JPH0559284A - Microsuspension of cured silicone and its production - Google Patents

Abstract

PURPOSE:To provide a microsuspension of a cured silicone excellent in storage stability wherein the average particle size of the cured silicone is 10mum or below and the content of the cured silicone is at least 50wt.% and a process for producing the same. CONSTITUTION:A microsuspension comprising a particulate cured silicone of an average particle size of 10mum or below, a nonionic surfactant of an HLB of below 10, another nonionic surfactant of an HLB of 10 or above, and water, wherein the content of component A in the suspension is 50wt.% or above; and a process for producing the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone cured product microsuspension and a method for producing the same, and more specifically, the silicone cured product has an average particle diameter of 10 μm or less and a content of the silicone cured product of 50% by weight or more. The present invention relates to a microsuspension of silicone cured product having excellent storage stability and a method for producing the same.

[0002]

2. Description of the Related Art Silicone cured microsuspension is used as a base for water-based paints or as a raw material for cured silicone in the form of fine particles. For example, it was obtained by removing water from silicone cured microsuspension. The particulate silicone cured product is used as an organic resin internal stress relaxation material, a lubricant, a filler, or the like. As a method for producing such a silicone cured product microsuspension, a liquid silicone rubber composition, a surfactant and water are mixed to form an emulsion of the liquid silicone rubber composition, and thereafter,
A method for curing the liquid silicone rubber composition is known (Japanese Patent Publication No. 58-17226, JP-A No. 62-2).
43621 or JP-A-1-306471).

[0003]

However, in the conventional manufacturing method, the average particle diameter of the cured silicone is 10 μm.
m or less and the content of the cured silicone is 5
It was not possible to obtain a silicone-cured product microsuspension having a high storage stability as high as 0% by weight or more.

The present inventors have made diligent efforts to solve the above problems, and as a result, different HLB (Hydrophilic-Lipo)
By using at least two kinds of nonionic surfactants having a numerical value of (philic balance: hydrophilic / lipophilic balance), the average particle diameter of the silicone cured product is as small as 10 μm or less without the above problems. Moreover, the inventors have found a silicone cured product microsuspension having a high content of 50% by weight or more and excellent storage stability, and a method for producing the same, and arrived at the present invention.

That is, an object of the present invention is to provide a silicone cured product micro that has an average particle size of 10 μm or less and a content of the silicone cured product of 50% by weight or more and is excellent in storage stability. It is to provide a suspension and a manufacturing method thereof.

[0006]

MEANS FOR SOLVING THE PROBLEMS AND ACTIONS OF THE INVENTION The present invention comprises: (A) a fine particle silicone cured product having an average particle size of 10 μm or less; and (B) a nonionic surface active agent having an HLB value of less than 10. Agent, (C) nonionic surfactant having a numerical value of HLB of 10 or more, and (D) water {however, during silicone suspension microsuspension,
The content of the component (A) is 50% by weight or more. } Silicone cured product microsuspension consisting of
(A ') curable liquid silicone composition, (B) nonionic surfactant having HLB value of less than 10, (C) H
Nonionic surfactant having a LB value of 10 or more and (D) water {however, (B) component, (C) component and (D)
The total amount of the components is 1 with respect to 100 parts by weight of the component (A ').
~ 100 parts by weight. } Is mixed to form an emulsion of the curable liquid silicone composition, and then the curable liquid silicone composition is cured, to a method for producing a silicone suspension microsuspension.

First, the silicone suspension microsuspension of the present invention will be described in detail.

The silicone cured product of the component (A) has an average particle diameter of 10 μm or less, a fine particle shape, and is uniformly dispersed in the component (D). In the silicone cured product microsuspension of the present invention,
The content of the component (A) is 50% by weight or more, practically preferably 50 to 90% by weight, particularly preferably 5%.
It is 0 to 70% by weight. The physical property of the component (A) is not particularly limited, and is, for example, gel, rubber or resin. The silicone cured product of the component (A) contains an organic compound having an epoxy group, an aryl group or an amino group when it is used as an internal stress relaxation material, a lubricant or a filler of an organic resin. It is preferably a silicone cured product, and particularly preferably a silicone cured product containing an epoxy group, an aryl group or an amino group in a silicon atom via a divalent organic group.

The component (B) is a nonionic surfactant having an HLB value of less than 10, specifically, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate,
Examples include propylene glycol monolaurate, sorbitan distearate, glyceryl monostearate, propylene glycol monostearate, sorbitan trioleate, and polyoxyethylene nonylphenyl ether. In the silicone suspension microsuspension of the present invention, two or more of the above nonionic surfactants having an HLB value of less than 10 may be used in combination.

The component (C) is a nonionic surfactant having an HLB value of 10 or more, specifically, polyoxyethylene octylphenol ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene sorbitan stearic acid. Examples thereof include esters. In the silicone cured product microsuspension of the present invention, two or more kinds of the above-mentioned nonionic surfactants having an HLB value of 10 or more may be used in combination.

In the silicone cured microsuspension of the present invention, the combination of the component (B) and the component (C) is not particularly limited, but the HLB of the component (B) is not limited.
It is preferable that the difference between the numerical value of and the numerical value of the HLB of the component (C) is 5 or more. When the difference between the HLB value of the component (B) and the HLB value of the component (C) is 5 or more, the silicone cured product microsuspension containing 50% by weight or more of the silicone cured product is stable in storage. This is because it has excellent properties. Further, the addition amounts of the component (B) and the component (C) are not particularly limited as long as it is an amount sufficient to stably disperse the component (A), and specifically, 100 parts by weight of the component (A). Is preferably 1 to 100 parts by weight,
It is particularly preferable that the amount is 5 to 50 parts by weight. The silicone cured product microsuspension of the present invention uses a nonionic surfactant having a specific HLB value as the component (B) and the component (C), so that the content of the silicone cured product is 50% by weight. Despite the above high concentration,
It is characterized by its excellent storage stability.

