JP2014194037A - Organopolysiloxane emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organopolysiloxane emulsion further inhibiting and reducing formation of a cyclic siloxane oligomer contained in organopolysiloxane by emulsion polymerization.SOLUTION: There is provided an organopolysiloxane emulsion containing (A) diorganopolysiloxane represented by the formula (1) and having contents of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane of each 1,000 ppm or less, (B) only alkyl sulfate ester salt as a surfactant, (C) polyhydric alcohol having 6 or less carbon atoms, and (D) water, obtained by emulsion polymerization of a mixture having the blending amount of the (C) component of 1 to 15 mass%, and having contents of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane in organopolysiloxane after the emulsion polymerization of each 10,000 ppm or less. H-[O-Si(R)]-OH (1), where Ris monovalent hydrocarbon group and n is 5≤n≤100.

Description

  The present invention relates to an organopolysiloxane emulsion in which the production of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) by-produced when organopolysiloxane is produced by emulsion polymerization is suppressed.

  Organopolysiloxane emulsions by emulsion polymerization are widely used as components such as mold release agents, fiber treatment agents and lubricants because of their excellent storage stability and dilution stability. As a recent movement, there are concerns about the environmental impact of D4 and D5 contained in the organopolysiloxane by emulsion polymerization, and there is a movement to limit the content thereof. For this reason, the organopolysiloxane emulsion which suppressed and reduced the production | generation of D4 and D5 more is calculated | required.

  Conventionally, as a method for producing an organopolysiloxane emulsion by emulsion polymerization, a method in which a cyclic siloxane oligomer is emulsified and polymerized using a strong acid or a strong alkali as a polymerization catalyst (Japanese Patent Publication No. 34-2041: Patent Document 1, Japanese Patent Publication No. 41). -13995 gazette: patent document 2). A method in which a cyclic siloxane oligomer is emulsified and dispersed in an aqueous salt type surfactant solution, an ion exchange resin is added to the dispersion, ion exchange of the salt type surfactant is performed, and polymerization is performed (Japanese Patent Publication No. 54-19440). : Patent Document 3), a method in which a cyclic siloxane oligomer and trialkoxysilane are emulsified and polymerized with an acid or alkali catalyst (Japanese Patent Publication No. 56-38609: Patent Document 4) is known.

  Also, a method of emulsion polymerization of a terminal hydroxy group-blocked diorganopolysiloxane with reduced cyclic siloxane oligomer at 40 ° C. or lower (JP-A-4-178429: Patent Document 5, JP-A-4-198321: Patent Document 6, JP 2003-252994 A: Patent Document 7), a method of emulsion polymerization of a terminal hydroxy group-blocked diorganopolysiloxane at a lower temperature (1-4 ° C.) (JP 2000-53769 A: Patent Document 8), terminal Known is a method of emulsion polymerization with a hydroxy-blocked diorganopolysiloxane and a specific anionic surfactant (Japanese Patent Laid-Open No. 11-222554: Patent Document 9; Japanese Patent Laid-Open No. 2002-20490: Patent Document 10). Yes.

  However, when these terminal hydroxy group-blocked diorganopolysiloxane is used as a raw material and emulsified with an emulsifier such as an anionic surfactant, and an acidic catalyst such as hydrochloric acid, sulfuric acid or sulfonic acid is used as a catalyst, it is 10 ° C. or lower Even when emulsion polymerization is carried out at a low temperature of 20 hours or less, the amount of D4 and D5 produced cannot be suppressed to 10,000 ppm or less, respectively, and high polymerization of organopolysiloxane is not inhibited. In addition, there is no description of additives that suppress the formation of cyclic siloxane oligomers such as D4 and D5. For example, in Japanese Patent Application Laid-Open No. 4-178429, the molecular chain terminal having a viscosity of 78 centistokes and a non-condensation reactive dimethylsiloxane oligomer having 20 or less silicon atoms (ΣD4 to D20) is 850 ppm is silanol-blocked dimethyl. When polysiloxane is emulsified with a nonionic surfactant and an anionic surfactant under high pressure and then subjected to emulsion polymerization at 25 ° C. for 24 hours, the content of non-condensation reactive dimethylsiloxane oligomer after polymerization is described as 3,770 ppm. However, the formation of non-condensation reactive dimethylsiloxane oligomers to this level cannot be achieved under the described conditions.

