JP2003252994A - Method for manufacturing emulsion-polymerized diorganopolysiloxane emulsion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for effectively preparing an emulsion composition containing a little amount of octamethylcyclotetrasiloxane after emulsion polymerization. <P>SOLUTION: The method for manufacturing an emulsion-polymerized diorganopolysiloxane emulsion composition comprises the following steps (1)-(3), where the content of octamethylcyclotetrasiloxane in the resultant diorganopolysiloxane is at most 0.5 wt.%: (1) a step for keeping a low-molecular diorganopolysiloxane bearing a condensation-reactive functional group on its molecular end and having an octamethylcyclotetrasiloxane content of higher than 0.3 wt.% at a temperature of 80-180°C and a pressure of not higher than 6.65 kPa (50 mmHg) while letting an inert gas flow to reduce the octamethylcyclotetrasiloxane content to at most 0.3 wt.%; (2) a step for emulsifying in water (d) the diorganopolysiloxane (a) obtained in the step (1) using an ionic emulsifier (b); and (3) a step for emulsion polymerizing the component (a) at 40°C or lower by adding, if required, a polymerization catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an emulsion-polymerized diorganopolysiloxane emulsion composition,
More specifically, it relates to a method for producing an emulsion-polymerized diorganopolysiloxane emulsion composition having a small content of octamethylcyclotetrasiloxane in the diorganopolysiloxane after emulsion polymerization.

[0002]

2. Description of the Related Art A low molecular weight diorganopolysiloxane having a molecular chain terminal blocked with a condensation-reactive functional group such as a silanol group is emulsion-polymerized in water using a surfactant and a catalyst to give a wide viscosity range. It is known to obtain emulsions of diorganopolysiloxanes having In this polymerization reaction, the cleavage reaction of the siloxane bond in the diorganopolysiloxane proceeds at the same time, and a low-molecular siloxane cyclic body is newly generated. Octamethylcyclotetrasiloxane is present in the order of 10% by weight.
Since this octamethylcyclotetrasiloxane is volatile, it has a drawback that various problems occur when the obtained diorganopolysiloxane emulsion is used at high temperature. For example, when a diorganopolysiloxane emulsion containing about 3 to 10% by weight of octamethylcyclotetrasiloxane is blended in a hair care cosmetic, when this is applied to hair and dried by heating with a hair dryer, octamethylcyclotetrasiloxane is added. There is a problem in that siloxane is volatilized to contaminate the surrounding environment and cause contact failure in a fan heater or the like. Therefore, an emulsion-polymerized diorganopolysiloxane emulsion composition having a low content of octamethylcyclotetrasiloxane has been earnestly desired.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors in order to solve the above problems, as a result of controlling the content of octamethylcyclotetrasiloxane to 0.3 wt% or less under specific conditions, It was found that the octamethylcyclotetrasiloxane content in the diorganopolysiloxane after emulsion polymerization can be controlled to 0.5% by weight or less by emulsion-polymerizing a diorganopolysiloxane having a molecular weight at a relatively low temperature. Reached That is, an object of the present invention is to provide a method for efficiently preparing an emulsion composition having a small content of octamethylcyclotetrasiloxane in the diorganopolysiloxane after emulsion polymerization.

[0004]