The component (D) is water as a dispersion medium in the silicone suspension microsuspension of the present invention. The cured silicone microsuspension of the present invention comprises components (A) to (D), and as other components, well-known additives used in silicone oil emulsions, such as preservatives for preventing spoilage of emulsions. Agents, thickeners or dyes can be added.

Next, the method for producing the silicone microsuspension of the present invention will be described in detail.

The curable liquid silicone composition as the component (A ') is not particularly limited as long as it is a curable liquid silicone composition that cures. For example, a curable liquid silicone composition that cures by an addition reaction in the presence of a platinum catalyst. Examples thereof include a silicone composition or a curable liquid silicone composition which is cured by a condensation reaction in the presence of a condensation reaction catalyst.

The curable liquid silicone composition which is cured by an addition reaction includes (a) an organopolysiloxane containing two or more silicon atom-bonded lower alkenyl groups in one molecule, and (b) a silicon atom bond in one molecule. 2 hydrogen atoms
A curable liquid silicone composition comprising an organohydrogenpolysiloxane containing 1 or more and a platinum catalyst (c) is preferable, and (a) an organopolysiloxane containing 2 or more silicon-bonded lower alkenyl groups in one molecule. , (B) Organohydrogenpolysiloxane containing two or more silicon-bonded hydrogen atoms in one molecule, (c) a catalyst for hydrosilylation reaction, and (d) curing comprising an organic compound containing an epoxy group or an aryl group. Liquid silicone compositions are preferred.

The component (a) is an organopolysiloxane containing two or more silicon atom-bonded lower alkenyl groups in one molecule, which is the main component of the component (A '). Specific examples of the silicon atom-bonded lower alkenyl group in the component (a) include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group and a decenyl group, and a vinyl group is particularly preferable. Preferably. Specific examples of the silicon atom-bonded organic group other than the lower alkenyl group in the component (a) include methyl group, ethyl group, propyl group,
Alkyl groups such as butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and xylyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; 3-chloropropyl group, Illustrative are monovalent hydrocarbon groups excluding lower alkenyl groups such as halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group. The molecular structure of the component (a) is not particularly limited, and may be, for example, linear, partially branched linear, or a mixture thereof, and particularly preferably linear. In the component (a), the silicon atom-bonded lower alkenyl group may be bonded to any position in the molecule, and is preferably bonded to the end of the molecular chain because of excellent reactivity. The viscosity of the component (a) at 25 ° C. is not particularly limited as long as it is a viscosity capable of forming an emulsion of the component (A ′). Specifically, it is a gum form having a viscosity of 1 centipoise to a high viscosity, and preferably Is 20 to 10
It is in the range of 10,000 centipoise, particularly preferably in the range of 20 to 10,000 centipoise.

The above-mentioned component (b) has two silicon-bonded hydrogen atoms in one molecule which acts as a crosslinking agent for the component (A ').
It is an organohydrogenpolysiloxane containing one or more. Specific examples of the silicon atom-bonded organic group in the component (b) include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl group and xylyl. An aryl group such as a group; an aralkyl group such as a 2-phenylethyl group and a 3-phenylpropyl group; a 3-chloropropyl group,
Illustrative are monovalent hydrocarbon groups excluding lower alkenyl groups such as halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group. The molecular structure of the component (b) is not particularly limited, and examples thereof include linear, cyclic, network, partially branched linear, or a mixture thereof. In the component (b), the silicon atom-bonded hydrogen atom may be bonded at any position in the molecule. The viscosity of the component (b) at 25 ° C. is not particularly limited as long as it can form an emulsion of the component (A ′), and specifically, 1 to 10,000.
It is preferably in the range of centipoise. Also,
The addition amount of the component (b) is not particularly limited, and may be an amount sufficient to cure the component (A ′), and specifically, it may be 0.1% based on 100 parts by weight of the component (a). 3-10
It is preferably in the range of 0 parts by weight.

The component (c) is a platinum-based catalyst for addition-reacting the alkenyl group in the component (a) and the silicon atom-bonded hydrogen atom in the component (b). As the component (c), a well-known platinum-based catalyst can be used, and specifically, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a complex of chloroplatinic acid and an aliphatic unsaturated hydrocarbon compound, platinum chloride. Examples thereof include a complex of an acid and an alkenylsiloxane, platinum black, platinum-supported silica, and the like. If necessary, a catalyst for hydrosilylation reaction other than a platinum-based catalyst can be used. Also,
The amount of the component (c) added is not particularly limited as long as it can accelerate the addition reaction of the component (A ′), and specifically, it is contained in the component (c) based on 100 parts by weight of the component (a). The amount of platinum metal is preferably in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻³ parts by weight.

The component (A ') can be prepared by uniformly mixing the components (a) to (c), and the mixing method is not particularly limited. In addition, (a) to
As a component other than the component (c), in order to improve the affinity and adhesiveness between the obtained silicone cured product and the organic resin,
(D) It is preferable to add an organic compound having an epoxy group or an aryl group. Specific examples of the organic compound having an epoxy group include allyl glycidyl ether, vinyl cyclohexene monooxide, glycidyl acrylate, glycidyl methacrylate,

[Chemical 1]

[Chemical 2]

[Chemical 3] (N and m are integers) and the like. Also,
As the organic compound having an aryl group, specifically,

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical formula 12]

[Chemical 13] Etc. are illustrated. The component (d) may be mixed with the components (a) to (c) at the same time, or may be subjected to an addition reaction with the component (b) in advance. The addition amount of the component (d) is not particularly limited as long as the fine particle silicone cured product of the component (A) has an excellent affinity for the organic resin, and specifically, the component (a) 0.1-5 for 100 parts by weight
It is preferably in the range of 0 parts by weight.

Further, a filler may be added in order to adjust the fluidity of the component (A ') and to improve the mechanical strength of the cured silicone product. Examples of usable fillers include reinforcing fillers such as precipitated silica, fumed silica, calcined silica, and fumed titanium oxide; ground quartz, diatomaceous earth, asbestos, aluminosilicate, iron oxide, zinc oxide, Examples include non-reinforcing fillers such as calcium carbonate. These fillers can be added directly to the component (A '), but they can also be added after the surface treatment of the above fillers with an organosilicon compound such as hexamethyldisilazane, trimethylchlorosilane or polydimethylsiloxane. ..

When the component (A ') is a curable liquid silicone composition which cures by an addition reaction, an acetylene compound, a hydrazine compound, a triazole compound phosphine compound is used for the purpose of controlling the curing reaction. The compound or mercaptan compound can be added in a trace amount or in a small amount. If necessary, a pigment, a heat-resistant agent, a flame retardant, a photosensitizer or a diorganopolysiloxane containing a silicon atom-bonded lower alkenyl group only at one end of the molecular chain can be added.

On the other hand, the curable liquid silicone composition which is cured by a condensation reaction includes (a ') an organopolysiloxane containing two or more silicon atom-bonded hydroxyl groups in one molecule, and (b') a silicon in one molecule. 2 atomically bonded hydrogen atoms
A curable liquid silicone composition comprising an organohydrogenpolysiloxane containing 2 or more and (c ') a catalyst for condensation reaction is preferable, and (a') an organopoly containing 2 or more silicon atom-bonded hydroxyl groups in one molecule. Curable liquid silicone comprising siloxane, (b ') organohydrogenpolysiloxane containing two or more silicon-bonded hydrogen atoms in one molecule, (c') condensation reaction catalyst, and (d ') silane coupling agent Compositions are preferred.

The component (a ') is an organopolysiloxane containing two or more silicon-bonded hydroxyl groups in one molecule, which is the main component of the component (A'). Specific examples of the silicon atom-bonded organic group in the component (a ') include alkyl groups such as methyl group, ethyl group, propyl group and butyl group;
Alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, decenyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; aryl groups such as phenyl group, xylyl group; 2
Examples include aralkyl groups such as -phenylethyl group and 3-phenylpropyl group; halogenated hydrocarbon groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group. The molecular structure of the component (a ') is not particularly limited, and may be, for example, linear, partially branched linear, or a mixture thereof, and particularly preferably linear.
In the component (a '), the silicon atom-bonded hydroxyl group may be bonded to any position in the molecule, but it is preferably bonded to the end of the molecular chain because of its excellent reactivity. Also,
The viscosity of the component (a ′) at 25 ° C. is not particularly limited,
The viscosity may be such that an emulsion of the component (A ′) can be formed. Specifically, it is in the form of a gum having a viscosity of from 1 centipoise to a high viscosity, preferably in the range of 20 to 100,000 centipoise, and particularly preferably. 20-10,000
It is in the range of 0 centipoise.

The component (b ') is an organohydrogenpolysiloxane containing two or more silicon-bonded hydrogen atoms in one molecule which acts as a crosslinking agent for the component (A'). Specific examples of the silicon atom-bonded organic group in the component (b ′) include a methyl group, an ethyl group, a propyl group,
Alkyl groups such as butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and xylyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; 3-chloropropyl group, Examples thereof include monovalent hydrocarbon groups excluding lower alkenyl groups such as halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group. The molecular structure of the component (b ') is not particularly limited, and examples thereof include linear, cyclic, network, partially branched linear, or a mixture thereof.
In the component (b '), the silicon atom-bonded hydrogen atom may be bonded at any position in the molecule. 25 ° C of component (b ')
The viscosity in is not particularly limited as long as it can form an emulsion of the component (A '), and specifically, it is preferably in the range of 1 to 10,000 centipoise. The addition amount of the component (b ') is not particularly limited as long as it is sufficient to cure the component (A'),
Specifically, it is 0.3 with respect to 100 parts by weight of the component (a ').
It is preferably in the range of 100 to 100 parts by weight.

The component (c ') is a catalyst for condensation reaction for subjecting the silicon atom-bonded hydroxyl group in the component (a') to the silicon atom-bonded hydrogen atom in the component (b) for condensation reaction. Specific examples of the component (c ') include dibutyltin dilaurate, dibutyltin diacetate, tin octenoate, dibutyltin dioctate, tin laurate, ferric stanooctenoate, lead octenoate, lead laurate, octenoic acid. Organic acid metal salt compounds such as zinc; tetrabutyl titanate, tetrapropyl titanate, organic titanium compounds such as dibutoxytitanium bis (ethyl acetate); chloroplatinic acid, alcohol solution of chloroplatinic acid, chloroplatinic acid and aliphatic unsaturated Complexes such as hydrocarbon compounds, chloroplatinic acid and alkenylsiloxanes, platinum-based compounds such as platinum black, platinum-supported silica, etc. It is shown. Further, the addition amount of the component (c ′) is not particularly limited as long as it can accelerate the condensation reaction of the component (A ′), and specifically, the component (a ′) 1
The amount is preferably 0.01 to 10 parts by weight with respect to 00 parts by weight.

