TW202128904A - Cationic emulsion composition of polyorganosiloxane, and method for producing same - Google Patents

Abstract

The present invention is a cationic emulsion composition of polyorganosiloxane, comprising (A) polyorganosiloxane given by average compositional formula (1) and having a viscosity at 25 DEG C of at least 300,000 mPa.s: 100 mass parts, (B-1) cationic surfactant: Q1 3(CH3)N+·X-: 0.1 to 30 mass parts, (B-2) cationic surfactant: Q2(CH3)3N+·X-: 0.1 to 30 mass parts, and (C) water: 30 to 3,000 mass parts. Thereby provided is a cationic emulsion composition of polyorganosiloxane having a high viscosity of at least 300,000 mP.s, that exhibits an excellent stability and durability.

Description

Cationic emulsion composition of polyorganosiloxane and its production method

The present invention relates to a cationic emulsion composition of polyorganosiloxane and a manufacturing method thereof.

Polyorganosiloxanes can impart smoothness or water repellency by processing the base material, so they are used in fiber treatment agents, mold release agents, water repellents, cosmetics, hair cosmetics, and the like. Among them, polysiloxane with a high degree of polymerization is excellent in the smoothness imparting effect. Moreover, as a surfactant when emulsifying these polysiloxanes, it is known that if a cationic surfactant such as a quaternary ammonium salt is used, the adsorptivity of the polysiloxane to the substrate is improved. Therefore, there is a high demand for an emulsion obtained by emulsifying a polysiloxane with a high degree of polymerization with a cationic surfactant.

The general method of emulsification and liquefaction of polysiloxane is to emulsify and disperse polysiloxane and surfactant in water by the mechanical shear of an emulsifier. However, polysiloxane with high degree of polymerization The viscosity is too high to apply mechanical shear evenly, and a stable emulsion cannot be obtained.

As a method for obtaining a polysiloxane emulsion with a high degree of polymerization, an emulsion polymerization method is known, which uses an acid or alkali catalyst to polymerize an emulsion of a silicone monomer in an emulsion (Patent Document 1, 2). However, in such an emulsion polymerization method, when a cationic surfactant such as a quaternary ammonium salt represented by cetyltrimethylammonium chloride is used in the literature, the polymerization rate is extremely slow, and therefore the polymerization rate is high. It takes a long time to increase the degree of polymerization. Even if the polymerization is carried out for about 150 hours, which is regarded as the practical limit in the industry, polysiloxane can only be polymerized until the viscosity after extraction is tens of thousands of mPa･s.

As a method of obtaining a cationic emulsion of a polysiloxane with a high degree of polymerization, a method of polymerization using a silicon alkoxide catalyst (Patent Document 3) and a method of polymerization using an ammonium hydroxide catalyst (Patent Document 4), but the degree of polymerization is similarly insufficient.

In addition, a method has also been proposed in which a cationic surfactant is added after an anionic surfactant is used to produce a highly polymerized polysiloxane emulsion (Patent Documents 5 and 6), but because an anionic surfactant is used in combination , So there are problems with stability.

Furthermore, a method has also been proposed in which polymerization is carried out under a two-stage temperature condition (Patent Document 7), but there is a problem in that a long polymerization time is required to increase the degree of polymerization.

In addition, in the field of fiber treatment agents, there have been increasing demands for washing durability of a level that is difficult to achieve with high polymerization degree polysiloxane alone. There are also the following examples: by adding a film strengthening agent such as silicon dioxide to the emulsion of a high degree of polymerization polysiloxane to increase the strength of the film, thereby enhancing the durability; but there are also the following problems: due to the addition of two Silicon oxide causes a decrease in stability or an increase in manufacturing steps. [Prior Technical Literature] (Patent Document)

Patent Document 1: Japanese Patent Publication No. 41-13995 Patent Document 2: Japanese Patent Publication No. 56-38609 Patent Document 3: Japanese Patent Laid-Open No. 08-104752 Patent Document 4: Japanese Patent Application Publication No. 2001-106787 Patent Document 5: Japanese Patent Laid-Open No. 09-137062 Patent Document 6: Japanese Patent Application Laid-Open No. 10-140480 Patent Document 7: Japanese Patent Laid-Open No. 09-278626

[The problem to be solved by the invention]

The present invention has been completed in view of the above circumstances, and its object is to provide a cationic emulsion composition of polyorganosiloxane, which has a high viscosity of 300,000 mP･s or more, and has good stability and durability. The object of the present invention is to provide a manufacturing method capable of polymerizing the emulsion composition in a relatively short time. [Technical means to solve the problem]

式(1)中，R¹ 相互獨立地為氫原子、或碳數1～20的一價有機基團，R² 相互獨立地為選自上述R¹ 的選項中的基團、羥基、或碳數1～20的烷氧基，a、b、c、d是該聚有機矽氧烷在25℃時的黏度滿足300000mPa･s以上的值，且a≧2、c＋d≧1； 0.1～30質量份的(B-1)陽離子系界面活性劑Q¹ ₃ (CH₃ )N^＋ ･X^－ ， 此處，Q¹ 是相同或不同種的碳數6～30的一價有機基團，X是鹵素原子或碳數1～6的一價羧基； 0.1～30質量份的(B-2)陽離子系界面活性劑Q² (CH₃ )₃ N^＋ ･X^－ ， 此處，Q² 是碳數17～30的一價有機基團，X是鹵素原子或碳數1～6的一價羧基； 30～3000質量份的(C)水。In order to achieve the above object, the present invention provides a cationic emulsion composition of polyorganosiloxane, which is characterized by containing the following components: 100 parts by mass of (A) polyorganosiloxane, which is averaged as follows The composition formula (1) indicates that the viscosity at 25°C is 300,000 mPa･s or more,

