus, which comprises adding a water-soluble alkaline substance to adjust the pH of the emulsion to 6 or more. 2. The stabilizing method according to claim 1, wherein the pH of the emulsion is adjusted to 6.5 to 9.0.