JP2000281903A - Emulsion, its preparation, and preparation of oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone oil or organic oil emulsion having crosslinked silicone particle-containing silicone oil or organic oil droplets dispersed in water, and an oil composition in which crosslinked silicone particles are uniformly dispersed. SOLUTION: A silicone oil or organic oil emulsion contains silicone oil or organic oil droplets having an average particle diameter of 0.1-500 μm dispersed in water which droplets contain crosslinked silicone particles having an average particle diameter of 0.05-100 μm (provided that the particles of the crosslinked silicone particles are smaller in particle diameter than the silicone oil or organic oil droplets). The silicone oil or organic oil emulsion can be obtained by dispersing a crosslinkable silicone composition containing a non-crosslinkable silicone oil or organic oil in water to effect crosslinking reaction. Further, a method for preparing an oil composition in which crosslinked silicone particles are dispersed comprises removing water from a crosslinked silicone particle- containing silicone oil or organic oil emulsion in silicone oil or organic oil droplets.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a silicone oil or organic oil emulsion, a method for producing the same, and a method for producing a silicone oil or organic oil composition. Emulsion of silicone oil or organic oil containing crosslinked silicone particles in oil droplets, method for producing the same, and method for producing oil composition in which crosslinked silicone particles are uniformly dispersed in silicone oil or organic oil About.

[0002]

2. Description of the Related Art There is known a method for producing crosslinked silicone particles containing silicone oil by dispersing a crosslinkable silicone composition containing a noncrosslinkable silicone oil in water and performing a crosslinking reaction. (Japanese Unexamined Patent Application Publication No. 64-81856 and Japanese Unexamined Patent Application Publication No.
Also, a method for producing crosslinked silicone particles containing an organic oil by dispersing a crosslinkable silicone composition containing a non-crosslinkable organic oil in water and performing a crosslinking reaction. Is also known (see JP-A-2-276864). However, with these production methods, it has not been possible to obtain an emulsion of silicone oil or organic oil in which crosslinked silicone particles are contained in droplets of silicone oil or organic oil dispersed in water.

On the other hand, a method of producing an emulsion in which silicone oil droplets and crosslinked silicone particles are dispersed in water by blending the silicone oil emulsion with silicone oil droplets dispersed in water and crosslinked silicone particles is known. It is known (Japanese Unexamined Patent Publication No.
1 and JP-A-9-53047),
Also known is a method of producing an emulsion in which organic oil droplets and crosslinked silicone particles are dispersed in water by blending the crosslinked silicone particles with an organic oil emulsion in which organic oil droplets are dispersed in water. I have.
However, in these production methods, the droplets of the silicone oil or the organic oil and the crosslinked silicone particles are independently dispersed in water, and the droplets of the silicone oil or the organic oil contain the crosslinked silicone particles. Such a silicone oil or organic oil emulsion could not be obtained.

Further, silicone oil compositions in which crosslinked silicone particles are dispersed in silicone oil are known (JP-A-63-152308;
-165509, JP-A-1-207354, JP-A-2-43263, and JP-T-6-6526.
No. 46, and JP-A-7-330537), and an organic oil composition in which crosslinked silicone particles are dispersed in an organic oil is also known (JP-A-9-30537).
No. 136813). As a method for producing such an oil composition, a method of simply mixing silicone oil and crosslinked silicone particles, or a method of producing a non-crosslinkable silicone oil as proposed in JP-A-2-43263. There is a method of treating the crosslinked product of the crosslinkable silicone composition containing under a shearing force, but in these production methods, it is not possible to uniformly disperse the crosslinked silicone particles in silicone oil or organic oil. However, the characteristics could not be fully exhibited.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have intensively studied the above-mentioned problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a silicone oil or organic oil emulsion containing crosslinked silicone particles in droplets of silicone oil or organic oil dispersed in water, a method for producing the same, and a silicone oil or organic oil. An object of the present invention is to provide a method for producing an oil composition in which crosslinked silicone particles are uniformly dispersed.

[0006]

The silicone oil or organic oil emulsion of the present invention is dispersed in water in the form of droplets of silicone oil or organic oil having an average particle size of 0.1 to 500 μm. 0.05 to 100
μm-crosslinked silicone particles (however, the particle size of the crosslinked silicone particles is smaller than the size of droplets of silicone oil or organic oil). The method for producing an emulsion of a silicone oil or an organic oil according to the present invention provides a cross-linkable silicone composition containing a non-crosslinkable silicone oil or an organic oil.
(However, the content of the non-crosslinkable silicone oil or organic oil is an amount exceeding the amount that the crosslinked product of the crosslinkable silicone composition can hold the non-crosslinkable silicone oil or organic oil.) And a cross-linking reaction. In addition, the method for producing a silicone oil composition or an organic oil composition of the present invention is characterized in that droplets of silicone oil or organic oil having an average particle size of 0.1 to 500 μm dispersed in water have an average particle size of 0.1. 0
Removing water from a silicone oil or organic oil emulsion containing 5-100 μm crosslinked silicone particles, where the particle size of the crosslinked silicone particles is smaller than the size of the droplets of silicone oil or organic oil. It is characterized by.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION First, the silicone oil or organic oil emulsion of the present invention will be described in detail. The emulsion of the present invention is characterized in that crosslinked silicone particles are contained in droplets of silicone oil or organic oil dispersed in water. In the emulsion of the present invention, the crosslinked silicone particles are used to crosslink a crosslinkable silicone composition.The crosslinkable silicone composition may be, for example, one obtained by a hydrosilylation crosslink reaction, one obtained by a condensation crosslink reaction, or an organic peroxide. And those subjected to a high energy ray crosslinking reaction. In particular, those subjected to a hydrosilylation crosslinking reaction or those subjected to a condensation crosslinking reaction are preferable.

In the emulsion of the present invention, the type of the silicone oil is not limited, but preferably has a molecular structure such as linear, partially branched linear, cyclic, or branched chain. Those having a chain or cyclic molecular structure are preferred. As the silicone oil, those which are compatible with the crosslinkable silicone composition forming the crosslinked silicone particles are preferable. The silicone oil is preferably one that does not participate in the crosslinking reaction when forming the crosslinked silicone particles. When the crosslinked silicone particles are those that have undergone a hydrosilylation crosslinking reaction, an alkenyl group or a silicon atom bond is contained in the molecule. No hydrogen atom, for example, dimethylpolysiloxane blocked with trimethylsiloxy group at both ends of molecular chain, methylphenylpolysiloxane blocked with trimethylsiloxy group at both ends of molecular chain, dimethylsiloxane / methylphenylsiloxane copolymer blocked with trimethylsiloxy group at both ends of molecular chain Trimethylsiloxy group-blocked dimethylsiloxane / methyl
(3,3,3-trifluoropropyl) siloxane copolymers, cyclic dimethylsiloxanes, and cyclic methylphenylsiloxanes. When the crosslinked silicone particles have been subjected to a condensation crosslinking reaction, silanol is contained in the molecule. In addition to the above-mentioned silicone oils having no groups, silicon-bonded hydrogen atoms or silicon-bonded hydrolyzable groups, for example, dimethylpolysiloxane capping dimethylvinylsiloxy groups at both ends of molecular chains, dimethylvinyl at both ends of molecular chains Siloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, trimethylsiloxy group-blocked methylvinylpolysiloxane at both ends of molecular chain, and cyclic methylvinylsiloxane. The viscosity of such a silicone oil is 1 to 100,000,000 mPa ·
s, and more preferably 2 to 10,000,000 mPa · s at 25 ° C.