The present invention comprises the following steps (1) to (3), and the content of octamethylcyclotetrasiloxane in the produced diorganopolysiloxane is 0.5% by weight or less. And a method for producing an emulsion-polymerized diorganopolysiloxane emulsion composition. (1) A low molecular weight diorganopolysiloxane having a condensation-reactive functional group at the end of the molecular chain and having an octamethylcyclotetrasiloxane content of more than 0.3% by weight is heated at a temperature of 80- 180 ℃, pressure 6.65kP
a (50 mmHg) or less, and a step of reducing the content of octamethylcyclotetrasiloxane to 0.3% by weight or less. (2) (a) A low molecular weight diorganopolypolyamide obtained in the above step (1) having a content of octamethylcyclotetrasiloxane of 0.3% by weight or less and having a condensation-reactive functional group at the molecular chain end. Step of emulsifying siloxane in (d) water with (b) ionic surfactant. (3) To the emulsion obtained in the above step (2), (c) a polymerization catalyst [unnecessary when the component (b) has sufficient catalytic activity] is added, and (a) is added under a temperature condition of 40 ° C. or lower. Emulsion polymerization of the components.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The diorganopolysiloxane used in the step (1) of the present invention is a main raw material for emulsion polymerization,
It is a relatively low molecular weight siloxane whose molecular chain ends are blocked with condensation-reactive functional groups. The condensation-reactive functional group is not particularly limited, but a hydroxy group; an alkoxy group such as a methoxy group and an ethoxy group; a carboxyl group such as an acetoxyl group are preferable. The number average molecular weight of this diorganopolysiloxane is preferably 300 to 15,000, more preferably 2,000 to 10,000. This is because it is difficult to stably synthesize diorganopolysiloxane having a number average molecular weight of less than 300, and 15,000.
This is because emulsification becomes difficult when it exceeds. The molecular structure is generally linear, but a part thereof may have a branched or crosslinked structure. Such a diorganopolysiloxane is usually produced by equilibrium polymerization of a cyclic siloxane oligomer using an acidic catalyst such as sulfuric acid or an alkaline catalyst such as potassium hydroxide or potassium silanolate. Since the reaction product after equilibrium polymerization generally contains about 3 to 10% by weight of octamethylcyclotetrasiloxane, in the step (1) of the present invention, such a low content of octamethylcyclotetrasiloxane is contained. The molecular weight of diorganopolysiloxane is 80-180 ° C under an inert gas flow, and the pressure is 6.65 kPa (50 mmHg).
Stripping is carried out while maintaining the content below to reduce the octamethylcyclotetrasiloxane content to 0.3% by weight or less. Examples of the inert gas include nitrogen gas, dry air, and argon gas, and stripping is preferably performed while continuously blowing the inert gas with stirring.
The temperature and pressure conditions are preferably maintained at 3.99 kPa (30 mmHg) or less when the temperature is 80 ° C or higher and lower than 130 ° C, and 5.32 kPa (40 mmHg) or lower when the temperature is 130 ° C or higher and 180 ° C or lower. Preferably. By holding the raw material diorganopolysiloxane and performing stripping under such conditions, the content of octamethylcyclotetrasiloxane can be efficiently controlled to 0.3% by weight or less. In order to further reduce the content of octamethylcyclotetrasiloxane, the temperature is 140 ° C or higher and 180 ° C or lower, and the pressure is 1.3.
It is preferable to hold at 3 kPa (10 mmHg) or less for 1 hour or more. Further, this step (1) can be performed by a batch type (discontinuous type) stirring device such as an evaporator or a reaction vessel. Therefore, a special thin film evaporation device that has been used to reduce organosiloxane oligomers,
It has an advantage that complicated steps such as organic solvent extraction can be omitted. Specific examples of the diorganopolysiloxane include α, ω-dihydroxydimethylpolysiloxane,
Examples include α, ω-dimethoxydimethylpolysiloxane. Further, some of the methyl groups in these dimethylpolysiloxanes are hydrogen atoms, or ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl groups. Group, tridecyl group, tetradecyl group, pentadecyl group,
Hexadecyl, heptadecyl, octadecyl, nonadecyl, and other saturated aliphatic hydrocarbon groups; vinyl, allyl, hexenyl, and other unsaturated aliphatic hydrocarbon groups;
Saturated alicyclic hydrocarbon group such as cyclopentyl group and cyclohexyl group; aromatic hydrocarbon group such as phenyl group, tolyl group and naphthyl group; hydroxy group; substituted with alkoxy group such as methoxy group, ethoxy group and propoxy group The thing is also illustrated. Furthermore, the saturated aliphatic hydrocarbon group described above, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group,
A hydrogen atom in the aromatic hydrocarbon group may be partially substituted with a halogen atom or an organic group containing an epoxy group, an amino group, a methacryl group, a mercapto group or the like.

The low molecular weight diorganopolysiloxane having a condensation-reactive functional group at the molecular chain end of the component (a) used in the step (2) of the present invention is the octamethylcyclotetrasiloxane prepared in the step (1). Content of 0.3
It is controlled to be less than or equal to weight%. Further, the octamethylcyclotetrasiloxane content is 0.25% by weight.
It is preferably not more than 0.20% by weight, more preferably not more than 0.20% by weight, still more preferably not more than 0.10% by weight. The condensation-reactive functional group, molecular weight, and specific examples are the same as above. As the component (a), one kind of diorganopolysiloxane may be used alone, or a mixture of plural kinds may be used.

