JP4557147B2 - Method for producing organopolysiloxane emulsion - Google Patents

Description

The present invention relates to a manufacturing method of the organopolysiloxane emulsion obtainable by emulsion polymerization of organopolysiloxane mixture.

  Conventionally, as a production method by emulsion polymerization of an organopolysiloxane emulsion, a method of polymerizing an organopolysiloxane in an emulsified state with an acid or an alkali catalyst (Japanese Patent Publication No. 34-2041: Patent Document 1, Japanese Patent Publication No. 41-13995). Publication: Patent Literature 2, Japanese Patent Publication No. 46-41038: Patent Literature 3), a method of polymerizing cyclic siloxane and trialkoxysilane with an acid or an alkali catalyst in an emulsified state (Japanese Patent Publication No. 56-38609: Patent Literature 4) JP-A-63-286434: Patent Document 5) is known. Also, a method of emulsion polymerization of terminal hydroxyorganopolysiloxane at low temperature in order to reduce low-molecular siloxane produced as a by-product (JP-A-4-178429: Patent Document 6, JP-A-2003-252994: Patent Document 7). ), A method of polymerizing an organosiloxane and a branched siloxane oligomer which is a terminal hydroxy group in order to obtain a branched organosiloxane (JP 2001-163981 A: Patent Document 8) is known.

  However, emulsion polymerization using cyclic siloxane as a raw material requires a long time for the equilibration reaction. Although the equilibration reaction time can be shortened by heat polymerization, the stability of the emulsion tends to decrease. In addition, emulsion polymerization using terminal hydroxyorganopolysiloxane as a raw material has a problem in emulsion stability. In addition, in a conventionally well-known technique, the description of manufacturing together using cyclic organopolysiloxane and terminal hydroxy linear organopolysiloxane is not seen.

Japanese Patent Publication No.34-2041 Japanese Patent Publication No.41-13995 Japanese Patent Publication No.46-41038 Japanese Patent Publication No. 56-38609 JP-A 63-286434 JP-A-4-178429 JP 2003-252994 A JP 2001-163981 A

The present invention has been made in view of the above circumstances, a good stability, and to provide a method for producing a short organopolysiloxane emulsion equilibration reaction time.

  As a result of intensive studies to achieve the above object, the present inventors have (A) cyclic organopolysiloxane, (B) both-end hydroxyl group-capped diorganopolysiloxane, and (C) both-end trialkylsiloxy group-capped. Polymerization is carried out in the presence of an acidic or alkaline catalyst in an emulsion obtained by emulsifying a polysiloxane mixture containing a diorganopolysiloxane in a specific ratio in (D) a surfactant added (E) water. Thus, the equilibration reaction time is shortened, so that an organopolysiloxane emulsion can be produced in a short time. This organopolysiloxane emulsion has been found to have good stock solution stability and dilution stability. It came to make this invention.

Accordingly, the present invention is,
( A) cyclic organopolysiloxane,
(B) a hydroxyl-blocked diorganopolysiloxane at both ends,
(C) It contains a trialkylsiloxy group-blocked diorganopolysiloxane at both ends, and the blending ratio of the components (A) and (B) is (A) / (B) = 10/90 to 80/20 (mass ratio). Yes, the blending amount of the component (C) is 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and the viscosity at 25 ° C. is 50 mm ² / s or less. An organopolysiloxane emulsion characterized by emulsifying and dispersing a siloxane mixture in (D) a surfactant added, (E) water, and polymerizing the polysiloxane mixture in the presence of an acidic or alkaline catalyst. of production how
Provide .

  According to the production method of the present invention, an emulsion polymerization emulsion having good stability can be produced in a short time even at a low temperature. In addition, the organopolysiloxane emulsion thus obtained is useful as a fiber treatment agent, a release agent, and the like because both the stock solution stability and the dilution stability are good.

（式中、Ｒは同一又は異種の炭素数１〜２０の１価有機基であり、ｎは３≦ｎ≦２０の整数である。） As cyclic organopolysiloxane which is (A) component of this invention, what is represented by the following general formula can be used.

(In the formula, R is the same or different monovalent organic group having 1 to 20 carbon atoms, and n is an integer of 3 ≦ n ≦ 20.)

