WO2016111225A1 - Polyoxyalkylene-modified diorganopolysiloxane compound, method for producing same, and organopolysiloxane emulsion composition - Google Patents

Polyoxyalkylene-modified diorganopolysiloxane compound, method for producing same, and organopolysiloxane emulsion composition Download PDF

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WO2016111225A1
WO2016111225A1 PCT/JP2015/086486 JP2015086486W WO2016111225A1 WO 2016111225 A1 WO2016111225 A1 WO 2016111225A1 JP 2015086486 W JP2015086486 W JP 2015086486W WO 2016111225 A1 WO2016111225 A1 WO 2016111225A1
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polyoxyalkylene
organopolysiloxane
diorganopolysiloxane
general formula
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PCT/JP2015/086486
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French (fr)
Japanese (ja)
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有子 高田
晃司 作田
青木　俊司
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol

Definitions

  • the present invention relates to a polyoxyalkylene-modified diorganopolysiloxane compound and a method for producing the same.
  • the present invention also relates to an organopolysiloxane emulsion composition that is excellent in solvent resistance and salt resistance, and is particularly suitable as a softener for cosmetics and clothing, a coating agent for resins, a release agent, and the like.
  • Organopolysiloxane is excellent in chemical stability, heat resistance, weather resistance, releasability, water repellency, and physiological inertness, so it is used in various fields such as plastics, fibers, paints, cosmetics, and resin coatings. ing.
  • organopolysiloxanes are hydrophobic and have poor compatibility with water, alcohol, etc., and nonionic surfactants have been conventionally used to emulsify, compatibilize and disperse hydrophobic organopolysiloxanes. Have been used.
  • emulsions with nonionic surfactants are unstable with respect to alcohols and salts, and if alcohols or salts are added to the emulsions, they may be separated or broken.
  • Cosmetics contain a lot of alcohols as moisturizers and fragrances, and softeners such as clothes contain a lot of alcohols that are fragrances.
  • Organopolysiloxane can be added to many products such as cosmetics and softeners because it can provide slipperiness and flexibility, but the stability of the emulsion of organopolysiloxane is reduced by the alcohols contained in these products. There is a problem of doing. Therefore, there has been a demand for an emulsion of organopolysiloxane that is highly stable against alcohol.
  • Emulsions of organopolysiloxane with a high degree of polymerization are widely used in resin coating agents and hair care products, but it is difficult to emulsify with a high degree of polymerization of organopolysiloxane alone, and usually a high degree of polymerization is required.
  • These organopolysiloxanes and low-polymerization organopolysiloxanes are mixed and emulsified.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2007-126359
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2007-126359
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2007-126359
  • the structure is a polyoxyalkylene-modified organopolysiloxane added with polyglyceryl ether, and the structure is different from the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
  • Patent Document 2 Japanese Patent No. 513649 (Patent Document 2) exemplifies the bubble stability in the presence of salt when nitrogen is blown into a water-diluted product of a side-chain polyoxyalkylene-modified organopolysiloxane compound.
  • the side chain polyoxyalkylene-modified organopolysiloxane is characterized by salt resistance and is not intended for emulsification of organopolysiloxane having a high degree of polymerization. Further, it is a side chain polyoxyalkylene-modified organopolysiloxane compound, which is different in structure from the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
  • Patent Document 3 is a branched polyglycerol-modified silicone, which was developed for the purpose of adsorption onto fibers and the like, and was developed as an emulsifier or emulsification aid for polysiloxane having a high degree of polymerization. It is not what was done. Further, the structure is branched polyglycerol-modified silicone, and the structure is different from the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
  • Patent Document 4 is a co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group, and imparts excellent feel and texture when blended in cosmetics. In addition, it works as an excellent emulsification aid or emulsifier that can stably emulsify various oils. Examples of emulsification of dimethylpolysiloxane at 2 mm 2 / s and 6 mm 2 / s are given, but there is no example of polysiloxane having a high degree of polymerization.
  • the co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group has a structure different from that of the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
  • JP 2007-126359 A Japanese Patent No. 5136849 Japanese Patent No. 4485134 International Publication No. 2011/049247
  • the present invention has been made in view of the above circumstances, is excellent in compatibility with high-polymerization degree organopolysiloxane, can easily emulsify high-polymerization degree organopolysiloxane, and can also be used in the presence of alcohol or salt.
  • Another object of the present invention is to provide an organopolysiloxane emulsion composition that is excellent in solvent resistance and salt resistance and is particularly effective as a cosmetic, a softening agent, a coating agent, a release agent and the like.
  • the present invention provides the following polyoxyalkylene-modified diorganopolysiloxane compound and a method for producing the same.
  • R and R 1 may be the same or different and each is a substituted or unsubstituted linear or branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, polyoxy group having 1 to 20 carbon atoms.
  • L is a two-chain polyoxyalkylene alkyl group represented by the following general formula (3).
  • EO represents a polyoxyethylene group
  • AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms
  • R 2 may be the same or different, and may be a hydrogen atom
  • 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group
  • R 1 and L are as defined above.
  • R 3 may be the same or different and each represents a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group having 1 to 20 carbon atoms, A monovalent hydrocarbon group having an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group,
  • R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group.