The ionic surfactant (b) is a component that emulsifies the component (a), and examples thereof include an anionic surfactant and a cationic surfactant. Specific examples of the anionic surfactant include sodium laurylbenzenesulfonate, a mixture of sodium tetradecenesulfonate and sodium hydroxytetradecanesulfonate, sodium alkanesulfonate, N-acyl-L-glutamate diethanolamine, N-acyl-L. -Triethanolamine glutamate, sodium N-acyl-L-glutamate, ammonium alkyl (12,14,16) sulfate, alkyl (11,13,15) sulfate triethanolamine (1), alkyl (11,13,15) sulfate Triethanolamine (2), alkyl (12-14) sulfate triethanolamine, alkyl sulfate triethanolamine solution, sodium alkyl (12,13) sulfate, sodium alkyl sulfate solution, sodium isethionate Sodium isostearate, undecylenoylamide disodium sulfosuccinate, triethanolamine oleate sulfate, sodium oleate sulfate, disodium oleateamide sulfosuccinate, potassium oleate, sodium oleate, morpholine oleate, oleoyl sarcosine, oleoyl Methyl taurine sodium, potassium-containing soap base, potassium soap base solution, potassium soap, carboxylated polyoxyethylene tridodecyl ether, carboxylated polyoxyethylene tridodecyl ether sodium salt (3EO),
N-hardened tallow fatty acid acyl-L-glutamic acid triethanolamine, N-hardened tallow fatty acid acyl-L-glutamate sodium, hardened coconut oil fatty acid sodium glyceryl sulfate, sodium diundecylenoylamide ethyl sulfosuccinate, sodium stearyl sulfate, stearic acid Potassium, triethanolamine stearate, sodium stearate, sodium N-stearoyl-L-glutamate, disodium stearoyl-L-glutamate, sodium stearoylmethyl taurine,
Dioctyl sodium sulfosuccinate, dioctyl sodium sulfosuccinate solution, polyoxyethylene monooleylamide disodium sulfosuccinate (2EO)
Liquid, polyoxyethylene lauroyl ethanolamide disodium sulfosuccinate (5EO), disodium lauryl sulfosuccinate, diethanolamide cetyl sulfate, sodium cetyl sulfate, soap base, sodium cetostearyl sulfate, triethanolamine tridecyl sulfate, palmitin Potassium salt, sodium palmitate, sodium palmitoylmethyl taurine, sodium castor oil fatty acid solution (30%), polyoxyethylene alkyl ether ammonium sulfate (3EO) solution, polyoxyethylene alkyl (12,13) ether sulfate diethanolamine (3E) .O.) Liquid, polyoxyethylene alkyl ether triethanolamine sulfate (3
E. O. ) Liquid, polyoxyethylene alkyl (11,1)
3,15) triethanolamine ether sulfate (1E.
O. ), Polyoxyethylene alkyl (12, 13) ether sulfate triethanolamine (3EO), polyoxyethylene alkyl ether sodium sulfate (3
E. O. ) Liquid, polyoxyethylene alkyl (11,1)
3,15) Sodium ether sulfate (1E.O.), sodium polyoxyethylene alkyl (11-15) ether (3E.O.), sodium polyoxyethylene alkyl (12,13) ether sulfate (3E.O.).
O. ), Polyoxyethylene alkyl (12-14) sodium ether sulfate (3EO), polyoxyethylene alkyl (12-15) sodium ether sulfate (3EO), polyoxyethylene alkyl (12-).
14) Disodium sulfosuccinate (7EO), sodium polyoxyethylene undecyl ether sulfate,
Polyoxyethylene octyl phenyl ether sodium sulfate liquid, polyoxyethylene oleyl ether ammonium sulfate, polyoxyethylene disodium lauryl sulfosuccinate, sodium polyoxyethylene nonyl phenyl ether sulfate, sodium polyoxyethylene pentadecyl ether sulfate, polyoxyethylene myristyl ether sulfate Triethanolamine, sodium polyoxyethylene myristyl ether sulfate, sodium polyoxyethylene myristyl ether sulfate (3E.
O. ), Polyoxyethylene lauryl ether sodium acetate (16 EO) liquid, polyoxyethylene lauryl ether ammonium sulfate (2 EO), polyoxyethylene lauryl ether sulfate triethanolamine, polyoxyethylene lauryl ether sulfate sodium, myristyl sulfate Diethanolamine, sodium myristyl sulfate, potassium myristate, sodium N-myristoyl-L-glutamate, sodium myristoylmethylaminoaminoacetate, sodium myristoylmethyl-β-alanine solution, myristoylmethyltaurine sodium, medicinal soap, coconut oil alkyl magnesium sulfate
Triethanolamine, N-coconut oil fatty acid acyl-L-
Glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-sodium glutamate, coconut oil fatty acid ethyl ester sodium sulfonate, coconut oil fatty acid potassium, coconut oil fatty acid potassium liquid, N-coconut oil fatty acid / hardened beef tallow fatty acid acyl-L- Sodium glutamate, coconut oil fatty acid sarcosine triethanolamine, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid triethanolamine, coconut oil fatty acid triethanolamine solution, coconut oil fatty acid sodium, coconut oil fatty methylalanine sodium, coconut oil fatty methylalanine sodium Liquid, coconut oil fatty acid methyl taurine potassium, coconut oil fatty acid methyl taurine sodium, sodium lauryl aminodipropionate, sodium lauryl amino dipropionate liquid (30%), lauri Sodium sulfoacetate, ammonium lauryl sulfate, potassium lauryl sulfate, diethanolamine lauryl sulfate, triethanolamine lauryl sulfate, sodium lauryl sulfate, magnesium lauryl sulfate, monoethanolamine lauryl sulfate, potassium laurate, triethanolamine laurate, triethanolamine laurate Liquid, sodium laurate, myristate triethanolamine laurate, lauroyl-L-glutamate triethanolamine, sodium N-lauroyl-L-glutamate, lauroylsarcosine, lauroylsarcosine potassium, lauroylsarcosine triethanolamine solution, lauroylsarcosine sodium, Lauroyl methyl β-alanine sodium solution, lauroyl methyl taurine natri Um, sodium lauroyl methyl taurine solution is mentioned.

Specific examples of the cationic surfactant include:
Ethanol sulfate lanolin fatty acid aminopropylethyldimethylammonium, alkyltrimethylammonium chloride, alkyl (16,18) trimethylammonium chloride, octadecyltrimethylammonium chloride, octyldihydroxyethylmethylammonium chloride, γ chloride
-Gluconamidopropyldimethylhydroxyethylammonium, dialkyl (12-15) dimethylammonium chloride, dialkyl (14-18) dimethylammonium chloride, dicocoyldimethylammonium chloride, disteryldimethylammonium chloride powder, disteryldimethylammonium chloride, dichloride Cetyldimethylammonium liquid, di (polyoxyethylene) oleylmethylammonium chloride, di (polyoxyethylene) oleylmethylammonium chloride (2EO), dipolyoxyethylenestearylmethylammonium chloride, stearyldihydroxyethylbetaine sodium chloride, chloride Stearyl dimethyl benzyl ammonium, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride solution, chloride Thearoylcholaminoformylmethylpyridinium, cetyltrimethylammonium chloride, cetylpyridinium chloride, dodecyldimethylethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride (5EO), behenyltrimethylammonium chloride, benzalkonium chloride, chloride Benzalkonium liquid, benzethonium chloride, benzethonium chloride liquid, polyoxyethylene (1) polyoxypropylene (25) diethylmethylammonium chloride, polyoxypropylenemethyldiethylammonium chloride, myristyldimethylbenzylammonium chloride, methylbenzethonium chloride, lauryltrimethyl chloride Ammonium, laurylpyridinium chloride, lauroylcoraminoformylmethylpyridinium chloride, alkyl bromide Isoquinolinium solution, bromide stearyltrimethylammonium, cetyltrimethylammonium bromide, cetyltrimethylammonium bromide powder, bromide lauryl trimethyl ammonium, stearyl trimethyl ammonium saccharinate, cetyltrimethylammonium saccharin, lauryl isoquinolinium saccharin.

