阅读说明：本技术 有机聚硅氧烷乳液组合物 (Organopolysiloxane emulsion composition ) 是由 多和田华子 小林亮広 井口良范 于 2019-07-18 设计创作，主要内容包括：本发明是鉴于所述情况而成,目的在于提供一种有机聚硅氧烷中所含的八甲基环四硅氧烷少、粒径小且经时稳定性良好的具有高粘度的有机聚硅氧烷乳液组合物。一种乳液组合物,包括：(A)下述(A-1)成分中的氢化硅烷基与下述(A-2)成分中的烯基进行加成反应而成的有机聚硅氧烷,(A-1)为在分子链两末端具有氢化硅烷基且在分子链末端不具有氢化硅烷基以外的官能基的直链状有机聚硅氧烷、或所述含有氢化硅烷基的直链状有机聚硅氧烷与在分子链末端具有至少一个氢化硅烷基以外的官能基(可任意地在分子链末端具有氢化硅烷基)的直链状有机聚硅氧烷的混合物,氢化硅烷基以外的官能基所键结的末端硅原子的个数相对于(A-1)成分中的全部有机聚硅氧烷所具有的末端硅原子的合计个数的比例未满5％,(A-2)为在分子链两末端具有烯基硅烷基且在分子链末端不具有烯基硅烷基以外的官能基的直链状有机聚硅氧烷、或所述含有烯基硅烷基的直链状有机聚硅氧烷与在分子链末端具有至少一个烯基硅烷基以外的官能基(可任意地在分子链末端具有烯基硅烷基)的直链状有机聚硅氧烷的混合物,烯基硅烷基以外的官能基所键结的末端硅原子的个数相对于(A-2)成分中的全部有机聚硅氧烷所具有的末端硅原子的合计个数的比例未满5％,所述直链状有机聚硅氧烷,(A-2)成分中的烯基硅烷基的个数相对于(A-1)成分中的氢化硅烷基的个数的比：0.5～2；(B)表面活性剂：相对于所述(A)成分100质量份而为0.1质量份～12质量份；以及(C)水：相对于所述(A)成分100质量份而为10质量份～200质量份。(The present invention has been made in view of the above circumstances, and an object thereof is to provide an organopolysiloxane emulsion composition having a high viscosity, which contains a small amount of octamethylcyclotetrasiloxane and has a small particle size and good stability over time. An emulsion composition comprising: (A) an organopolysiloxane obtained by addition reaction of a hydrosilyl group in component (A-1) with an alkenyl group in component (A-2), wherein component (A-1) is a linear organopolysiloxane having hydrosilyl groups at both ends of the molecular chain and having no functional group other than a hydrosilyl group at the end of the molecular chain, or a mixture of the above-mentioned hydrosilyl group-containing linear organopolysiloxane and a linear organopolysiloxane having at least one functional group other than a hydrosilyl group (optionally having a hydrosilyl group at the end of the molecular chain), the ratio of the number of terminal silicon atoms to which functional groups other than a hydrosilyl group are bonded to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-1) is less than 5%, and component (A-2) is an organopolysiloxane having alkenyl groups at both ends of the molecular chain and having no alkenylsilyl group at the end of the molecular chain A linear organopolysiloxane containing a functional group other than the above-mentioned functional groups, or a mixture of the above-mentioned linear organopolysiloxane containing an alkenylsilyl group and a linear organopolysiloxane having at least one functional group other than an alkenylsilyl group (optionally having an alkenylsilyl group at a molecular chain terminal), wherein the ratio of the number of terminal silicon atoms to which the functional group other than the alkenylsilyl group is bonded to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-2) is less than 5%, the ratio of the number of alkenylsilyl groups in component (A-2) to the number of hydrosilyl groups in component (A-1): 0.5 to 2; (B) surfactant (b): 0.1 to 12 parts by mass per 100 parts by mass of the component (A); and (C) water: 10 to 200 parts by mass per 100 parts by mass of the component (A).)

1. An emulsion composition comprising:

(A) an organopolysiloxane obtained by addition reaction of a hydrosilyl group in the following component (A-1) with an alkenyl group in the following component (A-2)

(A-1) is a linear organopolysiloxane having hydrosilyl groups at both molecular chain terminals and having no functional groups other than hydrosilyl groups at molecular chain terminals, or a mixture of the above-mentioned linear organopolysiloxane containing hydrosilyl groups and a linear organopolysiloxane having at least one functional group other than hydrosilyl groups (optionally having hydrosilyl groups at molecular chain terminals) at molecular chain terminals, and the ratio of the number of terminal silicon atoms to which the functional groups other than hydrosilyl groups are bonded to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-1) is less than 5%

(A-2) is a linear organopolysiloxane having alkenylsilyl groups at both molecular chain terminals and having no functional groups other than alkenylsilyl groups at molecular chain terminals, or a mixture of the linear organopolysiloxane containing alkenylsilyl groups and a linear organopolysiloxane having at least one functional group other than alkenylsilyl groups (optionally having alkenylsilyl groups at molecular chain terminals) at molecular chain terminals, wherein the ratio of the number of terminal silicon atoms to which the functional groups other than alkenylsilyl groups are bonded to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-2) is less than 5%, and the ratio of the number of terminal silicon atoms to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-2) is less than 5%

The ratio of the number of alkenylsilyl groups in the component (A-2) to the number of hydrosilyl groups in the component (A-1): 0.5 to 2

(B) Surfactant (b): 0.1 to 12 parts by mass per 100 parts by mass of the component (A); and

(C) water: 10 to 200 parts by mass per 100 parts by mass of the component (A).

2. The emulsion composition according to claim 1, wherein the viscosity at 25 ℃ of the (a) organopolysiloxane is 1,000 ten thousand mPa-s or more.

3. The emulsion composition according to claim 1 or 2, wherein in the emulsion composition, the volume average particle diameter of the dispersed particles is 1,000nm or less.

4. The emulsion composition according to any one of claims 1 to 3, wherein the component (A-1) and/or the component (A-2) comprises octamethylcyclotetrasiloxane in an amount of 1,000ppm by mass or less relative to the total mass of the components (A-1) and (A-2).

