JP2003183501A - Aqueous suspension of cross-linked silicone particle and aqueous oil emulsion containing cross-linked silicone particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous suspension of cross-linked silicone particles and an aqueous oil emulsion containing cross-linked silicone particles that have excellent stability, environment- and human-friendly. <P>SOLUTION: This aqueous suspension of cross-linked silicone particles comprises (A) cross-linked silicone particles having an average particle diameter of 0.1-500 μm, (B) an oxyethylene adduct of a 16C alcohol derived from a non- animal fat, and (C) water. The aqueous oil emulsion containing cross-linked silicone particles comprises (A) cross-linked silicone particles having an average particle diameter of 0.1-500 μm, (E) an oil, (B) the oxyethylene adduct of a 16C alcohol derived from the non-animal fat, and (C) water. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to an aqueous suspension of crosslinked silicone particles and an aqueous emulsion of oil containing the crosslinked silicone particles. More specifically, the present invention relates to a water-based suspension of crosslinked silicone particles which is excellent in stability and has less impact on the environment and human body, and a water-based emulsion of oil containing the crosslinked silicone particles.

[0002]

2. Description of the Related Art An aqueous suspension of crosslinked silicone particles comprising crosslinked silicone particles, a surfactant and water, and an aqueous emulsion of oil containing crosslinked silicone particles are known (Japanese Patent Laid-Open No. 309565/1988). Kaihei 11-140191, JP 2000-
No. 281,903). It has been proposed that when such a suspension is added to a water-based paint, the coating film exhibits matte properties (see JP-A-5-9409), and when it is used in a water-based cosmetic composition, the feeling of use is improved ( JP-A-10-139624 and JP-A-10-17
5816).

For these water-based suspensions and water-based emulsions, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants or surfactants composed of a mixture thereof are used. In particular, when used for cosmetics, a nonionic surfactant is preferably used because the dispersibility of the crosslinked silicone particles and the oil containing the crosslinked silicone particles is good.

In recent years, in these water-based suspensions and water-based emulsions, it has been required to select a surfactant having a low environmental load while improving its stability and dispersibility in a formulation. For example, having 12 to 12 carbon atoms
Alkyl polyethers with 15 alkyl groups are PRTR (Pollu
tant release and transfer register) emissions have been certified as mandatory chemical substances, and their use is becoming restricted. In addition, the raw material is a tallow-derived surfactant such as beef tallow, in particular, a surfactant having an alkyl group derived from tallow is the quality and safety of pharmaceuticals manufactured from materials derived from bovine etc. Regarding the assurance of sex (as of December 12, 2000), the use in cosmetics is being restricted.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that as a surfactant used in an aqueous suspension of crosslinked silicone particles or an aqueous emulsion of oil containing crosslinked silicone particles. The present inventors have found that the above problems can be solved by selecting an oxyethylene adduct of an alcohol having a carbon number of 16 and derived from non-tallow fat, and arrived at the present invention.

[0006] That is, an object of the present invention is to provide an aqueous suspension of crosslinked silicone particles which is excellent in stability and has less impact on the environment and human body, and an aqueous emulsion of oil containing the crosslinked silicone particles. .

[0007]

The present invention provides (A) a crosslinked silicone particle having an average particle size of 0.1 to 500 μm, (B) an oxyethylene adduct of a non-tallow-derived alcohol having 16 carbon atoms, and (C) ) Water-based suspension of crosslinked silicone particles consisting of water, and (A) average particle size 0.1-500 μm
(E) oil, (B) non-tallow-derived oxyethylene adduct of C 16 alcohol, and (C) water-based emulsion of oil containing crosslinked silicone particles.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION First, the aqueous suspension of the crosslinked silicone particles of the present invention will be described in detail. (A) The crosslinked silicone particles are the main component of the suspension of the present invention, and the average particle size thereof is 0.1 to 500 μm,
It is preferably 0.1 to 100 μm, more preferably 0.1 to 50 μm, and particularly preferably 0.5 to 50 μm.
μm. This is because it is difficult to prepare crosslinked silicone particles having an average particle size of less than the lower limit of the above range, and when the average particle size exceeds the upper limit of the above range, dispersibility in cosmetics, paints, etc. tends to decrease. Because. Examples of the shape of the component (A) include a spherical shape, a flat shape, and an indefinite shape, and the spherical shape is preferable because it has particularly good dispersibility in cosmetics and paints. Examples of the properties of the component (A) include hard rubber, soft rubber and gel.

Further, the component (A) may contain non-crosslinked oil. This oil is not limited, preferably it has a viscosity at 25 ° C. is not more than 100,000 mm ² / s, more preferably not more than 50,000 mm ² / s, particularly 10,000 mm ² / s or less Some are preferred. Examples of such oils include silicone oils and organic oils, and silicone oils are preferred because of their excellent affinity for crosslinked silicone particles.