In formula (1), R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons, and R ^{2 is} independently a group selected from the above-mentioned ^{options for R 1} , a hydroxyl group, or a carbon Alkoxy groups with a number of 1-20, a, b, c, d are the viscosity of the polyorganosiloxane at 25°C satisfying a value of 300,000 mPa･s or more, and a≧2, c+d≧1; 0.1-30 mass Parts of (B-1) cationic surfactant Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ , where Q ¹ is the same or different kind of monovalent organic group with 6 to 30 carbon atoms, and X is A halogen atom or a monovalent carboxyl group having 1 to 6 carbons; 0.1-30 parts by mass of (B-2) cationic surfactant Q ² (CH ₃ ) ₃ N ⁺ ･X ^－ , where Q ² is the number of carbons A monovalent organic group of 17-30, X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbons; 30-3000 parts by mass of (C) water.

Such a cationic emulsion composition of polyorganosiloxane is a cationic emulsion composition of highly polymerized polyorganosiloxane with high viscosity, and has good stability and durability.

In this case, the emulsion composition of the present invention preferably further contains a nonionic surfactant.

In this way, by using a cationic surfactant and a nonionic surfactant in combination, the emulsion can be easily reduced in particle size, thereby improving the stability of the emulsion.

In addition, the emulsion composition of the present invention preferably forms a film after drying.

In this way, the emulsion compound of the present invention can be dried to form a film.

In addition, the present invention provides a fiber treatment agent characterized by a cationic emulsion composition containing the above-mentioned polyorganosiloxane.

In addition, the present invention provides a release agent characterized by a cationic emulsion composition containing the above-mentioned polyorganosiloxane.

Furthermore, the present invention provides a water-repellent agent characterized by a cationic emulsion composition containing the above-mentioned polyorganosiloxane.

In addition, the present invention provides a cosmetic material characterized by a cationic emulsion composition containing the above-mentioned polyorganosiloxane.

In addition, the present invention provides a cosmetic material for hair characterized by a cationic emulsion composition containing the above-mentioned polyorganosiloxane.

In this way, the cationic emulsion composition of polyorganosiloxane of the present invention can be suitably used as a component contained in a fiber treatment agent, a mold release agent, a water repellent, a cosmetic material, and a hair cosmetic material.

In addition, the present invention provides a method for producing a cationic emulsion composition of polyorganosiloxane, which is characterized in that the emulsion is polymerized at 0-30°C for 1 to 150 hours in the presence of an alkali catalyst, and further carried out For neutralization, the emulsion is obtained by emulsifying and dispersing the following components: 100 parts by mass of (D) polydiorganosiloxane with two terminal hydroxyl groups, which is represented by the general formula HO-[R ¹ ₂ SiO] _j -H, Here, R ^{1 is} independently a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms, and j is a value that the viscosity of the polydiorganosiloxane with both terminal hydroxyl groups at 25° C. satisfies less than 2000 mPa･s ; 0-20 parts by mass of (E) any one or two or more of the organoalkoxysiloxanes shown below, Si(OR ³ ) ₄ , R ¹ Si(OR ³ ) ₃ , R ¹ ₂ Si(OR ³ ) ₂ , R ¹ ₃ Si(OR ³ ), where R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons, and R ^{3 is} independently a hydrogen atom, Or a monovalent organic group with 1-20 carbon atoms; 0.1-30 parts by mass of (B-1) cationic surfactant Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ , where Q ¹ is the same or Different kinds of monovalent organic groups with 6 to 30 carbons, X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbons; 0.1-30 parts by mass of (B-2) cationic surfactant Q ² (CH ₃ ) ₃ N ⁺ ･X ^－ , where Q ² is a monovalent organic group having 17 to 30 carbons, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbons; 30 to 3000 parts by mass of (C )water.

According to such a method for producing an emulsion composition, a cationic emulsion composition of a highly polymerized polyorganosiloxane with a relatively high viscosity can be polymerized in a relatively short time, and the stability of the emulsion composition is good, and Durability is also good. [Effect of Invention]

The cationic emulsion composition of polyorganosiloxane of the present invention is a cationic emulsion composition of highly polymerized polyorganosiloxane with higher viscosity, and has good stability and durability. In addition, this emulsion composition can form a film alone, and can further improve the durability of the film. Such an emulsion composition can be suitably used as a fiber treatment agent, a mold release agent, a water repellent, a cosmetic material, a cosmetic material for hair, and the like.

In addition, the method for producing a cationic emulsion composition of polyorganosiloxane of the present invention can polymerize the emulsion composition in a relatively short time, and is therefore industrially useful.