Technical Field

The present invention relates to an organopolysiloxane emulsion used in products such as cosmetics, personal care (personal care) compositions, home care (home care) compositions, mold release agents, lubricants, coating agents, and fiber treatment agents.

Background

There is a demand for a high-viscosity organopolysiloxane emulsion used in products such as cosmetics, personal care compositions, household care compositions, release agents, lubricants, coating agents, and fiber treatment agents to be an emulsion having a small particle size and good stability over time. Therefore, various studies have been made on a method for producing a high-viscosity organopolysiloxane emulsion composition.

For example, when a high-viscosity organopolysiloxane is mechanically emulsified, the particle size of the emulsion particles is limited to about several micrometers, and it is difficult to obtain an emulsion having a smaller particle size, and the stability of the obtained emulsion with time is poor. In addition, in patent document 1: japanese patent publication No. Sho 34-2041 and patent document 2: japanese patent publication No. 41-13995 discloses a method of ring-opening polymerization of a cyclic siloxane oligomer in an emulsified state by a strong acid or a strong base. By using these methods, an emulsion having a small particle size can be obtained. The emulsion polymerization of the cyclic siloxane oligomer requires a long polymerization step, and therefore, the production cost is high. In recent years, there has been a demand for a product in which the content of octamethylcyclotetrasiloxane is suppressed, but it is known that octamethylcyclotetrasiloxane is contained in emulsion polymerization of cyclic siloxane.

In addition, in patent document 3: japanese patent No. 5382273 discloses the following method: emulsifying the organopolysiloxane with two ends of molecular chain blocked by silanol, and condensation polymerizing at the low temperature of less than 40 ℃ in the presence of acid catalyst. According to the method, the amount of octamethylcyclotetrasiloxane in the organopolysiloxane can be reduced, but octamethylcyclotetrasiloxane is by-produced during polymerization.

In the emulsion polymerization described in the above patent document, the emulsifier needs to be anionic or cationic in order to proceed the polymerization. Further, in order to obtain a high-viscosity organopolysiloxane, the emulsifier needs to be anionic. However, when the anionic emulsion is mixed with a cationic emulsion or an aqueous solution of a cationic emulsifier, the emulsion is broken, and therefore, the anionic emulsion cannot be used by mixing with these emulsions, and the use is limited. In addition, in cosmetic applications, the anionic emulsifier may cause irritation to the skin and may be avoided intentionally.

In patent document 4: japanese patent No. 3927692 proposes the following method: an organopolysiloxane having hydrosilyl groups at both ends of a molecular chain and an organopolysiloxane having alkenylsilyl groups at both ends of a molecular chain are emulsified and then subjected to addition polymerization. In the addition polymerization, octamethylcyclotetrasiloxane is not by-produced during the polymerization, and polymerization can be carried out even when a nonionic surfactant is used. However, in the method described in patent document 4, the viscosity of the organopolysiloxane may not be increased depending on the type of siloxane used as a raw material or the production lot.

Documents of the prior art

Patent document

Patent document 1: japanese patent publication No. JP 34-2041

Patent document 2: japanese patent Japanese Kokoku publication Sho-41-13995

Patent document 3: japanese patent No. 5382273

Patent document 4: japanese patent No. 3927692

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide an organopolysiloxane emulsion composition having a high viscosity, which contains a small amount of octamethylcyclotetrasiloxane and has a small particle size and good stability over time.

Means for solving the problems

The present inventors have made extensive studies to achieve the above-mentioned object, and as a result, have found that in an addition polymerization type organopolysiloxane composition, all molecules obtained from an organopolysiloxane having hydrosilyl groups only at both molecular chain terminals and an organopolysiloxane having alkenylsilyl groups only at both molecular chain terminals do not have hydrosilyl groups and alkenylsilyl groups at their terminals. Further, it was found that when the raw material compound has a large amount of functional groups other than hydrosilyl groups or alkenylsilyl groups at the molecular chain terminals, the possibility of convergence of addition polymerization becomes high, and the target viscosity cannot be achieved.

That is, the present inventors have found that an organopolysiloxane obtained by using as a raw material an organopolysiloxane having hydrosilyl groups at both ends of a molecular chain, which contains a small amount of functional groups other than hydrosilyl groups at both ends of a molecular chain, and an organopolysiloxane having alkenylsilyl groups at both ends of a molecular chain, which contains a small amount of functional groups other than alkenylsilyl groups at both ends of a molecular chain, is an emulsion composition having a small particle diameter and good stability with time and having a high viscosity, and have completed the present invention.

Accordingly, the present invention provides the following emulsion compositions.

An emulsion composition comprising:

(A) an organopolysiloxane obtained by addition reaction of a hydrosilyl group in the following component (A-1) with an alkenyl group in the following component (A-2);

(B) surfactant (b): 0.1 to 12 parts by mass per 100 parts by mass of the component (A); and

(C) water: 10 to 200 parts by mass per 100 parts by mass of the component (A),

(A-1) is a linear organopolysiloxane having hydrosilyl groups at both molecular chain terminals and having no functional groups other than hydrosilyl groups at molecular chain terminals, or a mixture of the above-mentioned linear organopolysiloxane containing hydrosilyl groups and a linear organopolysiloxane having at least one functional group other than hydrosilyl groups (optionally having a hydrosilyl group at molecular chain terminal) at molecular chain terminals, the ratio of the number of terminal silicon atoms to which the functional groups other than hydrosilyl groups are bonded to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-1) is less than 5%,

(A-2) is a linear organopolysiloxane having alkenylsilyl groups at both molecular chain terminals and having no functional groups other than alkenylsilyl groups at molecular chain terminals, or a mixture of the linear organopolysiloxane containing alkenylsilyl groups and a linear organopolysiloxane having at least one functional group other than alkenylsilyl groups (optionally having alkenylsilyl groups at molecular chain terminals), wherein the ratio of the number of terminal silicon atoms to which the functional groups other than alkenylsilyl groups are bonded to the total number of terminal silicon atoms of all the organopolysiloxanes in component (A-2) is less than 5%,

in the linear organopolysiloxane, the ratio of the number of alkenylsilyl groups in component (A-2) to the number of hydrosilyl groups in component (A-1) is 0.5 to 2.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a high-viscosity organopolysiloxane emulsion composition can be obtained which contains less octamethylcyclotetrasiloxane, has a small particle size, and has good stability over time. The high-viscosity organopolysiloxane emulsion composition is useful as a main component or an additive for products such as cosmetics, personal care compositions, household care compositions, mold release agents, lubricants, coating agents, and fiber treatment agents.