The molecular structure of this silicone oil is, for example, linear, partially branched linear, cyclic,
Examples thereof include branched ones, preferably linear ones and cyclic ones.
Such silicone oils include, for example, dimethylpolysiloxanes capped with trimethylsiloxy groups at both molecular chain ends, cyclic dimethylsiloxanes, and some of the methyl groups in these silicone oils are substituted with alkyl groups such as ethyl groups, propyl groups, and butyl groups. Group, phenyl group, or silicone oil substituted with 3,3,3-trifluoropropyl group,
And mixtures of these silicone oils.

Examples of the organic oil include liquid paraffin, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, and the like. Butyl stearate, decyl oleate,
2-Octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, sesame oil, safflower oil, soybean oil, Camellia oil, squalane,
Persic oil, castor oil, cottonseed oil, coconut oil, polypropylene glycol monooleate, neopentyl glycol-2-ethylhexanoate, isostearic acid triglyceride, palm oil fatty acid triglyceride, polyoxyethylene lauryl ether, polyoxypropylene cetyl ether .

The content of these non-crosslinked oils in the component (A) is not limited, but is preferably 80% by weight or less, particularly preferably 50% by weight or less. This is because it is difficult to prepare crosslinked silicone particles that exceed the upper limit of the above range, and if it exceeds the upper limit of the above range, an aqueous emulsion of oil containing the crosslinked silicone particles described below may be formed. .

The content of the component (A) in the suspension of the present invention is not limited, but it is preferably 25 to 80% by weight, more preferably 40 to 80% by weight. this is,
If the content of the component (A) is less than the lower limit of the above range, the use thereof may be limited. On the other hand, if it exceeds the upper limit of the above range, handling workability may be deteriorated, and the composition may be used in cosmetics and paints. This is because the dispersibility tends to decrease.

(B) The oxyethylene adduct of an alcohol having a carbon number of 16 and derived from non-tallow is a characteristic component of the present invention, and acts as a nonionic surfactant. in addition,
Not only the stability of the suspension of the present invention alone, but also the dispersibility and stability when blended with other components is improved, and it is a component that considers the environment and the human body. As the component (B), an oxyethylene adduct of a long-chain alcohol having 16 carbon atoms derived from a vegetable oil or a synthetic compound can be used. In particular,
Examples thereof include oxyethylene adducts of non-tallow-derived n-cetyl alcohol (C16), and vegetable oil-derived polyoxyethylene n-cetyl ether is exemplified. Such polyoxyethylene n-cetyl ether is commercially available, for example, trade name of Nikko Chemicals Co., Ltd .; NI.
KKOLBC-2, NIKKOL BC-5.5, NI
KKOL BC-7, NIKKOL BC-10TX,
NIKKOL BC-15TX, NIKKOL BC-
20TX, NIKKOL BC-23, NIKKOL
BC-25TX, NIKKOL BC-30TX, NI
There is KKOL BC-40TX.

As the component (B), an oxyethylene adduct of a branched long chain alcohol can also be used. Specific examples thereof include an oxyethylene adduct of non-tallow-derived isocetyl alcohol (C16), and a vegetable oil-derived polyoxyethylene hexyl decyl ether represented by the following formula is exemplified.

[Chemical 5] In the above formula, m is 2 to 40. Such polyoxyethylene hexyl decyl ether is commercially available, for example, trade name of Nikko Chemicals Co., Ltd .; NIKKOL
BH-2, NIKKOL BH-5, NIKKOL
BH-7, NIKKOL BH-10, NIKKOL
BH-15, NIKKOL BH-20, NIKKOL
BH-25, NIKKOL BH-30 and trade name of Nippon Emulsion Co., Ltd .; EMALEX 160
5, EMALEX 1610, EMALEX 161
5, EMALEX 1620, EMALEX 1625
There is.

HLB (Hydrophile-Lipophi) in the component (B)
le Balance) is not particularly limited, but is preferably 10 or more, and particularly preferably 12-18. The HLB in the present invention means a value calculated by the Griffin equation shown by the following equation.

[Formula 1] As the component (B), one type may be used alone, or a mixture of two or more types having different HLBs 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 15 to 30 moles.
Mixing moles of oxyethylene adduct gives an average HLB of 1
It can be adjusted to be 0 or more. Also, (B)
The number of added moles of ethylene oxide in the component is not particularly limited, but is preferably 2 to 40, more preferably 2 to 30.

The content of the component (B) in the suspension of the present invention is not limited, but is preferably 0.001 to 20% by weight.
And particularly preferably 0.01 to 10% by weight.
This is because when the content of the component (B) is less than the lower limit of the above range, dispersibility in cosmetics, paints, etc. tends to decrease, while when it exceeds the upper limit of the above range, its use is limited. This is because there are concerns.

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

The suspension of the present invention comprises the above-mentioned component (A),
At least a component (B) and a component (C), and as an optional component, (D) a general formula:

[Chemical 6] You may contain the phenoxy ethanol shown by.
The component (D) improves the surface activity of the component (B) and, at the same time, the component (A) is stably dispersed in water even when the amount of the component (B) is reduced, and acts as a preservative. Is. R in the above formula is a hydrogen atom or a methyl group, preferably a hydrogen atom. Further, n in the above formula is an integer of 1 to 10, preferably an integer of 1 to 5, and particularly preferably 1. The purity of the component (D) is not limited, but preferably 90% by weight or more.