式(1)中，R¹ 相互獨立地為氫原子、或碳數1～20的一價有機基團，R² 相互獨立地為選自上述R¹ 的選項中的基團、羥基、或碳數1～20的烷氧基，a、b、c、d是該聚有機矽氧烷在25℃時的黏度滿足300000mPa･s以上的值，且a≧2、c＋d≧1。In order to achieve the above-mentioned object, the inventors have repeatedly and intensively studied and found that in the presence of an alkali catalyst, the emulsion can be polymerized at 0 to 30°C for 1 to 150 hours and further neutralized, thereby enabling the emulsion to be relatively Polymerization is carried out in a short time, and the emulsion is obtained by emulsifying and dispersing the following components: 100 parts by mass of (D) two-terminal hydroxyl polydiorganosiloxane, which is represented by the general formula HO-[R ¹ ₂ SiO] _j -H It means that, here, R ^{1 is} independently a hydrogen atom or a monovalent organic group with 1 to 20 carbons, and j is the viscosity of the polydiorganosiloxane with both terminal hydroxyl groups at 25°C is less than 2000mPa･s The value of; 0-20 parts by mass of (E) any one or more of the following organoalkoxysiloxanes, Si(OR ³ ) ₄ , R ¹ Si(OR ³ ) ₃ , R ¹ ₂ Si(OR ³ ) ₂ , R ¹ ₃ Si(OR ³ ), where R ^{1 is} independently a hydrogen atom or a monovalent organic group with 1 to 20 carbons, and R ^{3 is} independently hydrogen Atom or a monovalent organic group with 1-20 carbon atoms; 0.1-30 parts by mass of (B-1) cationic surfactant Q ¹ ₃ (CH ₃ )N ⁺ ･X ^－ , where Q ¹ is The same or different kinds of monovalent organic groups with 6 to 30 carbons, X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbons; 0.1-30 parts by mass of (B-2) cationic surfactant Q ² (CH ₃ ) ₃ N ^＋ ･X ^－ , where Q ² is a monovalent organic group with 17 to 30 carbons, and X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbons; 30 to 3000 parts by mass (C). In addition, the present inventors found that a cationic emulsion composition can be obtained by this, which contains as ( A) component, the stability of the emulsion composition is good, and the durability is also good, thus completing the present invention.

In formula (1), R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons, and R ^{2 is} independently a group selected from the above-mentioned ^{options for R 1} , a hydroxyl group, or a carbon Alkoxy groups with numbers from 1 to 20, a, b, c, and d have a viscosity of 300,000 mPa･s or more at 25°C, and a≧2, c+d≧1.

Such high-viscosity polyorganosiloxanes of 300,000 mPa･s or more are generally polyorganosiloxanes with a high degree of polymerization. Therefore, when describing the present invention, it may be referred to as a cationic emulsion composition of a polyorganosiloxane with a high degree of polymerization.

Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to this embodiment.

First, each component of the cationic emulsion composition of polyorganosiloxane of the present invention will be explained.

式(1)中，R¹ 相互獨立地為氫原子、或碳數1～20的一價有機基團，R² 相互獨立地為選自上述R¹ 的選項中的基團、羥基、或碳數1～20的烷氧基，a、b、c、d是該聚有機矽氧烷在25℃時的黏度滿足300000mPa･s以上的值，且a≧2、c＋d≧1。[Component (A)] The component (A) is a polyorganosiloxane represented by the following average composition formula (1) and has a viscosity of 300,000 mPa·s or more at 25°C. The emulsion composition of the present invention contains 100 parts by mass of this component (A).

In formula (1), R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons, and R ^{2 is} independently a group selected from the above-mentioned ^{options for R 1} , a hydroxyl group, or a carbon Alkoxy groups with numbers from 1 to 20, a, b, c, and d have a viscosity of 300,000 mPa･s or more at 25°C, and a≧2, c+d≧1.

As described above, R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Alkyl groups such as, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.; phenyl , Tolyl, naphthyl and other aryl groups; vinyl, allyl and other alkenyl groups; or, with halogen atoms, or amino groups, acryloxy groups, methacryloxy groups, epoxy groups, mercapto groups, etc. The polar group-containing organic groups are substituted for a part of the hydrogen atoms in the structure of these organic groups. Here, industrially and characteristically, it is more desirable that 80% or more of ^{R 1 is a methyl group.}

In addition, as described above, R ^{2 is} independently a group selected from the above-mentioned ^{options for R 1} , a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms. The alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, examples include methoxy, ethoxy, propoxy, butoxy, and pentoxy. Group, hexyloxy, octyloxy, decyloxy, dodecyloxy, 2-ethylhexyloxy, etc.; preferably methoxy, ethoxy, propoxy, butoxy, pentoxy The group is more preferably a methoxy group, an ethoxy group, or a propoxy group.

When a reactive functional group is present in the above average composition formula (1), the reactive functional group can react with other compounds. Specifically, when there is an amine group in the above average composition formula (1), it can undergo a ring-opening reaction with an epoxy group-containing polyoxyalkylene compound or an epoxy group-containing alkyl compound, and it can react with The following carboxylic anhydrides undergo acetylation reaction: acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride. In addition, when an epoxy group is present in the average composition formula (1), it can undergo a ring-opening reaction with an amine group-containing compound. In addition, the reaction with the reactive functional group shown above is not limited to these reactions.

The a, b, c, and d in the above average composition formula (1) are the viscosity of polyorganosiloxane at 25°C satisfying a value of 300,000 mPa･s or more, more preferably a value of 400,000 mPa･s or more, and more Preferably, it satisfies a value of 500000 mPa･s or more. Furthermore, this viscosity is absolute viscosity. Those that can be measured in a liquid state are directly measured by a rotary viscometer at 25°C. If the viscosity is too high to be measured, it is measured by a rotary viscometer at 25°C. The value obtained by measuring the solubility viscosity of toluene. Also, a≧2, c+d≧1.

In the above average composition formula (1), b can typically take a value of 50 or more, and preferably can take a value of 100 or more. Among them, when the value of c+d is large, the number of cross-linking units increases, so even if b is 50 or less, the viscosity may become 300,000 mPa·s or more.

As a specific example of (A) component, the following average composition formula can be mentioned, but it is not limited to these average composition formula. In the following average composition formula, a, b, c, d, e, and f mean that the viscosity of polyorganosiloxane at 25°C satisfies a value of 300,000 mPa·s or more, and a≧2, c+d≧1. In addition, b+e+f in the following average composition formula can typically take a value of 50 or more, and preferably can take a value of 100 or more.