Japanese Patent Publication No.34-2041 Japanese Patent Publication No.41-13995 Japanese Patent Publication No.54-19440 Japanese Patent Publication No. 56-38609 JP-A-4-178429 Japanese Patent Laid-Open No. 4-198321 JP 2003-252994 A JP 2000-53769 A JP-A-11-222554 JP 2002-20490 A

  The present invention has been made in view of the above circumstances, and is by-produced in a high-molecular-weight organopolysiloxane obtained by emulsion polymerization by adding a polyhydric alcohol using a hydroxy-terminated diorganopolysiloxane as a raw material. An object is to provide an organopolysiloxane emulsion in which the production of D4 and D5 is further suppressed.

  As a result of intensive studies to solve the above object, the present inventors have found that (A) both terminal hydroxy group-blocked diorganopolysiloxane, (B) an anionic surfactant, and a specific amount of (C) carbon number. The emulsion obtained by emulsifying 6 or less polyhydric alcohol and (D) water is emulsion-polymerized at low temperature in the presence of an acidic catalyst, so that D4 after emulsion polymerization does not hinder high polymerization. The inventors found that an organopolysiloxane emulsion in which the generation of D5 was further suppressed was obtained, and the present invention was made.

Accordingly, the present invention provides the organopolysiloxane emulsion shown below.
[1] (A) The following general formula (1)
^{H- [O-Si (R 1} ) 2] n -OH (1)
(In the formula, R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is an integer satisfying 5 ≦ n ≦ 100.)
Both end hydroxy group-blocked diorganopolysiloxane having a content of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane of 1,000 ppm or less,
(B) Only alkyl sulfate salts as surfactants,
(C) a polyhydric alcohol having 6 or less carbon atoms,
(D) An organopolysiloxane emulsion obtained by emulsion polymerization of a mixture containing water and having a blending amount of component (C) of 1 to 15% by mass, the octamethyl in the organopolysiloxane after emulsion polymerization An organopolysiloxane emulsion, wherein the content of cyclotetrasiloxane and decamethylcyclopentasiloxane is 10,000 ppm or less, respectively.
[2] The polyhydric alcohol of component (C) is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol The organopolysiloxane emulsion according to [1], which is at least one selected from 1,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, and glycerin.
[3] The organopolysiloxane according to [1] or [2], further comprising at least one selected from organoalkoxysilane represented by the following general formula (2) or a partial hydrolyzate thereof as component (E): Emulsion.
R ¹ _a Si (OR ² ) _4-a (2)
(Wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 4 carbon atoms, and a is 1 It is an integer of ~ 3.)

  According to the present invention, it is possible to produce an organopolysiloxane emulsion in which the contents of D4 and D5 in the highly polymerized organopolysiloxane obtained by emulsion polymerization are each 10,000 ppm or less. Since this organopolysiloxane emulsion has good storage stability, dilution stability, etc., it provides an emulsion useful as a mold release agent, fiber treatment agent, lubricant, and the like.

(A) Component As the (A) component used in the present invention, the both-end hydroxy group-blocked diorganopolysiloxane represented by the following general formula (1) can be used. It is an organopolysiloxane in which the content of D4 and D5 is 1,000 ppm or less and both terminal groups have hydroxy groups.
^{H- [O-Si (R 1} ) 2] n -OH (1)
(In the formula, R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is an integer satisfying 5 ≦ n ≦ 100.)

In the above formula, R ¹ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl. Group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, etc. alkyl group, phenyl group, tolyl group, naphthyl group etc. aryl group, vinyl, allyl etc. alkenyl group, or these In which a part of the hydrogen atoms in the monovalent hydrocarbon group structure is substituted with a halogen atom, an organic group containing a polar group such as an amino group, an acryloxy group, a methacryloxy group, an epoxy group, a mercapto group, or a carboxyl group Can be mentioned. Among these, it is desirable that 90 mol% or more is a methyl group.

  On the other hand, if n is smaller than 5, it is difficult to adjust the contents of D4 and D5 to 1,000 ppm or less, and if it is larger than 100, the average particle size when made into an emulsion becomes large, and the storage stability becomes poor. , N is 5 ≦ n ≦ 100, preferably 20 ≦ n ≦ 60.