Detailed Description

The present invention will be described in detail below.

< component (A) >

(A) The component (A-1) is an organopolysiloxane obtained by addition reaction of a hydrosilyl group in the component (A-1) and an alkenylsilyl group in the component (A-2), wherein the component (A-1) is a linear organopolysiloxane having hydrosilyl groups at both molecular chain terminals and having no functional groups other than hydrosilyl groups at molecular chain terminals, and the component (A-2) is a linear organopolysiloxane having alkenylsilyl groups at both molecular chain terminals and having no functional groups other than alkenylsilyl groups at molecular chain terminals.

The component (A-1) in the present invention is a linear organopolysiloxane having hydrosilyl groups at both molecular chain terminals and having no functional groups other than hydrosilyl groups at molecular chain terminals, or a mixture of the above-mentioned hydrosilyl group-containing organopolysiloxane and a linear organopolysiloxane having at least one functional group other than hydrosilyl groups at molecular chain terminals. In the production of an organopolysiloxane having no functional group other than a hydrosilyl group at both ends of the molecular chain, it is difficult to produce an organopolysiloxane having a functional group other than a hydrosilyl group at the ends so that the functional groups do not exist in a mixed state. In the present invention, the proportion of the functional group-containing organopolysiloxane is less than 5%, preferably less than 2%, in terms of the proportion of the number of terminal silicon atoms of the functional group relative to the total number of terminal silicon atoms of all organopolysiloxanes in component (a-1). When the content of the functional group other than the hydrosilyl group is 5% or more, the probability of convergence of addition polymerization becomes high, and the component (a) may not reach the target viscosity.

Examples of functional groups other than the hydrosilyl group include: hydroxyl, and alkoxy such as methoxy or ethoxy. For example, an organopolysiloxane produced by polymerization of tetramethyldisiloxane and octamethylcyclotetrasiloxane contains functional groups such as hydroxyl groups at some of its terminals due to the influence of moisture contained in the raw materials and the polymerization catalyst. In addition, when the catalyst contains methanol or ethanol, a compound having a methoxy group or an ethoxy group may be by-produced. As a method for reducing the proportion of such a compound having a functional group other than a hydrosilyl group at the terminal, it is effective to reduce impurities such as moisture at the time of production of a raw material or to use a raw material having a small molecular weight.

The linear organopolysiloxane having hydrosilyl groups at both molecular chain terminals and having no functional groups other than hydrosilyl groups at molecular chain terminals preferably has hydrosilyl groups only at both molecular chain terminals. For example, the compound is represented by the following general formula (1). The linear organopolysiloxane may be used singly or in any combination of two or more.

[ solution 1]

In the formula¹Independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms other than the alkenyl group. n is an integer of 0 or more and is a viscosity of the diorganopolysiloxane of 0.1mm at 25 DEG²More than s and less than 100,000mm²The number of/s. n is preferably 1mm in viscosity at 25 DEG C²More than or equal to s and less than 10,000mm²The number in terms of/s is preferably, and the viscosity is more preferablyIs 1mm²More than or equal to s and less than 1,000mm²The number of units per second, more preferably the viscosity, is 10mm²More than s and less than 500mm²Number in/s.

As R¹Examples thereof include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, and triacontyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and the like; and hydrocarbon groups obtained by substituting a part or all of hydrogen atoms bonded to carbon atoms of these groups with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or other atom and/or a substituent such as a hydroxyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a glycidyloxy group, or a carboxyl group. Among them, industrially, all of R are preferable¹At least 50 mol% of the groups are methyl groups.

For example, at R¹When all of them are methyl groups, they are represented by the following formula (2).

[ solution 2]

n is as described above.

The linear organopolysiloxane having at least one functional group other than a hydrosilyl group at a molecular chain end is, for example, a compound represented by the general formula (1) below, in which at least one of hydrogen atoms bonded to a silicon atom at the end is substituted with a functional group such as a hydroxyl group, a methoxy group, or an ethoxy group. Therefore, there are mentioned a linear organopolysiloxane having a hydrosilyl group only at one end and a functional group other than a hydrosilyl group at the other end, and a linear organopolysiloxane having a functional group other than a hydrosilyl group at both ends and having no hydrosilyl group.

The component (A-2) in the present invention is a linear organopolysiloxane having alkenylsilyl groups at both molecular chain terminals and having no functional groups other than alkenylsilyl groups at the molecular chain terminals, or a mixture of the above-mentioned alkenylsilyl-containing organopolysiloxane and a linear organopolysiloxane having at least one functional group other than alkenylsilyl groups at the molecular chain terminals. In the production of an organopolysiloxane having no functional group other than an alkenyl group at both ends of the molecular chain, it is difficult to produce an organopolysiloxane having a functional group other than an alkenyl group at the ends so as not to be present in a mixture. Therefore, in the present invention, the proportion of the functional group-containing organopolysiloxane is less than 5%, preferably less than 2%, in terms of the proportion of the number of terminal silicon atoms of the functional group relative to the total number of terminal silicon atoms of all organopolysiloxanes in component (a-2). When the content of the functional group other than the alkenyl group is 5% or more, the probability of convergence of addition polymerization becomes high, and the component (a) may not reach the target viscosity.

Examples of the functional group other than the alkenyl group include: hydroxyl, and alkoxy such as methoxy or ethoxy. For example, an organopolysiloxane produced by polymerization of tetramethyldisiloxane and octamethylcyclotetrasiloxane contains functional groups such as alkenyl groups at some of its terminals due to the influence of moisture contained in the raw materials and the polymerization catalyst. In addition, when the catalyst contains methanol or ethanol, a compound having a methoxy group or an ethoxy group may be by-produced. As a method for reducing the proportion of such a compound having a functional group other than an alkenyl group at the terminal, it is effective to reduce impurities such as moisture at the time of production of a raw material, or to use a raw material having a small molecular weight.

