JP2003128926A - Organosilicon polymer emulsion and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organosilicon polymer emulsion having excellent storage stability and little load on the environment, and a method for manufacturing the same. SOLUTION: The organosilicon polymer emulsion contains (A) an organosilicon polymer particles obtained by subjecting (a-1) a diorganopolysiloxane having a silicon-bound hydrogen only on both the ends of the molecular chain and (a-2) a diorganopolysiloxane having a silicon-bound alkenyl only on both the ends of the molecular chain to a hydrosililation reaction, and having an average particle size of 0.1-500 μm, (B) an oxyethylene adduct of a 16-20 C long chain alcohol and (C) water as main components. The method for manufacturing the emulsion.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organosilicon polymer emulsion and a method for producing the same, and more particularly to an organosilicon polymer emulsion having excellent storage stability and a method for producing the same.

[0002]

2. Description of the Related Art Organosilicon polymers having a siloxane bond and a silalkylene bond have releasability and water repellency similar to diorganopolysiloxane consisting of only siloxane bonds, and therefore their use in various fields is being investigated. Has been done. Further, since this organosilicon polymer has better acid resistance and alkali resistance than diorganopolysiloxane, it has been studied as an antifoaming agent having alkali resistance (see JP-A-7-60008). .

When such an organosilicon polymer is used, the form of emulsion tends to be preferred recently because it can be treated in an aqueous system and is excellent in safety. As a method for preparing the organosilicon polymer emulsion,
A known method is to emulsify a diorganopolysiloxane having a silicon atom-bonded hydrogen atom only at both ends of a molecular chain and a diorganopolysiloxane having a silicon atom-bonded alkenyl group at both ends of a molecular chain in water to carry out a hydrosilylation reaction. As the emulsifier used, nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants are mentioned (JP-A-11-7).
1459 and Japanese Patent Laid-Open No. 11-246769). Among these, for emulsions used for skin cosmetics, nonionic surfactants are preferred because of their low irritation and good mixability, and usually alkylaryl polyethers such as polyoxyethylene nonylphenyl ether, and Alkyl polyethers having alkyl groups with 15 or less carbon atoms have been used. However,
The organosilicon polymer emulsion emulsified with such a polyether has insufficient storage stability and has a drawback that emulsion separation occurs after a long period of time. Also,
BACKGROUND ART In recent years, alkyl polyethers having an alkyl group having 12 to 15 carbon atoms have been recently used as PRTR (Pollutant Release and Transfer Reagent) as a chemical substance that may have an environmental impact.
gister) emissions have been certified as mandatory chemical substances, and their use tends to be restricted.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive investigations by the present inventors, the use of an oxyethylene adduct of a long chain alcohol having 16 to 20 carbon atoms as an emulsifier for an organosilicon polymer emulsion results in the above problems. The inventors have found that the above can be solved and reached the present invention. That is, an object of the present invention is to provide an organosilicon polymer emulsion having excellent storage stability and a low environmental load, and a method for producing the same.

[0005]

The present invention provides (A) (a-1) a diorganopolysiloxane having a silicon atom-bonded hydrogen atom only at both ends of the molecular chain, and (a-2) only both ends of the molecular chain. An organosilicon polymer particle having an average particle size of 0.1 to 500 μm obtained by hydrosilylating a diorganopolysiloxane having a silicon atom-bonded alkenyl group, (B) a long chain alcohol having 16 to 20 carbon atoms Oxyethylene adduct, (C) Water-based organosilicon polymer emulsion characterized by the main component and its production method, and (D) (a
-1) a diorganopolysiloxane having a silicon atom-bonded hydrogen atom only at both molecular chain ends, and (a-2) a diorganopolysiloxane having a silicon atom-bonded alkenyl group only at both molecular chain ends, (a-3 ) Organosilicon polymer particles having an average particle size of 0.1 to 500 μm obtained by hydrosilylation reaction of a diorganopolysiloxane having a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkenyl group only at one end of the molecular chain, (B) It is an object to provide an organosilicon polymer emulsion characterized by mainly containing an oxyethylene adduct of a long-chain alcohol having 16 to 20 carbon atoms and (C) water, and a method for producing the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The organosilicon polymer, which is the main ingredient of the emulsion of the present invention, comprises (A) (a-1) a diorganopolysiloxane having silicon-bonded hydrogen atoms at both ends of the molecular chain and (a-2) ) Hydrosilylation reaction product with a diorganopolysiloxane having a silicon atom-bonded alkenyl group only at both ends of the molecular chain, or (D) (a-1) Diorgano having a silicon atom-bonded hydrogen atom at both ends of the molecular chain Polysiloxane, (a-2) a diorganopolysiloxane having a silicon atom-bonded alkenyl group at both ends of the molecular chain, and (a-3) a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkenyl group at only one end of the molecular chain. Is a hydrosilylation reaction product with a diorganopolysiloxane having, and is a polymer having a main chain composed of a siloxane bond and a silalkylene bond. In the emulsion of the present invention, the organosilicon polymer is dispersed as particles having an average particle size of 0.1 to 500 μm. The average particle size is preferably 0.1 to 100 μm, more preferably 0.1 to 50 μm, and 0.5 to 50 μm.
μm is particularly preferred. This is because it is difficult to prepare organosilicon polymer particles having an average particle size of less than 0.1 μm, and when the average particle size exceeds 500 μm, the dispersibility of the obtained organosilicon polymer particles in cosmetics, paints, etc. It tends to decrease. Examples of the shape of the particles include a spherical shape, a flat shape, and an indefinite shape, and among these, a spherical shape having good dispersibility in cosmetics and paints is preferable.
The properties of the particles include, for example, hard rubber, soft rubber and gel. The viscosity of the organosilicon polymer is not limited and is usually 10 to 10 at 25 ° C.
It is in the range of 0,000,000 mPa · s, but 10,000 mP
It is preferably an organosilicon polymer having a relatively high viscosity of a · s or more, and more preferably 100,000 mPa · s or more. To measure the viscosity of the organosilicon polymer in the emulsion of the present invention, the organosilicon polymer is removed by removing water from the emulsion of the present invention by means such as air drying, hot air drying, vacuum drying, and heat drying. You can take it out and measure it separately.