  Each content of D4 and D5 contained in this both terminal hydroxy-blocked diorganopolysiloxane needs to be 1,000 ppm or less. When the content of each of D4 and D5 exceeds 1,000 ppm, D4 and D5 increase even at −10 to 10 ° C. and the emulsification weight is within 20 hours. This is because the content of each of D4 and D5 in the polysiloxane exceeds 10,000 ppm.

  The both-end hydroxy group-capped diorganopolysiloxane used in the present invention is a nitrogen-terminated hydroxy-group-capped diorganopolysiloxane containing 5,000 to 10,000 ppm of D4 and D5, respectively, which are industrially mass-produced. It can be obtained by stripping under conditions of 120 to 150 ° C. and 5 to 10 mmHg under bubbling.

Component (B) Component (B) is a surfactant for uniformly dispersing component (A) in water, and since an acidic catalyst is used as a polymerization catalyst, a cationic surfactant cannot be used. There are no particular restrictions. For example, alkyl sulfate salt, sulfonate salt, carboxylate salt, phosphate ester salt and the like can be mentioned. Examples of the alkyl sulfate ester salt include higher alcohol sulfate ester salt, higher alkyl ether sulfate ester salt, sulfated oil, sulfated fatty acid ester, sulfated olefin and the like. Examples of the sulfonate include alkyl benzene sulfonate, alkyl naphthalene sulfonate, paraffin sulfonate, and N-acyl taurate. Specific examples of the alkyl sulfate ester salt include sodium octyl sulfate, sodium 2-ethylhexyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, Examples thereof include sodium polyoxyethylene lauryl ether sulfate, and examples of the sulfonate include sodium octylbenzenesulfonate, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, and the like. . Particularly preferred are alkyl sulfate salts.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan alkyl esters, and the like.
These may be used alone or in combination of two or more.

Component (C) The component (C) is a polyhydric alcohol having 6 or less carbon atoms. A polyhydric alcohol is a compound having two or more hydroxy groups in one molecule. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, diols such as polyethylene glycol and polypropylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, , 4-cyclohexanediol, alicyclic diols such as 1,2-di (hydroxymethyl) cyclohexanone, aromatic diols such as 1,2-di (hydroxymethyl) benzene, alkane polyols such as pentaerythritol and glycerin, sorbitol, Such as mannitol Derivatives, pentaglycerol, etc. polyglycerol and poly alkane polyols such as dipentaerythritol hexa glycerin and the like, are used as these one or more thereof. Among these, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, , 5-pentanediol, 2-methyl-2,4-pentanediol, and a mixture of two or more of glycerin are preferably used, among which 1,2-butanediol, 1,3-butanediol, , 4-butanediol and 2,3-butanediol are preferably used.

(E) Component (E) Component includes organoalkoxysilane represented by the following general formula (2) or a partial hydrolyzate thereof.
R ¹ _a Si (OR ² ) _4-a (2)
(Wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 4 carbon atoms, and a is 1 It is an integer of ~ 3.)

In the above formula, R ¹ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms which is the same as described above, and the same can be exemplified. R ² is the same or different monovalent hydrocarbon group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. And the partial hydrolyzate is the oligomer of the said alkoxysilane, and is mainly a 2-15 mer.

  Disperse the components (A), (B), (C), (E), and other components as necessary, in water as component (D) using an emulsifier such as a homomixer or homogenizer. After cooling to 10 ° C. or less, an acidic catalyst such as a catalytic amount of hydrochloric acid, sulfuric acid, sulfonic acid or the like is added in order to ion-exchange the anionic surfactant as the component (B) into an acidic catalyst. The emulsion polymerization reaction is carried out at a temperature of −10 to 10 ° C. within 20 hours.

  In this case, when an anionic surfactant such as alkylbenzenesulfonic acid, alkylsulfuric acid or polyoxyethylene alkylsulfuric acid is used as the anionic surfactant which is component (B), Since it acts as an acidic catalyst, it is not necessary to add a new catalyst.