The component (A ') is the above (a') to (c ').
It can be prepared by uniformly mixing the ingredients,
The mixing method is not particularly limited. In addition, the above (a ')
As a component other than the components (c ′) to (c ′), a silane coupling agent (d ′) is preferably added in order to improve the affinity and adhesiveness between the obtained silicone cured product and the organic resin. Specific examples of the silane coupling agent as the component (d ′) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, 3-chloropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2
Examples include-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and the like. The component (d ') is the above (a')-
It may be mixed at the same time as the component (c '), or may be subjected to a condensation reaction with the component (b') in advance. The addition amount of the component (d ′) is not particularly limited, and specifically, it is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the component (a ′).

Further, a filler may be added to adjust the fluidity of the component (A ') and to improve the mechanical strength of the cured silicone product. Examples of usable fillers include reinforcing fillers such as precipitated silica, fumed silica, calcined silica, and fumed titanium oxide; ground quartz, diatomaceous earth, asbestos, aluminosilicate, iron oxide, zinc oxide, Examples include non-reinforcing fillers such as calcium carbonate. These fillers can be added directly to the component (A '), but they can also be added after the surface treatment of the above fillers with an organosilicon compound such as hexamethyldisilazane, trimethylchlorosilane or polydimethylsiloxane. ..

Further, if necessary, a pigment, a heat-resistant agent, a flame retardant, a photosensitizer or a diorganopolysiloxane containing a silicon atom-bonded hydroxyl group only at one end of the molecular chain can be added.

The component (B) is a nonionic surfactant having an HLB value of less than 10, specifically, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate,
Examples include propylene glycol monolaurate, sorbitan distearate, glyceryl monostearate, propylene glycol monostearate, sorbitan trioleate, and polyoxyethylene nonylphenyl ether. In the production method of the present invention, two or more kinds of the above nonionic surfactants having an HLB value of less than 10 may be used in combination. Further, since the component (B) has poorer dispersibility in water than the component (C), it is preferable to disperse it in the component (A ′) in advance.

The component (C) is a nonionic surfactant having an HLB value of 10 or more, specifically, polyoxyethylene octylphenol ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene sorbitan stearic acid. Examples thereof include esters. In the production method of the present invention, two or more kinds of the above nonionic surfactants having an HLB value of 10 or more may be used in combination.

In the production method of the present invention, the combination of the component (B) and the component (C) is not particularly limited,
The difference between the HLB value of the component (B) and the HLB value of the component (C) is preferably 5 or more. This is (B)
When the difference between the HLB value of the component and the HLB value of the component (C) is 5 or more, the emulsion of the curable liquid silicone composition is stable even when a high-concentration silicone cured product microsuspension is produced. It is also possible to obtain a fine particle silicone cured product having a small average particle diameter. Further, the addition amount of the component (B) and the component (C) is
It is not particularly limited as long as it can form an emulsion of the component (A ′), and specifically, it is preferably 1 to 100 parts by weight, and 5 to 100 parts by weight of the component (A ′).
It is particularly preferable that the amount is 50 parts by weight.

The component (D) is water as a dispersion medium in the production method of the present invention. In the manufacturing method of the present invention,
A well-known emulsifying machine such as a colloid mill or a homogenizer can be used in order to make the mixture of the components (A ′) to (D) a fine and uniform emulsion of the component (A ′). In the production method of the present invention, the total amount of the component (B), the component (C) and the component (D) is 10
It is 1 to 100 parts by weight with respect to 0 parts by weight, and when it is less than 1 part by weight, emulsification becomes difficult.
This is because if the amount is more than parts by weight, shearing becomes insufficient in a known emulsifying machine, and it becomes impossible to prepare a high-concentration fine emulsion of the component (A ′).

In the production method of the present invention, the component (D) is added to an emulsion of a curable liquid silicone composition having a high concentration or a microsuspension of a silicone cured product having a high concentration to arbitrarily adjust the concentration of the cured silicone. can do. The silicone cured product microsuspension obtained by the production method of the present invention has a silicone cured product content of 50% by weight or more, preferably 50 to 90% by weight, and particularly preferably 50% by weight.
Is about 70% by weight.

In the manufacturing method of the present invention, (A ') to
Although the component (D) may be mixed at the same time, preferably the component (B) is dispersed in the component (A ′) in advance, and the component (D) in which the component (C) is dispersed is added to the component and emulsified. You can In the production method of the present invention, the emulsion of the component (A ′) preferably has a liquid temperature of −10 ° C. to 90 ° C., more preferably 0 ° C. to 30 ° C. This is because if the liquid temperature of the emulsion is too low, it becomes difficult to emulsify it in the emulsifying machine, and if the liquid temperature is too high, the component (A ') is cured before emulsification. Since the emulsion of the component (A ') itself has excellent storage stability, the curing reaction of the component (A') gradually proceeds by leaving it at room temperature as it is, and eventually a silicone cured product microsuspension is formed. By heating the emulsion of the component (A ′), the curing time of the component (A ′) can be shortened. In this case, the liquid temperature of the emulsion is preferably 100 ° C or lower, and further 8
It is particularly preferably 0 ° C. or lower. This is because if the liquid temperature of the emulsion becomes too high, the water boils and the microsuspension of the silicone cured product becomes unstable.