(A-1) In the diorganopolysiloxane having silicon atom-bonded hydrogen atoms only at both ends of the molecular chain, the group bonded to a silicon atom other than hydrogen atom is a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; phenyl group, tolyl group, xylyl group And aryl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group.
Preferably, it is a methyl group only, or a methyl group and a phenyl group. The molecular structure is substantially linear, but part of the molecular chain may be branched. The viscosity is not limited, but when emulsified in water, the viscosity at 25 ° C is preferably 100,000 mPa · s or less,
It is more preferably 000 mPa · s or less. Examples of the component (a-1) include a dimethylhydrogensiloxy group-capped dimethylpolysiloxane having molecular chain terminals at both ends, and a part of the methyl group of the dimethylpolysiloxane is an ethyl group, a hexyl group, a phenyl group, 3,3, An example is a diorganopolysiloxane substituted with a 3-trifluoropropyl group.

(A-2) The alkenyl group of the diorganopolysiloxane having a silicon atom-bonded alkenyl group at both ends of the molecular chain includes vinyl group, allyl group, butenyl group,
Examples thereof include a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group. Among these, vinyl group, allyl group and hexenyl group are preferable. Examples of the group other than the alkenyl group which is bonded to a silicon atom include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group; cyclopentyl Group, cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, tolyl group, xylyl group; aralkyl group such as benzyl group, phenethyl group; 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. Examples of the halogenated alkyl group are, and preferably a methyl group alone, or a methyl group and a phenyl group. The molecular structure is substantially linear, but part of the molecular chain may be branched. Although the viscosity is not limited, when it is emulsified in water, the viscosity at 25 ° C is preferably 100,000 mPa · s or less, more preferably 10,000 mPa · s or less. Examples of such component (a-2) include a dimethylpolysiloxane endcapped with dimethylvinylsiloxy groups at both molecular chain ends, and a part of the methyl groups of this dimethylpolysiloxane is an ethyl group, a hexyl group, a phenyl group, 3,3,3 −
Examples thereof include diorganopolysiloxanes substituted with trifluoropropyl groups and the like, and diorganopolysiloxanes in which vinyl groups of these diorganopolysiloxanes are substituted with allyl groups, hexenyl groups and the like.

(A-3) The diorganopolysiloxane having a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkenyl group only at one end of the molecular chain is used for controlling the molecular weight of the organosilicon polymer or for the molecule of the organosilicon polymer. It is a component that forms a branch in the structure. In this diorganopolysiloxane, the alkenyl groups include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group,
Examples thereof include an octenyl group, a nonenyl group and a decenyl group, with a vinyl group and an allyl group being preferred. Further, as a group bonded to a silicon atom other than a hydrogen atom or an alkenyl group, a methyl group, an ethyl group, a propyl group, a butyl group,
Alkyl groups such as pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; cyclopentyl group,
Cycloalkyl group such as cyclohexyl group; phenyl group,
Aryl groups such as tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; 3-chloropropyl group,
Examples thereof include halogenated alkyl groups such as a 3,3,3-trifluoropropyl group, and preferably a methyl group alone or a methyl group and a phenyl group. The molecular structure is substantially linear, but part of the molecular chain may be branched. The viscosity is not limited, but when emulsifying in water,
The viscosity at 25 ° C. is preferably 100,000 mPa · s or less, more preferably 1,000 mPa · s or less. Examples of the component (a-3) include a dimethylpolysiloxane in which one end of the molecular chain is blocked with a dimethylhydrogensiloxy group and the other end of the molecular chain is blocked with a trimethylsiloxy group, and one end of the molecular chain is dimethylvinylsiloxane. Dimethylpolysiloxanes capped with siloxy groups and the other molecular chain ends capped with trimethylsiloxy groups, some of the methyl groups of these dimethylpolysiloxanes being ethyl groups, hexyl groups, phenyl groups, 3,3,3- Diorganopolysiloxane substituted with trifluoropropyl group,
The diorganopolysiloxane in which the vinyl group of these dimethylpolysiloxanes is substituted with an allyl group, a hexenyl group or the like is exemplified.