  • EO represents a polyoxyethylene group
  • AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms
  • R 2 may be the same or different, and may be a hydrogen atom
  • 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group
  • a diorganopolysiloxane containing hydrogen atoms at both ends represented by the following general formula (9) in each unsaturated group at both ends of the diorganopolysiloxane containing unsaturated groups at both ends represented by the following general formula (8)
  • R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group.
  • R 3 may be the same or different and is a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group having 1 to 20 carbon atoms And a monovalent hydrocarbon group having an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, n1 and n2 are each an integer of 0 or more, and n1 + n2 + n2 is an integer of 40 or more.)
  • EO represents a polyoxyethylene group
  • AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms
  • R 2 may be the same or different, and may be a hydrogen atom
  • 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group
  • the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention is excellent in compatibility with a high degree of polymerization organopolysiloxane.
  • the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention as an emulsifier or an emulsification aid, the high-polymerization degree organopolysiloxane can be easily emulsified.
  • the polyoxyalkylene-modified diorganopolysiloxane compound can emulsify the organopolysiloxane even in the presence of alcohol or salt, and can sufficiently maintain the surface activity.
  • the organopolysiloxane emulsion composition of the present invention is excellent in solvent resistance, it is stable without causing separation or destruction even when added to a polar solvent such as alcohol, ketone or ester. Moreover, since it is excellent also in salt tolerance, even if salts, such as sodium chloride and sodium sulfate, are mix
  • a polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal as an emulsifier or an emulsification aid, emulsification of an organopolysiloxane having a high degree of polymerization can be facilitated.
  • the highly polymerized organopolysiloxane emulsion composition is excellent in the coating effect on the resin and the hair, and is excellent in the mold and plastic mold release sustainability.
  • the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention has a structure in which a siloxane chain having a polyoxyalkylene group represented by the following general formula (1) is bonded to the terminal and is represented by the following general formula (2). It has 40 or more units in the molecule.
  • R and R 1 may be the same or different and each is a substituted or unsubstituted linear or branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, polyoxy group having 1 to 20 carbon atoms. It is a monovalent hydrocarbon group having an alkylene group or a hydrogen atom.
  • L is a two-chain polyoxyalkylene alkyl group represented by the following general formula (3).
  • EO represents a polyoxyethylene group
  • AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms
  • R 2 may be the same or different, and may be a hydrogen atom
  • 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group
  • the polyoxyalkylene-modified diorganopolysiloxane compound is particularly preferably a compound represented by the following general formula (4) or (5).
  • R 1 and L are as described above.
  • M is an integer of 40 or more.
  • the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention is highly compatible with organopolysiloxane having a high degree of polymerization, and can easily emulsify organopolysiloxane having a high degree of polymerization by using an emulsifier or an emulsification aid. be able to. Since the emulsion is excellent in solvent resistance, it is stable without causing separation or destruction even when added to a polar solvent such as alcohol, ketone or ester. Furthermore, since salt tolerance is excellent, even if salts, such as sodium chloride and sodium sulfate, are mix
  • the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention is specifically obtained by the following method i or ii.
  • ⁇ Method i> A silicon-bonded hydrogen atom-containing diorganopolysiloxane represented by the following general formula (6) is reacted with an unsaturated group-containing polyoxyalkylene compound represented by the following general formula (7).
  • R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group.
  • EO represents a polyoxyethylene group
  • AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms
  • R 2 may be the same or different, and may be a hydrogen atom
  • 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group
  • R 1 may be the same or different, and is a substituted or unsubstituted straight chain having 1 to 20 carbon atoms. Or a branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, monovalent hydrocarbon group having a polyoxyalkylene group, or a hydrogen atom, preferably a substituted or unsubstituted straight chain having 1 to 20 carbon atoms.
  • a chain or branched alkyl group, an aryl group, or an aralkyl group is preferred, and a methyl group or a phenyl group is more preferred from the standpoint of availability and synthesis.
  • M is m ⁇ 40, preferably 5,000 ⁇ m ⁇ 100, and more preferably 1,000 ⁇ m ⁇ 200.
  • m is less than 40, the solvent resistance and salt resistance of the emulsion of organopolysiloxane using polyoxyalkylene-modified diorganopolysiloxane as an emulsifier or emulsification aid are reduced, and when m is greater than 5,000, The emulsifiability of the oxyalkylene-modified diorganopolysiloxane compound is lowered, making it difficult to emulsify the organopolysiloxane.
  • Examples of the diorganopolysiloxane component represented by the general formula (6) include, but are not limited to, those represented by the following formula.
  • Ph is a phenyl group and Rf is a trifluoropropyl group.
  • P and q are each an integer of 0 or more, preferably p and q are each an integer of 1 or more, and p + q is 40 or more. , Preferably an integer of 100 or more.
  • EO represents a polyoxyethylene group
  • AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms.
  • R 2 may be the same or different and represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a carboxy group, an acyl group, or a phenyl group.
  • a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a hydroxy group is preferable, and a hydroxy group is more preferable from the viewpoint of availability and synthesis.
  • s 1 is the most preferable from a versatility viewpoint. Two or more types of unsaturated group-containing polyoxyalkylene compounds may be used in combination.
  • Examples of the polyoxyalkylene compound component represented by the general formula (7) include, but are not limited to, those represented by the following formula.