In the production method of the present invention, since the obtained silicone cured product microsuspension has excellent storage stability, it can be stored for a long period of time, and moisture can be removed from the silicone cured product microsuspension to obtain fine particles. A silicone-like cured product can be produced. As a method of removing water from the silicone cured product microsuspension of the present invention, for example, a method of heating the silicone cured product microsuspension to 100 ° C. or higher to remove the moisture, a hot air dryer such as a spray dryer or an oven is used. And a method of removing water is mentioned. The thus obtained fine particle-shaped silicone cured product has an average particle diameter of 10 μm or less, and thus can be used as an internal stress relieving material for an organic resin, and is particularly widely used as a sealing material for various semiconductor components. By adding and dispersing it in the thermosetting resin,
A stress relaxation effect on wiring and the like is expected.

[0036]

EXAMPLES The present invention will be described with reference to Examples and Comparative Examples. In the examples, the viscosity is a value measured at 25 ° C. The hardness of the fine particle silicone cured product is JIS K of a sheet silicone cured product obtained by curing the corresponding curable liquid silicone composition in hot air at 70 ° C. for 20 minutes.
It is a value measured by a JIS A type hardness meter specified in 6301.

[0037]

Example 1 A dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50.
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of siloxane and isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. HL
0.25 part by weight of polyoxyethylene nonylphenyl ether having a value of B of 5.7 was added. An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of the silicone suspension microsuspension was sampled and water was removed therefrom at room temperature to obtain a fine particle silicone cured product having a maximum particle diameter of 5 μm and an average particle diameter of 1 μm. It was The hardness of this silicone cured product was 30. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0039]

Comparative Example 1 A silicone suspension microsuspension was produced in the same manner as in Example 1 except that polyoxyethylene nonylphenyl ether was not used. It was observed that the silicone cured product microsuspension was left at room temperature for 1 day, and then the cured silicone cured product and the aqueous layer were separated.

[0040]

Example 2 Dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of siloxane and isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. HL
0.25 part by weight of polyoxyethylene nonylphenyl ether having a value of B of 5.7 was added. An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was allowed to stand at room temperature for 15 hours or longer to prepare a silicone cured product microsuspension.

When this silicone cured product microsuspension was dried using a spray dryer, a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm was obtained. The hardness of this silicone cured product was 30. In addition, this silicone cured product micro suspension, even after left at room temperature for 3 months or more,
No separation between the silicone cured product and the aqueous layer was observed.

[0042]

Comparative Example 2 A cured silicone microsuspension was prepared in the same manner as in Example 2, except that polyoxyethylene nonylphenyl ether was not used. When a part of this silicone cured product microsuspension was sampled and water was removed at room temperature, a silicone cured product having a maximum particle diameter of 500 μm and an average particle diameter of 100 μm was obtained. In addition, this silicone cured product microsuspension was observed to separate from the silicone cured product and the aqueous layer after being left at room temperature for 1 day.

[0043]

Example 3 A dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50.
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition consisting of 7.5 × 10 ⁻³ parts by weight of siloxane and a isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. H to this
0.25 parts by weight of polyoxyethylene nonylphenyl ether having an LB value of 5.7 and an HLB value of 18.
An aqueous solution of 1 part by weight of polyoxyethylene octylphenol ether (1) and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. 7 this emulsion
A silicone cured product microsuspension was manufactured by heating at 0 ° C. for 20 minutes.

A part of this silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 30. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0045]

Example 4 Dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50
Parts by weight, 1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), tetramethyltetravinylcyclo A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of tetrasiloxane and an isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. To this was added 0.25 part by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7. 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and pure water of 47.5 were added to this mixture.
An aqueous solution consisting of parts by weight was added dropwise over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 30 minutes, this was passed through a homogenizer to obtain an emulsion of a uniform curable liquid silicone composition. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of this silicone suspension microsuspension was sampled and water was removed at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 30. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0047]

Example 5 Dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of siloxane and an isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. To the product was added 0.25 part by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7. An aqueous solution of 1 part by weight of polyoxyethylene trimethylnonyl ether having an HLB value of 14.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of the silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 30. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0049]

Example 6 A dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 46.
3.2 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), vinylcyclohexene monooxide 2. Curable property consisting of 3 parts by weight, tetramethyltetravinylcyclotetrasiloxane 7.5 × 10 ⁻³ parts by weight, and isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal amount based on the total weight of the siloxane). A liquid silicone composition is prepared and HLB is added to the liquid silicone composition.
0.25 parts by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. To this mixture,
An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour,
This was passed through a colloid mill to give an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of this silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 30. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0051]

Example 7 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. A curable liquid silicone composition comprising 5.0 parts by weight of methylhydrogenpolysiloxane (having a silicon atom-bonded hydrogen atom equivalent weight of 67) and 0.25 parts by weight of dibutyltin dioctoate is prepared. 0.25 parts by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of the silicone suspension microsuspension was sampled and water was removed therefrom at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 70. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0053]

Comparative Example 3 A cured silicone microsuspension was produced in the same manner as in Example 1 except that polyoxyethylene nonylphenyl ether was not used. It was observed that the silicone cured product microsuspension was left at room temperature for 1 day, and then the cured silicone cured product and the aqueous layer were separated.