As the component (b), one type may be used alone, or a mixture of a plurality of types may be used.
The amount of component (b) used is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of component (a). If it is less than 0.05 parts by weight, the stability of the emulsion composition may be impaired and separation may occur, and if it exceeds 100 parts by weight, the stability of the emulsion composition may be impaired and the emulsion composition This is because the viscosity of the composition may be too high and the handleability may deteriorate.

When a neutralizing salt type surfactant is used as the component (b), sufficient catalytic activity for emulsion polymerization cannot be expected, so it is preferable to add the polymerization catalyst (c). . This component (c) contributes to the polymerization of the component (a) by converting at least one of the salts used for emulsification, and when an anionic surfactant is used as the component (b). Uses an acid type polymerization catalyst, and uses a basic type polymerization catalyst when a cationic surfactant is used as the component (b). Examples of the acid-type polymerization catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, alkylbenzene sulfonic acid, and a mixture of unsaturated aliphatic sulfonic acid and hydroxylated aliphatic sulfonic acid. Of these, phosphoric acid and acetic acid have low catalytic activity and require a long time to polymerize the component (a). Therefore, a mixture of hydrochloric acid, sulfuric acid, alkylbenzene sulfonic acid, unsaturated aliphatic sulfonic acid and hydroxylated aliphatic sulfonic acid is used. Such components having high catalytic activity are preferable, and hydrochloric acid is particularly preferable. Hydrochloric acid is harmless to humans and animals since sodium chloride is produced when it is neutralized with sodium carbonate or sodium hydroxide after emulsion polymerization. As the base-type polymerization catalyst, strong bases such as potassium hydroxide, calcium hydroxide and sodium hydroxide are preferable. (C)
The addition amount of the component is not particularly limited, but when a neutralizing salt type surfactant is used as the component (b), it is used in an amount of 0.01 to 100 parts by weight based on 100 parts by weight of the component (a). Is preferred.

Water (d) is a dispersion medium for the components (a) and (b). The amount of this component is 0 for the composition of the present invention.
The amount is not particularly limited as long as it is a / W emulsion, but is preferably 10 per 100 parts by weight of the component (a).
~ 1000 parts by weight.

In the step (2) and the step (3) of the present invention, the component (a) is emulsified in the component (b) in water (d), and then the component (c) is added, if necessary. a)
Polymerize the ingredients. Specifically, the components (a), (b) and (d) are pre-mixed and passed through an emulsifying machine such as a homogenizer, a colloid mill, a line mixer or a sonolator, and then (d) if necessary. ) Add ingredients. Next, if necessary, the component (c) is added and the temperature is adjusted to a predetermined temperature of 40 ° C. or lower to polymerize the component (a). The polymerization temperature is preferably −5 to 40 ° C., more preferably 0 to 30 ° C. This is because when the polymerization temperature exceeds 40 ° C,
This is because, as the polycondensation reaction of the component (a) proceeds, the production reaction of octamethylcyclotetrasiloxane is promoted at the same time, and the content of octamethylcyclotetrasiloxane increases at a remarkable rate. Also, if the polymerization is carried out at a temperature lower than -5 ° C, the emulsion may be frozen and the stability of the emulsion may be significantly impaired. The polymerization time is preferably 24 hours or less, more preferably 10 hours or less, but if the octamethylcyclotetrasiloxane content in the diorganopolysiloxane is within the range of not more than 0.5% by weight, the polymerization time is further extended. The polymerization may be continued. After reaching the desired degree of polymerization, the emulsion may be neutralized to stop the polymerization reaction. When an acid-type catalyst is used as the neutralizing agent, bases such as sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydroxide, potassium hydroxide, ammonia and triethanolamine can be used. Can be mentioned. When a basic catalyst is used, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and aliphatic-substituted benzenesulfonic acid can be used.

Further, in the production method of the present invention, the viscosity of the diorganopolysiloxane in the emulsion is controlled,
In order to introduce a functional group into the diorganopolysiloxane, to further reduce the particle size of the emulsion, or to improve the compounding stability when compounded in a cosmetic composition, as long as the object of the present invention is not impaired. Other components known as additives for the diorganopolysiloxane emulsion composition may be added and blended before emulsification, before emulsion polymerization or after emulsion polymerization. Such additives include hydrolyzable organosilanes, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, pH adjusters, preservatives, antifungal agents, rust preventives. An agent is illustrated. These components may be used alone or in combination.