In the suspension of the present invention, the content of the component (D) is not limited, but the components (A), (B) and
It is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight, and particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of the component (C). It is preferably part. This is because when the content of the component (D) is less than the lower limit of the above range, the stability of the suspension of the present invention when the component (B) is reduced tends to decrease.
On the other hand, if the upper limit of the above range is exceeded, the applications may be limited.

The method of blending the component (D) is not particularly limited, but it is preferable to mix the component (D) and the component (B) in advance and then blend them with other components. As a result, the component (B) can be easily blended, and the blending amount of the component (B) can be reduced.

Further, in the suspension of the present invention, as other optional components, for example, alcohols such as ethanol, i-propanol, t-butanol, ethylene glycol, propylene glycol, diethylene glycol;
A water-soluble polymer such as carboxyvinyl polymer or sodium carboxymethyl cellulose; and a preservative, an antibacterial agent, an antifungal agent, a rust preventive, an aromatic agent, and a pigment may be contained. Further, within a range not impairing the object of the present invention, in order to further improve the compounding stability to other components, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant. You may use various surfactants, such as. These components may be used alone or in combination, and the compounding procedure is not particularly limited.

The method for preparing the suspension of the present invention is not limited. For example, after adding and dispersing the crosslinkable silicone composition in an aqueous solution comprising the component (B), the component (C) and any other component, After the method for cross-linking the composition and adding the cross-linkable silicone composition excluding the catalyst for cross-linking to an aqueous solution containing the component (B), the component (C) and other optional components, and dispersing the composition. And a method of crosslinking the composition by adding the catalyst. In the latter method, the catalyst for crosslinking is preferably added in a state of being dispersed in the aqueous solution of the component (B).

Examples of the crosslinkable silicone composition used for preparing the suspension of the present invention include hydrosilylation reaction crosslinkable silicone composition, condensation reaction crosslinkable silicone composition, organic peroxide crosslinkable silicone composition, Examples of the UV-crosslinkable silicone composition include a hydrosilylation reaction-crosslinkable silicone composition and a condensation reaction-crosslinkable silicone composition.

Examples of the hydrosilylation reaction crosslinkable silicone composition include, for example, organopolysiloxane having at least two alkenyl groups in one molecule, organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, and A composition including at least a platinum-based catalyst may be mentioned.

The condensation reaction crosslinkable silicone composition has, for example, at least two hydrolyzable groups such as a hydroxyl group or an alkoxy group bonded to a silicon atom, an oxime group, an acetoxy group and an aminoxy group in one molecule. Condensation of organopolysiloxane, silicon-bonded alkoxy groups, oxime groups, acetoxy groups, aminoxy groups, and other silane-based cross-linking agents having at least three hydrolyzable groups in one molecule, and organotin compounds and organotitanium compounds. A composition comprising at least a reaction catalyst may be mentioned. Preferably, an organopolysiloxane having at least two silicon-bonded hydroxyl groups or alkoxy groups in one molecule, a silane-based cross-linking agent having at least three silicon-bonded alkoxy groups in one molecule, and an organotin compound, A dealcoholization condensation reaction crosslinkable silicone composition comprising at least a condensation reaction catalyst such as an organic titanium compound.

Next, the water-based emulsion of oil containing the crosslinked silicone particles of the present invention will be described in detail. The crosslinked silicone particles (A) are the main component of the emulsion of the present invention, and the average particle size thereof is 0.1 to 500 μm, preferably 0.1 to 100 μm, and more preferably 0.1.
1 to 50 μm, particularly preferably 0.5 to 50 μm
Is. This is because it is difficult to prepare crosslinked silicone particles having an average particle size of less than the lower limit of the above range, while on the other hand, when the average particle size exceeds the upper limit of the above range, dispersibility in cosmetics and paints tends to decrease. Because there is. Examples of the shape of the component (A) include a spherical shape, a flat shape, and an indefinite shape, and the spherical shape is preferable because it has particularly good dispersibility in cosmetics and paints. Examples of the properties of the component (A) include hard rubber, soft rubber and gel.

The oil (E) is also the main component of the emulsion of the present invention and is not particularly limited, but its viscosity at 25 ° C. is 1
Preferably it has 00,000mm at ² / s or less, more preferably not more than 50,000 mm ² / s, in particular from those preferably less 10,000 mm ² / s. Examples of such oils include silicone oils and organic oils, and silicone oils are preferable because of their excellent affinity for crosslinked silicone particles. Examples of the silicone oil and the organic oil are the same as those described above. It is preferable that the component (E) is dispersed in water as droplets and the crosslinked silicone particles (A) are contained in the droplets. The average particle size of the component (E) droplets is preferably 0.1 to 500 μm,
The thickness is more preferably 0.1 to 100 μm, still more preferably 0.1 to 50 μm.