In the component (A) or the component (D), the amount of the silicon atom-bonded hydrogen atom-containing diorganopolysiloxane with respect to the silicon atom-bonded alkenyl group-containing diorganopolysiloxane is not limited, but the former diorganopolysiloxane 1. The latter diorganopolysiloxane is preferably in the range of 0.5 to 1.5 mol per 0 mol. In particular, it is preferable that the number of moles is about 1.0 because a high molecular weight organosilicon polymer can be prepared.

The hydrosilylation reaction between a silicon atom-bonded hydrogen atom-containing diorganopolysiloxane and a silicon atom-bonded alkenyl group-containing diorganopolysiloxane is usually
(E) A catalyst for hydrosilylation reaction is used. This hydrosilylation reaction catalyst is a catalyst for promoting addition polymerization to prepare an organosilicon polymer having a siloxane bond and a silalkylene bond. Specific examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Platinum-based catalysts are preferable because they can significantly promote addition polymerization. Examples of the platinum-based catalyst include fine particle platinum, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, platinum-carbonyl complex. In particular, platinum-alkenylsiloxane complex is preferable. The alkenyl siloxane includes 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,
3,5,7-Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a part of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and these alkenyls An alkenyl siloxane in which the vinyl group of siloxane is substituted with an allyl group, a hexenyl group, etc. is exemplified. Among these, 1,3-divinyl-1,1,3,3-, because of its good stability as a platinum-alkenylsiloxane complex,
Tetramethyldisiloxane is preferred.

(B) The oxyethylene adduct of a long-chain alcohol having 16 to 20 carbon atoms is a characteristic component of the present invention and acts as an emulsifier. The component (B) not only improves the stability of the emulsion of the present invention, but also improves the dispersibility and stability when blended with other components, and has an advantage that the load on the environment and the human body is small. As the component (B), an oxyethylene adduct of a branched alcohol is preferable, and the formula:

[Chemical 2] (In the formula, R ¹ and R ² are each 2 to 16 carbon atoms.
Is a linear alkyl group. ). The polyether shown by these is mentioned. Specifically, the formula:

[Chemical 3] A polyoxyethylene hexyl decyl ether represented by the formula:

[Chemical 4] Polyoxyethylene isostearyl ether represented by the formula:

[Chemical 5] The polyoxyethylene octyl dodecyl ether represented by is exemplified. Among these, polyoxyethylene hexyl decyl ether is preferable. N in the formula, that is,
The number of moles of ethylene oxide (EO) added is not limited, but is preferably 2 to 40, and more preferably 2 to 30. This is because if the number of carbon atoms and the number of moles of ethylene oxide added deviate from this range, the stability of the emulsion may decrease. The average HLB (Hydrophile-Lipophile Balance) is 1
It is preferably 0 or more. The HLB referred to in the present invention
Means a value calculated by the Griffin formula represented by the following formula.

[Chemical 6] As the component (B), one type of oxyethylene adduct may be used alone, or a mixture of two or more types may be used. For example, the addition mole number of ethylene oxide is 2 to 10 moles, and the addition mole number of ethylene oxide is 1
Mixing 5 to 30 moles of oxyethylene adduct and averaging H
A mixture adjusted so that LB is 10 or more can be mentioned. The blending amount of both is the former oxyethylene adduct 10
The latter oxyethylene adduct 1 to 100 parts by weight
It is preferably part by weight. Such oxyethylene adducts are commercially available and can be easily obtained from the market. For example, product name of Nikko Chemicals Co., Ltd .: NIKKOL BH-2, NIKKOL BH-
5, NIKKOL BH-7, NIKKOL BH-1
0, NIKKOL BH-15, NIKKOL BH-
20, NIKKOL BH-25, NIKKOL BH
-30 or trade name of Nippon Emulsion Co., Ltd .: EM
ALEX 1605, EMALEX 1610, EMA
LEX 1615, EMALEX 1620, EMAL
EX 1625, EMALEX 1805, EMALE
X 1810, EMALEX 1815, EMALEX
1820, EMALEX 1825, EMALEX
OD-5, EMALEX OD-10, EMALEX
OD-16, EMALEX OD-20, EMALEX
There is OD-25.

As the component (B), it is also possible to use an oxyethylene adduct of a long-chain alcohol without branching.
The hydrocarbon group of the long-chain alcohol may be a saturated hydrocarbon group or a hydrocarbon group containing an unsaturated bond. Examples of such oxyethylene adducts of long-chain alcohols without branching include Nikko Chemicals Co., Ltd., trade name: NI
KKOL BS-2, NIKKOL BS-4, NIK
KOL BS-20, NIKKOL BO-2, NIK
KOL BO-7, NIKKOL BO-10, NIK
KOL BO-15, NIKKOL BO-20, NI
KKOL BO-50 is mentioned.