[(B-1) component and (B-2) component] (B-1) component and (B-2) component are as follows. (B-1) Cationic surfactant: Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ (here, Q ¹ is the same or different kind of monovalent organic group with 6 to 30 carbon atoms, and X is halogen Atom or a monovalent carboxyl group with 1 to 6 carbon atoms.) (B-2) Cationic surfactant: Q ² (CH ₃ ) ₃ N ^＋ ･X ^－ (here, Q ² is one with 17 to 30 carbon atoms A valent organic group, X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbons.)

The emulsion composition of the present invention contains 0.1 to 30 parts by mass of the component (B-1) and 0.1 to 30 parts by mass of the component (B-2) with respect to 100 parts by mass of the (A) component.

These (B-1) and (B-2) components are cationic surfactants, which are used to emulsify and disperse polyorganosiloxanes in water, but about (B-1) and (B-2) As for the mechanism of action of the ingredients, the present inventors believe that in addition to the mechanism of action as an emulsifier, there is a mechanism of action as described below. In the method for producing polyethylene is considered alumoxane silicones of the present invention a cationic emulsion composition, the poly siloxane emulsified silicones, dispersed in water, is added an alkali catalyst, the aqueous phase resulting OH ^- and (B-1) component and (B-2) component, that is, the relative ion of the cationic surfactant is exchanged, whereby the cationic surfactant itself also acts as a catalyst. As a result, it can be used more efficiently The polyorganosiloxane of the component (A) increases the degree of polymerization.

As mentioned above, the component (B-1) is a cationic surfactant, which is a cationic surfactant represented by Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ , and Q ¹ is the same or a different kind of carbon number The monovalent organic group of 6 to 30 is preferably a monovalent organic group of 7 to 18 carbon atoms. When ^{the carbon number of Q 1} is less than 6, the hydrophilicity of the surfactant is too strong, and the frequency of contact with the polyorganosiloxane of component (A) is reduced, so it is necessary to increase the degree of polymerization of the polyorganosiloxane Long time aggregation. In addition, when ^{the carbon number of Q 1} exceeds 30, the emulsifying power as a surfactant is weak, and a stable emulsion may not be obtained.

Specific examples of Q ¹ include: hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, decyl Alkyl groups such as hexaalkyl, heptadecyl, octadecyl, nonadecyl, eicosyl, behenyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.; phenyl, benzyl Aryl groups such as phenyl group, tolyl group and naphthyl group; alkenyl groups such as octadecenyl group and the like. Among them, octyl, dodecyl, hexadecyl, and octadecyl are preferred.

And, X ^- is a halide or a monovalent carboxylate ion having a carbon number of 1 to 6. Specific examples thereof ^{include: Cl -, Br -, I} - and other halide _{^{ions; HCOO -, CH 3 COO -}} , C 2 H ₅ COO ^- and other carboxylic acid ions. Of these, preferred are _{^{Cl -, HCOO -, CH 3}} COO -.

(B-1) Specific examples of the component include: trihexyl methyl ammonium chloride, triheptyl methyl ammonium chloride, trioctyl methyl ammonium chloride, trinonyl methyl ammonium chloride, chlorine Tridecyl methyl ammonium chloride, trilauryl methyl ammonium chloride, trioctyl methyl ammonium acetate, trilauryl methyl ammonium acetate, etc.; but not limited to these examples.

The usage amount of the cationic surfactant as the component (B-1) can be 0.1-30 parts by mass, preferably 0.5-20 parts by mass, and more preferably 1 to 100 parts by mass of the component (A). 15 parts by mass. When it is less than 0.1 parts by mass, the (A) component may not be able to efficiently increase the degree of polymerization during the polymerization process, and when it is more than 30 parts by mass, the stability of the emulsion tends to become unstable.

In addition, as described above, the cationic surfactant of the component (B-2) is a cationic surfactant represented by Q ² (CH ₃ ) ₃ N ⁺ ･X ⁻ and can improve the stability of the emulsion. Here, Q ² is a monovalent organic group having 17 to 30 carbon atoms, preferably a monovalent organic group having 18 to 28 carbon atoms. When ^{the carbon number of Q 2} is less than 17, the compatibility with the cationic surfactant represented by (B-1) is poor, and the stability of the emulsion may decrease. When ^{the carbon number of Q 2} is more than 30, the emulsifying power as a surfactant is weak as in the case of ^{Q 1, and a stable emulsion may not be obtained.} X ^-of Q ^{2 is} the same as X ^{-of Q 1} described above.

(B-2) Specific examples of the component include: octadecyl trimethyl ammonium chloride, eicosyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, decyl acetate Octalyl trimethyl ammonium, eicosyl trimethyl ammonium acetate, behenyl trimethyl ammonium acetate, etc., but not limited to these examples.

The usage amount of the cationic surfactant of the component (B-2) can be 0.1-30 parts by mass, preferably 0.5-20 parts by mass, and more preferably 1 to 100 parts by mass of the component (A). 15 parts by mass. When it is less than 0.1 part by mass, the stability of the emulsion is likely to become unstable, and when it is more than 30 parts by mass, the (A) component may not be able to efficiently increase the degree of polymerization during the polymerization process.