[0054]

Example 8 50 parts by weight of dimethylpolysiloxane containing hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. A curable liquid silicone composition comprising 5.0 parts by weight of methylhydrogenpolysiloxane (having a silicon atom-bonded hydrogen atom equivalent weight of 67) and 0.25 parts by weight of dibutyltin dioctoate is prepared. 0.25 parts by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This was left at room temperature for 15 hours or more to produce a silicone cured microsuspension.

When this silicone cured product microsuspension was dried using a spray dryer, a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm was obtained. The hardness of this silicone cured product was 70. In addition, this silicone cured product micro suspension, even after left at room temperature for 3 months or more,
No separation between the silicone cured product and the aqueous layer was observed.

[0056]

Comparative Example 4 A cured silicone microsuspension was prepared in the same manner as in Example 2, except that polyoxyethylene nonylphenyl ether was not used. When a part of this silicone cured product microsuspension was sampled and water was removed at room temperature, a silicone cured product having a maximum particle diameter of 500 μm and an average particle diameter of 100 μm was obtained. In addition, this silicone cured product microsuspension was observed to separate from the silicone cured product and the aqueous layer after being left at room temperature for 1 day.

[0057]

Example 9 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. A curable liquid silicone composition comprising 5.0 parts by weight of methylhydrogenpolysiloxane (having a hydrogen atom equivalent to a silicon atom of 67) containing 0.25 parts by weight and 0.25 parts by weight of dibutyltin dioctoate was prepared. An aqueous solution containing 0.25 parts by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7, 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1, and 10 parts by weight of pure water was added thereto. The solution was added dropwise with stirring for about 5 minutes. After that, it takes about 1 hour, 600rp
After stirring and mixing at m, this was passed through a colloid mill to give an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of the silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 70. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0059]

Example 10 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. 5.0 parts by weight of methyl hydrogen polysiloxane containing (hydrogen atom equivalent of silicon atom is 67).
A curable liquid silicone composition consisting of 0.25 parts by weight of dibutyltin dioctoate was prepared. To this was added 0.25 part by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7. To this mixture, HL
An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having a numerical value of B of 18.1 and 47.5 parts by weight of pure water was added dropwise while stirring for about 5 minutes. Then, after stirring and mixing at 600 rpm for about 30 minutes,
This was passed through a homogenizer to obtain a uniform curable liquid silicone composition emulsion. Then the solid content is 50
It was put into pure water so as to have a weight% and stirred to obtain a homogeneous curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of this silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 70. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0061]

Example 11 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. 5.0 parts by weight of methyl hydrogen polysiloxane containing (hydrogen atom equivalent of silicon atom is 67).
A curable liquid silicone composition comprising 0.25 parts by weight of dibutyltin dioctoate was prepared, and HLB was added to the composition.
0.25 parts by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. To this mixture,
An aqueous solution containing 1 part by weight of polyoxyethylene trimethylnonyl ether having an HLB value of 14.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then the solid content is 5
It was poured into pure water so as to be 0% by weight and stirred to obtain a homogeneous curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of this silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 67. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0063]

Example 12 50 parts by weight of dimethylpolysiloxane having a hydroxyl group at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl equivalent is 450), and a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. 3.3 parts by weight of methyl hydrogen polysiloxane containing (hydrogen atom equivalent of silicon atom is 67).
A curable liquid silicone composition consisting of 1.7 parts by weight of 3-glycidoxypropyltrimethoxysilane and 0.25 parts by weight of dibutyltin dioctoate was prepared, and HLB was added thereto.
0.25 parts by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. To this mixture,
An aqueous solution containing 1 part by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour,
This was passed through a colloid mill to give an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

A part of the silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 70. In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[0065]

The silicone microsuspension of the present invention comprises components (A) to (D), and in particular,
Since a nonionic surfactant having a specific HLB value is used for the component (B) and the component (C), the average particle diameter of the silicone cured product is as small as 10 μm or less and the content of the silicone cured product is small. Has a characteristic that it is excellent in storage stability despite its high concentration of 50% by weight or more. Further, the production method of the present invention has a feature that such a silicone cured product microsuspension can be efficiently produced.

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[Procedure amendment]

[Submission date] February 6, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

The component (c ') is a condensation reaction catalyst for subjecting the silicon atom-bonded hydroxyl group in the component (a') to the silicon atom-bonded hydrogen atom in the component (b ') .
Specific examples of the component (c ') include dibutyltin dilaurate, dibutyltin diacetate, tin octenoate, dibutyltin dioctate, tin laurate, ferric stanooctenoate, lead octenoate, and lead laurate. , Organic acid metal salt compounds such as zinc octenoate; organotitanium compounds such as tetrabutyl titanate, tetrapropyl titanate, dibutoxy titanium bis (ethyl acetate); chloroplatinic acid, alcohol solutions of chloroplatinic acid, chloroplatinic acid and fats Examples thereof include complexes with group unsaturated hydrocarbon compounds, complexes of chloroplatinic acid with alkenyl siloxanes, platinum-based compounds such as platinum black and platinum-supported silica. The amount of the component (c ') added is not particularly limited as long as it can accelerate the condensation reaction of the component (A'). Specifically, it is 0. It is preferably in the range of 01 to 10 parts by weight.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

[0037]

Example 1 A dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50.
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of siloxane and isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. HL
0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of B of 5.7 was added. To this mixture,
An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour,
This was passed through a colloid mill to give an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure 3]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