  • a step of addition reaction of one terminal silicon atom-bonded hydrogen atom of siloxane, and, after this step, the other terminal silicon atom-bonded hydrogen atom of the above-mentioned silicon atom-bonded hydrogen atom-containing diorganopolysiloxane has the above general formula (7)
  • An unsaturated group of the unsaturated group-containing polyoxyalkylene compound represented by (In the formula, R 1 is as described above.
  • R 3 may be the same or different and is a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group having 1 to 20 carbon atoms.
  • R 3 may be the same or different, and is a linear or branched substituted or unsubstituted having 1 to 20 carbon atoms.
  • a monovalent hydrocarbon group having an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group.
  • Preferred is a linear or branched halogen atom-substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and a methyl group or a phenyl group is more preferred from the standpoint of availability and synthesis. .
  • n1 is an integer from 0 to 10,000.
  • n1 is greater than 10,000, the synthesized polyoxyalkylene-modified diorganopolysiloxane compound has a high viscosity and is difficult to handle.
  • the emulsifying power is lowered due to the high hydrophobicity.
  • Examples of the diorganopolysiloxane component represented by the general formula (8) include, but are not limited to, those represented by the following formula. (In the formula, Vi is a vinyl group, Ph is a phenyl group, and Rf is a trifluoropropyl group. X and y are each an integer of 0 or more.)
  • the above-mentioned diorganopolysiloxane containing unsaturated groups at both terminals is a raw material blended for the purpose of adjusting the hydrophobicity of the polyoxyalkylene-modified diorganopolysiloxane compound, and may be blended as necessary. Two or more kinds of unsaturated group-containing diorganopolysiloxanes can be mixed and used.
  • R 1 is as described above.
  • examples of the diorganopolysiloxane component represented by the general formula (9) include, but are not limited to, those represented by the following formula.
  • the diorganopolysiloxane of the formula (9) is one in which two molecules are added to one molecule of the diorganopolysiloxane of the formula (8). (In the formula, Ph is a phenyl group and Rf is a trifluoropropyl group. P and q are each an integer of 0 or more.)
  • n1 + n2 + n2 is an integer of 40 or more.
  • n1 + n2 + n2 is smaller than 40 or n1 + n2 + n2 is larger than 5,000, the emulsifiability of the synthesized polyoxyalkylene-modified diorganopolysiloxane compound is lowered, and it becomes difficult to emulsify polysiloxane having a high polymerization degree.
  • n1 + n2 + n2 m (m1 + m2 + m3).
  • a polyoxyalkylene-modified diorganopolysiloxane compound is produced by performing an addition reaction in the presence or absence of a solvent using a hydrosilylation catalyst.
  • the diorganopolysiloxane containing hydrogen atoms at both ends of the formula (6) and the polyoxyalkylene compound containing an unsaturated group of the formula (7) are hydrosilylated in a hydrosilylation reaction catalyst.
  • a polyoxyalkylene-modified diorganopolysiloxane compound is synthesized by a conversion reaction.
  • the number of moles of unsaturated groups in the unsaturated group-containing polyoxyalkylene compound is equal to the number of moles of silicon-bonded hydrogen atoms in the diorganopolysiloxane containing silicon-bonded hydrogen atoms at both ends, or the number of unsaturated groups.
  • the remaining silicon-bonded hydrogen atoms can be reduced by adding olefins such as hexene and heptene and further hydrosilylation reaction. it can.
  • both ends of silicon atom-bonded hydrogen atom-containing diorganopolysiloxane of the above formula (9) and diorganopolysiloxane of both ends unsaturated group containing the formula (8) are hydrosilylated in a hydrosilylation reaction catalyst. Perform the chemical reaction. At that time, the number of moles of silicon atom-bonded hydrogen atoms in the diorganopolysiloxane having silicon atoms bonded to hydrogen atoms at both ends of formula (9) is the unsaturated group of diorganopolysiloxane having unsaturated groups at both ends of formula (8). It is necessary to leave silicon-bonded hydrogen atoms in excess of the number of moles.
  • the ratio (number of moles of silicon atom-bonded hydrogen atoms in diorganopolysiloxane containing both ends of silicon atom-bonded hydrogen atoms / number of moles of unsaturated groups in diorganopolysiloxane containing both ends unsaturated groups) is preferably 1.1 or more. Yes, more preferably 1.3 or more.
  • the hydrophilicity of the polyoxyalkylene-modified diorganopolysiloxane compound to be synthesized becomes low, and the emulsifiability may be lowered.
  • an unsaturated group-containing polyoxyalkylene compound of the formula (7) is added, and a polyoxyalkylene-modified diorganopolysiloxane compound is synthesized by a hydrosilylation reaction.
  • the number of moles of unsaturated groups in which the unsaturated group-containing polyoxyalkylene compound of formula (7) and the diorganopolysiloxane having unsaturated groups at both ends of formula (8) are combined is the silicon atom bond at both ends of formula (9).
  • the hydrogen atom-containing diorganopolysiloxane it is preferable to react in an amount that is equal to the number of moles of silicon-bonded hydrogen atoms or an amount in which the number of unsaturated groups is excessive.