  Here, as a mixture ratio of the said component, (A) component is 5-80 mass%, especially 10-70 mass%, (B) component is 0.1-10 mass%, especially 0.2-5 mass%. The component (C) is 1 to 15% by mass, particularly 3 to 10% by mass, the acidic catalyst is particularly 0.1 to 0.5% by mass, and the water of the component (D) is the balance, but the component (D) The water is preferably 20 to 95% by mass, more preferably 30 to 80% by mass. (E) Component amount is 0.1-20 mass parts per 100 mass parts of (A) component, especially 1-20 mass parts.

  When the component (A) is less than 5% by mass, it is not economical, and when it is more than 80% by mass, an oil-in-water emulsion may not be obtained. If the amount of the component (B) is too small, the stability of the emulsion may be lowered. If the amount is too large, an organopolysiloxane having a predetermined polymerization degree may not be obtained. Furthermore, when there are too many acidic catalysts, the stability of an emulsion may fall.

  In the present invention, 1 to 15% by mass of a polyhydric alcohol having 6 or less carbon atoms as component (C) is blended and emulsion-polymerized, thereby producing D4 and D5 in the organopolysiloxane at 10,000 ppm or less, respectively. Can be suppressed. (C) When the amount of components is less than 1% by mass, the effect of sufficiently suppressing the generation of D4 and D5 is reduced. When it is more than 15% by mass, the stability of the emulsion may be lowered. More preferably, it is 3-10 mass%.

  Moreover, it is preferable that the average particle diameter of the emulsion after this emulsification dispersion is 100 to 800 nm, particularly 200 to 600 nm. In the present invention, the average particle size is measured by a Coulter N4 Plus submicron particle size distribution measuring device (Beckman Coulter, Inc.), a laser diffraction / scattering particle size distribution measuring device LA-920 (Horiba, Ltd.), or the like. be able to.

  Moreover, it is preferable that the liquid temperature at the time of emulsion polymerization shall be -10-10 degreeC. More preferably, it is around 0 ° C. When the liquid temperature is higher than 10 ° C., the production of D4 and D5 increases and cannot be suppressed to 10,000 ppm or less. When the temperature is lower than −10 ° C., D4 and D5 are hardly formed, but the condensation reaction of the hydroxyl group is lowered, and an organopolysiloxane having a predetermined polymerization degree may not be obtained. An acidic catalyst such as hydrochloric acid, sulfuric acid or sulfonic acid is added as an acidic catalyst, and an emulsion polymerization reaction is carried out within 20 hours, preferably 5 to 20 hours.

  After completion of the emulsion polymerization, neutralization is performed with an alkaline substance such as sodium carbonate, sodium hydroxide, triethanolamine, or ammonia.

  In addition, in order to improve the stability of the organopolysiloxane emulsion of the present invention obtained by emulsion polymerization, after neutralizing other nonionic surfactants, amphoteric surfactants and the like within a range not impairing the object of the present invention. It may be added.

  By this emulsion polymerization, an organopolysiloxane having a degree of polymerization of 300 to 3,000, particularly 1,000 to 2,000, and a viscosity at 25 ° C. by a rotational viscometer of 10,000 to 1,000,000 mPa · s is obtained. . The organopolysiloxane is obtained as an emulsion emulsified in water. In this case, the solid content concentration in the emulsion is preferably 10 to 70% by mass.

  The organopolysiloxane emulsion obtained by the emulsion polymerization of the present invention is an emulsion in which the formation of D4 and D5 is suppressed to 10,000 ppm or less without inhibiting the high polymerization of the organopolysiloxane, and its storage stability, dilution Because of its excellent stability and the like, it is an emulsion useful as a mold release agent, fiber treatment agent, lubricant and the like.

  Hereinafter, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited to the following examples. In the following examples, the viscosity is a value measured at 25 ° C. measured with a TVB-10M viscometer (manufactured by Toki Sangyo Co., Ltd.), and the average particle size is an N4 Plus submicron particle size distribution analyzer (Beckman Coulter, Inc.). The value measured by (made) is shown.