Although the content of the component (E) is not limited and depends on the oil absorption of the component (A), it is preferably 50% by weight or more based on the total weight of the components (A) and (E). And particularly preferably 60% by weight or more. When the content of the component (E) is less than the lower limit of the above range, it is dispersed in water.
This is because there is a concern that the component (A) cannot be contained in the component (E).

The contents of the components (A) and (E) in the emulsion of the present invention are not limited, but are preferably in the range of 25 to 90% by weight, more preferably 40 to 80% by weight.
Is. This is because if the contents of the components (A) and (E) are less than the lower limit of the above range, the application may be limited, while if it exceeds the upper limit of the above range, handling workability may deteriorate.
This is because the dispersibility in cosmetics and paints tends to decrease.

The component (B) is a feature of the present invention, and examples thereof include those mentioned above.

The content of the component (B) in the emulsion of the present invention is not limited, but is preferably 0.001 to 20% by weight.
And particularly preferably 0.01 to 10% by weight.
This is because when the content of the component (B) is less than the lower limit of the above range, dispersibility in cosmetics, paints, etc. tends to decrease, while when it exceeds the upper limit of the above range, applications may be limited. Because there is.

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

The emulsion of the present invention comprises the above-mentioned component (A),
At least a component (E), a component (B) and a component (C), and as an optional component, a general formula (D):

[Chemical 7] You may contain the phenoxy ethanol shown by.
The component (D) improves the surface activity of the component (B), and at the same time, when the amount of the component (B) is reduced, the components (A) and (E)
It is a component that stably disperses the component in water and acts as a preservative. R and n in the above formula are the same as above. The purity and the compounding method are also the same as above.

In the emulsion of the present invention, the content of the component (D) is not limited, but it is 0.01 per 100 parts by weight of the total of the components (A), (E), (B) and (C).
It is preferably from 10 to 10 parts by weight, more preferably 0.0
It is preferably from 1 to 1 part by weight, and particularly from 0.1 to 1.
It is preferably 1 part by weight. This is because if the content of the component (D) is less than the lower limit of the above range, the stability of the emulsion of the present invention may decrease when the amount of the component (B) is reduced, while the upper limit of the above range is set. This is because if it exceeds the limit, there is a concern that the use will be limited.

Furthermore, the above-mentioned various additives can be added and blended as other optional components to the emulsion of the present invention.

The method for preparing the emulsion of the present invention is not limited. For example, a crosslinkable silicone composition containing the component (E) is added to an aqueous solution containing the component (B), the component (C) and other optional components. And then dispersing the composition, and a method of crosslinking the composition, and removing the catalyst for crosslinking, the crosslinkable silicone composition containing the component (E), the component (B),
After adding and dispersing in an aqueous solution consisting of the component (C) and other optional components, by adding the catalyst,
A method of crosslinking the composition may be mentioned. In the latter method, the crosslinking catalyst is preferably added in a state of being dispersed in the aqueous solution of the component (B).

Examples of the crosslinkable silicone composition used for preparing the emulsion of the present invention include hydrosilylation reaction crosslinkable silicone composition, condensation reaction crosslinkable silicone composition, organic peroxide crosslinkable silicone composition, Examples of the UV-crosslinkable silicone composition include a hydrosilylation reaction-crosslinkable silicone composition and a condensation reaction-crosslinkable silicone composition. Examples of the hydrosilylation reaction-crosslinkable silicone composition and the condensation reaction-crosslinkable silicone composition include the same compositions as described above.

The aqueous suspension of the crosslinked silicone particles and the aqueous emulsion of the oil containing the crosslinked silicone particles of the present invention are excellent in stability and have a characteristic that they have little impact on the environment and human body. In addition, dispersibility in cosmetics and paints is good,
When added to these, the effect of adding the crosslinked silicone particles can be sufficiently exerted, and therefore it is useful as a raw material for cosmetics or a raw material for paints.

[0040]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, the viscosity is the value at 25 ° C. Also,
The polyoxyethylene hexyl decyl ether used in the examples has the formula:

[Chemical 8] And C ₆ H ₁₃ and C ₈ H ₁₇ are both linear. The aqueous suspension of crosslinked silicone particles and the aqueous emulsion of oil containing crosslinked silicone particles were evaluated as follows.

[Average Particle Size of Crosslinked Silicone Particles in Aqueous Suspension] An aqueous suspension was measured by a laser diffraction type particle size distribution measuring device (LA-50 manufactured by Horiba, Ltd.).
0), the median diameter obtained (5 of the cumulative distribution)
The particle size corresponding to 0%: 50% particle size) was taken as the average particle size of the crosslinked silicone particles. Also, the cumulative 90% particle size is 90%
The particle size was used. [Average particle size of oil droplets in water-based emulsion] The water-based emulsion was measured with a laser diffraction particle size distribution analyzer (LA-500 manufactured by Horiba Ltd.) to obtain a median diameter (50% of cumulative distribution). Particle size equivalent to: 5
(0% particle size) was defined as the average particle size of oil droplets. Further, the cumulative 90% particle size was defined as 90% particle size. [Average Particle Size of Cross-Linked Silicone Particles in Aqueous Emulsion] An oil composition containing cross-linked silicone particles obtained by removing water from an aqueous emulsion is observed under a microscope to determine the particle size of 10 cross-linked silicone particles. The average value was calculated. [Stability] A water-based suspension or water-based emulsion was diluted with water so that the solid content concentration was 50% by weight, and then 150 ml was charged in a 225 ml mayonnaise bottle.
It was left at 50 ° C. for 2 weeks. Stability was evaluated by measuring the thickness of the aqueous layer separated after 2 weeks. The smaller the thickness, the better the stability.