In the emulsion of the present invention, the kind of the organic oil is not limited, but those which are compatible with the crosslinkable silicone composition forming the crosslinked silicone particles are preferable. The organic oil is preferably an aliphatic oil having a molecular structure such as linear, partially branched linear, cyclic, or branched, or an aromatic oil. Or an organic oil having a cyclic molecular structure. Further, this organic oil may have volatility. Such organic oils are preferably those that do not participate in the crosslinking reaction when forming the crosslinked silicone particles, and those having no alkenyl group in the molecule when the crosslinked silicone particles have been subjected to a hydrosilylation crosslinking reaction. And, for example, alkanes such as hexane, heptane, paraffin, and isoparaffin; aromatics such as toluene and xylene; carbon tetrachloride;
Chlorinated compounds such as methylene chloride; ketones such as methyl isobutyl ketone; alcohols such as undecyl alcohol;
Examples include ethers such as dibutyl ether; esters such as isopropyl laurate and isopropyl palmitate, and particularly preferably alkane having volatility. The viscosity of such an organic oil is preferably in the range of 1 to 100,000,000 mPa · s at 25 ° C., and in particular, 2 to 10,000, 25 ° C.
It is preferably within the range of 000 mPa · s.

[0010] Such a silicone oil or an organic oil may be used in combination with each other, or may have other components dissolved therein. By removing water and volatile silicone oils or organic oils from the emulsions of silicone oils or organic oils used, a mixture of crosslinked silicone particles with other components dissolved in the silicone oils or organic oils, or other Crosslinked silicone particles containing the components can be prepared. The other components that can be dissolved in the silicone oil or the organic oil are not particularly limited as long as they are soluble in the silicone oil or the organic oil. Organosilicon compounds such as rubber-like silicone oils; waxes such as carnauba wax, candelilla wax, mokuro, whale wax, jojoba oil, montan wax, beeswax, lanolin; liquid paraffin, isoparaffin;
Hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate, isopropyl palmitate,
2-ethylhexyl palmitate, 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,
Cacao oil, jojoba oil, sesame oil, safflower oil, soybean oil,
Oils such as camellia oil, squalane, persic oil, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, lard, etc .; glycol ester oils such as polypropylene glycol monooleate, neopentyl glycol-2-ethylhexanoate; isostearin Polyhydric alcohol ester oils such as acid triglyceride and coconut oil fatty acid triglyceride; and polyoxyalkylene ether oils such as polyoxyethylene lauryl ether and polyoxypropylene cetyl ether.

In the emulsion of the present invention, the average particle size of the silicone oil or organic oil droplets is 0.1 to 0.1.
It is necessary to be within the range of 500 μm, preferably within the range of 0.2 to 500 μm, more preferably within the range of 0.5 to 500 μm, and particularly preferably within the range of 0.5 to 200 μm. Is within the range. This is because it tends to be difficult to prepare an emulsion in which the average particle size of the droplets is less than the lower limit of the above range, whereas an emulsion exceeding the upper limit of the above range tends to have reduced stability. is there.

In the emulsion of the present invention, the average particle size of the crosslinked silicone particles must be in the range of 0.05 to 100 μm, and preferably in the range of 0.1 to 100 μm.
μm, particularly preferably 0.1 to 50 μm.
m. When the average particle size of the silicone oil or organic oil droplets is in the range of 0.2 to 500 μm, the average particle size of the crosslinked silicone particles is 0.2.
It is preferably in the range of 1 to 100 μm, in particular,
It is preferable that the thickness be in the range of 0.1 to 50 μm. When the average particle size of the silicone oil or organic oil droplets is in the range of 0.5 to 500 μm, the average particle size of the crosslinked silicone particles is preferably in the range of 0.1 to 100 μm. It is particularly preferable that the thickness be in the range of 0.1 to 50 μm. Further, the average particle size of the silicone oil or organic oil droplets is 0.5 to 200 μm.
When it is in the range of m, the average particle size of the crosslinked silicone particles is preferably in the range of 0.1 to 100 μm, and particularly preferably in the range of 0.1 to 50 μm. This tends to make it difficult to prepare crosslinked silicone particles having an average particle size less than the lower limit of the above range, while crosslinked silicone particles exceeding the upper limit of the above range tend to reduce the stability of the emulsion. Because there is. It goes without saying that in the emulsion of the present invention, the particle size of the crosslinked silicone particles is smaller than the particle size of the droplets of silicone oil or organic oil. The shape of the crosslinked silicone particles includes, for example, a sphere, a spindle shape, a flat shape, and an irregular shape, and is preferably a sphere.

The emulsion of the present invention can be used as a raw material for cosmetics or medical use, and by removing water from the emulsion, the crosslinked silicone particles are uniformly dispersed in silicone oil or organic oil. A liquid, cream, paste, or grease-like silicone oil composition or organic oil composition can be prepared. In addition, if the silicone oil or organic oil is volatile,
By dissolving other components in this silicone oil or organic oil, water and volatile silicone oil or organic oil are removed from the obtained silicone oil or organic oil emulsion, and the crosslinked silicone particles and silicone oil or It is possible to prepare a mixture with other components dissolved in an organic oil, or to prepare a crosslinked silicone particle containing an organosilicon compound or an organic compound as described above, which was conventionally difficult to contain in a crosslinked silicone particle. can do.

Next, the method for producing the silicone oil or organic oil emulsion of the present invention will be described in detail.
The crosslinkable silicone composition that can be used in the production method of the present invention is preferably a composition that forms an elastomer-like crosslinked product such as a rubbery or gel-like product by a crosslinking reaction. Cross-linking reaction type, condensation cross-linking reaction type, organic peroxide cross-linking reaction type, high-energy ray cross-linking reaction type, and preferably, hydrosilylation cross-linking reaction type or condensation cross-linking reaction Type.

Examples of the hydrosilylation crosslinkable silicone composition include an organopolysiloxane having at least two alkenyl groups in one molecule and an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. Examples include those comprising at least a siloxane and a catalyst for a hydrosilylation reaction.

Examples of the alkenyl group in the former organopolysiloxane include a vinyl group, an allyl group, a butenyl group, a pentenyl group and a hexenyl group, and a vinyl group is preferred. The groups other than the alkenyl group in the organopolysiloxane include a methyl group, an ethyl group,
Alkyl groups such as propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group, phenethyl group and 3-phenylpropyl group; Monovalent hydrocarbon groups such as halogenated hydrocarbon groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group are exemplified. The molecular structure of the organopolysiloxane includes, for example, linear, cyclic, network, and partially branched linear chains. In order to form elastomer-like crosslinked silicone particles, the molecular structure is linear or partially branched. It is preferred that the compound is linear. The viscosity of the organopolysiloxane is not limited as long as the crosslinkable silicone composition can be dispersed in water, but is preferably in the range of 20 to 100,000 mPas at 25 ° C., and particularly preferably, 20 at 25 ° C.
It is within the range of 10,000 mPa · s.