  • the number of moles of silicon-bonded hydrogen atoms is greater than the number of moles of unsaturated groups, and silicon-bonded hydrogen atoms remain after the hydrosilylation reaction, by adding an olefin such as hexene or heptene, the hydrosilylation reaction is further performed. This residual silicon atom-bonded hydrogen atom can be reduced.
  • the ratio of the number of moles of the unsaturated group-containing polyoxyalkylene compound to the unsaturated group-containing diorganopolysiloxane is 0.1 or more. It is desirable that If it is less than 0.1, the synthesized polyoxyalkylene-modified diorganopolysiloxane compound has high hydrophobicity and may have low emulsifying power.
  • the hydrosilylation catalyst is a catalyst for promoting the hydrosilylation reaction, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferable.
  • the platinum-based catalyst includes chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complex, platinum ketone complex, platinum vinylsiloxane complex, platinum tetrachloride, platinum fine powder, solid platinum on alumina or silica carrier , Platinum black, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes are exemplified, but chloroplatinic acid or platinum vinylsiloxane complexes are preferred from the standpoint of stability and versatility.
  • the amount of the catalyst metal is within the range of 0.1 to 1,000 ppm by mass with respect to the total mass of the diorganopolysiloxane and the unsaturated group-containing polyoxyalkylene compound of the formula (7), In particular, the amount is preferably within the range of 0.5 to 100 ppm.
  • Examples of the solvent used for the hydrosilylation reaction include aromatic hydrocarbon solvents such as toluene and xylene, hydrocarbon solvents such as hexane and octane, ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran, ethyl acetate, and butyl acetate. And ester solvents such as methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol and 1-butanol, and chlorinated hydrocarbon solvents.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • hydrocarbon solvents such as hexane and octane
  • ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran
  • ethyl acetate ethyl acetate
  • butyl acetate ethyl acetate
  • ester solvents such
  • the solvent content is 0 to 1,000. Part by mass.
  • the amount is preferably 10 to 1,000 parts by mass. If the content of the solvent is small, the progress of the hydrosilylation reaction may be slow. On the other hand, if the content of the solvent is large, there is a problem that waste increases.
  • the reaction temperature of the hydrosilylation reaction is preferably in the range of 50 to 150 ° C. When the reaction temperature is lower than 50 ° C., the reaction rate may decrease. When the reaction temperature is higher than 150 ° C., the unsaturated hydrocarbon may undergo internal transfer and the hydrosilylation reaction may not proceed.
  • a hydrocarbon having 4 to 16 carbon atoms having a double bond at the end specifically 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like can be added and reacted.
  • a pH adjuster such as potassium acetate (Japanese Patent Publication No. 62-34039) in order to prevent or suppress the dehydrogenation reaction.
  • the organic solvent solution of the polyoxyalkylene-modified diorganopolysiloxane compound can be produced by a known method. More specifically, in the case of the method i, ethanol of potassium acetate as a pH adjuster in a isopropyl alcohol solvent of a diorganopolysiloxane containing hydrogen atoms containing silicon atoms at both ends and an unsaturated group-containing polyoxyalkylene compound in a nitrogen atmosphere. After the solution is added, it is heated to bring the internal temperature to 50-80 ° C.
  • a polyoxyalkylene-modified diorganopolysiloxane compound can be synthesized by adding a toluene solution of a platinum vinylsiloxane complex and stirring for 2 to 12 hours. Furthermore, the isopropyl alcohol solvent can be distilled off by heating and reducing the pressure. At that time, the heating temperature is preferably less than 120 ° C. If the temperature is higher than 120 ° C., the polyalkyl ether moiety may be oxidized.
  • an ethanol solution of potassium acetate is added as a pH adjuster to an isopropyl alcohol solvent of both ends of silicon atom-bonded hydrogen atom-containing diorganopolysiloxane and both ends of unsaturated group-containing diorganopolysiloxane in a nitrogen atmosphere. After the addition, it is heated to bring the internal temperature to 50-80 ° C. Next, platinum vinylsiloxane complex is added and stirred for 2 to 12 hours, and then an unsaturated group-containing polyoxyalkylene compound is added and stirred for 2 to 12 hours to synthesize a polyoxyalkylene-modified diorganopolysiloxane compound.
  • the isopropyl alcohol solvent can be distilled off by heating and reducing the pressure.
  • the heating temperature is preferably less than 120 ° C. If the temperature is higher than 120 ° C., the polyalkyl ether moiety may be oxidized.
  • the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention may be solid.
  • the organic solvent solution of the polyoxyalkylene-modified diorganopolysiloxane compound can be handled as it is.
  • it can also be used by dissolving in a nonionic surfactant.
  • a nonionic surfactant is mix
  • the nonionic surfactant used when replacing the solvent is not particularly limited as long as it can dissolve the polyoxyalkylene-modified diorganopolysiloxane compound, but is preferably liquid at 25 ° C., for example, polyoxyethylene alkyl Nonionic surfactants such as ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester it can. These surfactants can be used alone or in combination of two or more.
  • nonionic surfactant When a polyoxyalkylene-modified diorganopolysiloxane compound dissolved in an organic solvent is replaced with a nonionic surfactant, the nonionic surfactant is not distilled off, and only the organic solvent is distilled off.
  • a lower vapor pressure nonionic surfactant among the above surfactants, more preferable are those having an addition mole number of ethylene oxide of 2 to 12 and an HLB of 7.5 to 14.0.