The water (C) is a dispersion medium for the component (A), and for example, pure water or ion-exchanged water can be used.

The blending amount of each of the above-mentioned components is not limited, but the organosilicon polymer particles in the emulsion of the present invention are contained in an amount of 10-9.
The range is preferably 0% by weight, and more preferably 30 to 80% by weight. The ratio of the component (B) is preferably in the range of 0.05 to 10% by weight,
It is more preferably 0.2 to 5% by weight. this is,
This is because if the content of the organosilicon polymer particles is less than 10% by weight, the efficiency of the compounding may decrease, and if it exceeds 90% by weight, the emulsion may have too high a viscosity. If the amount of the component (B) is less than 0.05% by weight, the effect is difficult to be expressed, and 1
This is because if it exceeds 0% by weight, components not involved in emulsification may remain.

The emulsion of the present invention essentially comprises the above (A).
Component or component (D), component (B) and component (C), but other optional components such as ethanol,
Alcohols such as i-propanol, t-butanol, ethylene glycol, propylene glycol and diethylene glycol; water-soluble polymers such as carboxyvinyl polymer and sodium carboxymethylcellulose; preservatives,
It may contain an antifungal agent, a rust preventive agent, an antibacterial agent, an aromatic agent, and a pigment. Further, in order to further improve the compounding stability to other components, anionic surfactants, cationic surfactants, amphoteric surfactants, (B) within the range not impairing the object of the present invention. A nonionic surfactant other than the components may be added and blended. These components may be used alone or in combination. Moreover, the compounding procedure is not particularly limited.

Such an emulsion of the present invention can be prepared by a method of previously synthesizing an organosilicon polymer by a hydrosilylation reaction, and then emulsifying the organosilicon polymer in water with (B) an oxyethylene adduct of a long-chain alcohol. . However, when the organosilicon polymer has a high viscosity, the emulsification process becomes complicated, the particle system increases, and a large amount of a surfactant is required. Therefore, the above diorganopolysiloxane is emulsified in water. A method in which the hydrosilylation reaction is performed after that is preferable. For example, (a-1) a diorganopolysiloxane having silicon atom-bonded hydrogen atoms only at both ends of the molecular chain and (a-2) a diorganopolysiloxane having silicon atom-bonded alkenyl groups at both ends of the molecular chain ) An oxyethylene adduct of a long-chain alcohol, and optionally (a
-3) Mixing a diorganopolysiloxane having a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkenyl group only at one end of the molecular chain with (C) water to give an average particle size of 0.1 to 5
An emulsion having a size of 00 μm was prepared, and then a catalyst for hydrosilylation reaction (E) was added to carry out addition polymerization to obtain an average particle size of 0.1.
A method for preparing an organosilicon polymer emulsion having a thickness of 1 to 500 μm can be mentioned.

As a method for emulsifying the diorganopolysiloxane, a mixture of the above-mentioned component (a-1), the component (a-2) and the component (B) or the above-mentioned component (a-1) and the component (a-2) is used. And a mixture of components (a-3) and (B) with a homomixer, paddle mixer, Henschel mixer, homodisper, colloid mill, propeller stirrer, homogenizer, in-line continuous emulsifier,
Examples thereof include a method of dispersing in water using a known stirring / mixing device such as an ultrasonic emulsifier or a vacuum kneader. Further, at this time, each diorganopolysiloxane may be dispersed in water by the above-mentioned stirring / mixing device to prepare each emulsion, and then these may be mixed. Used
The (E) hydrosilylation reaction catalyst is preferably an emulsion obtained by emulsifying a liquid catalyst containing a platinum-alkenylsiloxane complex as a main component in water. In this emulsion, the volume average particle diameter of the liquid catalyst dispersed in the form of liquid particles, that is, the average particle diameter in the volume particle diameter distribution is preferably 1 μm or less, more preferably 0.8 μm or less. , 0.5 μm or less is more preferable. The addition amount of the catalyst for hydrosilylation reaction is not limited, but since the addition polymerization reaction can be efficiently promoted, the amount by which the weight of platinum metal is 0.1 to 1,000 ppm relative to the total weight of the above diorganopolysiloxane. As long as it is 0.1 to 500 ppm,
An amount of 1 to 50 ppm is more preferable. The addition polymerization proceeds if left standing, but at 100 ° C to accelerate the reaction.
You may heat below. It is particularly preferable to heat to 70 ° C. or lower.

The organosilicon polymer emulsion of the present invention as described above has excellent storage stability and high safety,
It is characterized by less burden on the environment and problems on the human body. In addition, the dispersibility in cosmetics and paints is good, and there is an advantage that the effect of adding the organosilicon polymer to these compounds can be sufficiently exhibited. Further, the organosilicon polymer in the emulsion of the present invention has a low surface tension and is unlikely to cause the molecular chain to be cleaved by ionic substances such as acids and alkalis, and therefore can be used as an acid-resistant or alkali-resistant emulsion. Such an emulsion of the present invention is useful as an additive for paints and cosmetics and as a release agent for organic resin molding, and is particularly suitable as a raw material for cosmetics and a raw material for paints.