  Here, R is the same or different monovalent organic 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. Group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and other alkyl groups, phenyl group, tolyl group, naphthyl group and other aryl groups, vinyl group, allyl group and other alkenyl groups Alternatively, a part of hydrogen atoms in these monovalent hydrocarbon group structures are substituted with halogen atoms, organic groups containing polar groups such as amino groups, acryloxy groups, methacryloxy groups, epoxy groups, mercapto groups, carboxyl groups, etc. Things. Here, 90 mol% or more of R is preferably a methyl group. Further, if n is larger than 20, the stability during emulsification is lowered, and therefore, 3 ≦ n ≦ 20, particularly 3 ≦ n ≦ 10.

Next, the both-end hydroxyl group-blocked diorganopolysiloxane which is the component (B) is one in which the end group is a hydroxyl group in terms of reactivity during the condensation reaction, and is represented by the following general formula: Things can be used.
H- [O-Si (R) ₂ ] _m- OH
(In the formula, R is the same as described above, and m is an integer of 2 ≦ m ≦ 100.)

  Here, R is the same or different monovalent organic group having 1 to 20 carbon atoms as described above, and can be exemplified by the same, preferably a methyl group. Further, if m is larger than 100, the stability when emulsified becomes poor, and therefore 2 ≦ m ≦ 100, especially 2 ≦ m ≦ 70.

Next, (C) component both terminal trialkylsiloxy group-blocked diorganopolysiloxane is used to adjust the viscosity of the polysiloxane after polymerization, and is represented by the following general formula: Can be used.
_{^{(R 1) 3 Si- [O}} -Si (R) 2] p -O-Si (R 1) 3
(In the formula, R is the same as above, R ¹ is the same or different alkyl group having 1 to 20 carbon atoms, and p is an integer of 0 ≦ p ≦ 20.)

Here, R is the same or different monovalent organic group having 1 to 20 carbon atoms as described above, and can be exemplified by the same, preferably a methyl group. R ¹ is the same or different alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, A decyl group etc. are mentioned. Here, 90 mol% or more of R ¹ is preferably a methyl group. Furthermore, if p is larger than 20, the effect as a viscosity modifier is weakened, and therefore 0 ≦ p ≦ 20, especially 0 ≦ p ≦ 15.

  The blending ratio of the components (A) and (B) is (A) / (B) (mass ratio) = 10/90 to 80/20, preferably 20/80 to 70/30. When (A) / (B) is smaller than 10/90, the stability of the emulsion is lowered, and when it is larger than 80/20, the equilibration reaction time becomes too long.

  Moreover, the compounding quantity of (C) component is 0.05-5 mass parts with respect to 100 mass parts of total amounts of (A), (B) component, Preferably it is 0.06-3 mass parts. When the blending amount of the component (C) is less than 0.05 parts by mass, the viscosity adjusting effect is insufficient, and when it is more than 5 parts by mass, the viscosity of the polysiloxane after polymerization becomes too low to be practical. .

In the present invention, in addition to these components (A), (B), and (C), organoalkoxysilanes represented by the following general formula are used in combination as raw materials for the organopolysiloxane within a range that does not impair the object of the present invention. You can also
R _a Si (OR) _4-a
(Here, R is the same as above, and a is an integer of 0-2.)

The viscosity at 25 ° C. of the polysiloxane mixture containing the components (A), (B), and (C) is 50 mm ² / s or less, preferably 40 mm ² / s or less. When the viscosity of the polysiloxane mixture is larger than 50 mm ² / s, the stability of the emulsion is lowered. The lower limit of the viscosity is not particularly limited, but is preferably 2 mm ² / s or more. Here, the viscosity is a value at 25 ° C. measured with an Ostwald viscometer.

  Next, the surfactant as component (D) is for uniformly dispersing the organopolysiloxane in water, and is not particularly limited. For example, alkyl sulfates, alkyl benzene sulfonates, and alkyl phosphates. , Anionic surfactants such as polyoxyethylene alkyl sulfates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, quaternary ammonium salts, alkylamine acetic acids Examples thereof include cationic surfactants such as salts, and amphoteric surfactants such as alkylbetaines and alkylimidazolines, and these can be used alone or in admixture of two or more.