  • Such a nonionic emulsifier is liquid at 25 ° C., and the diluted organic solvent of the polyoxyalkylene-modified diorganopolysiloxane compound can be easily replaced with the emulsifier.
  • HLB is according to the Griffin equation.
  • the ratio of the polyoxyalkylene-modified diorganopolysiloxane compound to the nonionic surfactant is not specified, but the mass ratio (polyoxyalkylene-modified diorganopolysiloxane compound / nonionic surfactant) is preferably 0.1 or more. .
  • the surfactant solution of the polyoxyalkylene-modified diorganopolysiloxane compound is less than 0.1 as an emulsifier or an emulsification aid for the organopolysiloxane having a high degree of polymerization, emulsification to the organopolysiloxane having a high degree of polymerization There is a risk of lowering the force and the solvent resistance and salt resistance of the emulsion.
  • the polyoxyalkylene-modified diorganopolysiloxane compound is thus suitably used for emulsification of high-polymerization degree organopolysiloxane and the like, and therefore the present invention provides the following organopolysiloxane emulsion composition.
  • D Water
  • the components (B) and (D) are optional components.
  • the polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal is used as an emulsification aid or emulsifier for the component (C).
  • the component (C) By including the polyoxyalkylene-modified diorganopolysiloxane compound as the component (A), the organopolysiloxane emulsion composition as the component (C) exhibits the effects of solvent resistance and salt resistance.
  • the emulsifying power of the polyoxyalkylene-modified diorganopolysiloxane compound (A) relative to the organopolysiloxane (C) is determined by the degree of polymerization of the organopolysiloxane (C) and the general formula (2) in the molecule (A). ).
  • degree of polymerization of the component (C) organopolysiloxane is low, emulsification is possible only when the number of structural units of the general formula (2) contained in the polyoxyalkylene-modified diorganopolysiloxane compound (A) is small to some extent. There are cases where it is not possible.
  • the degree of polymerization of the organopolysiloxane of component (C) is high, the number of structural units of general formula (2) contained in the polyoxyalkylene-modified diorganopolysiloxane compound of component (A) is large to some extent. Emulsification is possible.
  • the organopolysiloxane of component (C) is silicone oil, silicone gum, silicone resin, etc. in the range of 2 to 100,000,000 mPa ⁇ s at 25 ° C.
  • those of 500,000 mPa ⁇ s or more are preferable, preferably 500,000 to 100,000,000 mPa ⁇ s, more preferably 750,000 to 100,000,000 mPa ⁇ s. .
  • the viscosity is lower than 500,000 mPa ⁇ s, there is a risk that the wear resistance and the like will be reduced when used as a coating agent.
  • the viscosity is higher than 100,000,000 mPa ⁇ s, the emulsification will be applied to the apparatus. There is a risk of heavy load.
  • the viscosity is an absolute viscosity measured at 25 ° C. with a rotational viscometer.
  • organopolysiloxanes include cyclic siloxane, dimethylpolysiloxane, dimethylphenylpolysiloxane, methylhydrogenpolysiloxane, methyltrifluoropropylpolysiloxane, high degree of polymerization gum dimethylpolysiloxane, gum dimethylsiloxane Silicone raw rubber such as methylphenylsiloxane copolymer, cyclic siloxane solution of silicone raw rubber, trimethylsiloxysilicic acid, cyclic siloxane solution of trimethylsiloxysilicic acid, alkyl-modified silicone, aralkyl-modified silicone, vinyl-modified silicone, amino-modified silicone, amino acid Examples include modified silicone, fluorine-modified silicone, epoxy-modified silicone, (meth) acryl-modified silicone, and hydroxy-modified silicone.
  • the content of the polyoxyalkylene-modified diorganopolysiloxane compound as the component (A) is 1 to 50 parts by mass when the content of the organopolysiloxane as the component (C) is 100 parts by mass.
  • the amount is preferably 10 to 40 parts by mass, and more preferably 20 to 35 parts by mass. If the content of the polyoxyalkylene-modified diorganopolysiloxane compound is too small, the organopolysiloxane of component (C) may not be emulsified due to a decrease in emulsification. Moreover, there exists a possibility that the solvent resistance and salt resistance may fall. On the other hand, if the amount of the polyoxyalkylene-modified diorganopolysiloxane compound (A) is too large, the properties such as the wear resistance of the organopolysiloxane (C) may be impaired.
  • Component surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
  • Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and glycerin fatty acid ester. Such nonionic surfactants can be mentioned.
  • polyoxyethylene octyl ether examples thereof include polyoxyethylene octyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Examples thereof include oxyethylene polyoxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene polyoxypropylene tridecyl ether, and polyoxyethylene cetyl ether. It is also possible to use a reactive surfactant having a functional group.
  • Anionic surfactants include alkyl sulfates such as lauryl sulfate, alkylbenzene sulfonic acids and salts thereof, sulfate salts of monoalkyl polyoxyethylene ethers, acetate salts of monoalkyl polyoxyethylene ethers, alkyl naphthyl sulfones.
  • alkali metal sulforesinates alkali metal sulfosuccinates, alkyl phosphoric acids and salts thereof, phosphate esters of monoalkyl polyoxyethylene ethers, sulfonated glyceryl esters of fatty acids, alkali metal sulfates and sulfates of alkyl sulfateskind.
