JPH08208987A - Organopolysiloxane emulsion and production thereof - Google Patents

Abstract

PURPOSE: To obtain an emulsion excellent in storage stability, mechanical stability, and dilution stability by compounding a specific diorganopolysiloxane oil with an emulsifying agent, water, and an alkali and regulating the pH to a given value. CONSTITUTION: This emulsion comprises 100 pts.wt. diorganopolysiloxane oil having one or more phenol groups per molecule (e.g. the compound represented by the formula); 5-200 pts.wt. emulsifying agent, preferably nonionic surfactant (e.g. polyoxyethylene lauryl ether); an appropriate amount of water; and an appropriate amount of an alkali, preferably triethanolamine or diethylamine. The emulsion has a pH of 7.0-13.0.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an organopolysiloxane emulsion and a method for producing the same. For more information,
The present invention relates to an organopolysiloxane emulsion having excellent storage stability, mechanical stability and dilution stability, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, emulsions of dimethylpolysiloxane oil have been widely used because they are useful as a release agent and a fiber treating agent. However, this emulsion has a problem that it has insufficient heat resistance and cannot be used depending on the intended use. The present inventors have previously found that a phenol group-containing diorganopolysiloxane oil having an average phenol equivalent within a specific range is superior in heat resistance to dimethylpolysiloxane oil (Japanese Patent Application No. 6-25990). reference). However, the emulsion of phenol group-containing diorganopolysiloxane oil has storage stability when stored for a long period of time, mechanical stability when it is circulated by a pump or agitated by a stirrer to give a mechanical share, and water stability. There was a problem that the dilution stability when diluted with was poor.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above problems, the present inventors have found that the above problems can be solved by adjusting the pH of a phenol group-containing diorganopolysiloxane emulsion within a specific range. The inventors have found that the points are resolved and have reached the present invention. That is, an object of the present invention is to provide an organopolysiloxane emulsion having excellent storage stability, mechanical stability and dilution stability, and a method for producing the same.

[0004]

Means for Solving the Problem and Its Action The present invention provides (A) 100 parts by weight of a diorganopolysiloxane oil having at least one phenol group in one molecule, (B) an emulsifier of 5 to 200 parts by weight, An organopolysiloxane emulsion comprising (C) an arbitrary amount of water, (D) an arbitrary amount of an alkaline substance, and having a pH in the range of 7.0 to 13.0, and (A) at least 1 in one molecule. To 100 parts by weight of diorganopolysiloxane oil having one phenol group, (B) an emulsifier of 5 to 200 parts by weight, and (C) an arbitrary amount of water, (D) an arbitrary amount of an alkaline substance is added to adjust the pH to 7 The present invention relates to a method for producing the organopolysiloxane emulsion, which is characterized in that the content is adjusted to the range of 0.0-13.0.

To explain this, the component (A), the diorganopolysiloxane oil, is the main component of the emulsion of the present invention, and it is necessary that it has at least one phenol group in one molecule. The bonding position of the phenol group may be at the terminal of the molecular chain in the diorganopolysiloxane, at the side chain, or at both. The phenol group in this component may be directly bonded to the silicon atom in the siloxane chain, but in general, the formula:

Embedded image {Wherein, R is a divalent hydrocarbon group, an ethylene group, a propylene group, a butylene group, an alkylene group such as isobutylene; Formula _{:-( CH 2) 2 -C 6 H} 4 - in so represented The alkylene arylene group is exemplified. Of these, the propylene group is the most common. The hydroxyl group in the phenol group may be bonded to any position of ortho, meta and para. }, It is preferable to be bonded to the silicon atom via a divalent hydrocarbon group. Further, as the group bonded to the silicon atom other than the phenol group, a methyl group,
Alkyl groups such as ethyl group, propyl group, hexyl group, octyl group; alkenyl groups such as vinyl group, allyl group, hexenyl group; aryl groups such as phenyl group;
formula:

Embedded image An arylene alkyl group represented by: a substituted or unsubstituted monovalent hydrocarbon group exemplified by a substituted hydrocarbon group such as a 3,3,3-trifluoropropyl group, a formula:-(C
H ₂₎ in _x -COOH (wherein, x is an integer of 1 or more.)
A carboxyl group-containing monovalent hydrocarbon group represented by the formula:-
Hydroxyl group-containing monovalent hydrocarbon group represented by (CH ₂ ) _x —OH (where x is the same as above), formula: — (CH ₂ ) <sub>x
- (C 2 H 4 O)</sub> 2 H ( wherein, x is the same as defined above.)
In represented by such an oxyalkylene group-containing monovalent hydrocarbon group, the formula :-( CH _{2) x} -SH (wherein, x is the same as defined above.) Mercapto group-containing monovalent hydrocarbon represented by Basis,
A hydroxyl group is mentioned. The viscosity of this diorganopolysiloxane oil at 25 ° C is preferably in the range of 10 to 100,000 centistokes, and particularly preferably in the range of 100 to 1,000 centistokes. Such a diorganopolysiloxane oil is obtained, for example, by adding p-vinylphenol or p-allylphenol to a diorganopolysiloxane oil having a silicon-bonded hydrogen atom in the presence of a catalyst for addition reaction such as chloroplatinic acid. It can be easily produced by reacting.

The emulsifier of the component (B) is a component for emulsifying and dispersing the diorganopolysiloxane oil of the component (A) in the water of the component (C), and is generally a nonionic surfactant or anion (anionic). (Ionic) type surfactants, or a combination thereof. It is also useful to use a polymeric emulsifier such as polyvinyl alcohol, carboxymethyl cellulose or methyl cellulose in combination with these. Among these, nonionic surfactants are most preferable. Examples of the nonionic surfactant include polyalkylene glycol ester of higher fatty acid, polyalkylene glycol ether of higher alcohol, polyalkylene glycol ether of polyhydric alcohol, and polyalkylene glycol ether of alkylphenol. Here, as the higher fatty acid used in the polyalkylene glycol ester of higher fatty acid, for example,
Examples include lauric acid, myristic acid, palmitic acid, and stearic acid. Examples of the higher alcohol used in the polyalkylene glycol ether of higher alcohol include octyl alcohol, lauryl alcohol, cetyl alcohol and oleyl alcohol. Examples of the polyhydric alcohol used for the polyalkyleneglycol ether of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbit and sorbitan. Examples of the alkylphenol used in the polyalkylene glycol ether of alkylphenol include octylphenol, dodecylphenol and nonylphenol. The polyalkylene glycol used in these esters and ethers is typically polyethylene glycol or a copolymer of polyethylene glycol and polypropylene glycol, and the degree of polymerization thereof is preferably in the range of 5 to 30. is there. Examples of anionic surfactants include alkylbenzene sulfonates and sulfuric acid ester salts of higher alcohols.
Examples of the alkylbenzene sulfonate include sodium salt of octylbenzene sulfonic acid, sodium salt of dodecylbenzene sulfonic acid, and sodium salt of nonylbenzene sulfonic acid. Examples of the sulfate ester salt of higher alcohol include sodium salt and potassium salt of sulfate ester of octyl alcohol, sodium salt and potassium salt of sulfate ester of lauryl alcohol,
Examples thereof include sodium salts and potassium salts of sulfate esters of cetyl alcohol, and sodium salts and potassium salts of sulfate esters of oleyl alcohol. The blending amount of the component (B) is in the range of 5 to 200 parts by weight, preferably 10 to 50 parts by weight, relative to 100 parts by weight of the component (A).

The component (C) water is composed of the components (A) and (B).
It is a dispersion medium for dispersing the components. The blending amount of this component is an arbitrary amount, but it is generally within a range such that the component (C) in the emulsion of the present invention is 95 to 20% by weight.