Compared with component (B-2), component (B-1) has higher hydrophobicity, so the contact frequency with the polyorganosiloxane of component (A) is higher, and the effect of accelerating the polymerization rate can be expected. On the one hand, sometimes the hydrophobicity is too high and the emulsification ability is poor. Therefore, when only (B-1) is used, depending on the composition of the emulsion, or conditions such as particle size, viscosity, and pH, the stability of the emulsion may deteriorate over time. Therefore, compared with the component (B-1), the combination of the component (B-2) with higher emulsification ability can improve the stability of the emulsion while increasing the polymerization rate.

In addition, in the cationic emulsion composition of the polyorganosiloxane of the present invention, by using a cationic surfactant and a nonionic surfactant in combination, the emulsion can be easily reduced in particle size, thereby emulsifying The stability of the liquid is improved. Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl Ester, polyethylene glycol, polypropylene glycol, diethylene glycol, etc.; it can be used alone or by appropriately selecting two or more kinds. Among them, a nonionic surfactant represented by the following general formula (2) is preferred: R ⁴ O(EO) _P (PO) _q H (2) In formula (2), R ⁴ is 8 carbon atoms ～30 linear or branched alkyl, EO stands for oxyethylene group, PO stands for oxypropylene group, the arrangement of these groups can be block or random. p and q are independently integers from 0 to 100, and p+q>0. In particular, in the above general formula (2), R ^{4 is} preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and p and q are preferably independently 0-25 and 0<p+q≦50 .

In addition, for the purpose of supplementing the stability of the emulsion, there is no problem in adding the following surfactants: quaternary ammonium salts other than the components (B-1) and (B-2), alkyl amine acetates, etc. Cationic surfactants; amphoteric surfactants such as alkyl betaine and alkyl imidazoline.

[(C) Ingredient] With respect to 100 parts by mass of (A) component, the emulsion composition of the present invention blends 30 to 3000 parts by mass of water as the (C) component, preferably 40 to 2400 parts by mass. If there is too little water, it cannot become a water-in-oil emulsion, and if it is too much, it is uneconomical.

[Manufacturing method of emulsion composition] Next, the manufacturing method of the emulsion composition of the present invention is as follows. That is, in the presence of an alkali catalyst, the emulsion is polymerized at 0-30°C for 1 to 150 hours, and further neutralized. The emulsion is obtained by emulsifying and dispersing the following components: 100 parts by mass (D) Polydiorganosiloxane with both terminal hydroxyl groups, which is represented by the general formula HO-[R ¹ ₂ SiO] _j -H (here, R ^{1 is} independently a hydrogen atom or a monovalent organic group with 1 to 20 carbons Group, j is the viscosity of the polydiorganosiloxane with both terminal hydroxyl groups at 25°C satisfies the value of less than 2000mPa･s); 0-20 parts by mass of (E) any one or two or more of the following Si(OR ³ ) ₄ , R ¹ Si(OR ³ ) ₃ , R ¹ ₂ Si(OR ³ ) ₂ , R ¹ ₃ Si(OR ³ ), where R ^{1 is} mutually Independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons; R ³ independently of each other is a hydrogen atom or a monovalent organic group having 1 to 20 carbons; 0.1 to 30 parts by mass of (B- 1) Cationic surfactant Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ , where Q ¹ is the same or different type of monovalent organic group with 6 to 30 carbon atoms, and X is a halogen atom or carbon number 1 to 6 monovalent carboxyl groups; 0.1 to 30 parts by mass of (B-2) cationic surfactant Q ² (CH ₃ ) ₃ N ^＋ ･X ^－ , where Q ² is one with 17 to 30 carbon atoms A valent organic group, X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbons; 30 to 3000 parts by mass of (C) water.

[Component (D)] First, component (D) is a polydiorganosiloxane with two terminal hydroxyl groups represented ^{by the general formula HO-[R 1} ₂ SiO] _j ^{-H (here, R 1 is} independently hydrogen Atom, or a monovalent organic group with 1 to 20 carbon atoms, j is the viscosity of the polydiorganosiloxane with both terminal hydroxyl groups at 25°C satisfies the value of less than 2000mPa･s), it is used as component (A), that is The raw material of polyorganosiloxane.

J in the above general formula can typically take a value of 1 to 400.

As a specific example of (D) component, the following average composition formula can be mentioned, but it is not limited to these average composition formula. The j, k+1, and k+1+m in the following average composition formula are values that satisfy the viscosity of the polydiorganosiloxane with both terminal hydroxyl groups at 25°C to be less than 2000 mPa･s. In addition, j, k+1, and k+1+m in the following general formulas can typically take values from 1 to 400.

[Component (E)] The organoalkoxysiloxane as the component (E) is a raw material for the polyorganosiloxane as the component (A), and is any one or two or more of the following general formulas The organic alkoxy siloxane. Si(OR ³ ) ₄ , R ¹ Si(OR ³ ) ₃ , R ¹ ₂ Si(OR ³ ) ₂ , R ¹ ₃ Si(OR ³ ), where R ^{1 is} independently a hydrogen atom or carbon number A monovalent organic group of 1-20. Examples of monovalent organic groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Alkyl groups such as tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, aryl group such as phenyl group, tolyl group, naphthyl group, vinyl group, allyl group, etc. Alkenyl; or, replace part of the structure of these organic groups with halogen atoms, or amine groups, acryloxy groups, methacryloxy groups, epoxy groups, mercapto groups and other organic groups containing polar groups Groups derived from hydrogen atoms, etc. Here, industrially and characteristically, it is more desirable that 80% or more of ^{R 1 is a methyl group.} In addition, R ^{3 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons. The monovalent organic group having 1 to 20 carbon atoms in ^{R 3 is the same as the above-mentioned R 1} , preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group.