  Using the emulsifier such as a homomixer or a homogenizer, uniformly mix the component (A), component (B), component (C), component (D), and other components, if necessary, in water as component (E). After emulsifying and dispersing, an acidic substance such as sulfuric acid, sulfonic acid or hydrochloric acid, or an alkaline substance such as potassium hydroxide or sodium hydroxide is added as a catalyst, if necessary, preferably at a temperature of 20 to 60 ° C. The polymerization reaction is carried out for ~ 42 hours.

  At this time, as the surfactant which is component (D), acid type surfactants such as alkylbenzene sulfonic acid, alkyl sulfuric acid and polyoxyethylene alkyl sulfuric acid, and cationic surfactants such as quaternary ammonium hydroxide are used. When an agent is used, it does not need to be newly added since it acts as a catalyst.

  Here, as a blending ratio of each of the above components, the polysiloxane mixture containing the component (A), the component (B) and the component (C) is 5 to 80% by mass, particularly 10 to 70% by mass, and the component (D). Is 0.1 to 30% by mass, particularly 0.2 to 15% by mass, the catalyst is preferably 0 to 2% by mass, particularly 0 to 1% by mass, and the balance is preferably water. If the amount of the polysiloxane mixture is too small, it is uneconomical, and if it is too much, an O / W emulsion may not be obtained. Moreover, when there are too few (D) components, stability of an emulsion may fall, and when too large, polysiloxane of a predetermined | prescribed polymerization degree may not be obtained. Furthermore, if there is too much catalyst, the stability of the emulsion may be reduced. The blending ratio of the components (A), (B) and (C) in the polysiloxane mixture is as described above.

  The average particle size of the polysiloxane mixture emulsion is preferably 50 to 800 nm, particularly preferably 100 to 600 nm. In the present invention, the average particle diameter can be measured with an N4 type measuring device manufactured by Coulter.

  Moreover, when the liquid temperature at the time of superposition | polymerization is higher than 60 degreeC, there exists a possibility that stability of an emulsion may worsen, and when it is lower than 20 degreeC, a long time may be required for equilibration reaction, and it is uneconomical. More preferably, it is 20-50 degreeC. If the polymerization time is shorter than 1 hour, the equilibration reaction may be insufficient, and if it exceeds 42 hours, the polymerization degree may not change due to the equilibration reaction, which is uneconomical. More preferably, it is 1-36 hours, More preferably, it is 1-30 hours.

  After completion of the polymerization, if necessary, an alkaline substance such as sodium carbonate, ammonia, sodium hydroxide, or triethanolamine is used when an acidic catalyst is used, and acetic acid, formic acid, phosphoric acid is used when an alkaline catalyst is used. Neutralize with an acidic substance such as hydrochloric acid.

By this polymerization, an organopolysiloxane having a degree of polymerization represented by the following formula of 150 to 3,000, particularly 200 to 2,000 is obtained.
(R ¹ ) ₃ Si— [O—Si (R) ₂ ] _q —OSi (R ¹ ) ₃
(However, R and R ¹ are the same as described above, and q is an integer of 148 ≦ q ≦ 2,998, particularly 198 ≦ q ≦ 1,998.)

This organopolysiloxane is obtained as an emulsion emulsified in water. In this case, the solid content (the above-mentioned target organopolysiloxane) concentration in this emulsion is 4.5 to 72% by mass, particularly 9 to 63% by mass. It is preferable that
Moreover, it is preferable that the average particle diameter of this emulsion is 50-800 nm, especially 100-600 nm.

  The organopolysiloxane emulsion thus obtained is useful as a fiber treatment agent, a mold release agent, and the like because both the stock solution stability and the dilution stability are good.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, parts and% represent parts by mass and mass%, respectively, the viscosity represents a value at 25 ° C. measured with an Ostwald viscometer, and the average particle diameter represents a value measured with a Coulter N4 type measuring device. Show.