Examples of the group other than the hydrogen atom in the latter organopolysiloxane include the same monovalent hydrocarbon groups as described above. The molecular structure of the organopolysiloxane includes, for example, linear, cyclic, network, and partially branched linear. The viscosity of the organopolysiloxane is not limited as long as the crosslinkable silicone composition can be dispersed in water, and is preferably in the range of 1 to 10,000 mPa · s at 25 ° C. In the above-mentioned crosslinkable silicone composition, the compounding amount of the latter organopolysiloxane may be an amount sufficient to cure the above-mentioned composition, and is preferably 0.1 to 100 parts by weight of the former organopolysiloxane. It is in the range of 3 to 200 parts by weight.

In the crosslinkable silicone composition, the hydrosilylation reaction catalyst is a catalyst for accelerating the crosslinking reaction of the composition, and is preferably a platinum-based catalyst. This platinum-based catalyst includes chloroplatinic acid,
Alcohol solution of chloroplatinic acid, olefin complex of platinum,
Examples thereof include an alkenylsiloxane complex of platinum, platinum black, and platinum-supported silica. In the production method of the present invention, the crosslinkable silicone composition preliminarily containing the above-mentioned hydrosilylation reaction catalyst may be dispersed in water, or the crosslinkable silicone composition excluding the catalyst may be dispersed in water. Thereafter, by adding this catalyst to water, a crosslinkable silicone composition containing a hydrosilylation reaction catalyst in water can also be prepared. At this time, it is preferable to use an aqueous dispersion in which the hydrosilylation reaction catalyst is dispersed to an average particle size of 1 μm or less. In the above-mentioned crosslinkable silicone composition, the compounding amount of the hydrosilylation reaction catalyst may be an amount sufficient to promote the crosslinking reaction of the above-mentioned crosslinkable silicone composition. When a platinum-based catalyst is used, the amount of platinum metal in the present catalyst is preferably in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻³ parts by weight based on 100 parts by weight of the former organopolysiloxane.

The condensation-crosslinking reaction type silicone composition includes, for example, a hydroxyl group or an alkoxy group, an oxime group bonded to at least two silicon atoms in one molecule,
Organopolysiloxane having hydrolyzable groups such as acetoxy group and aminoxy group, silane having hydrolyzable groups such as alkoxy group, oxime group, acetoxy group and aminoxy group bonded to at least 3 silicon atoms in one molecule Examples include those comprising at least a system crosslinking agent and a condensation reaction catalyst such as an organotin compound and an organotitanium compound.

Examples of the alkoxy group in the organopolysiloxane include a methoxy group, an ethoxy group and a methoxyethoxy group. Examples of the oxime group in the organopolysiloxane include a dimethyl ketoxime group and a methyl ethyl ketoxime group. Other groups in this organopolysiloxane include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group, allyl group, butenyl group and pentenyl group. Hexenyl group; aryl group such as phenyl group, tolyl group and xylyl group; aralkyl group such as benzyl group, phenethyl group and 3-phenylpropyl group; 3-chloropropyl group;
Monovalent hydrocarbon groups such as halogenated hydrocarbon groups such as 3,3-trifluoropropyl group are exemplified. The molecular structure of the organopolysiloxane includes, for example, linear, cyclic, network, and partially branched linear, and in order to form elastomer-like crosslinked silicone particles, linear, cyclic,
Alternatively, it is preferably a straight chain having a partial branch. The viscosity of the organopolysiloxane is not limited as long as the crosslinkable silicone composition can be dispersed in water.
000 mPa · s, particularly preferably 2 mPa · s.
It is in the range of 20 to 10,000 mPa · s at 5 ° C.

The alkoxy group and the oxime group in the silane-based crosslinking agent include the same groups as described above. Examples of such a silane-based crosslinking agent include methyltrimethoxysilane, vinyltrimethoxysilane, methyltrioximesilane, and vinyltrioximesilane. In the above-mentioned crosslinkable silicone composition, the amount of the silane-based crosslinking agent to be added may be an amount sufficient to cure the above-mentioned composition, and is preferably 0.1 to 100 parts by weight of the above-mentioned organopolysiloxane. It is in the range of 3 to 200 parts by weight.

The catalyst for the condensation reaction of an organotin compound, an organotitanium compound or the like is a catalyst for accelerating the crosslinking reaction of the above-mentioned crosslinkable silicone composition. Examples thereof include dibutyltin dilaurate, dibutyltin diacetate, and the like. Examples include tin octenoate, dibutyltin dioctate, tin laurate, tetrabutyl titanate, tetrapropyl titanate, and dibutoxybis (ethylacetoacetate). In the above-mentioned crosslinkable silicone composition, the amount of the condensation reaction catalyst may be any amount that is sufficient to cause the above-mentioned composition to undergo a cross-linking reaction. It is in the range of 0.01 to 5 parts by weight, particularly preferably 0.05 to 2 parts by weight.

A filler may be added to the above-mentioned crosslinkable silicone composition as an optional component for adjusting its fluidity or improving the mechanical strength of the obtained crosslinked silicone particles. Examples of the filler include reinforcing fillers such as precipitated silica, fumed silica, calcined silica, and fumed titanium oxide; non-reinforcing fillers such as crushed quartz, diatomaceous earth, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate; A filler obtained by treating these surfaces with an organosilicon compound such as hexamethylsilazane, trimethylchlorosilane, polydimethylsiloxane, or polymethylhydrogensiloxane is exemplified.

The non-crosslinkable silicone oil contained in the crosslinkable silicone composition does not participate in the crosslinking reaction of the composition, and is linear, partially branched linear, cyclic, or branched. Those having a molecular structure such as a chain are preferable, and those having a linear or cyclic molecular structure are particularly preferable. As the silicone oil, those which are compatible with the crosslinkable silicone composition are preferred. As the non-crosslinkable silicone oil, when the composition is a hydrosilylation crosslinkable reaction type, it does not have an alkenyl group or a silicon-bonded hydrogen atom in the molecule, for example, trimethylsiloxy at both ends of the molecular chain. Group-blocked dimethylpolysiloxane, molecular chain terminal trimethylsiloxy group-blocked methylphenylpolysiloxane, molecular chain terminal trimethylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain terminal-trimethylsiloxy group-blocked dimethylsiloxane
Methyl (3,3,3-trifluoropropyl) siloxane copolymer, cyclic dimethyl siloxane, cyclic methyl phenyl siloxane, and when the composition is of a condensation crosslinking reaction type, In addition to the same silicone oil having no silanol group, silicon-bonded hydrogen atom, or silicon-bonded hydrolyzable group, for example, dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain, dimethyl at both ends of a molecular chain Examples thereof include a vinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, a molecular vinyl chain-terminated trimethylsiloxy group-blocked methylvinylpolysiloxane, and a cyclic methylvinylsiloxane. The viscosity of such a non-crosslinkable silicone oil ranges from 1 to 100,000,000 mP at 25 ° C.
It is preferably in the range of a · s, and particularly preferably in the range of 2 to 10,000,000 mPa · s at 25 ° C.

The non-crosslinkable organic oil contained in the crosslinkable silicone composition does not participate in the crosslinking reaction of the composition, and is obtained by subjecting the crosslinked silicone particles to a hydrosilylation crosslinking reaction. In some cases, the compound does not have an alkenyl group in the molecule. The organic oil is preferably compatible with the crosslinkable silicone composition. Examples of such non-crosslinkable organic oils include alkanes such as hexane, heptane, paraffin and isoparaffin; aromatics such as toluene and xylene; chlorinated compounds such as carbon tetrachloride and methylene chloride;
Ketones such as methyl isobutyl ketone; alcohols such as undecyl alcohol; ethers such as dibutyl ether; esters such as isopropyl laurate and isopropyl palmitate; and especially volatile alkane. preferable. The viscosity of such a non-crosslinkable organic oil is 1 to 100,0 at 25 ° C.
It is preferably in the range of 00,000 mPa · s, and particularly preferably in the range of 2 to 10,000,000 mPa · s at 25 ° C.