The linear organopolysiloxane having alkenylsilyl groups at both molecular chain terminals and having no functional group other than the alkenylsilyl group at the molecular chain terminals is preferably a linear organopolysiloxane having alkenylsilyl groups only at both molecular chain terminals. For example, represented by the following general formula (3). The linear diorganopolysiloxane may be used singly or in any combination of two or more.

[ solution 3]

In the formula²Independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms other than the alkenyl group. m is an integer of 0 or more and is a viscosity of the organopolysiloxane at 25 ℃ of 0.1mm²More than s and less than 100,000mm²S, preferably 1mm²More than or equal to s and less than 10,000mm²An integer of s, more preferably a viscosity of 5mm²More than or equal to s and less than 6,000mm²An integer of s, more preferably a viscosity of 10mm²More than or equal to s and less than 1,000mm²Integer in terms of/s. Further, as R²Examples of the same and the same R¹The same is true.

As R³Examples thereof include: vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, and the like, with vinyl being industrially preferred. For example, at R²All are methyl, R³When all are vinyl groups, a compound represented by the following formula (4-1) wherein R is²All are methyl, R³In the case where both are hexenyl groups, the compound is represented by the following formula (4-2).

[ solution 4]

m is as described above.

The linear organopolysiloxane having at least one functional group other than an alkenyl group at a molecular chain end is, for example, one in which R is positioned at the end in the above general formula (3)³A compound in which at least one of the groups is substituted with a functional group such as a hydroxyl group, a methoxy group, or an ethoxy group. Therefore, there are exemplified a linear organopolysiloxane having an alkenyl group only at one end and a functional group other than an alkenyl group at the other end, and a linear organopolysiloxane having a functional group other than an alkenyl group at both ends and having no alkenyl group.

Mixing the component (A-1) and the component (A-2)The obtained solution has viscosity of less than 100,000mm at 25 deg.C²Preferably, the thickness is 10,000mm²Less than s, more preferably 1,000mm²The ratio of the water to the water is less than s. If the viscosity of the mixed solution exceeds the above upper limit, it may be difficult to reduce the particle size of the emulsion to be obtained.

The mass ratio of the (A-1) hydrosilyl group-containing organopolysiloxane to the (A-2) alkenylsilyl group-containing organopolysiloxane is preferably in the range of 0.5 to 2, more preferably in the range of 0.8 to 1.5, relative to the number of alkenylsilyl groups in the (A-2) component.

The component (A-1) and the component (A-2) may further contain octamethylcyclotetrasiloxane as an impurity, and the content thereof is preferably 1000 mass ppm or less, particularly preferably 500 mass ppm or less, based on the total mass of the component (A-1) and the component (A-2). The lower limit is not particularly limited, and the lower limit is more preferable, and therefore, the lower limit may be 0 mass ppm.

(A) Component (a) is an addition reaction product of the (a-1) hydrosilyl-containing organopolysiloxane and the (a-2) alkenylsilyl-containing organopolysiloxane. In the addition reaction, a known platinum group metal-based catalyst can be used. Examples thereof include: platinum group metal simple substances such as platinum (including platinum black), rhodium, palladium, and the like; h₂PtCl₄·kH₂O、H₂PtCl₆·kH₂O、NaHPtCl₆·kH₂O、KHPtCl₆·kH₂O、Na₂PtCl₆·kH₂O、K₂PtCl₄·kH₂O、PtCl₄·kH₂O、PtCl₂、Na₂HPtCl₄·kH₂Platinum chloride, chloroplatinic acid, and chloroplatinic acid salts such as O (wherein k is an integer of 0 to 6, preferably 0 or 6); alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972); a complex of platinum chloride, chloroplatinic acid and an olefin (see U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662, and U.S. Pat. No. 3,775,452), a complex of chloroplatinic acid and a vinyl group-containing siloxane, a complex of platinum and a vinyl group-containing siloxane; making platinum black, palladium, etcA carrier such as alumina, silica or carbon on which a group metal is supported; a rhodium-olefin complex; tris (triphenylphosphine) rhodium chloride (Wilkinson's catalyst), and the like.

The amount of the platinum group metal-based catalyst may be an effective amount for carrying out the addition reaction. For example, in the catalyst containing platinum, the amount of platinum in the catalyst is about 0.1ppm (by mass) to about 100ppm (by mass), preferably about 0.5ppm to about 50ppm, and more preferably about 1ppm to about 30ppm, in terms of mass, based on the total mass of the component (A-1) and the component (A-2).

< ingredient (B) >

(B) The surfactant functions as a dispersant for the component (a) in the aqueous silicone dispersion. In addition, in the production method in which the component (a-1) and the component (a-2) are emulsified in water using a surfactant and then an addition reaction is performed by adding a platinum group metal catalyst, the additive also functions as an emulsifier in the emulsification of the components (a-1) and (a-2) or a dispersant for the platinum group metal catalyst.

The surfactant may be used singly or in any suitable combination of two or more kinds independently selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.

Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, polyoxyethylene polyoxypropylene-modified organopolysiloxanes, and the like. When two or more kinds are used in combination, a nonionic surfactant containing no polyether, such as sorbitan fatty acid ester and glycerin fatty acid ester, may be used in combination.

As cationic surface active agentsExamples of the agent include: surfactants containing ammonium groups, such as alkyldimethylammonium halides, and surfactants having the formula R⁴R⁵R⁶R⁷N⁺X^-

(in the formula, R⁴、R⁵、R⁶、R⁷Independently selected from the group of alkyl, aryl, alkylalkoxy, arylalkoxy and alkoxy, X is an anion).

Examples of the anionic surfactant include: alkyl sulfate ester salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfate ester salts, sulfuric acid ester salts of fatty acid alkylolamides, alkylbenzenesulfonates, polyoxyethylene alkyl phenyl ether sulfonates, α -olefin sulfonates, α -sulfo fatty acid ester salts, alkylnaphthalenesulfonic acids, alkyldiphenylether disulfonates, alkanesulfonates, N-acyltaurates, dialkylsulfosuccinates, monoalkylsulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acylamino acid salts, monoalkyl phosphate ester salts, dialkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, and the like.

Examples of the amphoteric surfactant include: anionic groups, betaine derivatives, and amphoteric derivatives of secondary and/or tertiary amines comprising combinations of these.