[0042]

Example 1 about 20 mm ² / s of the cyclic dimethylsiloxane mixture containing 2.5 wt%, 400mm ² / s of the dimethylpolysiloxane with both molecular chain terminals blocked with dimethylvinylsiloxy groups 94.8 parts by weight, 50 mm ² / Dimethyl siloxane / methyl hydrogen siloxane copolymer with trimethylsiloxy group blocked at both ends of s molecular chain (content of hydrogen atoms bonded to silicon atom = 0.31% by weight) 5.2 parts by weight (vinyl group in the dimethylpolysiloxane) (A molar ratio of silicon atom-bonded hydrogen atoms to 0.95) was uniformly mixed. Then, polyoxyethylene hexyl decyl ether, which is an ethylene oxide adduct of isocetyl alcohol derived from vegetable oil (NIK manufactured by Nikko Chemicals Co., Ltd.
KOL BH-10; the number of added moles of ethylene oxide = 10, HLB: 13.4, room temperature liquid) 1.0 part by weight and an aqueous solution consisting of 30 parts by weight of pure water were added and emulsified by a colloid mill, followed by pure water 30. An aqueous emulsion of the silicone composition was prepared by diluting with 1 part by weight.

On the other hand, 1 part by weight of a mixed solution of 1,3-divinyltetramethyldisiloxane of 1,3-divinyltetramethyldisiloxane complex of platinum and isopropyl alcohol was mixed with 27 parts by weight of deionized water and the same polyoxygen as above. Ethylenehexyl decyl ether (NIKKOL BH-10 manufactured by Nikko Chemicals Co., Ltd .; the number of moles of ethylene oxide added = 10, HLB: 13.4, room temperature liquid), uniformly stirred in an aqueous solution of 0.3 parts by weight,
An aqueous emulsion of a platinum catalyst having an average particle size of 0.2 μm was prepared.

Next, the above platinum catalyst aqueous emulsion (amount of platinum metal in the silicone composition is 5 ppm by weight) was added to the above silicone composition aqueous emulsion, and the mixture was stirred uniformly and then allowed to stand for 1 day. Then, the silicone composition was crosslinked by a hydrosilylation reaction to prepare an aqueous suspension of crosslinked silicone particles. With respect to the obtained water-based suspension, the average particle size and stability of the crosslinked silicone particles were measured. The results are shown in Table 1.

[0045]

Example 2 about 20 mm ² / s of the cyclic dimethylsiloxane mixture containing 2.5 wt%, 400 mm ² / s of the dimethylpolysiloxane with both molecular chain terminals blocked with dimethylvinylsiloxy groups 94.8 parts by weight, 50 mm ² / Dimethyl siloxane / methyl hydrogen siloxane copolymer with trimethylsiloxy group blocked at both ends of s molecular chain (content of hydrogen atoms bonded to silicon atom = 0.31% by weight) 5.2 parts by weight (vinyl group in the dimethylpolysiloxane) (A molar ratio of silicon atom-bonded hydrogen atoms to 0.95) was uniformly mixed. Then, polyoxyethylene n-cetyl ether which is an ethylene oxide adduct of cetyl alcohol derived from vegetable oil (NIKKOL manufactured by Nikko Chemicals Co., Ltd.
BC-10TX; HLB: 13.5, addition mole number of ethylene oxide = 10, solid at room temperature)

[Chemical 9] Phenoxyethanol (PHE-S manufactured by Yokkaichi Gosei Co., Ltd .; purity 92 to 94% by weight) as shown in FIG. After that, it was diluted with 30 parts by weight of pure water to prepare an aqueous emulsion of the silicone composition. To this water-based emulsion, the water-based emulsion of the platinum catalyst prepared in Example 1 (the amount of platinum metal being 5 ppm by weight with respect to the silicone composition) was added and stirred uniformly. Then, this was allowed to stand for one day to crosslink the silicone composition by a hydrosilylation reaction to prepare an aqueous suspension of crosslinked silicone particles. With respect to the obtained water-based suspension, the average particle size and stability of the crosslinked silicone particles were measured. The results are shown in Table 1.