The content of the non-crosslinkable silicone oil or organic oil in the crosslinkable silicone composition depends on whether the crosslinked product of the crosslinkable silicone composition contains non-crosslinkable silicone oil or organic oil in the crosslinked product. It is necessary that the amount exceeds the amount that can hold the oil, that is, the amount of the non-crosslinkable silicone oil or organic oil that can be contained in the crosslinked product. The amount that can be held is
Although it depends on the combination of the crosslinkable silicone composition and the non-crosslinkable silicone oil or organic oil, generally, based on 100 parts by weight of the crosslinkable silicone composition,
200 non-crosslinkable silicone or organic oils
It is preferably in the range of 5,000 to 5,000 parts by weight, and particularly preferably in the range of 250 to 2,000 parts by weight. Other components may be dissolved in the non-crosslinkable silicone oil or organic oil in the crosslinkable silicone composition in advance. Other components include
Those exemplified above are mentioned. The content of other components that can be blended in the crosslinkable silicone composition varies depending on the combination of the crosslinkable silicone composition and the non-crosslinkable silicone oil or organic oil. The other component is preferably in the range of 0.001 to 200 parts by weight, and particularly preferably in the range of 0.1 to 50 parts by weight with respect to parts.

The production method of the present invention is characterized in that a crosslinkable silicone composition containing such a non-crosslinkable silicone oil or an organic oil is dispersed in water and then subjected to a crosslinking reaction. . As a method of dispersing this crosslinkable silicone composition in water, there are a homomixer, a paddle mixer, a Henschel mixer, a homodisper, a colloid mill, a propeller stirrer, a homogenizer, an in-line continuous emulsifier, an ultrasonic emulsifier, and vacuum kneading. A method of dispersing this composition in water by an apparatus such as a machine is exemplified.

In the production method of the present invention, the amount of water used is not limited, but is preferably in the range of 5 to 99% by weight of the whole emulsion, and particularly preferably in the range of 10 to 80% by weight. Is preferred.

In order to stably disperse the crosslinkable silicone composition in water, it is preferable to use a nonionic surfactant, a cationic surfactant, or an anionic surfactant. Preferably, an activity is used. The amount of the surfactant used is 0.1 to 100 parts by weight of a crosslinkable silicone composition containing a non-crosslinkable silicone oil or an organic oil.
It is preferably in the range of 20 parts by weight, in particular,
It is preferably in the range of 0.5 to 10 parts by weight.

By heating the emulsion of the crosslinkable silicone composition thus prepared, leaving it at room temperature, or irradiating it with a high energy ray,
The crosslinkable silicone composition dispersed in water can be crosslinked.

In the production method of the present invention, the average particle size of the droplets of silicone oil or organic oil dispersed in water needs to be within the range of 0.1 to 500 μm, and preferably 0.2. ５００500 μm,
More preferably, it is in the range of 0.5 to 500 μm,
Particularly preferably, it is in the range of 0.5 to 200 μm.
This is because it tends to be difficult to prepare emulsions in which the average particle size of the droplets is less than the lower limit of the above range, while emulsions exceeding the upper limit of the above range tend to have reduced stability. Because there is.

The average particle size of the crosslinked silicone particles contained in the droplets of the silicone oil or the organic oil must be in the range of 0.05 to 100 μm, preferably 0.1. To 100 μm, particularly preferably 0.1 to 50 μm. When the average particle size of the silicone oil or organic oil droplets is in the range of 0.2 to 500 μm, the average particle size of the crosslinked silicone particles is 0.1 to 100 μm.
m, preferably 0.1 to 50.
It is preferably within the range of μm. In addition, the average particle size of the silicone oil or organic oil droplets is 0.5 to 5%.
When it is within the range of 00 μm, the average particle size of the crosslinked silicone particles is preferably within the range of 0.1 to 100 μm, and particularly preferably within the range of 0.1 to 50 μm. Furthermore, when the average particle size of the silicone oil or organic oil droplets is in the range of 0.5 to 200 μm, the average particle size of the crosslinked silicone particles is 0.1 to 200 μm.
It is preferably within a range of 100 μm, and particularly preferably 0.1 μm.
It is preferable that the thickness be in the range of 1 to 50 μm. this is,
It tends to be difficult to prepare crosslinked silicone particles having an average particle size less than the lower limit of the above range, whereas crosslinked silicone particles exceeding the upper limit of the above range tend to reduce the stability of the emulsion. It is. In the production method of the present invention, it goes without saying that the particle size of the crosslinked silicone particles is smaller than the particle size of the droplets of silicone oil or organic oil. The shape of the crosslinked silicone particles is
For example, a spherical shape, a spindle shape, a flat shape, and an irregular shape are mentioned, and a spherical shape is preferable.

Next, the method for producing the silicone oil composition or the organic oil composition of the present invention will be described in detail.
The production method of the present invention is characterized in that water is removed from an emulsion of silicone oil or organic oil containing crosslinked silicone particles in droplets of silicone oil or organic oil dispersed in water. In the emulsion of the silicone oil or the organic oil used in the production method of the present invention, the crosslinked silicone particles are obtained by crosslinking a crosslinkable silicone composition, and the crosslinkable silicone composition is, for example, obtained by a hydrosilylation crosslinking reaction, Those subjected to a condensation cross-linking reaction, those subjected to an organic peroxide cross-linking reaction, those subjected to a high-energy ray cross-linking reaction, and particularly, those subjected to a hydrosilylation cross-linking reaction,
Alternatively, it is preferable that the resin is subjected to a condensation crosslinking reaction.

In the emulsion of the silicone oil used in the production method of the present invention, the type of the silicone oil is not limited, but it may have a molecular structure such as linear, partially branched linear, cyclic, or branched. Are preferred, and particularly preferred are those having a linear or cyclic molecular structure. As the silicone oil, those which are compatible with the crosslinkable silicone composition forming the crosslinked silicone particles are preferable. The silicone oil is preferably one that does not participate in the crosslinking reaction when forming the crosslinked silicone particles. When the crosslinked silicone particles are those that have undergone a hydrosilylation crosslinking reaction, an alkenyl group or a silicon atom bond is contained in the molecule. Those having no hydrogen atom, for example, dimethylpolysiloxane capped with trimethylsiloxy groups at both ends of molecular chains, methylphenylpolysiloxane capped with trimethylsiloxy groups at both ends of molecular chains, dimethylsiloxane / methylphenylsiloxane capped with trimethylsiloxy groups at both ends of molecular chains Copolymer, both ends of molecular chain trimethylsiloxy group-blocked dimethylsiloxane / methyl
(3,3,3-trifluoropropyl) siloxane copolymers, cyclic dimethylsiloxanes, and cyclic methylphenylsiloxanes. When the crosslinked silicone particles have been subjected to a condensation crosslinking reaction, silanol is contained in the molecule. In addition to the above-mentioned silicone oils having no groups, silicon-bonded hydrogen atoms or silicon-bonded hydrolyzable groups, for example, dimethylpolysiloxane capping dimethylvinylsiloxy groups at both ends of molecular chains, dimethylvinyl at both ends of molecular chains Siloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, trimethylsiloxy group-blocked methylvinylpolysiloxane at both ends of molecular chain, and cyclic methylvinylsiloxane. The viscosity of such a silicone oil is 1 to 100,000,000 mPa ·
s, and more preferably 2 to 10,000,000 mPa · s at 25 ° C.