The amount of the (E) component used is 0 to 20 parts by mass, preferably 0 to 15 parts by mass relative to 100 parts by mass of the (D) component, that is, polydiorganosiloxane with both terminal hydroxyl groups. If the blending amount of the component (E) is too large, the film may become brittle and the durability may decrease.

As specific examples of component (E), methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, benzene Triethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , 2-(3,4-Epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, 3-glycidoxy propyl trimethoxy silane Silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxysilane Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane Oxypropyl triethoxysilane, 3-propenyloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane -N-(1,3-Dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. ; But not limited to these examples.

[(B-1) component, (B-2) component, (C) component] The (B-1) component, (B-2) component, and (C) component used in the manufacturing method of the emulsion composition of the present invention are the same as described above.

Use an emulsifier such as a homomixer, homogenizer, colloid mill, homodisperser, and in-tube mixer to combine these (D) components, which are the two-terminal hydroxyl polydiorganosilicon Oxyane, (E) component is organic alkoxy siloxane, the above (B-1) component and (B-2) component are cationic surfactants, and (C) component is water to make uniform After the emulsified liquid, add alkali catalyst, and carry out polymerization at 0～30℃ for 1～150 hours.

Here, as the alkali catalyst, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium fluoride, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylphosphonium hydroxide, trifluoromethylphenyltrimethylammonium hydroxide, etc. Among them, sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and tetrabutylphosphonium hydroxide are preferred.

The amount of the alkali catalyst used is preferably 0.01 to 5 parts by mass, and more preferably 0.03 to 5 parts by mass relative to 100 parts by mass of the (D) component, that is, the organosiloxane at both ends of hydroxy groups.

Furthermore, if ion exchange resins are used to make (B-1) and (B-2) components, that is, cationic surfactants, into quaternary ammonium hydroxide, the quaternary ammonium hydroxide itself can be used as an alkali catalyst The ingredients play a role, so there is no need to add an alkali catalyst. In this way, when the (B-1) component or the (B-2) component itself functions as an alkali catalyst component, it is equivalent to the presence of the alkali catalyst in the method for producing the emulsion composition of the present invention Next, the emulsion obtained by emulsifying and dispersing the above-mentioned (D), (E), (B-1), (B-2) and (C) components is polymerized.

In addition, the polymerization temperature is 0 to 30°C. When it is lower than 0°C, the polymerization progresses slowly and is not practical, and when it is higher than 30°C, the stability of the emulsion becomes unstable. Preferably it is 5-25 degreeC. In addition, the polymerization time is 1 to 150 hours. When it is less than 1 hour, the polymerization is insufficient, and when it is longer than 150 hours, it becomes non-industrial. The polymerization time is preferably 5 to 120 hours.

After a predetermined polymerization time, the polymerization reaction can be stopped by performing neutralization. The neutralization here can be performed with acidic compounds. Examples of acidic compounds include hydrochloric acid, formic acid, acetic acid, propionic acid, etc.; hydrochloric acid, formic acid, and acetic acid are preferred. Furthermore, instead of using acidic compounds, ion exchange resins can be used for neutralization.

The cationic emulsion composition of the high degree of polymerization organosiloxane of the present invention obtained by the above method can be suitably used as a fiber treatment agent, mold release agent, water repellent, cosmetic raw material, etc., by treating various fibers , Leather, paper, hair, etc., can impart excellent softness, slippery, water repellency, volume feel, etc. Furthermore, examples of fibers include natural fibers such as cotton, hemp, silk, and wool; polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene, vinylon, polyvinyl chloride, and elastic fiber. (spandex) and other synthetic fibers; semi-synthetic fibers such as acetate; but not limited to these fibers.

In the cationic emulsion composition of the high degree of polymerization organosiloxane of the present invention, various tackifiers, pigments, dyes, penetrants, antistatic agents, defoamers, flame retardants, and antibacterial agents can be appropriately blended , Preservative, water repellent, crosslinking agent, adhesion enhancer, or other silicone oil, silicone resin, silicon dioxide, acrylic resin, polyurethane resin, etc.

The cationic emulsion composition of the high degree of polymerization organosiloxane of the present invention can form a film after drying, and can be used by treating the surface of various substrates such as fiber, paper, metal, wood, rubber, plastic, and glass. As a method of coating the substrate, various conventionally known coating methods such as dipping, spraying, roll coating, bar coating, and brush coating can be used. [Example]

Hereinafter, examples and comparative examples are shown to specifically explain the present invention, but the present invention is not limited to the following examples. Furthermore, in the following examples, "%" means "mass%".

[Example 1] A homomixer and a disperser were used to make 300 g of polydimethylsiloxane (component (D)) represented _{by the general formula HO-[(CH 3} ) ₂ SiO] _{n -H at both ends} Where n is about 310, the viscosity at 25°C is 1500mPa･s), 4.3g triethoxyphenylsilane ((E) component), 24.0g trioctylmethylammonium chloride ((B-1) Ingredients) The active ingredient is a 75% isopropyl alcohol (IPA) solution (trade name TOMAC-75: manufactured by Lion King Special Chemical Co., Ltd.), 18.0 g of behenyl trioctyl ammonium chloride ((B-2) Ingredients) 80% ethanol product (trade name LIPOQUAD 22-80: manufactured by Lion King Special Chemical Co., Ltd.) and 239.3 g of ion exchange water ((C) ingredient) are uniformly emulsified and dispersed to obtain an emulsion. Add 6.6 g of 30% ammonia solution (alkali catalyst) to this emulsion. Then, the liquid temperature was lowered to 15°C, and polymerization was carried out for 24 hours, and then neutralized with 7.8 g of acetic acid, whereby an emulsion A was obtained.