  • lauryl sulfate examples thereof include lauryl sulfate, sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether acetate, sodium dodecylbenzenesulfonate, polyoxyethylenesulfosuccinic acid.
  • examples thereof include disodium lauryl, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl ether phosphate, sodium alkylnaphthalene sulfonate, and the like. It is also possible to use a reactive surfactant having a functional group.
  • Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, sulfonium salts, phosphonium salts, and acetates. Specific examples thereof include stearylamine acetate, lauryltrimethylammonium chloride, cetyltrimethylammonium, stearyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride.
  • amphoteric surfactants include alkyl betaines and alkyl imidazolines. Specific examples thereof include lauryldimethylaminoacetic acid betaine, lauryldimethylamine oxide, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.
  • Anionic surfactants, cationic surfactants, and amphoteric surfactants have a charge in the molecule, which may limit their use. Accordingly, nonionic surfactants are preferred, and polyoxyalkylene alkyl ethers or polyoxyethylene sorbitan fatty acid esters are more preferred from the viewpoint of emulsifying properties.
  • the content of the component (B) surfactant is 0 to 50 parts by mass when the content of the component (C) organopolysiloxane is 100 parts by mass. .
  • the amount is preferably 0 to 40 parts by mass, and more preferably 0 to 35 parts by mass.
  • the amount of the component (B) surfactant is more than 50 parts by mass, the water repellency and wear resistance of the component (C) organopolysiloxane may be impaired.
  • blending (B) component it is preferable that it is 1 mass part or more, Especially 5 mass parts or more.
  • the water of component (D) is added as required from the viewpoint of the required product form such as self-emulsification type or emulsion type, or emulsification properties. Therefore, (D)
  • the water content of the component is 0 to 10,000 parts by mass when the content of the organopolysiloxane of component (C) is 100 parts by mass.
  • the amount is preferably 0 to 5,000 parts by mass, and more preferably 0 to 1,000 parts by mass. When the amount is more than 1,000 parts by mass, the stability is lowered and there is a risk of separation. If the water content of the component (D) is within the above range, the particle size is stable without changing over time.
  • blending the water of a component 1 mass part or more is preferable, More preferably, it is 5 mass parts or more, More preferably, it is 10 mass parts or more.
  • the organopolysiloxane emulsion composition of the present invention includes polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl pyrrolidone, alginate, xanthan gum, acrylic acid polymer as a protective colloid agent or thickener. You may mix
  • antibacterial agents or antiseptics such as oxazoline compounds and aromatic carboxylates, fragrances, antioxidants, rust inhibitors, dyes, fillers, curing catalysts, organic powders, inorganic powders and the like may be blended. .
  • the specific emulsification method of the organopolysiloxane emulsion composition of the present invention is as follows.
  • the (A) component polyoxyalkylene-modified diorganopolysiloxane compound and, if necessary, the (B) surfactant are added to the organopolysiloxane of the component (C), and the phase is inverted by a gate mixer. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, a surfactant and / or water is further added as necessary, and a gate mixer, T.M. K. Homo disperse (trade name, manufactured by Primix) or T. K. Dilute with a homomixer (trade name, manufactured by Primics).
  • a specific emulsification method in the case of adding water at the time of phase inversion is as follows. To the organopolysiloxane (C), add the polyoxyalkylene-modified diorganopolysiloxane compound (A), the surfactant (B) if necessary, the water (D), and gate mixer. Phase inversion. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, a surfactant and / or water is further added as necessary, and a gate mixer, T.M. K. Homo disperse (trade name, manufactured by Primix) or T. K. Dilute with a homomixer (trade name, manufactured by Primics).
  • the concentration of the organopolysiloxane of component (C) in the emulsion is preferably in the range of 1 to 90% by mass. If it is less than 1% by mass, there is a problem in the stability of the emulsion, and if it is more than 90% by mass, the viscosity of the emulsion is high and handling becomes difficult.
  • the temperature during emulsification is preferably 0 to 80 ° C., more preferably 0 to 50 ° C. If the temperature is less than 0 ° C. or higher than 80 ° C., the emulsion may not be emulsified or the produced emulsion may become unstable. About the pressure at the time of emulsification, not only a normal pressure but pressure reduction or pressurization may be sufficient. When emulsifying in a reduced pressure or pressurized environment, bubbles are less likely to be mixed and may be effectively emulsified. The pressure for reducing the pressure should be higher than the vapor pressure of the raw material so that the raw material does not volatilize.
  • T.M. K. Homomixer (trade name, manufactured by Primics), T.M. K. Homo disperse (trade name, manufactured by Primics), T. K. Combimix (trade name, manufactured by Primix), Ajihomo mixer (trade name, manufactured by Primics), triaxial dispersion kneader combination mix (trade name, manufactured by Primics), a combination of homomixer, homodisper and anchor mixer, Hibis Disper Mix (trade name, manufactured by Primics), T.M. K.
  • Hibismix product name made by Primix
  • planetary mixer product name made by Inoue Seisakusho
  • HAAKE Mini Lab II product name made by Thermo scientific
  • MC15 which is a twin screw mixer having the same direction screw or different direction screw.
  • MC5 (trade name, manufactured by Leo Laboratories Inc.) can also be used.