The surfactant to be used is not limited, but a compound containing an amine may inhibit the action of the platinum group metal-based catalyst, and therefore, a nonionic surfactant and an anionic surfactant are preferably used.

The amount of the component (B) is 0.1 to 12 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the component (A). If the amount is less than 0.1 part by mass, the particle size of the raw material for component (A) to be described later becomes large or the raw material cannot be emulsified.

[ (C) ingredient ]

In the present invention, (C) water is a dispersion medium of the component (A). The amount of the component (C) to be blended is 10 to 200 parts by mass, preferably 25 to 150 parts by mass, per 100 parts by mass of the component (A). If the amount is less than 10 parts by mass, the viscosity of the aqueous silicone dispersion increases, making production difficult or handling difficult.

[ other ingredients ]

The emulsion composition of the present invention may contain a water-soluble polymer compound for the purpose of improving the dispersibility of the component (a). The water-soluble polymer compound is not particularly limited, and includes: a nonionic water-soluble polymer compound, an anionic water-soluble polymer compound, a cationic water-soluble polymer compound, and a zwitterionic water-soluble polymer compound.

Examples of the nonionic water-soluble polymer compound include: polymers of vinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, polymers of acrylamide, polymers of vinyl pyrrolidone, copolymers of vinyl pyrrolidone and vinyl acetate, polyethylene glycol, polymers of isopropyl acrylamide, polymers of methyl vinyl ether, starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, xanthan gum, and the like.

Examples of the anionic water-soluble polymer compound include: polymers of sodium acrylate, copolymers of sodium acrylate and sodium maleate, copolymers of sodium acrylate and acrylamide, polymers of sodium styrene sulfonate, copolymers of sodium polyisoprene sulfonate and styrene, polymers of sodium naphthalene sulfonate, carboxymethyl starch, starch phosphate, carboxymethyl cellulose, sodium alginate, gum arabic, carrageenan, sodium chondroitin sulfate, sodium hyaluronate, and the like.

Examples of the cationic water-soluble polymer compound include: polymers of dimethyldiallylammonium chloride, polymers of vinylimidazoline, polymers of methylvinylchloroimidazolium, polymers of ethyltrimethylammonium acrylate, polymers of ethyltrimethylammonium methacrylate, polymers of acrylamidopropyltrimethylammonium chloride, polymers of methacrylamidopropyltrimethylammonium chloride, polymers of epichlorohydrin/dimethylamine, polymers of ethyleneimine, quaternary products of ethyleneimine, polymers of allylamine hydrochloride, polylysine, cationic starch, cationized cellulose, glycosaminoglycan, and derivatives thereof obtained by copolymerizing these with monomers having nonionic or anionic groups.

Examples of the zwitterionic water-soluble polymer compound include: copolymers of ethyltrimethylammonium chloride acrylate with acrylic acid and acrylamide; copolymers of ethyltrimethylammonium methacrylate with acrylic acid and acrylamide; and Hofmann decomposition products of acrylamide polymers.

Antimicrobial preservatives or antimicrobial agents may also be included in the emulsion compositions of the present invention. Examples of the antibacterial preservative include: alkyl parabens, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, and the like; as the antibacterial agent, there may be mentioned: benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl parabens, p-chloro-m-cresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, triclocarban (a), a photosensitizer, phenoxyethanol, and the like.

< manufacturing method >

The emulsion composition of the present invention can be produced by emulsifying the (a-1) hydrosilyl-containing linear organopolysiloxane and the (a-2) alkenylsilyl-containing linear organopolysiloxane in (C) water using (B) a surfactant, and then adding a platinum group metal-based catalyst to the emulsion to perform an addition reaction.

The emulsification may be performed using a general emulsification and dispersion machine. Examples of the emulsifying and dispersing machine include: a high-speed rotary centrifugal radiation type mixer such as a homogenizer (homostirrer), a high-speed rotary shear type mixer such as a homomixer, a high-pressure jet type emulsification disperser such as a pressure type homogenizer (homogenerator), a colloid mill, an ultrasonic emulsifier, or the like.

The platinum group metal-based catalyst may be added after the emulsification step as described above, or may be dissolved in advance in the raw material of component (A) (i.e., a mixed solution of component (A-1) and component (A-2)). When the platinum group metal-based catalyst is added after the emulsification step, the platinum group metal-based catalyst may be dissolved in a solvent and added. In addition, when the dispersibility in water is poor, the platinum group metal-based catalyst may be added in a state of being dissolved in the nonionic surfactant. When the platinum group metal-based catalyst is dissolved in the raw material of the component (a) in advance, the raw material may be cooled to a low temperature of, for example, 5 ℃. The addition reaction can be carried out, for example, at 15 ℃ to 60 ℃. When the reaction is not completed, the reaction may be carried out under heating at less than 100 ℃. The stirring time for the reaction is not particularly limited, and is usually 1 to 24 hours.

< emulsion composition >

The emulsion composition of the present invention contains dispersed therein (A) an organopolysiloxane which is an addition reaction product of (A-1) a linear organopolysiloxane having hydrosilyl groups at both molecular chain terminals and (A-2) a linear organopolysiloxane having alkenylsilyl groups at both molecular chain terminals.

The addition reaction product extends the chain length by forming silalkylene (silalkylene) bonds in addition reaction portions of (A-1) an organopolysiloxane having hydrosilyl groups at both molecular chain terminals and (A-2) an organopolysiloxane having alkenylsilyl groups at both molecular chain terminals. For example, the addition reaction product of the compound represented by the formula (2) as the component (A-1) and the compound represented by the formula (4-1) as the component (A-2) is an organopolysiloxane having a structure represented by the following general formula (5).

[ solution 5]

l, m, and n are each independently an integer of 0 or more.

The viscosity of the organopolysiloxane (A) dispersed in the emulsion composition at 25 ℃ is 1,000 ten thousand mPas or more, preferably 3,000 ten thousand mPas or more. The upper limit is not limited, but is, for example, 500 ten thousand Pa · s or less, preferably 300 ten thousand Pa · s or less.