The cosmetics to which the emulsion of the present invention is applied include various cosmetics used for hair, skin, mucous membranes and teeth. For example, skin creams, skin care lotions, moisturizers, facial treatments such as acne or wrinkle removal, personal and facial cleansers,
Bath oil, fragrance, perfume, cologne, perfume, sunscreen, preshave and aftershave lotion, shaving soap, hair shampoo, hair conditioner, hair spray, mousse, permanent,
When added to a hair remover or cuticle coating agent, its lubricity and foam characteristics are improved. In addition, in the makeup, colored cosmetics, foundation, blusher, lipstick, eyeliner, mascara, oil remover, colored cosmetic remover and powder, the emulsion of the present invention acts as a leveling agent and a spreading agent for pigments. Similarly, it is also used for oil-soluble and water-soluble substances such as vitamins, organic sunscreens, ceramides and pharmaceuticals. When the emulsion of the present invention is blended with a stick-like, gel-like, lotion-aerosol-like, or roll-on-like cosmetic, it imparts dry silky smoothness thereto.

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples. The viscosity in the examples is a value at 25 ° C., and the volume particle size distribution of a liquid catalyst containing a platinum-alkenylsiloxane complex emulsified in water as a main component, the stability of an organosilicon polymer emulsion, the organosilicon polymer particles The average particle diameter, the viscosity and the molecular weight of the organosilicon polymer were measured according to the following methods. The polyoxyethylene hexyl decyl ether used in the examples has the formula:

[Chemical 7] And C ₆ H ₁₃ and C ₈ H ₁₇ are both linear. ○ Volume particle size distribution of liquid catalyst emulsified in water Volume average particle size and content of catalyst having particle size of 1 μm or less in volume particle size distribution of liquid catalyst mainly composed of platinum-alkenylsiloxane complex emulsified in water %) Was determined by a laser scattering type submicron particle analyzer (COULTER N4 type manufactured by Coulter Electronics Co.). ○ Stability of organosilicon polymer emulsion 225ml glass bottle of organosilicon polymer emulsion
180 ml (depth 105 mm, caliber 50 mm) was put and left in a sealed state at room temperature for 1 week, 2 weeks and 3 weeks. The appearance of the organosilicon polymer emulsion after standing was observed to measure the thickness of the water layer separated at the bottom of the bottle.
If the thickness is less than mm, it is marked with a circle.
When the thickness is less than Δ, Δ is indicated, and when the thickness is 15 mm or more, is indicated by X. -Average particle size of organosilicon polymer particles The median diameter (particles corresponding to 50% of cumulative distribution) of an organosilicon polymer emulsion measured by a laser diffraction type particle size distribution analyzer (LA-500 manufactured by Horiba Ltd.) The average particle diameter of the organosilicon polymer particles was determined from the (diameter). Viscosity and Molecular Weight of Organosilicon Polymer The organic silicon polymer emulsion was air-dried at room temperature for 1 week in a fume hood, and it was confirmed that moisture was removed by weight reduction.
Viscometer (DV-U-EI manufactured by Tokimec Co., Ltd.
The viscosity was measured with an I-type viscometer) under the conditions of 0.5 rpm, 5 minutes, and 25 ° C. Also, the organosilicon polymer is dissolved in toluene,
The polystyrene-equivalent weight average molecular weight of the top peak was measured by gel permeation chromatography.

[0022]

Example 1 57.1 parts by weight of a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 mPa · s (vinyl group content = 0.48% by weight) and a viscosity of 13
42.9 parts by weight of a dimethylhydrogensiloxy group capped with dimethylhydrogensiloxy groups at both ends of a molecular chain of 0 mPa · s was mixed with 42.9 parts by weight, and then polyoxyethylene ( Addition mole number of ethylene oxide = 10) hexyl decyl ether (NIKKOL BH-1 manufactured by Nikko Chemicals Co., Ltd.)
0) and polyoxyethylene (the number of moles of ethylene oxide added = 25) hexyldecyl ether (NIKKOL BH-25 manufactured by Nikko Chemicals Co., Ltd.) (the mixing ratio of the former and the latter polyoxyethylene hexyldecyl ether is 2). : 3, HLB = 15.3) 1.7
An emulsion was prepared by adding 30 parts by weight of a wt% aqueous solution and emulsifying with a colloid mill, and then adding 25 parts by weight of pure water. Next, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex prepared separately from this emulsion was prepared. Liquid catalyst emulsion consisting of siloxane solution
(Volume average particle diameter of liquid catalyst = 0.05 μm, ratio of catalyst of 1 μm or less = 95% by weight, platinum metal concentration = 0.04% by weight) based on the total weight of diorganopolysiloxane in the emulsion. The amount of platinum metal was 20 ppm, and the mixture was mixed uniformly. 1 this emulsion at room temperature
The mixture was allowed to stand for a day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0023]