  • emulsification can be performed only with an anchor. It is also possible to emulsify using a continuous apparatus such as a colloid mill or a high-pressure homogenizer.
  • the average particle size of the organopolysiloxane emulsion composition of the present invention is preferably 100 ⁇ m or less. When the average particle size is larger than 100 ⁇ m, the stability of the emulsified composition is lowered, and separation or the like may occur.
  • the average particle size when the average particle size is 2 ⁇ m or more, it can be measured by Multisizer 3 manufactured by Beckman Coulter. When the average particle size is less than 2 ⁇ m, it can be measured with LA960 or LA920 manufactured by Horiba, Ltd., or N4 PLUS manufactured by Beckman Coulter.
  • the lower limit of the average particle diameter is not particularly limited, but is usually 0.1 ⁇ m or more, particularly 0.5 ⁇ m or more.
  • the organopolysiloxane emulsion composition of the present invention is an emulsion composition using a polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal as an emulsifier or an emulsification aid.
  • the organopolysiloxane emulsion composition of the present invention is resistant to polar solvents such as alcohols, ketones and esters, and is also resistant to salts such as sodium chloride and sodium sulfate.
  • cosmetics and the like are blended with alcohols that are perfumes and moisturizers, and softeners also contain alcohols that are perfumes.
  • the organopolysiloxane emulsion composition of the present invention can be stably blended in such cosmetics and softener products.
  • a polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal as an emulsifier or an emulsifying aid, an organopolysiloxane emulsion composition having a high degree of polymerization can be easily produced. Therefore, the emulsion composition of the present invention can use polysiloxane having a high degree of polymerization as the base oil.
  • Such a highly polymerized organopolysiloxane emulsion composition has an excellent coating effect, and is therefore useful as a resin coating agent, hair care product, mold, plastic and tire release agent.
  • the viscosity is a value at 25 ° C. measured with a BM type or BH type rotational viscometer.
  • the 30% by mass toluene solution viscosity is a value of an absolute viscosity at 25 ° C. measured with a BM type or BH type rotational viscometer after dilution with toluene so that the target compound becomes 30% by mass.
  • the viscosity of the diorganopolysiloxane containing silicon atoms bonded to hydrogen atoms at both ends is a kinematic viscosity measured with an Ostwald viscometer at 25 ° C.
  • GPC manufactured by TOSOH, HLC8220
  • the average particle diameter of the emulsion is a volume-based volume average particle diameter measured at 25 ° C. by a Multisizer 3 manufactured by Beckman Coulter.
  • Nonionic surfactant Sannonic SS-120 100 parts by mass (100 g) was added, and isopropyl alcohol was added under the conditions of 10 to 15 mmHg and 35 to 40 ° C.
  • the surfactant solution A of the polyoxyalkylene modified diorganopolysiloxane compound was obtained. Subsequently, the following general formula (10) (K indicates the number of the following viscosity) 27.5 parts by mass (27.5 g) of both ends hydroxydimethylpolysiloxane (30% by weight toluene solution viscosity 1,400 mPa ⁇ s) represented by the above, and surfactant solution A10 of polyoxyalkylene-modified diorganopolysiloxane compound 12.5 parts by mass (12.5 g) of Sannonic SS-120 (manufactured by Sanyo Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB 14.5) K.
  • Emulsion A was obtained by stirring with a homodisper (Primix) at 500 to 2,000 rpm for about 10 minutes. The average particle diameter was measured with a Multisizer 3 manufactured by Beckman Coulter and found to be 22.5 ⁇ m.
  • K ′ represents the number of the following viscosity.
  • Example 3 Surfactant dissolution of polyoxyalkylene-modified diorganopolysiloxane synthesized with 69 parts by mass (44.5 g) of both ends hydroxydimethylpolysiloxane [general formula (11)] (30 mass% toluene solution viscosity 47,000 mPa ⁇ s) 29 parts by mass (18.7 g) of liquid B and 2 parts by mass (1.3 g) of water K.
  • Emulsion C was obtained by stirring for 20 minutes at 40-50 rpm with Hibismix (Primix). The average particle size was 4.0 ⁇ m as measured by Multisizer 3 manufactured by Beckman Coulter.
  • Example 4 Surface activity of polyoxyalkylene-modified diorganopolysiloxane synthesized with 59.5 parts by mass (44.6 g) of both ends hydroxydimethylpolysiloxane [general formula (11)] (30 mass% toluene solution viscosity 47,000 mPa ⁇ s) Agent solution B 25.5 parts by mass (19.1 g) and 2 parts by mass of water (1.5 g) K. Hibismix (Primics) was stirred at 40-50 rpm for 20 minutes. Further, 13 parts by mass of water (9.8 g) was added and T.W. K. Hibismix (Primics Co., Ltd.) was stirred at 40-50 rpm for 20 minutes to obtain Emulsion D. The average particle size was 4.4 ⁇ m as measured by Multisizer 3 manufactured by Beckman Coulter.
  • the temperature was 75 ° C.
  • 5 ppm of a toluene solution of a platinum vinylsiloxane complex as platinum metal was added to the siloxane and stirred for 8 hours to synthesize a polyoxyalkylene-modified diorganopolysiloxane compound.