[Example 1]
The octamethylcyclotetrasiloxane (D4) content is 260 ppm and the decamethylcyclopentasiloxane (D5) content is 730 ppm.
_{H- [O-Si (CH 3} ) 2] 40 -OH
750 g (viscosity: 61 mPa · s) and 90 g of 1,3-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) are charged into a 2 liter polyethylene beaker and 10% by mass lauryl After adding 75 g of sodium sulfate and 75 g of water and uniformly emulsifying with a homomixer, 465 g of water was further added and emulsified and dispersed three times at a pressure of 50 MPa with a high-pressure homogenizer to obtain a milky white emulsion having an average particle size of 290 nm. . The obtained emulsion was cooled in a low-temperature incubator set at 0 ° C. for 12 hours, the emulsion internal temperature was set to 1 ° C., 37.5 g of 10% by mass dodecylbenzenesulfonic acid as a catalyst was added and stirred, and then 20 hours. Emulsion polymerization was performed. Next, 7.5 g of 10% by mass sodium carbonate was added to neutralize to pH 7 to prepare a uniform milky white “emulsion (1)”. This emulsion had a non-volatile content of 46.4% by mass at 105 ° C. after 3 hours, and the content of D4 and D5 was measured by gas chromatography. As a result, the amount of D4 was 7,430 ppm and the amount of D5 was 3,880 ppm. Met. The physical properties are shown in Table 1.

[Example 2]
A uniform milky white “emulsion (2)” having an average particle diameter of 300 nm was prepared in the same manner as in Example 1 except that 30 g of 1,3-butanediol and 525 g of water added after emulsification were used. did. This emulsion had a non-volatile content of 47.8% by mass after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Example 3]
A uniform milky white “emulsion (3)” having an average particle size of 290 nm was prepared in the same manner as in Example 1 except that 150 g of 1,3-butanediol and 405 g of water added after emulsification were used. did. This emulsion had a non-volatile content of 45.0 mass% after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Example 4]
A uniform milky white “emulsion (4)” having an average particle diameter of 280 nm was prepared in the same manner as in Example 1 except that the emulsion polymerization time was 10 hours in Example 1. This emulsion had a non-volatile content of 47.8 mass% after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Example 5]
A uniform milky white having an average particle size of 290 nm in the same manner as in Example 1 except that 1,3-butanediol was changed to 1,4-butanediol (Wako Pure Chemical Industries, Ltd.) in Example 1. “Emulsion (5)” was prepared. This emulsion had a non-volatile content of 46.5% by mass after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Example 6]
A uniform milky white having an average particle size of 280 nm in the same manner as in Example 1 except that 1,3-butanediol was changed to 1,3-propanediol (Wako Pure Chemical Industries, Ltd.) in Example 1. “Emulsion (6)” was prepared. This emulsion had a non-volatile content of 46.7 mass% after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Example 7]
In Example 1, after cooling for 12 hours in a low temperature incubator set at −5 ° C., the emulsion internal temperature was set to −4 ° C., and the average particle size was 280 nm uniform milky white as in Example 1. “Emulsion (7)” was prepared. This emulsion had a non-volatile content of 46.5% by mass after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Comparative Example 1]
The octamethylcyclotetrasiloxane (D4) content is 260 ppm and the decamethylcyclopentasiloxane (D5) content is 730 ppm.
_{H- [O-Si (CH 3} ) 2] 40 -OH
750 g (viscosity: 61 mPa · s) of both-end hydroxy group-blocked dimethylpolysiloxane represented by the formula (1) was charged into a 2 liter polyethylene beaker, added with 75 g of 10% by mass sodium lauryl sulfate and 75 g of water, and uniformly emulsified with a homomixer. Thereafter, 555 g of water was further added and emulsified and dispersed three times at a pressure of 50 MPa with a high-pressure homogenizer to obtain a milky white emulsion having an average particle size of 320 nm. The obtained emulsion was cooled in a low-temperature incubator at 0 ° C. for 12 hours, the emulsion internal temperature was 1 ° C., 37.5 g of 10% by mass dodecylbenzenesulfonic acid as a catalyst was added and stirred, and then emulsion polymerization was performed for 20 hours. Went. Subsequently, 7.5 g of 10% by mass sodium carbonate was added to neutralize to pH 7 to prepare a uniform milky white “emulsion (8)” having an average particle size of 320 nm. This emulsion had a non-volatile content of 48.3 mass% after 3 hours at 105 ° C., and the content of D4 and D5 was measured by gas chromatography. As a result, the amount of D4 was 18,300 ppm and the amount of D5 was 9,490 ppm. Met. The physical properties are shown in Table 1.