[Comparative Example 1] 57.1 parts by weight of a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 mPa · s (vinyl group content = 0.48% by weight) and a viscosity of 13
A mixture of 42.9 parts by weight of dimethylpolysiloxane with a dimethylhydrogensiloxy group blocked at both ends of the molecular chain of 0 mPa · s (content of hydrogen atoms bonded to silicon atoms = 0.025% by weight) was mixed, and then polyoxyethylene nonyl was added. After adding 30 parts by weight of a 1.7% by weight aqueous solution of phenyl ether (HLB = 13.1, PRTR method designated chemical substance 1) and emulsifying with a colloid mill, add 25 parts by weight of pure water to prepare an emulsion. did. Next, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 1,3-divinyl-1,
Liquid catalyst emulsion consisting of 1,3,3-tetramethyldisiloxane solution (volume average particle size of liquid catalyst = 0.05μ
m, 1 μm or less catalyst ratio = 95% by weight, platinum metal concentration = 0.04% by weight), and the platinum metal amount was 2 with respect to the total weight of the diorganopolysiloxane in the emulsion.
An amount of 0 ppm was added and mixed uniformly. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0024]

[Example 2] 89.1 parts by weight of a dimethylpolysiloxane having a dimethylvinylsiloxy group blocked at both molecular chain ends and a viscosity of 10 m and a viscosity of 400 mPa · s.
Mixing 10.9 parts by weight of dimethylpolysiloxane with a dimethylhydrogensiloxy group blocked at both ends of the Pa · s molecular chain (content of silicon atom-bonded hydrogen atoms = 0.15% by weight), and then adding polyoxyethylene ( Addition mol number of ethylene oxide = 10) Hexyldecyl ether (NIKKOL BH-10 manufactured by Nikko Chemicals Co., Ltd.) and polyoxyethylene (addition mol number of ethylene oxide =
25) 1.7% by weight of a mixture of hexyldecyl ether (NIKKOL BH-25 manufactured by Nikko Chemicals Co., Ltd. (mixing ratio of former polyoxyethylene hexyldecyl ether of the latter is 2: 3, HLB = 15.3)). After 30 parts by weight of an aqueous solution was added and emulsified by a colloid mill, 25 parts by weight of pure water was added to prepare an emulsion.
Next, platinum-1, which was prepared separately from this emulsion,
Liquid catalyst emulsion consisting of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of 3-divinyl-1,1,3,3-tetramethyldisiloxane complex (volume average particle size of liquid catalyst The ratio of the catalyst having a diameter of 0.20 μm, a particle size of 1 μm or less = 80% by weight, and the platinum metal concentration = 0.04% by weight) is determined by the amount of platinum metal based on the total weight of the diorganopolysiloxane in the emulsion. An amount of 20 ppm was added and mixed uniformly. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0025]

[Comparative Example 2] 89.1 parts by weight of a dimethylpolysiloxane having a viscosity of 400 mPa · s and dimethylvinylsiloxy groups blocked at both ends of the molecular chain (vinyl group content = 0.48% by weight) and a viscosity of 10 m
A mixture of 10.9 parts by weight of dimethylpolysiloxane with a dimethylhydrogensiloxy group blocked at both ends of the Pa · s molecular chain (content of silicon-bonded hydrogen atoms = 0.15% by weight), and then mixed with polyoxyethylene nonyl After adding 30 parts by weight of a 1.7% by weight aqueous solution of phenyl ether (HLB = 13.1, PRTR method designated chemical substance 1) and emulsifying with a colloid mill, add 25 parts by weight of pure water to prepare an emulsion. did. Next, 1,3-divinyl-1,1,3,1,3 of the platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex prepared separately from this emulsion was prepared.
Liquid catalyst emulsion consisting of 3-tetramethyldisiloxane solution (volume average particle size of liquid catalyst = 0.20 μm,
The ratio of the catalyst having a particle diameter of 1 μm or less = 80% by weight, the platinum metal concentration = 0.04% by weight) was used as
An amount of 0 ppm was added and mixed uniformly. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0026]