[Example 1]
600 g of octamethylcyclotetrasiloxane, 400 g of terminal hydroxyl group-blocked dimethylpolysiloxane represented by H— [O—Si (CH ₃ ) ₂ ] ₄₀ —OH having a viscosity of 63.3 mm ² / s, and 1 g of hexamethyldisiloxane Mixed. The viscosity of this product was 9.9 mm ² / s. 840 g of this mixed siloxane solution, 6 g of sodium lauryl sulfate, 14 g of dodecylbenzenesulfonic acid, and 1140 g of water were charged in a 2 liter polyethylene beaker, uniformly emulsified with a homomixer, and then passed twice through a high pressure homogenizer at a pressure of 50 MPa to obtain an average particle size. A uniform white emulsion of 280 nm was obtained. This emulsion was polymerized at 25 ° C. for 24 hours. Thereafter, the solution was neutralized to pH 7 with 22 g of 10% aqueous sodium carbonate solution to obtain “Emulsion (1)”. This emulsion had a non-volatile content of 37.5% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Example 2]
200 g of octamethylcyclotetrasiloxane, 800 g of a terminal hydroxyl group-blocked dimethylpolysiloxane represented by H— [O—Si (CH ₃ ) ₂ ] ₄₀ —OH, and 1 g of hexamethyldisiloxane were uniformly mixed. The viscosity of this product was 32.1 mm ² / s. 840 g of this mixed siloxane solution, 6 g of sodium lauryl sulfate, 14 g of dodecylbenzenesulfonic acid, and 1140 g of water were charged into a 2 liter polyethylene beaker, uniformly emulsified with a homomixer, passed twice through a high pressure homogenizer at a pressure of 75 MPa, and the average particle size A uniform white emulsion with a diameter of 250 nm was obtained. This emulsion was polymerized at 25 ° C. for 20 hours. Thereafter, the mixture was neutralized to pH 7 with 22 g of 10% aqueous sodium carbonate solution to obtain “Emulsion (2)”. This emulsion had a non-volatile content of 37.6% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Example 3]
700 g of octamethylcyclotetrasiloxane, 300 g of terminal hydroxyl group-blocked dimethylpolysiloxane represented by H— [O—Si (CH ₃ ) ₂ ] ₄₀ —OH, and 1 g of hexamethyldisiloxane were uniformly mixed. The viscosity of this product was 6.7 mm ² / s. 840 g of this mixed siloxane solution, 6 g of sodium lauryl sulfate, 14 g of dodecylbenzenesulfonic acid, and 1140 g of water were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, and then passed twice through a high pressure homogenizer at a pressure of 40 MPa to obtain an average particle size. A uniform white emulsion with a diameter of 300 nm was obtained. This emulsion was polymerized at 25 ° C. for 24 hours. Thereafter, the mixture was neutralized to pH 7 with 22 g of 10% aqueous sodium carbonate solution to obtain “Emulsion (3)”. This emulsion had a non-volatile content of 37.6% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Example 4]
“Emulsion (4)” was obtained in the same manner as in Example 1 except that the polymerization was carried out at 50 ° C. for 12 hours, and further aging was carried out at 25 ° C. for 12 hours. This emulsion had a non-volatile content of 37.7% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Comparative Example 1]
839.16 g of octamethylcyclotetrasiloxane, 0.84 g of hexamethyldisiloxane, 6 g of sodium lauryl sulfate, 14 g of dodecylbenzene sulfonic acid, and 1140 g of water were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer. Were passed through a high-pressure homogenizer twice to obtain a uniform white emulsion having an average particle size of 300 nm. This emulsion was polymerized at 25 ° C. for 24 hours. Thereafter, the solution was neutralized to pH 7 with 22 g of 10% aqueous sodium carbonate solution to obtain “Emulsion (5)”. This emulsion had a non-volatile content of 29.8% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Comparative Example 2]
“Emulsion (6)” was obtained in the same manner as in Comparative Example 1 except that the polymerization time was changed to 48 hours. This emulsion had a non-volatile content of 37.6% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Comparative Example 3]
An “emulsion (7)” was obtained in the same manner as in Comparative Example 1 except that the polymerization was carried out at 70 ° C. for 12 hours and aging was further carried out at 25 ° C. for 12 hours. This emulsion had a non-volatile content of 37.7% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Comparative Example 4]
839.16 g of a terminal hydroxyl group-blocked dimethylpolysiloxane represented by H- [O—Si (CH ₃ ) ₂ ] ₄₀ —OH, 0.84 g of hexamethyldisiloxane, 6 g of sodium lauryl sulfate, 14 g of dodecylbenzenesulfonic acid, 1140 g of water Was put into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, and then passed twice through a high pressure homogenizer at a pressure of 100 MPa to obtain a uniform white emulsion having an average particle size of 270 nm. This emulsion was polymerized at 25 ° C. for 20 hours. Thereafter, the mixture was neutralized to pH 7 with 22 g of 10% aqueous sodium carbonate solution to obtain “Emulsion (8)”. This emulsion had a non-volatile content of 37.6% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