[Comparative Example 2]
H— [O—Si (CH ₃ ) ₂ ] ₄₀ —OH used in Comparative Example 1
750 g (viscosity: 61 mPa · s) and 1-octanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 2-terminal polyethylene beaker, 75 g of 10% by mass sodium lauryl sulfate and After adding 75 g of water and uniformly emulsifying with a homomixer, 525 g of water was further added, and in the same manner as in Comparative Example 1, a uniform milky white “emulsion (9)” having an average particle diameter of 310 nm was prepared. This emulsion had a non-volatile content of 46.4% by mass after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Comparative Example 3]
In Comparative Example 2, the average particle size was the same as in Comparative Example 2 except that 1-octanol was changed to 30 g of polyoxyethylene (4 mol) branched decyl ether (Neugen XL40, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). A uniform milky white “emulsion (10)” of 300 nm was prepared. This emulsion had a non-volatile content of 46.4% by mass after 3 hours at 105 ° C. The physical properties are shown in Table 1.

[Comparative Example 4]
In Comparative Example 1, “Emulsion (11)” was prepared in the same manner as in Comparative Example 1, except that the temperature of emulsion polymerization was 15 ° C. The average particle size was 310 nm, and the nonvolatile content after 3 hours at 105 ° C. was 48.5% by mass. The physical properties are shown in Table 1.

[Comparative Example 5]
D4 content is 260ppm, D5 content is 730ppm,
_{H- [O-Si (CH 3} ) 2] 40 -OH
2 g of dimethylpolysiloxane blocked with hydroxy groups at both ends represented by formula (viscosity: 61 mPa · s), 20 g of polyoxyethylene (9 mol) lauryl ether (Emulgen 109P, Kao Corporation), 20 g of dodecylbenzenesulfonic acid and 50 g of water In a polyethylene beaker, the mixture was uniformly emulsified with a homomixer, 510 g of water was added, emulsified and dispersed three times at a pressure of 50 MPa with a high-pressure homogenizer, and emulsion polymerization was performed at 25 ° C. for 20 hours. Next, 36 g of 10% by mass sodium carbonate was added to neutralize to pH 7 to prepare a uniform milky white “emulsion (12)” having an average particle diameter of 370 nm. This emulsion had a non-volatile content of 38.0 mass% after 3 hours at 105 ° C.

Quantitative method for D4 and D5 0.1 g of the prepared emulsion was extracted with 10 mL of internal standard acetone (shaking for 1 hour), allowed to stand overnight, and then the acetone layer was quantified by gas chromatography analysis.

Viscosity at 25 ° C. measured by a rotational viscometer obtained by adding 300 g of isopropyl alcohol with stirring to 300 g of the extracted siloxane viscosity while stirring and drying only the precipitated dimethylsiloxane at 105 ° C. for 3 hours.

Dilution stability The prepared emulsion was diluted to 2% by mass with ion-exchanged water, and the surface state after 24 hours was visually observed.
○: No interference film or oil spot.
X: Interference film, oil spot.

Claims (3)

(A) The following general formula (1)
^{H- [O-Si (R 1} ) 2] n -OH (1)
(In the formula, R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is an integer satisfying 5 ≦ n ≦ 100.)
Both end hydroxy group-blocked diorganopolysiloxane having a content of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane of 1,000 ppm or less,
(B) Only alkyl sulfate salts as surfactants,
(C) a polyhydric alcohol having 6 or less carbon atoms,
(D) An organopolysiloxane emulsion obtained by emulsion polymerization of a mixture containing water and having a blending amount of component (C) of 1 to 15% by mass, the octamethyl in the organopolysiloxane after emulsion polymerization An organopolysiloxane emulsion, wherein the content of cyclotetrasiloxane and decamethylcyclopentasiloxane is 10,000 ppm or less, respectively.   The polyhydric alcohol as component (C) is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2, The organopolysiloxane emulsion according to claim 1, which is at least one selected from 3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, and glycerin. Furthermore, the organopolysiloxane emulsion of Claim 1 or 2 which contains at least 1 sort (s) chosen from the organoalkoxysilane shown by following General formula (2), or its partial hydrolyzate as (E) component.
R ¹ _a Si (OR ² ) _4-a (2)
(Wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 4 carbon atoms, and a is 1 It is an integer of ~ 3.)