The alkaline substance as the component (D) is a component for adjusting the pH of the emulsion of the present invention within the range of 7.0 to 13.0, and is, for example, a monovalent alkali metal compound, an amine compound or ammonia. Water. Examples of the monovalent alkali metal compound include sodium hydroxide, potassium hydroxide and cesium hydroxide, and examples of the amine compound include diethylamine, diethanolamine and triethanolamine. Among these, when heat resistance is particularly required, those which evaporate by heating diethanolamine, aqueous ammonia, etc. are preferable. The addition amount of this component depends on the content of the phenol group in the component (A). The pH of the emulsion of the present invention is 7.0
In order to adjust to the range of 13.0, the added amount of the component (D) is inevitably increased as the content of the phenol group in the component (A) increases.

The emulsion of the present invention comprises the above component (A)
(D) component, but in addition to these components, preservatives, fungicides, rust preventives, colorants, diorganopolyphenols containing no phenol group such as dimethylpolysiloxane and methylphenylpolysiloxane Addition of siloxane may be carried out without impairing the object of the present invention.

In the emulsion of the present invention, for example, the component (D) is added to the emulsion consisting of the components (A) to (C) to adjust the pH to the range of 7.0 to 13.0. Manufactured by. To emulsify the components (A) to (C), for example, the component (B) is first added to the component (A) and mixed uniformly, and then a small amount of water is added, and then a colloid mill type emulsifier. It may be emulsified with an emulsifying machine such as a homomixer. After the emulsification, it is preferable that water is further added and the mixture is passed through an emulsifier such as a homogenizer or a sonolator. When the content of the phenol group in the component (A) is large, a microemulsion having a particle size of 0.01 to 0.05 μm can be prepared only by stirring.

The pH of the emulsion of the present invention as described above
Is in the range of 7.0 to 13.0, preferably 7.0 to 1
It is in the range of 2.0, particularly preferably in the range of 7.5 to 9.5. The emulsion of the present invention is excellent in storage stability, mechanical stability and dilution stability, and is used as a mold release agent for rubber, plastics, etc., and a carbon fiber raw thread or synthetic fiber raw thread that requires heat resistance. It is useful as a fiber treating agent.

[0012]

EXAMPLES Next, the present invention will be described with reference to examples. In the examples, “part” means “part by weight”, “%” means “% by weight”, and the viscosity is a value measured at 25 ° C.

[0013]

Example 1 General formula:

Embedded image Viscosity 104 centistokes, refractive index 1.4
21 phenol group-containing diorganopolysiloxane oil 2
After adding 55 parts of polyoxyethylene (6 mol) trimethylnonanol ether and 20 parts of polyoxyethylene (10 mol) octylphenyl ether as a nonionic surfactant to 00 parts and mixing them uniformly, a further 60 parts of Water was added and emulsified using a colloid mill type emulsifier. After the emulsification, 57.5 parts of water was further added and mixed until uniform, to prepare an organopolysiloxane emulsion. The pH of this emulsion was 3.8 when measured with a pH meter. 2 this emulsion
Add 50 cc each to a 500 cc beaker, and then add triethanolamine to adjust the pH to 7.0 and 8.
Adjusted to 5, 10.0. Each emulsion thus obtained was put into a 300 cc glass bottle, covered with a lid, and allowed to stand at 50 ° C. for 1 week. The appearance after standing was measured, and this was defined as storage stability. The results are shown in Table 1.
For comparison, the emulsion to which triethanolamine was not added in the above was left in the same manner as above. The appearance after standing was measured, and this was defined as storage stability. The results are shown in Table 1.