[Comparative Example 5]
“Emulsion (9)” was obtained in the same manner as in Comparative Example 1 except that the polymerization time was changed to 42 hours. This emulsion had a non-volatile content of 36.3% after drying at 105 ° C. for 3 hours. The physical properties are shown in Table 1.

（＊１）不揮発分から乳化剤量を除き、仕込みシロキサン量で割って算出：８５〜９０％で平衡状態
（＊２）イソプロピルアルコール（ＩＰＡ）１リットルに撹拌しながらエマルジョン３００ｇを徐々に添加し、析出したシロキサン層のみを１０５℃で３時間乾燥したものの回転粘度計により測定した２５℃における粘度：仕込み設定粘度（反応率が８５〜９０％になった場合の原料配合比から推定した仕上がりポリシロキサン粘度）は４０，０００〜８０，０００ｍＰａ・ｓ
（＊３）エマルジョン原液を３，０００ｒｐｍ／１５分間遠心分離した後の上／下ＮＶ（不揮発分）比：１．０±０．２は良好
（＊４）エマルジョン／水＝２／９８（質量比）で希釈し、２４時間後の表面状態を評価：（○：オイルスポットなし、×：オイルスポットあり）

(* 1) Calculated by removing the amount of emulsifier from the non-volatile content and dividing by the amount of charged siloxane: 85-90% in an equilibrium state (* 2) Gradually add 300 g of emulsion with stirring to 1 liter of isopropyl alcohol (IPA), and precipitate The dried siloxane layer was dried at 105 ° C. for 3 hours, and the viscosity at 25 ° C. measured with a rotational viscometer: the set viscosity of the preparation (the finished polysiloxane viscosity estimated from the raw material blending ratio when the reaction rate was 85 to 90%) ) Is 40,000-80,000 mPa · s
(* 3) Upper / lower NV (non-volatile content) ratio after centrifuging the emulsion stock solution at 3,000 rpm / 15 minutes: 1.0 ± 0.2 is good (* 4) Emulsion / water = 2/98 (mass) Ratio) and the surface condition after 24 hours was evaluated: (○: no oil spot, ×: oil spot)

Claims (3)

(A) cyclic organopolysiloxane,
(B) a hydroxyl-blocked diorganopolysiloxane at both ends,
(C) It contains a trialkylsiloxy group-blocked diorganopolysiloxane at both ends, and the blending ratio of the components (A) and (B) is (A) / (B) = 10/90 to 80/20 (mass ratio). Yes, the blending amount of the component (C) is 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and the viscosity at 25 ° C. is 50 mm ² / s or less. An organopolysiloxane emulsion characterized by emulsifying and dispersing a siloxane mixture in (D) a surfactant added, (E) water, and polymerizing the polysiloxane mixture in the presence of an acidic or alkaline catalyst. Manufacturing method. (A) component is the following general formula

(In the formula, R is the same or different monovalent organic group having 1 to 20 carbon atoms, and n is an integer of 3 ≦ n ≦ 20.)
In which the component (B) is represented by the following general formula H- [O-Si (R) ₂ ] _m -OH
(In the formula, R is the same as described above, and m is an integer of 2 ≦ m ≦ 100.)
And (C) component is represented by the following general formula (R ¹ ) ₃ Si— [O—Si (R) ₂ ] _p —O—Si (R ¹ ) ₃
(In the formula, R is the same as above, R ¹ is the same or different alkyl group having 1 to 20 carbon atoms, and p is an integer of 0 ≦ p ≦ 20.)
The method for producing an organopolysiloxane emulsion according to claim 1 , wherein the dialkylene is a diorganopolysiloxane having both terminal trialkylsiloxy groups blocked. The method for producing an organopolysiloxane emulsion according to claim 1 or 2 , wherein the polymerization temperature is 20 to 60 ° C and the polymerization time is 1 to 42 hours.