Example 3 60.8 parts by weight of a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 mPa · s (vinyl group content = 0.48% by weight) and a viscosity of 13
Dimethylpolysiloxane with 0 mPa · s capped at both ends of the dimethylhydrogensiloxy group (content of hydrogen atoms bonded to silicon atoms = 0.025% by weight) 39.0 parts by weight, one end of the molecular chain with a viscosity of 20 mPa · s is dimethyl 1.0 part by weight of dimethylpolysiloxane (hydrogen-bonded hydrogen atom content = 0.054% by weight) blocked with a hydrogensiloxy group and the other molecular chain end blocked with a trimethylsiloxy group was mixed, and then mixed. In addition, polyoxyethylene (number of moles of ethylene oxide added = 10) hexyl decyl ether (NIKKOL manufactured by Nikko Chemicals Co., Ltd.)
BH-10) and a mixture of polyoxyethylene (the number of moles of ethylene oxide added = 25) hexyldecyl ether (NIKKOL BH-25 manufactured by Nikko Chemicals Co., Ltd.) (the mixing ratio of the former and the latter polyoxyethylenehexyldecyl ether is 30 parts by weight of a 1.7% by weight aqueous solution of 2: 3, HLB = 15.3) was added and emulsified by a colloid mill, and then 25 parts by weight of pure water was added to prepare an emulsion. Next, 1,3-divinyl-1,1,3,3- of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex prepared separately from this emulsion was prepared.
Liquid catalyst emulsion consisting of tetramethyldisiloxane solution (volume average particle size of liquid catalyst = 0.05 μm, 1 μm
Ratio of the following catalyst = 95% by weight, platinum metal concentration = 0.0
4% by weight) was added in an amount such that the amount of platinum metal was 20 ppm with respect to the total weight of the diorganopolysiloxane in the above emulsion, and the mixture was mixed uniformly. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0027]

[Comparative Example 3] Dimethylpolysiloxane having a viscosity of 400 mPa · s and dimethylvinylsiloxy groups blocked at both ends of the molecular chain (vinyl group content = 0.48% by weight) 60.8 parts by weight, viscosity 13
Dimethylpolysiloxane with 0 mPa · s capped at both ends of the dimethylhydrogensiloxy group (content of hydrogen atoms bonded to silicon atoms = 0.025% by weight) 39.0 parts by weight, one end of the molecular chain with a viscosity of 20 mPa · s is dimethyl 1.0 part by weight of dimethylpolysiloxane (hydrogen-bonded hydrogen atom content = 0.054% by weight) blocked with a hydrogensiloxy group and the other molecular chain end blocked with a trimethylsiloxy group was mixed, and then mixed. To this, 30 parts by weight of a 1.7% by weight aqueous solution of polyoxyethylene nonyl phenyl ether (HLB = 13.1, PRTR method Class 1 designated chemical substance) was added and emulsified by a colloid mill, then 25 parts by weight of pure water Parts were added to prepare an emulsion. Next, platinum-1,3-divinyl-1, prepared separately from this emulsion,
Liquid catalyst emulsion consisting of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane complex (volume average particle diameter of liquid catalyst = 0.05 μm, 1 μm The following catalyst ratio = 95% by weight, platinum metal concentration = 0.04% by weight) was added uniformly so that the platinum metal amount was 20 ppm with respect to the total weight of the diorganopolysiloxane in the emulsion. Mixed. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0028]

Example 4 57 parts by weight of a dimethylpolysiloxane having a viscosity of 400 mPa · s and a dimethylvinylsiloxy group blocked at both ends of a molecular chain (vinyl group content = 0.48% by weight) and a viscosity of 130 mP
42 parts by weight of a / s dimethylpolysiloxane with dimethylhydrogensiloxy group blocked at both ends (content of silicon atom-bonded hydrogen atoms = 0.025% by weight), viscosity 20 mPa
A dimethylpolysiloxane in which one end of the molecular chain of s is blocked with a dimethylvinylsiloxy group and the other end of the molecular chain is blocked with a trimethylsiloxy group (content of vinyl group = 1.4
3% by weight) and mixed with polyoxyethylene (the number of moles of added ethylene oxide = 1).
0) Hexyldecyl ether (NIKKOL BH-10 manufactured by Nikko Chemicals Co., Ltd.) and polyoxyethylene (number of moles of ethylene oxide added = 25) Hexyldecyl ether (NIKKO manufactured by Nikko Chemicals Co., Ltd.)
L BH-25) (the mixing ratio of the former and the latter polyoxyethylene hexyl decyl ether is 2: 3, H
After 30 parts by weight of a 1.7% by weight aqueous solution of LB = 15.3) was added and emulsified by a colloid mill, 25 parts by weight of pure water was added to prepare an emulsion. Then, prepared separately from this emulsion, platinum-1,3-divinyl-1,1,
Liquid catalyst emulsion consisting of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of 3,3-tetramethyldisiloxane complex (volume average particle size of liquid catalyst =
% Of catalyst less than 0.05 μm, 1 μm = 95% by weight,
(Platinum metal concentration = 0.04% by weight) was added and mixed uniformly so that the amount of platinum metal was 20 ppm with respect to the total weight of the diorganopolysiloxane in the emulsion. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0029]