The volume average particle diameter of the dispersed particles in the emulsion composition is preferably 1,000nm or less, more preferably 700nm or less. The lower limit is not particularly limited, and is about 30nm or more. In the present invention, the volume average particle diameter is a value of the volume average particle diameter measured by a laser diffraction/scattering particle diameter measuring apparatus LA-960 (manufactured by horiba, Ltd.).

The content of octamethylcyclotetrasiloxane contained as an impurity in the component (A) is 1,000ppm or less, and particularly preferably 500ppm or less. The lower limit of the content of octamethylcyclotetrasiloxane is preferably as small as possible, and the most preferably 0 ppm.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

In the following, "parts" means parts by mass. The "amount of terminal impurities" means the ratio of the number of silicon atoms having a functional group (hydroxyl group) other than a hydrosilyl group to the total number of terminal silicon atoms of all organopolysiloxanes in the component (A-1). Or, it means the ratio of the number of silicon atoms having a functional group (hydroxyl group) other than an alkenylsilyl group to the total number of terminal silicon atoms of all organopolysiloxanes in component (A-2). The terminal impurity amount is as follows²⁹Si-Nuclear Magnetic Resonance (NMR) spectrum was calculated.

Specifically, the component (a-1) is calculated from the ratio of the peak area of the terminal Si atoms derived from the functional group (hydroxyl group) other than the hydrosilyl group to the peak area derived from all the terminal Si atoms [ i.e., the peak area of the Si atoms derived from the hydrosilyl group + the peak area of the Si atoms derived from the functional group (hydroxyl group) other than the hydrosilyl group ].

With respect to the component (a-2), it is calculated from the ratio of the peak area derived from the terminal Si atom having a functional group other than an alkenylsilyl group to the peak area derived from all the terminal Si atoms [ i.e., the peak area derived from the Si atom having an alkenylsilyl group + the peak area derived from the Si atom having a functional group other than an alkenylsilyl group ]. The peak area is proportional to the number and mole of Si atoms.

The following examples and comparative examples used the following hydrosilyl-containing organopolysiloxanes.

(1) The component (A-1) used in examples 1 and 2: organopolysiloxane 1 containing hydrosilyl groups

R represented by the following general formula (1)¹An organopolysiloxane containing hydrosilyl groups at both ends of a molecular chain, which is entirely methyl, as a main component, and containing, in an amount of 1.0 mol% of terminal impurities: an organopolysiloxane represented by the following formula (1) in which at least one of hydrogen atoms bonded to silicon atoms located at the molecular chain terminals is substituted with a hydroxyl group.

The viscosity of the organopolysiloxane 1 containing hydrosilyl groups was 16mm²The content of octamethylcyclotetrasiloxane is 200ppm or less, and the hydrogen value is 0.13mol/100 g.

[ solution 6]

(2) Component (A-1) used in example 3: organopolysiloxane 2 containing hydrosilyl groups

R represented by the general formula (1)¹An organopolysiloxane containing hydrosilyl groups at both ends of a molecular chain, which is entirely methyl, as a main component, and containing, in an amount of terminal impurities of 0.8 mol%: an organopolysiloxane represented by the formula (1) in which at least one of hydrogen atoms bonded to silicon atoms located at the ends of a molecular chain is substituted with a hydroxyl group.

The viscosity of the organopolysiloxane 2 containing hydrosilyl groups was 136mm²The octamethylcyclotetrasiloxane content is less than 200ppm, and the hydrogen number is 0.033mol/100 g.

(3) The component (A-1) used in example 4 and comparative example 4: organopolysiloxane 3 containing hydrosilyl groups

R represented by the general formula (1)¹Molecular chains all of methylAn organopolysiloxane containing hydrosilyl groups at both ends as a main component, and containing, in an amount of 1.0 mol% of end impurities: an organopolysiloxane represented by the formula (1) in which at least one of hydrogen atoms bonded to silicon atoms located at the ends of a molecular chain is substituted with a hydroxyl group.

The viscosity of the organopolysiloxane 3 containing hydrosilyl groups was 131mm²The octamethylcyclotetrasiloxane content is less than 200ppm, and the hydrogen number is 0.033mol/100 g.

(4) Component (A-1) used in comparative example 1: organopolysiloxane 4 containing hydrosilyl groups

R represented by the general formula (1)¹An organopolysiloxane containing hydrosilyl groups at both ends of a molecular chain, which is entirely methyl, as a main component, and containing, in an amount of terminal impurities of 9.0 mol%: an organopolysiloxane represented by the formula (1) in which at least one of hydrogen atoms bonded to silicon atoms located at the ends of a molecular chain is substituted with a hydroxyl group.

The viscosity of the hydrosilyl-containing organopolysiloxane 4 was 2,330mm²The octamethylcyclotetrasiloxane content is less than 200ppm, and the hydrogen number is 0.0061mol/100 g.

(5) Component (A-1) used in comparative example 2: organopolysiloxane 5 containing hydrosilyl groups

R represented by the general formula (1)¹An organopolysiloxane containing hydrosilyl groups at both ends of a molecular chain, which is entirely methyl, is a main component, and contains, in an amount of terminal impurities of 6.4 mol%: an organopolysiloxane represented by the formula (1) in which at least one of hydrogen atoms bonded to silicon atoms located at the ends of a molecular chain is substituted with a hydroxyl group.

The viscosity of the organopolysiloxane 5 containing hydrosilyl groups was 5,990mm²The content of octamethylcyclotetrasiloxane is 200ppm or less, and the hydrogen value is 0.0050mol/100 g.

(6) Component (A-1) used in comparative example 3: organopolysiloxane 6 containing hydrosilyl groups

R represented by the general formula (1)¹Organopolysiloxane containing hydrosilyl groups at both ends of an overall methyl molecular chainComponent (b), and contains, in an amount of terminal impurities of 6.4 mol%: an organopolysiloxane represented by the formula (1) in which at least one of hydrogen atoms bonded to silicon atoms located at the ends of a molecular chain is substituted with a hydroxyl group.

The viscosity of the organopolysiloxane 6 containing hydrosilyl groups was 130mm²The octamethylcyclotetrasiloxane content is less than 200ppm, and the hydrogen number is 0.033mol/100 g.

The alkenyl silyl group-containing organopolysiloxanes used in the following examples and comparative examples were as follows.