[Example 2] Except that the ion-exchange water of Example 1 was changed to 215.3 g, and 24.0 g of polyoxyethylene alkyl ether, EMULGEN 109P (manufactured by Kao Corporation), was added as a non-ionic emulsifier, the same as Example 1 Proceed to obtain emulsion B.

[Example 3] Except that the IPA solution (TOMAC-75: manufactured by Lion Special Chemical Co., Ltd.) in which the active ingredient of trioctylmethylammonium chloride of Example 2 is 75% was changed to 3.0 g, and the ion exchange water was changed to 236.3 g, This was carried out in the same manner as in Example 2, and an emulsion C was obtained.

[Example 4] Except that the IPA solution (TOMAC-75: manufactured by Lion Special Chemical Co., Ltd.) in which the active ingredient of trioctylmethylammonium chloride of Example 2 is 75% was changed to 12.0 g, and the ion exchange water was changed to 227.3 g, In the same manner as in Example 2, an emulsion D was obtained.

[Example 5] Except that the polymerization conditions in Example 4 were set to 15°C for 48 hours to perform polymerization, the same procedure was performed as in Example 4, and an emulsion E was obtained.

[Example 6] Except changing the ion-exchanged water of Example 4 to 231.6 g, and adding 2.3 g of 85% KOH instead of the 30% ammonia aqueous solution, the same procedure as in Example 4 was carried out to obtain an emulsion F.

[Comparative Example 1] In addition to changing the triethoxy phenyl silane of Example 1 to 1.1 g, changing the ion exchange water to 258.7 g, and further changing the active ingredient of trioctyl methyl ammonium chloride to 75% IPA solution (TOMAC-75 (LIPOQUAD 22-80: manufactured by Lion Special Chemical Company) and ethanol product (LIPOQUAD 22-80: manufactured by Lion Special Chemical Company) whose active ingredient is 80% behenyl trioctyl ammonium chloride was changed to 25.8 g of hexadecyl chloride Except that the active ingredient of the alkyltrimethylammonium is a 30% aqueous solution (QUARTAMIN 60W: manufactured by Kao Corporation), the same procedure as in Example 1 was carried out to obtain an emulsion G.

[Comparative Example 2] Except that the polymerization conditions in Comparative Example 1 were set to 15°C for 96 hours to perform polymerization, the same procedure as in Comparative Example 1 was carried out, and an emulsion H was obtained.

[Comparative Example 3] Except changing the triethoxyphenylsilane of Comparative Example 1 to 4.3 g and changing the ion-exchange water to 255.5 g, the same procedure as in Comparative Example 1 was carried out to obtain an emulsion I.

[Comparative Example 4] Except that the 30% aqueous solution (QUARTAMIN 60W: manufactured by Kao Corporation) in which the effective ingredient of cetyltrimethylammonium chloride in Comparative Example 3 was changed to 24.0g of trioctylmethylammonium chloride, the effective ingredient was 75%. Except for changing the ion-exchange water to 257.3 g of the IPA solution (TOMAC-75: manufactured by Lion Special Chemical Co., Ltd.), the same procedure as in Comparative Example 3 was carried out to obtain Emulsion J.

[Comparative Example 5] Except for adding 25.8g of cetyltrimethylammonium chloride 30% aqueous solution (QUARTAMIN 60W: manufactured by Kao Corporation) in Comparative Example 4, and changing the ion-exchange water to 231.5g, the same as the Comparative Example 4 The production was carried out in the same manner, but the emulsion K could not be produced with this composition, so physical properties and characteristics were not evaluated.

[Comparative Example 6] Use a homomixer and a disperser to make 300 g of linear dimethyl polysiloxane with a viscosity of 800,000 mPa･s at 25°C, and 21.6 g of cetyltrimethylammonium chloride as a 30% aqueous solution ( QUARTAMIN 60W: manufactured by Kao Corporation) and 235.2 g of ion-exchanged water were uniformly emulsified and dispersed to obtain an emulsion L.

The physical properties and characteristics of the emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were measured according to the following evaluation methods, and the results are shown in Tables 1 and 2.

(Viscosity of the polysiloxane extracted) Add 300g of emulsion A to L while stirring in 2L of IPA to break the emulsion to extract polydiorganosiloxane. After drying the polydiorganosiloxane at 105°C for 3 hours, it is heated at 25°C. BH type rotary viscometer measures the viscosity. In addition, if the viscosity can be measured in a liquid state, it is directly measured, and if the viscosity is too high to be measured, the 10% toluene solubility viscosity is measured. If the viscosity is too high to be measured, the viscosity is all 300,000mPa･s or more.

(With or without film formation) After distributing 20 g of emulsions A to L into polypropylene (PP) trays and drying them at 25°C for 48 hours, they were further dried at 105°C for 1 hour, and whether or not a film was formed was evaluated. ○: Film formation ×: No film is formed (remains liquid)

(Storage stability) After standing at 25°C for 1 month, the appearance was evaluated visually. ○: No separation △: Slightly separated ×: completely separated

(Texture of processing cloth) The emulsions A to L were diluted with ion-exchanged water so that the concentration of polyorganosiloxane became 1% to prepare a treatment solution. After immersing the polyester/cotton broadcloth (T/C broadcloth) in the treatment liquid for 10 seconds, the liquid was squeezed using a roller under the condition that the squeezing rate was 100%, and it was dried at 150°C for 2 minutes. Then, the handle of the treated cloth was evaluated, and the softness and smoothness were compared with that of the untreated cloth. ○: Good ×: Untreated cloth grade

(Washing durability of the processing cloth) The emulsions A to L were diluted with ion-exchanged water so that the concentration of polyorganosiloxane became 1% to prepare a treatment solution. After immersing the polyester/cotton muslin cloth in the treatment liquid for 10 seconds, the liquid was squeezed using a roller under the condition that the squeezing rate was 100%, and it was dried at 150° C. for 2 minutes. Then, the treated cloth was cut into half, and one of the treated cloths was washed once with a washing machine according to a method based on JIS LO217 103, and then dried at room temperature for 1 day. A fluorescent X-ray analyzer (manufactured by Rigaku Corporation) was used to measure the residual amount of silicone on the fiber surface of the treated cloth before and after washing, and calculate the residual rate (%) after washing.