[Comparative Example 4] 57 parts by weight of a dimethylpolysiloxane having a viscosity of 400 mPa · s and a dimethylvinylsiloxy group blocked at both ends of a molecular chain (vinyl group content = 0.48% by weight) and a viscosity of 130 mP
42 parts by weight of a / s dimethylpolysiloxane with dimethylhydrogensiloxy group blocked at both ends (content of silicon atom-bonded hydrogen atoms = 0.025% by weight), viscosity 20 mPa
A dimethylpolysiloxane in which one end of the molecular chain of s is blocked with a dimethylvinylsiloxy group and the other end of the molecular chain is blocked with a trimethylsiloxy group (content of vinyl group = 1.4
3% by weight), and then mixed with 4% by weight of polyoxyethylene nonylphenyl ether (HL
B = 13.1, in the PRTR method, 30 parts by weight of an aqueous solution of designated chemical substance 1) was added and emulsified by a colloid mill, and then 20 parts by weight of pure water was added to prepare an emulsion. next,
From a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex prepared separately from this emulsion The following liquid catalyst emulsion (volume average particle diameter of liquid catalyst = 0.05 μm, ratio of catalyst of 1 μm or less = 95% by weight, platinum metal concentration = 0.04% by weight) was added to the above-mentioned emulsion of diorganopolysiloxane. An amount of platinum metal of 20 ppm was added to the total weight and mixed uniformly. This emulsion was allowed to stand at room temperature for 1 day for addition polymerization to prepare an organosilicon polymer emulsion having a siloxane bond and a silethylene bond. The stability of the obtained organosilicon polymer emulsion, the average particle size of the organosilicon polymer particles, and the viscosity and molecular weight of the organosilicon polymer were measured, and these are shown in Table 1.

[0030]

[Table 1]

[0031]

The organosilicon polymer emulsion of the present invention uses (B) an oxyethylene adduct of a long chain alcohol having 16 to 20 carbon atoms as an emulsifier.
It is characterized by excellent storage stability and low environmental load. Further, the production method of the present invention is characterized in that an organosilicon polymer emulsion having a relatively high viscosity can be prepared without gelation.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaru Ozaki             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Co., Ltd. R & D             In headquarters F-term (reference) 4J002 CH022 CP191 GB00 HA07

Claims (9)

[Claims] 1. (A) (a-1) A diorganopolysiloxane having silicon-bonded hydrogen atoms only at both ends of a molecular chain,
(a-2) Organosilicon polymer particles having an average particle size of 0.1 to 500 μm obtained by hydrosilylation reaction of a diorganopolysiloxane having a silicon atom-bonded alkenyl group only at both ends of a molecular chain, (B) carbon An organosilicon polymer emulsion, which comprises, as main components, an oxyethylene adduct of a long-chain alcohol having 16 to 20 atoms and (C) water. 2. A diorganopolysiloxane (D) (a-1) having a silicon atom-bonded hydrogen atom only at both ends of a molecular chain,
(a-2) a diorganopolysiloxane having a silicon atom-bonded alkenyl group only at both ends of the molecular chain, and (a-3) a diorgano having a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkenyl group at only one end of the molecular chain. An average particle size of 0.1 to 0.1 obtained by hydrosilylation reaction of polysiloxane
An organosilicon polymer emulsion comprising 500 μm of organosilicon polymer particles, (B) an oxyethylene adduct of a long-chain alcohol having 16 to 20 carbon atoms, and (C) water as main components. 3. The organosilicon polymer emulsion according to claim 1 or 2, wherein the component (B) is an oxyethylene adduct of a branched alcohol. 4. The organosilicon polymer emulsion according to claim 3, wherein the oxyethylene adduct of branched alcohol is an oxyethylene adduct of isocetyl alcohol. 5. An oxyethylene adduct of isocetyl alcohol has the formula: The organosilicon polymer emulsion according to claim 4, which is a polyoxyethylene hexyl decyl ether represented by the formula (n is 2 to 40). 6. The organosilicon polymer emulsion according to claim 1, wherein the HLB of the component (B) is 10 or more. 7. (a-1) A diorganopolysiloxane having silicon-bonded hydrogen atoms only at both ends of a molecular chain, and (a-
2) In a state where (B) a diorganopolysiloxane having a silicon atom-bonded alkenyl group only at both ends of the molecular chain is emulsified in water with (B) an oxyethylene adduct of a long-chain alcohol having 16 to 20 carbon atoms, E) The method for producing an organosilicon polymer emulsion according to claim 1, wherein the addition polymerization is carried out in the presence of a hydrosilylation reaction catalyst. 8. (a-1) a diorganopolysiloxane having silicon-bonded hydrogen atoms only at both ends of a molecular chain, and (a-
2) a diorganopolysiloxane having a silicon atom-bonded alkenyl group only at both ends of the molecular chain, and (a-3) a diorganopolysiloxane having a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkenyl group only at one end of the molecular chain, To
(B) Addition polymerization in the presence of a catalyst for hydrosilylation reaction (E) in a state of being emulsified in water with an oxyethylene adduct of a long-chain alcohol having 16 to 20 carbon atoms. 2. The method for producing an organosilicon polymer emulsion according to item 2. 9. The organosilicon polymer according to claim 7, wherein the (E) catalyst for hydrosilylation reaction is an emulsion obtained by emulsifying a liquid catalyst containing a platinum-alkenylsiloxane complex as a main component in water. Method for producing emulsion.