[0014]

[Table 1]

[0015]

Example 2 General formula:

[Chemical 4] The viscosity is 702 centistokes and the refractive index is 1.
409 phenol group-containing diorganopolysiloxane oil 200 parts, polyoxyethylene (6 mol) trimethylnonanol 55 parts and polyoxyethylene (7 mol) nonylphenol ether 20 parts, anionic surfactant as nonionic surfactant As an agent, 10 parts of polyoxyethylene (4 mol) lauryl ether sulfate sodium salt was added and uniformly mixed. Then, 75 parts of water was added and emulsified using a colloid mill type emulsifier. After the emulsification, 640 parts of water was further added and uniformly mixed to prepare an organopolysiloxane emulsion. PH of this emulsion
Was 4.1 with a pH meter. The emulsion was placed in a 500 cc beaker of 250 cc each, and then diethylamine was added to adjust the pH to 7.0, 8.5 and 10.0, respectively. Each emulsion thus obtained was put into a 300 cc glass bottle, covered with a lid, and allowed to stand at 50 ° C. for 1 week. The appearance after standing was measured, and this was defined as storage stability. The results are shown in Table 2. For comparison, the emulsion to which diethylamine was not added was left in the same manner as above. The appearance after standing was measured, and this was defined as storage stability. The results are shown in Table 2.

[0016]

[Table 2]

[0017]

Example 3 General formula:

Embedded image 20 parts of a phenol group-containing diorganopolysiloxane oil represented by the following formula, 5.5 parts of polyoxyethylene (6 mol) lauryl ether and 2.0 parts of polyoxyethylene (10 mol) octylphenol ether as a nonionic surfactant After adding and mixing uniformly, 7.5 parts of water was added and the mixture was stirred again uniformly. Then, it was emulsified by using a colloid mill type emulsifying machine, and 65 parts of water was added and uniformly dissolved and dispersed. This emulsion was further diluted 20 times with water to prepare a diluted emulsion of 2% diorganopolysiloxane. The pH of this diluted emulsion was 4.3 when measured with a pH meter. The emulsion was divided in half and triethanolamine was added to one emulsion to adjust its pH to 8.5. The emulsion thus obtained (250 cc) was placed in 250 cc mayonnaise bottle and left at 25 ° C. for 10 days. The presence or absence of oil floating on the surface of the emulsion and the destruction of the emulsion after standing was measured, and this was defined as the dilution stability.
Further, 500 cc of the emulsion whose pH was adjusted to 8.5 as described above was put in a household juicer mixer, stirred at 7,000 rpm for 20 minutes, transferred to a 500 cc mayonnaise bottle and left for 30 minutes. The presence or absence of floating of oil on the surface of the emulsion and the breakage of the emulsion after standing were measured, and this was defined as mechanical stability. The results are shown in Table 3. For comparison, the dilution stability and mechanical stability of the emulsion to which triethanolamine was not added above were measured in the same manner as above. Table 3 shows the results.

[0018]

[Table 3]

[0019]

The organopolysiloxane emulsion of the present invention comprises (A) a phenol group-containing diorganopolysiloxane oil, (B) an emulsifier, (C) water and (D) an alkaline substance, and has a pH of 7.0. Since it is in the range of 13.0, it is characterized by very good storage stability, mechanical stability and dilution stability. Further, the production method of the present invention is characterized in that such an emulsion can be produced with high productivity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C08K 5/17 (72) Inventor Isao Ona 2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow Corning・ Silicone Co., Ltd. Research & Development Division

Claims (4)

[Claims] 1. (A) 100 parts by weight of diorganopolysiloxane oil having at least one phenol group in one molecule, (B) 5 to 200 parts by weight of emulsifier, (C) arbitrary amount of water and (D) alkaline An organopolysiloxane emulsion comprising an arbitrary amount of a substance and having a pH in the range of 7.0 to 13.0. 2. The organopolysiloxane emulsion according to claim 1, wherein the component (B) is a nonionic surfactant. 3. The organopolysiloxane emulsion according to claim 1, wherein the component (D) is triethanolamine or diethylamine. 4. An emulsion comprising (A) 100 parts by weight of a diorganopolysiloxane oil having at least one phenol group in one molecule, (B) an emulsifier of 5 to 200 parts by weight, and (C) an arbitrary amount of water, (D) The method for producing an organopolysiloxane emulsion according to claim 1, wherein the pH is adjusted to a range of 7.0 to 13.0 by adding an arbitrary amount of an alkaline substance.