In the emulsion of the organic oil used in the production method of the present invention, the type of the organic oil is not limited, but those which are compatible with the crosslinkable silicone composition forming the crosslinked silicone particles are preferable. This organic oil is linear, partially branched linear, cyclic,
It is preferably an aliphatic oil having a molecular structure such as a branched chain, or an aromatic oil, and particularly preferably an organic oil having a linear or cyclic molecular structure. Further, this organic oil may have volatility. Such organic oils preferably do not participate in a crosslinking reaction when forming crosslinked silicone particles, and when the crosslinked silicone particles have undergone a hydrosilylation crosslinking reaction, those having no alkenyl group in the molecule. For example, alkanes such as hexane, heptane, paraffin, and isoparaffin; aromatics such as toluene and xylene; chlorinated products such as carbon tetrachloride and methylene chloride; ketones such as methyl isobutyl ketone; undecyl alcohol; Alcohols; ethers such as dibutyl ether; esters such as isopropyl laurate and isopropyl palmitate; and volatile alkane is particularly preferable. The viscosity of such organic oils is between 1 and 100,000,
It is preferably within the range of 000 mPa · s, in particular,
It is preferably in the range of 2 to 10,000,000 mPa · s at 25 ° C.

In the emulsion of silicone oil or organic oil used in the production method of the present invention, the average particle size of the droplets of silicone oil or organic oil is 0.1 to 0.1.
It is necessary to be within the range of 500 μm, preferably within the range of 0.2 to 500 μm, more preferably within the range of 0.5 to 500 μm, and particularly preferably within the range of 0.5 to 200 μm. Is within the range. This is because there is a tendency that it is difficult to prepare an emulsion in which the average particle size of the droplets is less than the lower limit of the above range, whereas an emulsion exceeding the upper limit of the above range tends to have reduced stability. Because there is.

In the emulsion of silicone oil or organic oil used in the production method of the present invention, the average particle size of the crosslinked silicone particles must be in the range of 0.05 to 100 μm, preferably 0.1 to 100 μm. 100
μm, particularly preferably 0.1 to 50 μm.
m. When the average particle size of the silicone oil or organic oil droplets is in the range of 0.2 to 500 μm, the average particle size of the crosslinked silicone particles is 0.2.
It is preferably in the range of 1 to 100 μm, in particular,
It is preferable that the thickness be in the range of 0.1 to 50 μm. When the average particle size of the silicone oil or organic oil droplets is in the range of 0.5 to 500 μm, the average particle size of the crosslinked silicone particles is preferably in the range of 0.1 to 100 μm. It is particularly preferable that the thickness be in the range of 0.1 to 50 μm. Further, the average particle size of the silicone oil or organic oil droplets is 0.5 to 200 μm.
When it is in the range of m, the average particle size of the crosslinked silicone particles is preferably in the range of 0.1 to 100 μm, and particularly preferably in the range of 0.1 to 50 μm. This tends to make it difficult to prepare crosslinked silicone particles having an average particle size less than the lower limit of the above range, while crosslinked silicone particles exceeding the upper limit of the above range tend to reduce the stability of the emulsion. Because there is. It goes without saying that in the emulsion of the present invention, the particle size of the crosslinked silicone particles is smaller than the particle size of the droplets of silicone oil or organic oil. The shape of the crosslinked silicone particles includes, for example, a sphere, a spindle shape, a flat shape, and an irregular shape, and is preferably a sphere.

The method for preparing the emulsion of silicone oil or organic oil used in the production method of the present invention is not limited, but it is preferable to use the above-mentioned method for producing an emulsion of silicone oil or organic oil. The production method of the present invention is characterized in that water is removed from such a silicone oil or organic oil emulsion by means such as air drying, hot air drying, vacuum drying, and heat drying. The silicone oil composition or the organic oil composition thus obtained has the crosslinked silicone particles uniformly dispersed in the silicone oil or the organic oil, and the shape is, for example, liquid, cream, paste, Or it is grease-like. Such a silicone oil composition or an organic oil composition can be used for lubricants, additives for resins, cosmetics, pharmaceuticals, and the like.

[0039]

EXAMPLES The emulsion of the silicone oil or organic oil of the present invention, the method for producing the same, and the method for producing the silicone oil composition or the organic oil composition will be described in detail with reference to examples. In addition, the viscosity in an Example is a value measured at 25 degreeC.

The average particle size and stability of the silicone oil emulsion, the average particle size of the crosslinked silicone particles, and the characteristics of the silicone oil composition were determined as follows. [Average particle size of silicone oil emulsion] Laser diffraction particle size distribution analyzer
(LA-500 of HORIBA, Ltd.), and the obtained median diameter (particle diameter corresponding to 50% of the cumulative distribution) was defined as the average particle diameter. [Stability of Silicone Oil Emulsion] 180 mL of the silicone oil emulsion was sealed in a 225 mL glass bottle (105 mm in depth, 50 mm in diameter) and left at room temperature for one week. After standing, the thickness of the aqueous layer separated from the silicone oil emulsion was measured. [Dispersibility of Crosslinked Silicone Particles] The silicone oil emulsion was air-dried in the form of a glass plate, and the shape, aggregation state, and distribution of the crosslinked silicone particles were observed under a stereoscopic microscope. If all the crosslinked silicone particles are dispersed as primary particles, it is evaluated as ○, and aggregated particles of several 100 μm or 500
When primary particles having a size of μm or more were present, it was evaluated as ×, and between them was evaluated as Δ. [Average Particle Size of Crosslinked Silicone Particles] A silicone oil emulsion was air-dried in a glass plate shape, and a crosslinked silicone particle was collected under a stereoscopic microscope to prepare a sample, which was observed under an electron microscope. The average particle size was determined from the above. [Viscoelasticity of Silicone Oil Composition] The storage elastic modulus G ′ (× 10 ³ dyne / cm ² ), loss elastic modulus G ″ (× 10 ³ dyne / cm ² ), and loss tangent tan δ of the silicone oil composition were determined. ARES
Viscoelasticity measuring device (Reometric Scienti)
fic). The measurement conditions were room temperature, 25 mm parallel plate, gap: 0.5 to 0.6.
mm, strain: 10%, frequency: 0.1 to 50 rad / s.

Example 1 18.8 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of molecular chain having a viscosity of 400 mPa · s, and dimethylsiloxane methylhydrogen blocked with trimethylsiloxy groups at both ends of molecular chain having a viscosity of 30 mPa · s. 1.2 parts by weight of siloxane copolymer (content of silicon-bonded hydrogen atoms = 0.5% by weight), viscosity 100 mPa
A crosslinkable silicone composition was prepared by mixing 80 parts by weight of dimethylpolysiloxane capped with trimethylsiloxy groups at both ends of the molecular chain of s. Then, 53 parts by weight of a 3% by weight aqueous solution of polyoxyethylene nonylphenyl ether (HLB = 13.1) was added to the crosslinkable silicone composition, and the mixture was emulsified by a colloid mill. Then, 50 parts by weight of pure water was further added to perform crosslinking. An aqueous emulsion of a water-soluble silicone composition was prepared.