For example, when a hydrolyzable organosilane having an organic functional group or a hydrolyzate thereof is added during emulsion polymerization, a siloxane unit having an organic functional group can be introduced into the diorganopolysiloxane after emulsion polymerization. it can. As such hydrolyzable organosilanes,
3-aminopropyldimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane,
3-chloropropyltrimethoxysilane, 3-chloropropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-mercaptopropylmethyldimethoxysilane,
3-carboxypropylmethyldimethoxysilane, p-
Vinylphenyltrimethoxysilane, 2- (vinylphenyl) ethyltrimethoxysilane, 3- (p-isopropenylbenzoylamino) propyltrimethoxysilane, N-methacryloyl-N-methyl-3-aminopropyltrimethoxysilane, N- Lauroyl-N-methyl-3-aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-3-aminopropyltrimethoxysilane, N-lauroyl-N-methyl-3-aminopropyltrimethoxysilane, N, N- Bis (methacryloyl) -3-aminopropylmethyldimethoxysilane, N, N-bis (lauroyl) -3-aminopropyltrimethoxysilane, 3-aminopropyldiethoxysilane, 3-aminopropyltriethoxysilane, N-
(2-Aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyldiethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyldiethoxysilane, 3-
Methacryloxypropyltriethoxysilane, 3-acryloxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-carboxypropyl Methyldiethoxysilane, p-vinylphenyltriethoxysilane, 2- (vinylphenyl) ethyltriethoxysilane, 3- (p-isopropenylbenzoylamino) propyltriethoxysilane, N-methacryloyl-N-methyl-3-amino Propyltriethoxysilane, N-lauroyl-N-methyl-3-aminopropylmethyldiethoxysilane, N-acryloyl-N-methyl-3-aminopropyltriethoxysilane, N-lauroyl-N
-Methyl-3-aminopropyltriethoxysilane,
N, N-bis (methacryloyl) -3-aminopropylmethyldiethoxysilane, N, N-bis (lauroyl)
Examples include -3-aminopropyltriethoxysilane and its hydrolyzate.

Examples of the anionic surfactant and the cationic surfactant are the same as those mentioned above.

Specific examples of the nonionic surfactant include:
Ethylene glycol fatty acid ethyl ester, polyethylene glycol fatty acid ester, propylene glycol fatty acid ester, polypropylene glycol fatty acid ester, glycol fatty acid ester, trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester, glucoside derivative, glycerin alkyl ether Fatty acid esters, trimethylolpropaneoxyethylene alkyl ethers, fatty acid amides, alkylol amides, alkylamine oxides, lanolin and its derivatives, castor oil derivatives, hydrogenated castor oil derivatives, sterols and their derivatives, Polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl amines, polyoxy Ethylene fatty acid amides, polyoxyethylene alkylol amides, polyoxyethylene diethanolamine fatty acid esters, polyoxyethylene trimethylolpropane fatty acid esters, polyoxyethylene alkyl ether fatty acid esters, polyoxyethylene polyoxypropylene glycols, poly Oxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene polyhydric alcohol ethers, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid Esters,
Examples thereof include sucrose fatty acid esters, methyl (polyoxyethylene) siloxane / dimethylsiloxane copolymer, and methyl (polyoxypropylene) siloxane / dimethylsiloxane copolymer.

Specific examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, undecyl carboxymethoxyethyl carboxymethyl imidazolinium betaine sodium and undecyl hydroxyethyl imidazoline. Sodium betaine, undecyl-N-hydroxyethyl-N-carboxymethylimidazolinium betaine, alkyldiaminoethylethylglycine hydrochloride solution, stearyldihydroxyethylbetaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, stearyldimethylbetaine sodium solution, Bis (stearyl-N-hydroxyethylimidazoline) chloroacetic acid complex, coconut oil alkyl-N-carboxyethyl-N-hydride Xyethyl imidazolinium betaine sodium, coconut oil alkyl-N-carboxyethoxyethyl-N-carboxyethyl imidazolinium disodium hydroxide, coconut oil alkyl-N-carboxymethoxyethyl-N-carboxymethyl imidazolinium disodium hydroxy De, palm oil alkyl-N
-Carboxymethoxyethyl-N-carboxymethyl imidazolinium disodium lauryl sulfate, coconut oil alkyl betaine, coconut oil fatty acid amide propyl betaine,
Coconut oil fatty acid-N-carboxymethoxyethyl-N-carboxyethyl imidazolinium betaine sodium,
Lauryl aminopropionate triethanolamine, β
-Sodium lauryl aminopropionate, lauryl-
Examples include N-carboxymethoxyethyl-N-carboxymethylimidazolinium disodium dodecanoylsarcosine, sodium lauryldiaminoethylglycine sodium, lauryldimethylaminoacetic acid betaine, and lauric acid amidopropyl betaine solution.

Specific examples of the pH adjuster include hydrochloric acid, sulfuric acid, phosphoric acid, diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid. Potassium dihydrogen, trisodium phosphate, tripotassium phosphate, acetic acid,
Ammonium acetate, sodium acetate, potassium acetate, citric acid, sodium citrate, diammonium citrate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonia, triethanol Examples include amines.

Specific examples of the preservatives, fungicides and rust preventives include benzoic acid, aluminum benzoate, sodium benzoate, isopropylmethylphenol, ethylhexanediol, lysozyme chloride, chlorhexidine hydrochloride, octylphenoxyethanol and orthophenylphenol. , Sodium perborate, photosensitive element 101, photosensitive element 20
No. 1, Photosensitizer 301, Photosensitizer 401, Chlorhexidine gluconate solution, Cresol, Chloramine T, Chlorxylenol, Chlorcresol, Chlorphenesin,
Chlorhexidine, chlorobutanol, resorcin acetate, salicylic acid, sodium salicylate, domiphen bromide, zinc pyrithione, zinc pyrithione solution, sorbic acid, potassium saorbate, thiantol, thioxolone, thymol, tiram, dehydroacetic acid, sodium dehydroacetate, trichlorocarbanilide, trichloro. Hydroxydiphenyl ether, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, benzyl paraoxybenzoate, methyl paraoxybenzoate, methyl sodium paraoxybenzoate, parachlorophenol, paraphenol Sodium sulfonate (dihydrate), halocarban, phenoxyethanol, pheno Le, hexachloro fan, mononitroguayacol, mononitroguayacol sodium iodide para-dimethylaminostyryl heptyl methyl rear sled chloride, lauryl trimethyl ammonium trichloro phenoxide, oxyquinoline sulfate, phosphate oxyquinoline include resorcin.