[0046]

Example 3 about 20 mm ² / s of the cyclic dimethylsiloxane mixture containing 2.5 wt%, 400mm ² / s of the dimethylpolysiloxane with both molecular chain terminals blocked with dimethylvinylsiloxy groups 94.8 parts by weight, 50 mm ² / Dimethyl siloxane / methyl hydrogen siloxane copolymer with trimethylsiloxy group blocked at both ends of s molecular chain (content of hydrogen atoms bonded to silicon atom = 0.31% by weight) 5.2 parts by weight (vinyl group in the dimethylpolysiloxane) (A molar ratio of silicon atom-bonded hydrogen atoms to 0.95) was uniformly mixed. Next, a polyoxyethylene n-cetyl ether having an ethylene oxide addition mol number of 5.5, which is an ethylene oxide addition product of cetyl alcohol derived from vegetable oil (NIKKOL BC-5.
5; HLB: 10.5, room temperature solid) 0.5 part by weight, a polyoxyethylene n-cetyl ether having ethylene oxide addition mol number of 20, which is an ethylene oxide adduct of cetyl alcohol derived from vegetable oil (manufactured by Nikko Chemicals Co., Ltd.) NIKKOL BC-20TX; HLB: 17.
0.5 parts by weight (0, room temperature solid) and 20 parts by weight of pure water were added and emulsified by a colloid mill, and then diluted with 30 parts by weight of pure water to prepare an aqueous emulsion of the silicone composition. Example 1 was added to this aqueous emulsion.
The aqueous emulsion of the platinum catalyst prepared in (1) (the amount of platinum metal in the silicone composition is 5 ppm by weight) was added and stirred uniformly. Then, this was allowed to stand for one day to crosslink the silicone composition by a hydrosilylation reaction to prepare an aqueous suspension of crosslinked silicone particles. With respect to the obtained water-based suspension, the average particle size and stability of the crosslinked silicone particles were measured. The results are shown in Table 1.

[0047]

Example 4 about 20 mm ² / s of the cyclic dimethylsiloxane mixture containing 2.5 wt%, 400mm ² / s of the dimethylpolysiloxane with both molecular chain terminals blocked with dimethylvinylsiloxy groups 94.8 parts by weight, 50 mm ² / Dimethyl siloxane / methyl hydrogen siloxane copolymer with trimethylsiloxy group blocked at both ends of s molecular chain (content of hydrogen atoms bonded to silicon atom = 0.31% by weight) 5.2 parts by weight (vinyl group in the dimethylpolysiloxane) (A molar ratio of silicon atom-bonded hydrogen atoms to 0.95) was uniformly mixed. Next, polyoxyethylene n-cetyl ether having an ethylene oxide addition mole number of 10 (NIKKOL BC-10T manufactured by Nikko Chemicals Co., Ltd.), which is an ethylene oxide adduct of cetyl alcohol derived from vegetable oil, is added thereto.
X; HLB: 13.5, room temperature solid) 0.2 part by weight, and polyoxyethylene n-cetyl ether having ethylene oxide addition mole number 25, which is an ethylene oxide addition product of vegetable oil-derived cetyl alcohol (Nikko Chemicals Co., Ltd.) NIKKOL BC-25TX manufactured by HLB: 1
8.5, solid at room temperature)

[Chemical 10] Phenoxyethanol (PHE-S manufactured by Yokkaichi Gosei Co., Ltd .; purity 92 to 94% by weight) as shown in FIG. 2 was mixed and dissolved, and an aqueous solution consisting of 20 parts by weight of pure water was added and emulsified by a colloid mill. After doing,
An aqueous emulsion of the silicone composition was prepared by diluting with 1 part by weight. To this water-based emulsion, the water-based emulsion of the platinum catalyst prepared in Example 1 (the amount of platinum metal being 5 ppm by weight with respect to the silicone composition) was added and stirred uniformly. Then, this was allowed to stand for one day to crosslink the silicone composition by a hydrosilylation reaction to prepare an aqueous suspension of crosslinked silicone particles. With respect to the obtained water-based suspension, the average particle size and stability of the crosslinked silicone particles were measured. The results are shown in Table 1.

[0048]

Comparative Example 1 In Example 1, instead of polyoxyethylene hexyl decyl ether, polyoxyethylene stearyl ether, which is an ethylene oxide adduct of stearyl alcohol derived from vegetable oil (NIKKOL BS-20; Nikko Chemicals Co., Ltd .; HLB). : 18.
An aqueous suspension of crosslinked silicone particles was prepared in the same manner as in Example 1 except that 0, the number of moles of ethylene oxide added = 18, and solid at room temperature) were used. With respect to the obtained water-based suspension, the average particle size and stability of the crosslinked silicone particles were measured. The results are shown in Table 1.

[0049]

[Comparative Example 2] In Example 1, instead of polyoxyethylene hexyl decyl ether, polyoxyethylene stearyl ether having ethylene oxide addition mol number 4 which is an ethylene oxide adduct of stearyl alcohol derived from vegetable oil (Nikko Chemicals Co., Ltd.). NIK made
KOL BS-4; HLB: 9.0, solid at room temperature) 0.2
Polyoxyethylene stearyl ether having 20 parts by weight of ethylene oxide, which is an ethylene oxide adduct of stearyl alcohol derived from vegetable oil (NIKKOL BS-20 manufactured by Nikko Chemicals Co., Ltd .;
HLB: 18.0, solid at room temperature) Attempting to prepare an aqueous suspension of crosslinked silicone particles in the same manner as in Example 1 except that 0.3 part by weight was used, did not emulsify and no aqueous suspension was obtained. .