A separately prepared aqueous emulsion of a platinum-based catalyst containing 1,1-divinyl-1,1,3,3-tetramethoxydisiloxane complex of platinum as a main component (average particle diameter of platinum-based catalyst) = 0.05 μm, platinum metal concentration = 0.0
5% by weight) in an aqueous emulsion of the crosslinkable silicone composition described above, in an amount such that platinum metal is 20 ppm by weight based on dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both molecular chain terminals in the emulsion. To form an aqueous emulsion of a crosslinkable silicone composition.

By leaving this emulsion at room temperature for one day, a hydrosilylation cross-linking reaction of the cross-linkable silicone composition is performed, and a silicone oil containing cross-linked silicone particles in silicone oil droplets dispersed in water. An emulsion was prepared.

Next, this emulsion was transferred to an aluminum dish having a diameter of 5 cm and air-dried in a fume hood for 3 days to remove water, thereby preparing a silicone oil composition comprising silicone oil and crosslinked silicone particles. This silicone oil composition was creamy. Observation of the silicone oil composition with a stereomicroscope revealed that the crosslinked silicone particles were uniformly dispersed in the silicone oil, and that the shape of the crosslinked silicone particles was spherical.

Example 2 The viscosity used in Example 1 was 10
Instead of 80 parts by weight of a dimethylpolysiloxane capped with trimethylsiloxy groups at both ends of the molecular chain of 0 mPa · s, a viscosity of 6 mPa · s
A water-based emulsion of a crosslinkable silicone composition was prepared in the same manner as in Example 1 except that 80 parts by weight of dimethylpolysiloxane capped with trimethylsiloxy groups at both ends of the molecular chain of s was used. This emulsion was subjected to a hydrosilylation crosslinking reaction in the same manner as in Example 1 to prepare a silicone oil emulsion containing silicone oil droplets dispersed in water in silicone oil droplets.

Next, water was removed from this emulsion in the same manner as in Example 1 to prepare a silicone oil composition comprising silicone oil and crosslinked silicone particles. This silicone oil composition was creamy. Observation of the silicone oil composition with a stereomicroscope revealed that the crosslinked silicone particles were uniformly dispersed in the silicone oil, and that the shape of the crosslinked silicone particles was spherical.

Example 3 Cooled to 5 ° C., viscosity 1.0
100 mPa · s 100 parts by weight of a dimethylpolysiloxane endblocked with hydroxyl groups at both molecular chains (hydroxyl content = 1.3% by weight),
4.83 parts by weight of a methylhydrogenpolysiloxane (content of silicon-bonded hydrogen atoms = 1.5% by weight) capped with trimethylsiloxy groups at both ends of a molecular chain having a viscosity of 10 mPa · s and a molecular chain having a viscosity of 1,000 mPa · s After uniformly mixing 500 parts by weight of dimethylpolysiloxane endblocked with trimethylsiloxy groups and 0.75 parts by weight of dibutyltin dioctate, Terditol TMN-6 (manufactured by Union Carbide, ethylene oxide adduct of trimethylnonanol) 5 A mixture of 80% by weight of ion-exchanged water and 80 parts by weight of emulsified water was added and emulsified by a colloid mill, and 35 parts by weight of pure water was further added to prepare an aqueous emulsion of a crosslinkable silicone composition.

When a part of this emulsion was sprayed with a spray drier (entrance temperature: 300 ° C., outlet temperature: 100 ° C.), crosslinked silicone particles could not be obtained because grease-like substances adhered to the inner wall of the dryer. .

By allowing the aqueous emulsion of the crosslinkable silicone composition to stand at room temperature for one week, a condensation crosslinking reaction of the crosslinkable silicone composition is performed, and the crosslinked silicone particles are dispersed in silicone oil droplets dispersed in water. A silicone oil emulsion containing was prepared.

Next, water was removed from this emulsion in the same manner as in Example 1 to prepare a silicone oil composition comprising silicone oil and crosslinked silicone particles. This silicone oil composition was creamy. Observation of the silicone oil composition with a stereomicroscope revealed that the crosslinked silicone particles were uniformly dispersed in the silicone oil, and that the shape of the crosslinked silicone particles was spherical.

[Comparative Example 1] 100 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 1,000 mPa · s (having a hydroxyl group content of 1.3% by weight) and trimethyl at both ends of a molecular chain having a viscosity of 10 mPa · s. 10 parts by weight of a siloxy group-blocked methyl hydrogen polysiloxane (content of silicon-bonded hydrogen atoms = 1.5% by weight), and 50 parts by weight of a dimethylpolysiloxane having a molecular weight at both ends of a trimethylsiloxy group and a viscosity of 1,000 mPa · s. Mixture A was prepared by mixing uniformly.

Further, a dimethylpolysiloxane having a hydroxyl group-terminated hydroxyl group at both molecular chains having a viscosity of 1,000 mPa · s (content of hydroxyl group =
(1.3% by weight) 100 parts by weight, 50 parts by weight of dimethylpolysiloxane capped with trimethylsiloxy groups at both molecular chains having a viscosity of 1,000 mPa · s, and 1.5 parts of dibutyltin dioctate.
The parts by weight were uniformly mixed to prepare a mixture B.

The mixture A and the mixture B were uniformly mixed at a weight ratio of 1: 1. Then, 5% by weight of Tergitol TMN-6 (manufactured by Union Carbide, an ethylene oxide adduct of trimethylnonanol) and ion-exchanged water were mixed. 1,700
The mixture by weight was added and emulsified by a colloid mill.
This emulsion is spray-dried (entrance temperature: 300
(C, outlet temperature: 100 ° C) to remove water, whereby crosslinked silicone particles could be obtained with a yield of 98%. The crosslinked silicone particles were rubber-like, and the shape was spherical. No bleeding of silicone oil from the crosslinked silicone particles was observed.

Comparative Example 2 44.5 parts by weight of a dimethylpolysiloxane having a vinylmethylsiloxy group at both ends of a molecular chain having a viscosity of 5 mPa · s and a viscosity of 20 mPa · s were placed in a planetary mixer.
100 parts by weight of methyl hydrogen polysiloxane (both containing silicon-bonded hydrogen atoms = 1.5% by weight) having a molecular chain at both ends of a molecular chain and having a viscosity of 6 mPa · s. After mixing 758 parts by weight, 2 parts of chloroplatinic acid was added thereto.
A cross-linkable silicone composition was prepared by adding 0.5 parts by weight of a% by weight-isopanol solution. The resulting crosslinkable silicone composition was stirred for 2 hours while being heated to 70 to 80 ° C., whereby a hydrosilylation crosslinking reaction of the crosslinkable silicone composition was performed to prepare a soft silicone oil composition. When this silicone oil composition was kneaded under shearing force with three rolls, a paste-like silicone oil composition was prepared. Observation of the silicone oil composition with a stereomicroscope revealed that irregularly shaped crosslinked silicone particles were dispersed in the silicone oil, but the dispersion was uneven, and the particle size of the crosslinked silicone particles was about 100 to 500 μm. It turned out to be big.