According to the manufacturing method of the present invention as described above,
It is possible to efficiently obtain a diorganopolysiloxane emulsion composition in which the content of octamethylcyclotetrasiloxane in the diorganopolysiloxane after emulsion polymerization is 0.5% by weight or less. The octamethylcyclotetrasiloxane content is preferably 0.4% by weight or less. The number average molecular weight of the diorganopolysiloxane after polymerization is preferably 5,000 or more, or twice or more that of the component (a). It is more preferably 30,000 or more, further preferably 50,000 or more. The emulsion composition obtained by the method of the present invention is extremely useful industrially because the amount of octamethylcyclotetrasiloxane generated is extremely small, particularly when used under heating, and is suitable for cosmetics. .

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, "part" represents "part by weight", "%" represents "% by weight", and the molecular weight is a number average molecular weight. The evaluation of the prepared emulsion composition was performed according to the following method.

<Content of octamethylcyclotetrasiloxane in diorganopolysiloxane> 5 parts of emulsion composition, 50 parts of methanol and 100 parts of n-hexane.
Parts were added and shaken vigorously. Then, this was left standing for 24 hours or more to completely separate the two layers. Thereafter, the n-hexane layer was collected with a microsyringe, and the extracted octamethylcyclotetrasiloxane was quantified by gas chromatography.

<Molecular weight of diorganopolysiloxane> 5 parts of the emulsion composition, 50 parts of methanol and n-
100 parts of hexane was added and shaken vigorously. Then, this was left standing for 24 hours or more to completely separate the two layers. Then, the n-hexane layer was put in another container, and n-hexane was completely distilled off under a dry nitrogen atmosphere. The polymer remaining after the distillation was diluted with toluene, and the number average molecular weight was measured by GPC using polystyrene as a standard substance.

[0024]

[Reference Example 1] In a 2000 ml eggplant-shaped flask, dimethylpolysiloxane produced by the equilibrium polymerization method and having both ends of the molecular chain blocked with silanol groups (octamethylcyclotetrasiloxane content 4.92%, molecular weight 4800) 1
000 g was added. Then, this flask was attached to an evaporator, and while continuously blowing dry nitrogen into dimethylpolysiloxane at a flow rate of about 10 ml / min, a vacuum pump was used to set the internal pressure to 1.33 kPa (1).
0 mmHg), the temperature was maintained at 150 ° C. using an oil bath, and stripping was performed for 1 hour while rotating at 100 rpm to obtain Sample-A. Obtained sample-A
The octamethylcyclotetrasiloxane content therein was 0.01%.

[0025]

COMPARATIVE REFERENCE EXAMPLE 1 A dimethylpolysiloxane (octamethylcyclotetrasiloxane content: 4.92%, molecular weight: 480) produced by equilibrium polymerization and having both ends of the molecular chain blocked with silanol groups was prepared in a 2000 ml round-bottomed flask.
0) 1000 g was added. The flask was then attached to an evaporator and dried nitrogen was added to about 10 ml / mi.
While continuously blowing into dimethylpolysiloxane at a flow rate of n, use a vacuum pump to increase the internal pressure to 6.65 k.
Pa (50 mmHg) and 150 ° C using an oil bath
The sample-B was obtained by carrying out stripping for 10 hours while rotating at 100 rpm. The octamethylcyclotetrasiloxane content in the obtained Sample-B was measured and found to be 3.15%.

[0026]

[Comparative Reference Example 2] A dimethylpolysiloxane (octamethylcyclotetrasiloxane content: 4.92%, molecular weight: 480) produced by equilibrium polymerization and having both ends of the molecular chain blocked with silanol groups was prepared in a 2000 ml eggplant-shaped flask.
0) 1000 g was added. The flask was then attached to an evaporator and dried nitrogen was added to about 10 ml / mi.
While continuously blowing into dimethylpolysiloxane at a flow rate of n, use a vacuum pump to increase the internal pressure to 1.33 k.
Pa (10 mmHg) and 100 ° C using an oil bath
The sample-C was obtained by carrying out stripping for 10 hours while rotating at 100 rpm. The content of octamethylcyclotetrasiloxane in the obtained Sample-C was measured and found to be 1.91%.

Table 1 shows the octamethylcyclotetrasiloxane contents of the samples A to C obtained above.