[0040]

Example 2 Dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of siloxane and isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. HL
0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of B of 5.7 was added. To this mixture,
An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour,
This was passed through a colloid mill to give an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was allowed to stand at room temperature for 15 hours or longer to prepare a silicone cured product microsuspension.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

Example 3 A dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50.
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition consisting of 7.5 × 10 ⁻³ parts by weight of siloxane and a isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. H to this
0.5 parts by weight of polyoxyethylene nonylphenyl ether having an LB value of 5.7 and an HLB value of 18.1
Is polyoxyethylene octylphenol ether
An aqueous solution consisting of 2 parts by weight and 10 parts by weight of pure water was added dropwise over about 5 minutes while stirring. After that, about 1 hour,
After stirring and mixing at 600 rpm, this was passed through a colloid mill to give an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion is 70 ℃
And heated for 20 minutes to prepare a cured silicone microsuspension.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045]

Example 4 Dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50
Parts by weight, 1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), tetramethyltetravinylcyclo A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of tetrasiloxane and an isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. To this was added 0.5 part by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7. To this mixture, an aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 47.5 parts by weight of pure water was added dropwise over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 30 minutes, this was passed through a homogenizer to obtain an emulsion of a uniform curable liquid silicone composition . This emul
John was heated at 70 ° C. for 20 minutes to produce a cured silicone microsuspension.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

[0047]

Example 5 Dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 50
1.5 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), and tetramethyltetravinylcyclotetra A curable liquid silicone composition comprising 7.5 × 10 ⁻³ parts by weight of siloxane and an isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal based on the total weight of the siloxane) was prepared. 0.5 parts by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7 was added to the product. An aqueous solution containing 2 parts by weight of polyoxyethylene trimethylnonyl ether having an HLB value of 14.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049]

Example 6 A dimethylpolysiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 centipoise (vinyl group equivalent is 5400) 46.
3.2 parts by weight of methylhydrogenpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise (silicon atom-bonded hydrogen atom equivalent is 67), vinylcyclohexene monooxide 2. Curable property consisting of 3 parts by weight, tetramethyltetravinylcyclotetrasiloxane 7.5 × 10 ⁻³ parts by weight, and isopropyl alcohol solution of chloroplatinic acid (120 ppm of platinum metal amount based on the total weight of the siloxane). A liquid silicone composition is prepared and HLB is added to the liquid silicone composition.
0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. To this mixture, add H
An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an LB value of 18.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then the solid content is 5
It was poured into pure water so as to be 0% by weight and stirred to obtain a homogeneous curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

[0051]

Example 7 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. A curable liquid silicone composition comprising 5.0 parts by weight of methylhydrogenpolysiloxane (having a silicon atom-bonded hydrogen atom equivalent weight of 67) and 0.25 parts by weight of dibutyltin dioctoate is prepared. 0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then about 1
After stirring and mixing at 600 rpm for a long time, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then the solid content is 50% by weight
The resulting mixture was poured into pure water and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0053

[Correction method] Change

[Correction content]

[0053]

Comparative Example 3 A silicone suspension microsuspension was produced in the same manner as in Example 7 , except that polyoxyethylene nonylphenyl ether was not used. It was observed that the silicone cured product microsuspension was left at room temperature for 1 day, and then the cured silicone cured product and the aqueous layer were separated.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

[0054]

Example 8 50 parts by weight of dimethylpolysiloxane containing hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. A curable liquid silicone composition comprising 5.0 parts by weight of methylhydrogenpolysiloxane (having a silicon atom-bonded hydrogen atom equivalent weight of 67) and 0.25 parts by weight of dibutyltin dioctoate is prepared. 0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1 and 10 parts by weight of pure water was added dropwise to this mixture over about 5 minutes while stirring. Then about 1
After stirring and mixing at 600 rpm for a long time, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then the solid content is 50% by weight
The resulting mixture was poured into pure water and stirred to obtain a uniform curable liquid silicone composition emulsion. This was left at room temperature for 15 hours or more to produce a silicone cured microsuspension.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

Comparative Example 4 A silicone suspension microsuspension was produced in the same manner as in Example 8 except that polyoxyethylene nonylphenyl ether was not used. When a part of this silicone cured product microsuspension was sampled and water was removed at room temperature, a silicone cured product having a maximum particle diameter of 500 μm and an average particle diameter of 100 μm was obtained. In addition, this silicone cured product microsuspension was observed to separate from the silicone cured product and the aqueous layer after being left at room temperature for 1 day.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction content]

[0057]

Example 9 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. A curable liquid silicone composition comprising 5.0 parts by weight of methylhydrogenpolysiloxane (having a hydrogen atom equivalent to a silicon atom of 67) containing 0.25 parts by weight and 0.25 parts by weight of dibutyltin dioctoate was prepared. An aqueous solution containing 0.5 parts by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7, 2 parts by weight of polyoxyethylene octylphenol ether having an HLB value of 18.1, and 10 parts by weight of pure water was added thereto. The solution was added dropwise with stirring for about 5 minutes. After that, about 1 hour, 600 rpm
After stirring and mixing with, the mixture was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

[0059]