[Table 1]

[Table 2]

As shown in Tables 1 and 2, the cationic emulsion composition of the high degree of polymerization polyorganosiloxane of the present invention can be polymerized in a relatively short time even if it has a high viscosity, and has the ability to form a film. The durability during the treatment is excellent, and the texture of the treated cloth is also good. Furthermore, the cationic emulsion composition of the polyorganosiloxane with a high degree of polymerization of the present invention is also excellent in storage stability. In contrast, the cationic emulsion composition obtained with the composition of the comparative example has high stability, but does not have the ability to form a film, and the durability during fiber treatment is poor, or although it has the ability to form a film, The stability of the emulsion is low and it separates quickly. [Industrial availability]

By using the cationic emulsion composition of the polyorganosiloxane with a high degree of polymerization of the present invention as a fiber treatment agent, it can impart good flexibility to the fiber and is also excellent in durability. Therefore, it can maintain good performance after washing treatment. Softness. Furthermore, when the cationic emulsion composition of the high degree of polymerization polyorganosiloxane of the present invention is treated and dried, the formed film has high durability and therefore has excellent versatility. In addition to the fiber treatment agent, it can also It is widely used in mold release agents, water repellents, cosmetic materials, and hair cosmetic materials.

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Claims (10)

A cationic emulsion composition of polyorganosiloxane, characterized in that it contains the following components: 100 parts by mass of (A) polyorganosiloxane, which is represented by the following average composition formula (1) and 25 The viscosity at ℃ is more than 300000mPa･s,

In formula (1), R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons, and R ^{2 is} independently a group selected from the above-mentioned ^{options for R 1} , a hydroxyl group, or a carbon Alkoxy groups with a number of 1-20, a, b, c, d are the viscosity of the polyorganosiloxane at 25°C satisfying a value of 300,000 mPa･s or more, and a≧2, c+d≧1; 0.1-30 mass Parts of (B-1) cationic surfactant Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ , where Q ¹ is the same or different kind of monovalent organic group with 6 to 30 carbon atoms, and X is A halogen atom or a monovalent carboxyl group having 1 to 6 carbons; 0.1-30 parts by mass of (B-2) cationic surfactant Q ² (CH ₃ ) ₃ N ⁺ ･X ^－ , where Q ² is the number of carbons A monovalent organic group of 17-30, X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbons; 30-3000 parts by mass of (C) water. The cationic polyorganosiloxane emulsion composition of claim 1, which further contains a nonionic surfactant. The cationic polyorganosiloxane emulsion composition of claim 1, wherein a film is formed after drying. The cationic polyorganosiloxane emulsion composition of claim 2, wherein a film is formed after drying. A fiber treatment agent characterized by comprising a cationic emulsion composition of polyorganosiloxane according to any one of claims 1 to 4. A release agent characterized by comprising the cationic emulsion composition of polyorganosiloxane according to any one of claims 1 to 4. A water-repellent agent characterized by comprising the cationic emulsion composition of polyorganosiloxane according to any one of claims 1 to 4. A cosmetic material characterized by comprising a cationic emulsion composition of polyorganosiloxane according to any one of claims 1 to 4. A cosmetic material for hair, characterized by comprising the cationic emulsion composition of polyorganosiloxane according to any one of claims 1 to 4. A method for producing a cationic emulsion composition of polyorganosiloxane, which is characterized in that, in the presence of an alkali catalyst, the emulsion is polymerized at 0-30°C for 1 to 150 hours, and further neutralization is performed. The liquid is obtained by emulsifying and dispersing the following components: 100 parts by mass of (D) polydiorganosiloxane with two terminal hydroxyl groups, which is represented by the general formula HO-[R ¹ ₂ SiO] _j -H, where R ¹ Independently of each other are hydrogen atoms, or monovalent organic groups with 1-20 carbons, j is the viscosity of the two-terminal hydroxyl polydiorganosiloxane at 25°C satisfies the value of less than 2000mPa･s; 0-20 mass Parts of (E) any one or two or more organoalkoxysiloxanes shown below, Si(OR ³ ) ₄ , R ¹ Si(OR ³ ) ₃ , R ¹ ₂ Si(OR ³ ) _2. R ¹ ₃ Si(OR ³ ), where R ^{1 is} independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons, and R ^{3 is} independently a hydrogen atom, or a carbon number of 1 to A monovalent organic group of 20; 0.1-30 parts by mass of (B-1) cationic surfactant Q ¹ ₃ (CH ₃ )N ^＋ ･X ^－ , where Q ¹ is the same or different carbon number A monovalent organic group of 6-30, X is a halogen atom or a monovalent carboxyl group with 1 to 6 carbons; 0.1-30 parts by mass of (B-2) cationic surfactant Q ² (CH ₃ ) ₃ N ⁺ ･X ^- , where Q ² is a monovalent organic group having 17 to 30 carbons, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbons; 30 to 3000 parts by mass of (C) water.