[Table 1]

[0028]

Example 1 Sample-A 400.0 obtained in Reference Example 1
g to polyoxyethylene lauryl ether (25E
O) 18.0 g, sodium tetradecene sulfonate 7
5% and sodium hydroxytetradecane sulfonate 2
20.0 g of anionic surfactant, which is a 5% mixture,
A mixed solution of 42.0 g of ion-exchanged water was added and thoroughly premixed. This mixed solution was passed through the colloid mill once to obtain an emulsion. This emulsion was weighed into a 1-liter four-necked flask equipped with a thermometer, a stirrer, and a condenser, diluted with 520.0 g of water, and the average particle size was 0.25 μm.
m precursor emulsion composition was obtained. This is 200r
While stirring at pm, 2.2 g of 10% hydrochloric acid was added.
Then, heating or cooling is performed from the outside of the four-necked flask using a heat medium or a refrigerant, and the temperature of the contents is adjusted to 0,1.
Polymerization was carried out while maintaining the temperature at 0.25 ° C. Then, while continuing stirring, the pH of the 10% sodium hydroxide aqueous solution was adjusted to 7
The polymerization reaction was stopped by dropping until it was around, and an emulsion composition of high molecular weight dimethylpolysiloxane having an average particle diameter of 0.25 μm was obtained. With respect to the emulsion composition thus obtained, the content of octamethylcyclotetrasiloxane in the high molecular weight dimethylpolysiloxane was measured. Moreover, the molecular weight of the high molecular weight dimethylpolysiloxane in the obtained emulsion composition was measured. The results are shown in Table 3. The composition of the raw materials used is shown in Table 2.

[0029]

[Comparative Example 1] The average particle size was 0.25 in the same manner as in Example 1.
A μm precursor emulsion composition was prepared and
2.2 g of 10% hydrochloric acid was added with stirring at 00 rpm. Next, heating was performed from the outside using a heat medium, and polymerization was carried out for 5 hours while maintaining the temperature of the contents at 55 ° C. Then, while continuing stirring, the polymerization reaction was stopped by dropwise addition of a 10% aqueous sodium hydroxide solution until the pH reached around 7, and an emulsion composition of high molecular weight dimethylpolysiloxane having an average particle diameter of 0.26 μm was obtained. Obtained. The composition of the obtained emulsion composition is shown in Table 2, and the content of octamethylcyclotetrasiloxane and the molecular weight of high molecular weight dimethylpolysiloxane are shown in Table 3.

[0030]

Comparative Example 2 Example 1 except that Sample-C of Comparative Reference Example 2 was used in place of Sample-A in Example 1.
A precursor emulsion composition having an average particle diameter of 0.25 μm was obtained in the same manner as in. While stirring this at 200 rpm, 2.2 g of 10% hydrochloric acid was added. Then, cooling was performed from the outside using a refrigerant, and polymerization was performed for 10 hours while maintaining the temperature of the contents at 10 ° C. Then, while continuing stirring, the polymerization reaction was stopped by dropwise addition of a 10% aqueous sodium hydroxide solution until the pH reached around 7, and an emulsion composition of high molecular weight dimethylpolysiloxane having an average particle diameter of 0.25 μm was obtained. Obtained. The composition of the obtained emulsion composition is shown in Table 2, and the content of octamethylcyclotetrasiloxane and the molecular weight of high molecular weight dimethylpolysiloxane are shown in Table 3.

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

Example 2 Sample-A 400.0 obtained in Reference Example 1
g to polyoxyethylene lauryl ether (25E
O) 18.0 g, dodecylbenzene sulfonic acid 20.0
g, and a mixed solution of 42.0 g of ion-exchanged water were added and thoroughly premixed. This mixed solution was passed through the colloid mill once to obtain an emulsion. Next, this emulsion was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and 520.0 g of water was added to dilute the emulsion to give an average particle size of 0.
A 25 μm precursor emulsion composition was obtained. While stirring the obtained precursor emulsion composition at 200 rpm, heating or cooling was carried out from the outside of the flask using a heat medium or a refrigerant, and the contents were kept at 0, 10, 25 ° C. for polymerization. It was Then, while stirring this,
The polymerization reaction was stopped by dropwise addition of a 10% aqueous sodium hydroxide solution until the pH was around 7, to obtain an emulsion composition of high molecular weight dimethylpolysiloxane having an average particle diameter of 0.24 μm. With respect to the emulsion composition thus obtained, the content of octamethylcyclotetrasiloxane in the high molecular weight dimethylpolysiloxane was measured. Moreover, the molecular weight of the high molecular weight dimethylpolysiloxane in the obtained emulsion composition was measured. The results are shown in Table 4. The composition of the raw materials used is shown in Table 2.

[0034]

[Comparative Example 3] The average particle size was 0.25 in the same manner as in Example 2.
A μm precursor emulsion composition was prepared and
Polymerization was carried out for 5 hours while the contents were heated at 55 ° C, 70 ° C, and 85 ° C by heating with a heating medium while stirring at 00 rpm. Then, while stirring this, 10%
The polymerization reaction was stopped by adding an aqueous solution of sodium hydroxide dropwise until the pH was around 7, and the average particle size was 0.2.
A 5 μm high molecular weight dimethylpolysiloxane emulsion composition was obtained. The composition of the obtained emulsion composition is shown in Table 2, and the content of octamethylcyclotetrasiloxane and the molecular weight of high molecular weight dimethylpolysiloxane are shown in Table 4.

[0035]

Comparative Example 4 Example 2 except that Sample-C of Comparative Reference Example 2 was used in place of Sample-A in Example 2.
A precursor emulsion composition having an average particle diameter of 0.25 μm was obtained in the same manner as in. Next, while stirring this at 200 rpm, cooling was performed from the outside using a refrigerant, and polymerization was carried out for 10 hours while maintaining the temperature of the contents at 10 ° C. Then, while continuing stirring, the polymerization reaction was stopped by dropwise addition of a 10% aqueous sodium hydroxide solution until the pH reached around 7, and an emulsion composition of high molecular weight dimethylpolysiloxane having an average particle diameter of 0.25 μm was obtained. Obtained. The composition of the obtained emulsion composition is shown in Table 2, and the content of octamethylcyclotetrasiloxane and the molecular weight of high molecular weight dimethylpolysiloxane are shown in Table 4.