Example 10 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. 5.0 parts by weight of methyl hydrogen polysiloxane containing (hydrogen atom equivalent of silicon atom is 67).
A curable liquid silicone composition consisting of 0.25 parts by weight of dibutyltin dioctoate was prepared. To this was added 0.5 part by weight of polyoxyethylene nonylphenyl ether having an HLB value of 5.7. To this mixture, add HLB
An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having a value of 18.1 and 47.5 parts by weight of pure water was added dropwise while stirring for about 5 minutes. Then, after stirring and mixing at 600 rpm for about 30 minutes, this was passed through a homogenizer to obtain an emulsion of a uniform curable liquid silicone composition. Then, the mixture was poured into pure water so that the solid content was 50% by weight and stirred to obtain a uniform curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

[0061]

Example 11 50 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl group equivalent is 450), and trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. 5.0 parts by weight of methyl hydrogen polysiloxane containing (hydrogen atom equivalent of silicon atom is 67).
A curable liquid silicone composition comprising 0.25 parts by weight of dibutyltin dioctoate was prepared, and HLB was added to the composition.
0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. To this mixture, add H
An aqueous solution containing 2 parts by weight of polyoxyethylene trimethylnonyl ether having an LB value of 14.1 and 10 parts by weight of pure water was added dropwise while stirring for about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then the solid content is 5
It was poured into pure water so as to be 0% by weight and stirred to obtain a homogeneous curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

A part of this silicone suspension microsuspension was sampled and water was removed from it at room temperature to obtain a fine particle silicone cured product having a maximum particle size of 5 μm and an average particle size of 1 μm. It was The hardness of this silicone cured product was 70 . In addition, the silicone cured product microsuspension was not observed to separate from the silicone cured product and the aqueous layer even after being left at room temperature for 3 months or more.

[Procedure 16]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

[0063]

Example 12 50 parts by weight of dimethylpolysiloxane having a hydroxyl group at both ends of a molecular chain having a viscosity of 40 centipoise (hydroxyl equivalent is 450), and a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 20 centipoise. 3.3 parts by weight of methyl hydrogen polysiloxane containing (hydrogen atom equivalent of silicon atom is 67).
A curable liquid silicone composition consisting of 1.7 parts by weight of 3-glycidoxypropyltrimethoxysilane and 0.25 parts by weight of dibutyltin dioctoate was prepared, and HLB was added thereto.
0.5 part by weight of polyoxyethylene nonylphenyl ether having a value of 5.7 was added. To this mixture, add H
An aqueous solution containing 2 parts by weight of polyoxyethylene octylphenol ether having an LB value of 18.1 and 10 parts by weight of pure water was added dropwise with stirring over about 5 minutes. Then, after stirring and mixing at 600 rpm for about 1 hour, this was passed through a colloid mill to obtain an emulsion of a curable liquid silicone composition having viscosity. Then the solid content is 5
It was poured into pure water so as to be 0% by weight and stirred to obtain a homogeneous curable liquid silicone composition emulsion. This emulsion was heated at 70 ° C. for 20 minutes to produce a silicone cured product microsuspension.

Claims (7)

[Claims] 1. A fine particle silicone cured product having (A) an average particle diameter of 10 μm or less, and (B) HLB having a numerical value of 1.
A nonionic surfactant having a value of less than 0, (C) a nonionic surfactant having an HLB value of 10 or more, and (D)
Water {However, the content of the component (A) in the silicone cured product microsuspension is 50% by weight or more. } Silicone cured product microsuspension consisting of. 2. The cured silicone microsuspension according to claim 1, wherein the difference between the HLB value of the component (B) and the HLB value of the component (C) is 5 or more. 3. A curable liquid silicone composition (A ′),
(B) Nonionic surfactant having an HLB value of less than 10; (C) Nonionic surfactant having an HLB value of 10 or more; and (D) water {however, (B) component and (C) ) Component and (D) component total amount is (A ') component 10
It is 1 to 100 parts by weight with respect to 0 parts by weight. } Is mixed to form an emulsion of the curable liquid silicone composition, and then the curable liquid silicone composition is cured, and the method for producing a cured silicone microsuspension of claim 1. .. 4. The component (A ′) is (a) an organopolysiloxane containing two or more silicon atom-bonded lower alkenyl groups in one molecule, and (b) two silicon atom-bonded hydrogen atoms in one molecule. A method for producing a microsuspension of silicone cured product according to claim 3, which is a curable liquid silicone composition comprising the organohydrogenpolysiloxane contained above and (c) a platinum-based catalyst. 5. The component (A ′) is (a) an organopolysiloxane having two or more silicon atom-bonded lower alkenyl groups in one molecule, and (b) two silicon atom-bonded hydrogen atoms in one molecule. 4. A curable liquid silicone composition comprising the above organohydrogenpolysiloxane, (c) a platinum-based catalyst, and (d) an organic compound containing an epoxy group or an aryl group.
A method for producing a cured silicone microsuspension as described above. 6. The component (A ') is (a') an organopolysiloxane having two or more silicon atom-bonded hydroxyl groups in one molecule, and (b ') has two silicon atom-bonded hydrogen atoms in one molecule. A method for producing a microsuspension of silicone cured product according to claim 3, which is a curable liquid silicone composition comprising the organohydrogenpolysiloxane and the catalyst (c ') for condensation reaction contained above. 7. The component (A ′) is (a ′) an organopolysiloxane having two or more silicon atom-bonded hydroxyl groups in one molecule, and (b ′) has two silicon atom-bonded hydrogen atoms in one molecule. 4. A silicone cured product micro according to claim 3, which is a curable liquid silicone composition comprising the above-mentioned organohydrogenpolysiloxane, (c ') condensation reaction catalyst and (d') silane coupling agent. Suspension manufacturing method.