[0050]

[Table 1]

[0051]

[Example 5] 400 mm ² / s molecular chain end-capped dimethylvinylsiloxy group-blocked methylvinylsiloxane / dimethylsiloxane copolymer (vinyl group content = 1.18% by weight)
18.02 parts by weight, 55 mm ² / s molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane-methylhydrogensiloxane copolymer (content of silicon atom-bonded hydrogen atoms = 0.48% by weight) 1.98 parts by weight (The molar ratio of silicon atom-bonded hydrogen atoms to vinyl groups in the methylvinylsiloxane / dimethylsiloxane copolymer is 0.95.
And an amount of 100 mm ² / s, and 80 parts by weight of dimethylpolysiloxane capped with trimethylsiloxy groups at both ends of the molecular chain were uniformly mixed. Next, polyoxyethylene hexyl decyl ether having an ethylene oxide addition mole number of 10 which is an ethylene oxide adduct of cetyl alcohol derived from vegetable oil (NI manufactured by Nikko Chemicals Co., Ltd.
KKOL BH-10; HLB: 13.4, room temperature liquid)
0.2 parts by weight, ethylene oxide adduct of cetyl alcohol derived from vegetable oil, polyoxyethylene hexyl decyl ether having 25 ethylene oxide addition moles (NIKKOL BH-2 manufactured by Nikko Chemicals Co., Ltd.
5TX; HLB: 16.6, room temperature solid) 0.3 parts by weight,
formula:

[Chemical 11] An aqueous solution consisting of 1.2 parts by weight of phenoxyethanol (PHE-S manufactured by Yokkaichi Gosei Co., Ltd .; purity 92 to 94% by weight) and 20.0 parts by weight of pure water was added and emulsified by a colloid mill. Further, an aqueous solution containing 28 parts by weight of pure water and 8 parts by weight of ethanol was added to prepare an aqueous emulsion of the silicone composition.

On the other hand, 1 part by weight of a mixed solution of 1,3-divinyltetramethyldisiloxane of 1,3-divinyltetramethyldisiloxane complex of platinum and isopropyl alcohol was mixed with 27 parts by weight of deionized water and the same ethylene as above. Polyoxyethylene hexyl decyl ether with 10 moles of oxide added (N produced by Nikko Chemicals Co., Ltd.
IKKOL BH-10; HLB: 13.4, liquid at room temperature), uniformly stirred in an aqueous solution of 0.3 parts by weight,
An aqueous emulsion of a platinum catalyst having an average particle size of 0.3 μm was prepared.

Next, the above platinum catalyst aqueous emulsion (amount of platinum metal in the silicone composition is 5 ppm by weight unit) was added to the above silicone composition aqueous emulsion, and the mixture was stirred uniformly and then allowed to stand for 1 day. Then, a hydrosilylation reaction was carried out to prepare an aqueous emulsion of silicone oil containing crosslinked silicone particles. The average particle size of the crosslinked silicone particles, the average particle size of the silicone oil droplets and the stability of the obtained aqueous emulsion were measured. The results are shown in Table 2.

[0054]

Example 6 400 mm ² / s molecular chain both ends dimethylvinylsiloxy group blocked methylvinylsiloxane / dimethylsiloxane copolymer (vinyl group content = 1.18% by weight)
18.02 parts by weight, 55 mm ² / s molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane-methylhydrogensiloxane copolymer (content of silicon atom-bonded hydrogen atoms = 0.48% by weight) 1.98 parts by weight (The molar ratio of silicon atom-bonded hydrogen atoms to vinyl groups in the methylvinylsiloxane / dimethylsiloxane copolymer is 0.95.
And an amount of 100 mm ² / s, and 80 parts by weight of dimethylpolysiloxane capped with trimethylsiloxy groups at both ends of the molecular chain were uniformly mixed. Next, to this, polyoxyethylene n- having an ethylene oxide addition mole number of 10 which is an ethylene oxide addition product of vegetable oil-derived cetyl alcohol.
Cetyl ether (NIKK manufactured by Nikko Chemicals Co., Ltd.
OL BC-10TX; HLB: 13.5, solid at room temperature)
0.2 parts by weight of polyoxyethylene n-cetyl ether having an ethylene oxide addition mole number of 25, which is an ethylene oxide adduct of cetyl alcohol derived from vegetable oil (NIKKOL BC-25T manufactured by Nikko Chemicals Co., Ltd.).
X; HLB: 18.5, room temperature solid) 0.3 parts by weight, formula:

[Chemical 12] An aqueous solution consisting of 1.2 parts by weight of phenoxyethanol (PHE-S manufactured by Yokkaichi Gosei Co., Ltd .; purity 92 to 94% by weight) and 20.0 parts by weight of pure water was added and emulsified by a colloid mill. Further, an aqueous solution containing 28 parts by weight of pure water and 8 parts by weight of ethanol was added to prepare an aqueous emulsion of the silicone composition. To this water-based emulsion, the water-based emulsion of the platinum catalyst prepared in Example 5 (the amount of platinum metal in the silicone composition was 5 ppm by weight) was added and stirred uniformly. Then, this was allowed to stand for 1 day to carry out a hydrosilylation reaction to prepare an aqueous emulsion of silicone oil containing crosslinked silicone particles. The average particle size of the crosslinked silicone particles, the average particle size of the silicone oil droplets and the stability of the obtained aqueous emulsion were measured. The results are shown in Table 2.

[0055]

COMPARATIVE EXAMPLE 3 In Example 5, instead of polyoxyethylene hexyl decyl ether having 10 moles of ethylene oxide added and polyoxyethylene hexyl decyl ether having 25 moles of ethylene oxide added,
Polyoxyethylene stearyl ether having ethylene oxide addition mol number 4, which is an ethylene oxide adduct of stearyl alcohol derived from vegetable oil (NIKKOL BS-4 manufactured by Nikko Chemicals Co., Ltd .; HLB: 9.
0, room temperature solid) 0.2 part by weight and polyoxyethylene stearyl ether having ethylene oxide addition mole number 20 (NIK manufactured by Nikko Chemicals Co., Ltd.), which is an ethylene oxide adduct of stearyl alcohol derived from vegetable oil.
(KOL BS-20; HLB: 18.0, room temperature solid)
When an aqueous emulsion of silicone oil containing crosslinked silicone particles was tried to be prepared in the same manner as in Example 5 except that 0.3 part by weight was used, no emulsion was obtained and no aqueous emulsion was obtained.

[0056]

[Table 2]

[0057]

INDUSTRIAL APPLICABILITY The aqueous suspension of crosslinked silicone particles and the aqueous emulsion of oil containing the crosslinked silicone particles of the present invention are characterized by excellent stability and less impact on the environment and human body.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Yamamoto             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Co., Ltd. R & D             In headquarters (72) Inventor Takashi Tachibana             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Co., Ltd. R & D             In headquarters F-term (reference) 4J002 AE003 CH022 CH054 CP031                       EJ066 FD206

Claims (16)

[Claims] 1. A crosslinked silicone particle comprising (A) a crosslinked silicone particle having an average particle diameter of 0.1 to 500 μm, (B) an oxyethylene adduct of an alcohol having a carbon number of 16 derived from non-tallow fat, and (C) water. Water based suspension. 2. The aqueous suspension according to claim 1, wherein the component (A) is a crosslinked silicone particle containing a non-crosslinked oil. 3. The aqueous suspension according to claim 1, wherein the component (B) is an oxyethylene adduct of a cetyl alcohol. 4. The water-based suspension according to claim 3, wherein the component (B) is an oxyethylene adduct of isocetyl alcohol. 5. The oxyethylene adduct of isocetyl alcohol as the component (B) has the formula: It is a polyoxyethylene hexyl decyl ether represented by (in formula, m is 2-40.), The water-based suspension of Claim 4 characterized by the above-mentioned. 6. The water-based suspension according to claim 1, wherein the HLB of the component (B) is 10 or more. 7. Further, (D) the general formula: (In the formula, R is a hydrogen atom or a methyl group, and n is 1 to
It is an integer of 10. ) The phenoxyethanols shown by these are contained, The aqueous suspension of Claim 1 characterized by the above-mentioned. 8. The aqueous suspension according to claim 7, wherein the component (D) is mixed with the component (B) in advance and then blended. 9. A crosslinked silicone particle having an average particle diameter of 0.1 to 500 μm, (E) an oil, (B) an oxyethylene adduct of a non-tallow-derived alcohol having 16 carbon atoms, and (C).
An aqueous emulsion of oil containing crosslinked silicone particles consisting of water. 10. The aqueous emulsion according to claim 9, wherein the component (A) is contained in the liquid droplets of the component (E) dispersed in water. 11. The water-based emulsion according to claim 9, wherein the component (B) is an oxyethylene adduct of cetyl alcohol. 12. The component (B) is an oxyethylene adduct of isocetyl alcohol, which is characterized in that
1. The water-based emulsion according to 1. 13. The oxyethylene adduct of isocetyl alcohol as the component (B) has the formula: It is a polyoxyethylene hexyl decyl ether represented by (in formula, m is 2-40.), The water-based emulsion of Claim 12 characterized by the above-mentioned. 14. The water-based emulsion according to claim 9, wherein the HLB of the component (B) is 10 or more. 15. Further, (D) the general formula: (In the formula, R is a hydrogen atom or a methyl group, and n is 1 to
It is an integer of 10. ) The water-based emulsion according to claim 9, which contains phenoxyethanols represented by 16. The water-based emulsion according to claim 15, wherein the component (D) is mixed with the component (B) in advance and then blended.