[0036]

[Table 4]

[0037]

Example 3 Sample-A 600.0 obtained in Reference Example 1
g and 10.0 g of methyltrimethoxysilane into a mixture,
A mixed solution of 66.7 g of cetyltrimethylammonium chloride (30% aqueous solution) and 320.0 g of ion-exchanged water was added and sufficiently premixed. This mixed solution was passed through a homogenizer twice under a pressure of 400 kg / cm ² to obtain a precursor emulsion composition having an average particle diameter of 0.35 μm. Transfer this to a four-necked flask and stir at 200 rpm while adding 2.5 g of sodium hydroxide (20% aqueous solution).
Was added. Then, the temperature of the contents is raised to 25 using a heating medium.
Polymerization was carried out for 5 hours while maintaining the temperature at ℃. Then, while continuing stirring, the polymerization reaction was stopped by dropping phosphoric acid until the pH reached around 7, and the average particle size was 0.34.
An emulsion composition of high molecular weight diorganopolysiloxane of μm was obtained. The octamethylcyclotetrasiloxane content in the high molecular weight diorganopolysiloxane was measured for the emulsion composition thus obtained. Further, the molecular weight of the high molecular weight diorganopolysiloxane in the obtained emulsion composition was measured. The results are shown in Table 6. Table 5 shows the composition of the raw materials used.
It was shown to.

[0038]

[Comparative Example 5] As in Example 3, the average particle size was 0.35.
A μm precursor emulsion composition was prepared and
Into a two-necked flask, 2.5 g of sodium hydroxide (20% aqueous solution) was added with stirring at 200 rpm. Next, heating is performed using a heat medium, and the temperature of the contents is 50 ° C.
Polymerization was carried out for 5 hours while maintaining the temperature at 70 ° C. Thereafter, while continuing stirring, the polymerization reaction was stopped by dropping phosphoric acid until the pH reached around 7, and the average particle size was adjusted to 0.
A 36 μm high molecular weight diorganopolysiloxane emulsion composition was obtained. The composition of the obtained emulsion composition is shown in Table 5, and the octamethylcyclotetrasiloxane content and the molecular weight of the high molecular weight diorganopolysiloxane are shown in Table 6.

[0039]

[Comparative Example 6] Example 3 except that Sample-C of Comparative Reference Example 2 was used instead of Sample-A in Example 3.
A precursor emulsion composition having an average particle diameter of 0.35 μm was obtained in the same manner as in. Take this in a four-necked flask, 2
While stirring at 00 rpm, sodium hydroxide (20%
2.5 g of aqueous solution) was added. Then, polymerization was carried out for 5 hours while maintaining the temperature of the contents at 25 ° C. using a heating medium. Then, while continuing stirring, the polymerization reaction was stopped by adding phosphoric acid dropwise until the pH reached around 7.
An emulsion composition of high molecular weight diorganopolysiloxane having an average particle diameter of 0.33 μm was obtained. The composition of the obtained emulsion composition is shown in Table 5, and the octamethylcyclotetrasiloxane content and the molecular weight of the high molecular weight diorganopolysiloxane are shown in Table 6.

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

According to the production method of the present invention, it is possible to efficiently prepare an emulsion composition in which the content of octamethylcyclotetrasiloxane in the diorganopolysiloxane after emulsion polymerization is 0.5% by weight or less. It has the feature that it can.

Claims (5)

[Claims] 1. An emulsion-polymerized diester comprising the following steps (1) to (3), wherein the content of octamethylcyclotetrasiloxane in the produced diorganopolysiloxane is 0.5% by weight or less. A method for producing an organopolysiloxane emulsion composition. (1) A low molecular weight diorganopolysiloxane having a condensation-reactive functional group at the end of the molecular chain and having an octamethylcyclotetrasiloxane content of more than 0.3% by weight is heated at a temperature of 80- 180 ℃, pressure 6.65kP
a (50 mmHg) or less, and a step of reducing the content of octamethylcyclotetrasiloxane to 0.3% by weight or less. (2) (a) A low molecular weight diorganopolypolyamide obtained in the above step (1) having a content of octamethylcyclotetrasiloxane of 0.3% by weight or less and having a condensation-reactive functional group at the molecular chain end. Step of emulsifying siloxane in (d) water with (b) ionic surfactant. (3) To the emulsion obtained in the above step (2), (c) a polymerization catalyst [unnecessary when the component (b) has sufficient catalytic activity] is added, and (a) is added under a temperature condition of 40 ° C. or lower. Emulsion polymerization of the components. 2. The method for producing an emulsion-polymerized diorganopolysiloxane emulsion composition according to claim 1, wherein the low-molecular weight diorganopolysiloxane has a number average molecular weight of 300 to 15,000. 3. The emulsion-polymerized diorganopolysiloxane emulsion composition according to claim 1, wherein the condensation-reactive functional group in the low molecular weight diorganopolysiloxane is a hydroxy group, an alkoxy group or a carboxyl group. Manufacturing method. 4. The method according to claim 1, wherein the component (b) is a cationic surfactant or an anionic surfactant.
A method for producing the emulsion-polymerized diorganopolysiloxane emulsion composition according to any one of 1. 5. The method for producing an emulsion-polymerized diorganopolysiloxane emulsion composition according to claim 1, wherein the component (c) is hydrochloric acid.