(1) (A-2) used in examples 1 and 3 and comparative example 1: organopolysiloxane 1 containing alkenyl groups

R represented by the following general formula (3)²All are methyl and R³An organopolysiloxane containing alkenyl silane groups at both ends of a molecular chain, both of which are vinyl groups, as a main component, and containing, in an amount of terminal impurities of 1.4 mol%: r to be located at the molecular chain terminal represented by the formula (3)³At least one of the alkenyl silyl group-containing organopolysiloxanes substituted with a hydroxyl group.

The organopolysiloxane 1 containing alkenyl groups had a viscosity of 9,950mm²The octamethylcyclotetrasiloxane content is 200ppm or less, and the vinyl value is 0.0052mol/100 g.

[ solution 7]

(2) (A-2) used in example 2: alkenyl-containing organopolysiloxane 2

R represented by the general formula (3)²All are methyl and R³An organopolysiloxane containing alkenyl silane groups at both ends of a molecular chain, both of which are vinyl groups, as a main component, and containing, in an amount of terminal impurities of 1.9 mol%: r at the molecular chain end represented by formula (3)³At least one hydroxyl-substituted organosilyl group-containing organopolysiloxane.

The viscosity of the alkenyl group-containing organopolysiloxane 2 was 5,040mm²(s), octamethylcyclotetrasiloxaneThe alkane content is less than 200ppm, and the vinyl value is 0.0064mol/100 g.

(3) (A-2) used in example 4 and comparative example 3: organopolysiloxane 3 containing alkenyl groups

R represented by the general formula (3)²All are methyl and R³An organopolysiloxane containing alkenyl silane groups at both ends of a molecular chain, both of which are vinyl groups, as a main component, and containing, in an amount of terminal impurities of 0.7 mol%: r at the molecular chain end represented by formula (3)³At least one hydroxyl-substituted organosilyl group-containing organopolysiloxane.

The viscosity of the alkenyl-containing organopolysiloxane 3 was 126mm²The octamethylcyclotetrasiloxane content is less than 200ppm, and the vinyl value is 0.035mol/100 g.

(4) (A-2) used in comparative example 2: organopolysiloxane 4 containing alkenyl groups

R represented by the general formula (3)²All are methyl and R³An organopolysiloxane containing alkenyl silane groups at both ends of a molecular chain, both of which are vinyl groups, as a main component, and containing, in an amount of terminal impurities of 2.0 mol%: r at the molecular chain end represented by formula (3)³At least one hydroxyl-substituted organosilyl group-containing organopolysiloxane.

The viscosity of the alkenyl-containing organopolysiloxane 4 was 9,950mm²The octamethylcyclotetrasiloxane content is 200ppm or less, and the vinyl value is 0.0052mol/100 g.

(5) (A-2) used in comparative example 4: alkenyl-containing organopolysiloxane 5

R represented by the general formula (3)²All are methyl and R³An organopolysiloxane containing alkenyl silane groups at both ends of a molecular chain, both of which are vinyl groups, as a main component, and containing, in an amount of terminal impurities of 6.0 mol%: r at the molecular chain end represented by formula (3)³At least one hydroxyl-substituted organosilyl group-containing organopolysiloxane.

The viscosity of the alkenyl-containing organopolysiloxane 5 was 126mm²(s) an octamethylcyclotetrasiloxane content of 200ppmThe vinyl value was 0.030mol/100 g.

[ example 1]

4.1 parts of the silyl group functionalized organopolysiloxane 1 (a-1), 95.9 parts of the silyl group functionalized organopolysiloxane 1 (SiVi group/SiH group is 0.91 (number ratio)), 5.0 parts of polyoxyethylene lauryl ether (EMALGEN 109P, wakame gmbh), and 5.8 parts of water (C) were emulsified with a homomixer and a homodisperser, and then 53.8 parts of water (C) were added to the emulsion, and the emulsion was diluted and dispersed with a homomixer. After the obtained emulsion was adjusted to 50 ± 2 ℃, a mixed dissolved substance of 0.13 parts of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.27 parts of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

[ example 2]

5.0 parts of the (a-1) hydrosilyl-containing organopolysiloxane 1, 95.0 parts of the (a-2) alkenylsilyl-containing organopolysiloxane 2, (B) polyoxyethylene lauryl ether (EMALGEN 109P, wakame gmbh) 5.8 parts, and (C) water 5.8 parts were emulsified with a homomixer and a homodisperser, and then (C) water 52.6 parts was added and diluted and dispersed with a homomixer. After the obtained emulsion was adjusted to 25 ± 2 ℃, a mixed dissolved substance of 0.13 parts of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.27 parts of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

[ example 3]

14.9 parts of the hydrosilyl-containing organopolysiloxane 2 (a-1), 85.1 parts of the alkenylsilyl-containing organopolysiloxane 1 (a-2) (SiVi group/SiH group is 0.91 (number ratio)), 5.0 parts of polyoxyethylene lauryl ether (EMALGEN 109P, wakame gmbh), and 6.7 parts of water were emulsified with a homomixer and a homodisperser, and then 52.6 parts of water (C) was added to the emulsion, and the emulsion was diluted and dispersed with a homomixer. After the obtained emulsion was adjusted to 50 ± 2 ℃, a mixed dissolved substance of 0.13 parts of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.27 parts of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

[ example 4]

53.6 parts of the hydrosilyl-containing organopolysiloxane 3 (a-1), 46.4 parts of the alkenylsilyl-containing organopolysiloxane 3 (a-2) (SiVi group/SiH group is 0.91 (number ratio)), polyoxyethylene stearyl ether (emmex (EMALEX)615, japan Emulsion (Nihon Emulsion) gmbh) 1.3 parts, polyoxyethylene stearyl ether (emmex (EMALEX)640, japan Emulsion gmbh) 3.8 parts, and water 20.9 parts are emulsified by a homomixer, added with (C) water 36.0 parts, diluted and dispersed by a homomixer, and subjected to 1 high-pressure treatment by a high-pressure emulsification apparatus at a treatment pressure of 100 MPa. After the obtained emulsion was adjusted to 25 ± 2 ℃, a mixed dissolved substance of 0.13 parts of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.27 parts of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