Comparative Example 3 94 parts by weight of a dimethylvinylsiloxane-blocked dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 mPa · s, and a dimethylsiloxane and methylhydrogensiloxane having a viscosity of 30 mPa · s blocked at both ends of a molecular chain at a trimethylsiloxy group. A crosslinkable silicone composition was prepared by mixing 6 parts by weight of a polymer (content of silicon-bonded hydrogen atoms = 0.5% by weight), and 3% by weight of polyoxyethylene nonyl phenyl ether (HLB = 13) was prepared. .1) 53 parts by weight of an aqueous solution was added and emulsified by a colloid mill, and 50 parts by weight of pure water was further added to prepare an aqueous emulsion of a crosslinkable silicone composition.

A separately prepared aqueous emulsion of a platinum-based catalyst containing 1,1-divinyl-1,1,3,3-tetramethoxydisiloxane complex of platinum as a main component (average particle diameter of platinum-based catalyst) : 0.05 μm, platinum metal concentration: 0.0
5% by weight) to the aqueous emulsion of the above-mentioned crosslinkable silicone composition, and 20 ppm by weight of platinum metal in the present catalyst with respect to dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both molecular chain terminals in the emulsion. The amounts were uniformly mixed to prepare an aqueous emulsion of the crosslinkable silicone composition.

By leaving this emulsion at room temperature for one day, a hydrosilylation cross-linking reaction of the cross-linkable silicone composition was carried out to prepare an aqueous suspension of cross-linked silicone particles in which cross-linked silicone particles were dispersed in water. An emulsion of dimethylpolysiloxane having a viscosity of 100 mPa · s and capped with trimethylsiloxy groups at both molecular ends, which is 4 times the amount of the crosslinked silicone particles, is added to this suspension.
(Concentration: 50% by weight) and uniformly mixed. The mixture was transferred to an aluminum dish having a diameter of 5 cm and air-dried in a fume hood for 3 days to remove water, thereby preparing a silicone oil composition comprising silicone oil and crosslinked silicone particles. Although this silicone oil composition was creamy, the silicone oil was floating on the liquid surface, and when observed with a stereoscopic microscope, it was found that the crosslinked silicone particles were unevenly dispersed in the silicone oil. Was.

[0058]

[Table 1]

The average particle size and stability of the organic oil emulsion, the average particle size of the crosslinked silicone particles, and the characteristics of the organic oil composition were determined as follows. [Average Particle Size of Organic Oil Emulsion] The organic oil emulsion was measured with a laser diffraction type particle size distribution analyzer (LA-500 manufactured by Horiba, Ltd.), and the obtained median diameter (particle size corresponding to 50% of the cumulative distribution) was measured. The average particle size was used. [Stability of Organic Oil Emulsion] A 225 mL glass bottle (105 mm deep,
(50 mm in diameter) and left at room temperature for 1 week. After standing, the thickness of the aqueous layer separated from the organic oil emulsion was measured. [Dispersibility of crosslinked silicone particles] The organic oil emulsion was dropped on a glass plate, the emulsion was broken with acetone, air-dried, and the shape, aggregation state, and distribution of the crosslinked silicone particles were observed under a stereoscopic microscope. When all the crosslinked silicone particles were dispersed as primary particles, it was evaluated as ○. When there were aggregated particles of several hundred μm or primary particles of 500 μm or more, it was evaluated as ×, and between them was evaluated as Δ. [Average particle size of crosslinked silicone particles] An organic oil emulsion is dropped on a glass plate, the emulsion is broken with acetone, air-dried, a crosslinked silicone particle is collected under a stereoscopic microscope, and a sample is prepared. The average particle diameter was determined from the particle diameters of 10 particles. [Viscoelasticity of Organic Oil Composition] About 10 g of an organic oil emulsion was placed in an aluminum dish, air-dried for one week at room temperature, and the storage elastic modulus G ′ of the organic oil composition from which water was removed (× 10 ³ d)
yne / cm ² ), loss elastic modulus G '' (× 10 ³ dyne / cm ² ), loss tangent tanδ and complex viscosity (η *)
(Manufactured by Reometric Scientific). The measurement conditions were room temperature, 25 mm parallel plate, gap: 0.5 to 0.6 mm, and strain: 10
%, Frequency: 0.1 to 50 rad / s.

Example 4 A dimethylsiloxane-methylvinylsiloxane copolymer having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 mPa · s (content of silicon-bonded vinyl group = 1.18% by weight) 9.01 0.99 parts by weight of a dimethylsiloxane / methylhydrogensiloxane copolymer (content of silicon-bonded hydrogen atoms = 0.44% by weight) having a trimethylsiloxy group at both ends of the molecular chain having a viscosity of 50 mPa · s and 0.99 parts by weight of isoparaffin ( 85 parts by weight of Isosol 400K, C ₁₆ H ₃₄ manufactured by Nippon Petrochemical Co., Ltd., 5 parts by weight of a dimethylpolysiloxane capped at both ends of a molecular chain with a viscosity of 10 million mPa · s and 5 parts by weight of dimethylpolysiloxane are mixed to form a crosslinkable silicone composition Was prepared. Next, 30 parts by weight of a 3% by weight aqueous solution of polyoxyethylene nonylphenyl ether (HLB = 13.1) was added to the crosslinkable silicone composition, and the mixture was emulsified by a colloid mill.
An aqueous emulsion of an organic oil containing the crosslinkable silicone composition was prepared by adding parts by weight.

A separately prepared aqueous emulsion of a platinum-based catalyst containing 1,1-divinyl-1,1,3,3-tetramethoxydisiloxane complex of platinum as a main component (average particle size of the platinum-based catalyst) = 0.05 μm, platinum metal concentration = 0.0
5% by weight) of an organic oil containing the above-mentioned crosslinkable silicone composition in an aqueous emulsion of an organic oil containing 20 ppm by weight of platinum metal based on dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both molecular chains at both ends of the emulsion.
(About 1 part by weight) was uniformly mixed to obtain an aqueous emulsion of an organic oil containing a crosslinkable silicone composition.

The emulsion is allowed to stand at room temperature for one day to perform a hydrosilylation crosslinking reaction of the crosslinkable silicone composition, and the organic oil containing the crosslinked silicone particles in the organic oil droplets dispersed in water. An emulsion was prepared.

Next, this emulsion was transferred to an aluminum dish having a diameter of 5 cm and air-dried in a fume hood for 3 days to remove water, whereby a paste-like organic oil composition was obtained. When this organic oil composition was confirmed with a stereomicroscope, it was confirmed that the crosslinked silicone particles were uniformly dispersed in isoparaffin and high-viscosity silicone oil, and that the crosslinked silicone particles were all spherical in shape.

Example 5 A dimethylsiloxane-methylvinylsiloxane copolymer having a viscosity of 400 mPa · s and a dimethylvinylsiloxy group at both ends of the molecular chain (silicon atom-bonded vinyl group content = 1.18% by weight) 22.0 8.0 parts by weight of a dimethylsiloxane-methylhydrogensiloxane copolymer (both content of silicon-bonded hydrogen atoms = 0.05% by weight) having a trimethylsiloxy group at both ends of the molecular chain having a viscosity of 75 mPas and a viscosity of 75 mPas. Nippon Petrochemicals Co. Isosol 400 K, and the C ₁₆ H ₃₄₎ 80 parts by weight with crosslinkable silicone composition was prepared. Next, a 3% by weight aqueous solution of polyoxyethylene nonylphenyl ether (HLB = 13.1) was added to the crosslinkable silicone composition.
After addition of 25 parts by weight of pure water, an aqueous emulsion of an organic oil containing a crosslinkable silicone composition was prepared.