Comparative example 1

48.3 parts of the above-mentioned hydrosilyl-containing organopolysiloxane 4 (A-1), 51.7 parts of the above-mentioned alkenylsilyl-containing organopolysiloxane 1 (A-2) (SiVi group/SiH group is 0.91 (number ratio)), 5.8 parts of polyoxyethylene lauryl ether (Emamegi (EMALGEN)109P, Kao corporation) and 7.5 parts of water were emulsified by a homomixer and a homodisperser, and then 50.9 parts of water (C) was added thereto and diluted and dispersed by a homomixer. After the obtained emulsion was adjusted to 50 ± 2 ℃, a mixed dissolved substance of 0.05 part of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.09 part of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

Comparative example 2

53.1 parts of the above-mentioned hydrosilyl-containing organopolysiloxane (a-1), 46.9 parts of the above-mentioned alkenylsilyl-containing organopolysiloxane (a-2) (SiVi group/SiH group is 0.91 (number ratio)), 5.8 parts of polyoxyethylene lauryl ether (EMALGEN 109P, wakame gmbh), and 5.8 parts of water (C) were emulsified by a homomixer and a homodisperser, and then 52.6 parts of water (C) was added thereto and diluted and dispersed by a homomixer. After the obtained emulsion was adjusted to 25 ± 2 ℃, a mixed dissolved substance of 0.3 part of isododecane solution (platinum content 0.5%) of platinum-vinyl group-containing siloxane complex and 0.6 part of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing organopolysiloxane was obtained.

Comparative example 3

After emulsifying 53.8 parts of (a-1) the hydrosilyl-containing organopolysiloxane 6, (46.2 parts of (a-2) the alkenylsilyl-containing organopolysiloxane 3, (B) polyoxyethylene lauryl ether (EMALGEN 104P, queen gmbh) 2.4 parts and polyoxyethylene lauryl ether (emargine 123P, queen gmbh) 3.6 parts, and (C) 32.0 parts of water, by a homomixer, (C) 59.6 parts of water was added, diluted and dispersed by a homomixer, and subjected to 1 high-pressure treatment by a high-pressure emulsification apparatus at a treatment pressure of 100 MPa. After the obtained emulsion was adjusted to 25 ± 2 ℃, a mixed dissolved substance of 0.16 parts of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.32 parts of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

Comparative example 4

After emulsifying 55.0 parts of (a-1) the hydrosilyl-containing organopolysiloxane 3, (a-2) the alkenylsilyl-containing organopolysiloxane 5, (B) polyoxyethylene lauryl ether (EMALGEN 104P, queen limited) 2.4 parts and polyoxyethylene lauryl ether (emargin 123P, queen limited) 3.6 parts, (C) water 32.0 parts by a homomixer, (C) water 59.6 parts was added, diluted and dispersed by the homomixer, and subjected to 1 high-pressure treatment by a high-pressure emulsification apparatus at a treatment pressure of 100 MPa. After the obtained emulsion was adjusted to 25 ± 2 ℃, a mixed dissolved substance of 0.16 parts of an isododecane solution (platinum content 0.5%) of a platinum-vinyl group-containing siloxane complex and 0.32 parts of polyoxyethylene lauryl ether was added under stirring, and stirred at the same temperature for 2 hours, whereby the (a-1) component and the (a-2) component were subjected to addition reaction, and an emulsion composition containing an organopolysiloxane was obtained.

The physical properties of each of the emulsion compositions obtained in the examples and comparative examples were measured or evaluated by the methods shown below. The results are shown in table 1.

[ volume average particle diameter of emulsion ]

The median particle diameter measured by a laser diffraction-scattering particle size distribution measuring apparatus LA-960 (horiba, Ltd.).

[ viscosity of organopolysiloxane ]

To 200g of each emulsion composition, 200g of isopropyl alcohol was added with stirring, and only the precipitated organopolysiloxane was separated and taken out, and dried at 105 ℃ for 3 hours. Thereafter, 10g of the organopolysiloxane was dissolved in 90g of toluene. The viscosity η was calculated from the viscosity η 1 and the specific gravity D of the diluted solution at 25 ℃ measured by a rotational viscometer by the following formula. The following equation is an empirical equation, and it was confirmed that a value obtained by directly measuring the viscosity of raw rubber in the Newton fluid field by a rheometer (rheometer) agrees with a value calculated from the following equation.

η2＝η1×D

η3＝0.5385×1n(η2)+0.1033

η4＝10^E、E＝1.19973×η3+0.974

η＝{462.551n(η4)-3405.2}×10000(η4＜10000)

η＝{1256.21n(η4)-10506}×10000(η4＞10000)

[ Octamethylcyclotetrasiloxane content in organopolysiloxane ]

After 0.1g of each emulsion composition was extracted (shaken for 3 hours) with 10ml of acetone containing 20ppm by mass of tetradecane as an internal standard, the acetone layer was extracted after standing overnight, and octamethylcyclotetrasiloxane was quantified by gas chromatography.

[ stability of emulsion ]

100g of the emulsion composition was placed in a 100ml glass bottle, and after standing at 40 ℃ for one month, the appearance was observed. When the emulsion formed a uniform single phase and no separation was observed, the emulsion was evaluated as "good" in stability, indicated by "o", and when the emulsion was observed to separate into two phases, the emulsion was evaluated as "poor" in stability, indicated by "x".

[ Table 1]

(Note) D₄: octamethylcyclotetrasiloxane

The emulsion composition of the present invention is produced by using a specific organopolysiloxane as a raw material, and can provide an emulsion containing an organopolysiloxane having a small particle diameter and a high viscosity. The emulsion composition has stability over time. As shown in comparative examples 1 to 4, if the raw material organopolysiloxane has a large amount of functional groups other than hydrosilyl groups at the terminal, an emulsion composition containing an organopolysiloxane having a desired high viscosity cannot be obtained.

Industrial applicability

According to the present invention, an emulsion composition containing a high-viscosity organopolysiloxane which contains less octamethylcyclotetrasiloxane as an impurity contained in the organopolysiloxane, has a small particle size, and has good stability over time can be obtained. The high-viscosity organopolysiloxane emulsion composition is useful as a main component or an additive for products such as cosmetics, personal care compositions, household care compositions, mold release agents, lubricants, coating agents, and fiber treatment agents.