The emulsion was subjected to a hydrosilylation crosslinking reaction in the same manner as in Example 4, to prepare an organic oil emulsion containing crosslinked silicone particles in organic oil droplets dispersed in water.

Next, water was removed from this emulsion in the same manner as in Example 4 to prepare a paste-like organic oil composition. Observation of this organic oil composition with a stereomicroscope revealed that the crosslinked silicone particles were uniformly dispersed in isoparaffin, and the shape of the crosslinked silicone particles was spherical.

Example 6 A dimethylsiloxane-methylvinylsiloxane copolymer having a viscosity of 400 mPa · s and a dimethylvinylsiloxy group at both ends of the molecular chain (silicon-bonded vinyl group content = 1.18% by weight) 15.30 4.70 parts by weight of a dimethylsiloxane-methylhydrogensiloxane copolymer (both content of silicon-bonded hydrogen atoms = 0.05% by weight) having a trimethylsiloxy group at both ends of the molecular chain having a viscosity of 75 mPa · s and isoparaffin ( A crosslinkable silicone composition was prepared by mixing 75 parts by weight of Isosol 400K, C ₁₆ H ₃₄ manufactured by Nippon Petrochemical Co., and 5 parts by weight of octamethylcyclotetrasiloxane. Next, 30 parts by weight of a 3% by weight aqueous solution of polyoxyethylene nonylphenyl ether (HLB = 13.1) was added to the crosslinkable silicone composition, and the mixture was emulsified by a colloid mill. An aqueous emulsion of a water-soluble silicone composition was prepared.

A separately prepared aqueous emulsion of a platinum-based catalyst containing 1,1-divinyl-1,1,3,3-tetramethoxydisiloxane complex of platinum as a main component (average particle diameter of platinum-based catalyst) = 0.05 μm, platinum metal concentration = 0.0
5% by weight) in the aqueous emulsion of the crosslinkable silicone composition-containing organic oil described above, and 20 ppm by weight of platinum metal based on the dimethylpolysiloxane endblocked by dimethylvinylsiloxy groups at both molecular chains in the emulsion. A water-based emulsion of an organic oil containing the crosslinkable silicone composition was prepared by mixing the mixture in a uniform amount.

The emulsion is allowed to stand at room temperature for one day to perform a hydrosilylation crosslinking reaction of the crosslinkable silicone composition, and the organic oil containing the crosslinked silicone particles in the organic oil droplets dispersed in water. An emulsion was prepared.

Next, the emulsion was transferred to an aluminum dish having a diameter of 5 cm and air-dried in a fume hood for 3 days to remove water and octamethylcyclotetrasiloxane (part), whereby a paste-like organic oil composition was obtained. Obtained.
When this organic oil composition was observed with a stereoscopic microscope,
The crosslinked silicone particles were uniformly dispersed in the isopaffine and octamethylcyclotetrasiloxane, confirming that the crosslinked silicone particles were spherical in shape.

Comparative Example 4 Crosslinked silicone particles (Trefle E-506 manufactured by Dow Corning Toray Silicone Co., Ltd.)
When 15 parts by weight (average particle size = 4 μm) and 85 parts by weight of isoparaffin (Isosol 400K, C ₁₆ H ₃₄ , manufactured by Nippon Petrochemical Co., Ltd.) were stirred and mixed, a thixotropic paste-like mixture was obtained. 3% by weight of polyoxyethylene nonylphenyl ether (HLB = 13.
1) After adding 53 parts by weight of an aqueous solution, 50 parts by weight of pure water was further added to prepare an aqueous emulsion of an organic oil containing a crosslinkable silicone composition. This emulsion was heterogeneous in that crosslinked silicone particles swollen with isoparaffin were aggregated on the surface.

[0072]

[Table 2] In Comparative Example 4, the crosslinked silicone particles were aggregated particles (the primary particle size was 4 μm).

[0073]

The emulsion of silicone oil or organic oil of the present invention is characterized in that the silicone oil or organic oil dispersed in water contains crosslinked silicone particles in droplets. Further, the method for producing an emulsion of the present invention is characterized in that such an emulsion of silicone oil or organic oil can be produced. Further, the production method of the oil composition of the present invention,
It is characterized in that an oil composition in which crosslinked silicone particles are uniformly dispersed in silicone oil or organic oil can be produced.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Tachibana 2-2 Chikusa Beach, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Research and Development Division F-term (reference) 4F070 AA60 AC06 AC92 AE08 AE28 CB05 CB15 4J002 AE04W CP03W CP05X CP06X CP08W CP08X CP09X CP13X CP14W CP14X EA016 EA026 EA056 EB026 EC066 ED026 EE036 EH036 GB00 GB04 HA07

Claims (9)

[Claims] An average particle size of 0.1 to 5 dispersed in water.
Crosslinked silicone particles having an average particle size of 0.05 to 100 μm in droplets of 00 μm silicone oil or organic oil (however, the particle size of the crosslinked silicone particles is smaller than that of the droplets of silicone oil or organic oil). An emulsion of a silicone oil or an organic oil, comprising: 2. Silicon oil or organic oil 2
The emulsion according to claim 1, wherein the emulsion has a viscosity at 5 ° C of 1 to 100,000,000 mPa · s. 3. The emulsion according to claim 1, wherein the crosslinked silicone particles have undergone a hydrosilylation crosslinking reaction or a condensation crosslinking reaction. 4. A crosslinkable silicone composition containing a non-crosslinkable silicone oil or an organic oil (provided that:
The content of the non-crosslinkable silicone oil or organic oil is an amount exceeding the amount that the crosslinked product of the crosslinkable silicone composition can hold the non-crosslinkable silicone oil or organic oil. ) Is dispersed in water and subjected to a crosslinking reaction, wherein the droplets of silicone oil or organic oil having an average particle size of 0.1 to 500 μm are dispersed in water droplets of an average particle size of 0.1 to 500 μm.
A method for producing an emulsion of silicone oil or organic oil containing crosslinked silicone particles having a particle size of 0.5 to 100 μm (the particle size of the crosslinked silicone particles is smaller than the particle size of droplets of silicone oil or organic oil). 5. A non-crosslinkable silicone oil or organic oil having a viscosity at 25 ° C. of 1 to 100,000,000.
The method for producing an emulsion according to claim 4, wherein the pressure is 0 mPa · s. 6. The method for producing an emulsion according to claim 4, wherein the crosslinkable silicone composition is of a hydrosilylation crosslinking reaction type or a condensation crosslinking reaction type. 7. An average particle size of 0.1 to 5 dispersed in water.
Crosslinked silicone particles having an average particle size of 0.05 to 100 μm in droplets of 00 μm silicone oil or organic oil (however, the particle size of the crosslinked silicone particles is smaller than that of the droplets of silicone oil or organic oil). Wherein water is removed from an emulsion of a silicone oil or an organic oil which contains 0.05 to 100 μm in the silicone oil or the organic oil.
A method for producing an oil composition in which m crosslinked silicone particles are dispersed. 8. Silicon oil or organic oil 2
The method for producing an oil composition according to claim 7, wherein the viscosity at 5 ° C is 1 to 100,000,000 mPa · s. 9. The method for producing an oil composition according to claim 7, wherein the crosslinked silicone particles have been subjected to a hydrosilylation crosslinking reaction or a condensation crosslinking reaction.