  • the pressure was reduced at 110 to 120 ° C. and 30 mmHg or less with nitrogen bubbling to distill off isopropanol, and the polyoxyalkylene-modified diorganopolysiloxane compound D (general formula (12), weight average molecular weight by GPC was 9,500).
  • silicon-bonded hydrogen atom-containing diorganopolysiloxane [general formula (13)] 77 parts by mass (77 g) and unsaturated group-containing polyoxyalkylene alkyl ether (CH 2 ⁇ CHCH 2 O (CH 2 CH 2 O) ) 24 (CH 2 CHCH 3 O) 8 H in 23 parts by mass (23 g), 150 parts by mass of isopropyl alcohol (150 g) and 1.0 part by mass of an isopropyl alcohol solution of 10% by mass potassium acetate as a pH adjuster (1.0 g ) And heated to an internal temperature of 75 ° C.
  • silicon-bonded hydrogen atom-containing diorganopolysiloxane [general formula (13)] 77 parts by mass (77 g) and unsaturated group-containing polyoxyalkylene alkyl ether (CH 2 ⁇ CHCH 2 O (CH 2 CH 2 O) ) 24 (CH 2 CHCH 3 O) 8 H in 23 parts by mass (23 g), 150 parts by mass of isopropy
  • a polysiloxane compound was synthesized, Sannonic SS-120 (manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene) Polyalkylene-modified organopolysiloxane by adding 50 parts by mass (50 g) of alkyl ether, HLB 14.5) and then depressurizing to 30 to 45 ° C. and 10 to 15 mmHg with nitrogen bubbling to distill off isopropyl alcohol.
  • a surfactant solution E of the compound (general formula (14), weight average molecular weight by GPC of 53,000) was obtained.
  • K The mixture was stirred at 500 to 2,000 rpm for about 10 minutes with a homodisper (manufactured by Primics), but the both end hydroxydimethylpolysiloxane was not emulsified.
  • Nonionic surfactant Sannonic SS-120 (manufactured by Sanyo Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB14.5) 10 parts by mass (10 g) and both ends hydroxydimethylpolysiloxane [general formula (10)] (30% by weight toluene solution Viscosity of 1,400 mPa ⁇ s) 55 parts by mass (55 g) and 7 parts by mass of ion-exchanged water (7 g) K. Homodisper (Primics Co., Ltd.) was stirred at 500 to 2,000 rpm for 10 minutes, and 28 parts by mass (28 g) of ion-exchanged water was added. K. Emulsion H was obtained by stirring at 800 to 4,000 rpm with a homomixer (Primics). The average particle size was 4.3 ⁇ m as measured by Multisizer 3 manufactured by Beckman Coulter.
  • Nonionic surfactant Sannonic SS-120 (manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene alkyl ether, HLB14.5) 10 parts by mass (10 g) and both ends hydroxydimethylpolysiloxane [general formula (11)] (30% by weight toluene solution Viscosity of 47,000 mPa ⁇ s) 55 parts by mass (55 g) and 7 parts by mass of ion-exchanged water (7 g) K. Homodisper (Primix Co., Ltd.) was stirred at 500 to 2,000 rpm for 10 minutes, but could not be emulsified.
  • Alcohol resistance 2.0 g of emulsions A to G and 8.0 g of isopropyl alcohol were placed in a glass bottle and shaken, and the state of the solution was observed.
  • ⁇ There is almost no precipitation of the organopolysiloxane, and the emulsion is dispersed in isopropyl alcohol.
  • X The emulsion is broken by isopropyl alcohol, and the organopolysiloxane is precipitated.

Abstract

Disclosed is a polyoxyalkylene-modified diorganopolysiloxane compound having a polyoxyalkylene-group-containing siloxane chain of formula (1) bonded to an end thereof, and including at least 40 structural units of formula (2) within the molecule thereof. (L is a double-chain polyoxyalkylene alkyl group represented by formula (3). (EO represents a polyoxyethylene group, AO represents a C3-10 polyoxyalkylene group, R2 represents a hydrogen atom, an alkyl group, a carboxy group, an acyl group, or a phenyl group, r = 0 to 10, s = 1 to 150, and t = 0 to 150.)] The present invention has excellent compatibility with high-polymerization-degree organopolysiloxanes. By using this polyoxyalkylene-modified diorganopolysiloxane compound as an emulsifier or an emulsification aid, a high-polymerization-degree organopolysiloxane can be emulsified easily.

Description

ポリオキシアルキレン変性ジオルガノポリシロキサン化合物及びその製造方法並びにオルガノポリシロキサン乳化組成物Polyoxyalkylene-modified diorganopolysiloxane compound, method for producing the same, and organopolysiloxane emulsion composition
　本発明は、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物及びその製造方法に関する。また、本発明は、耐溶剤性や耐塩性に優れ、特に化粧品、衣類等の柔軟剤、樹脂用コーティング剤、離型剤等として好適なオルガノポリシロキサン乳化組成物に関する。 The present invention relates to a polyoxyalkylene-modified diorganopolysiloxane compound and a method for producing the same. The present invention also relates to an organopolysiloxane emulsion composition that is excellent in solvent resistance and salt resistance, and is particularly suitable as a softener for cosmetics and clothing, a coating agent for resins, a release agent, and the like.
　オルガノポリシロキサンは、化学的安定性、耐熱性、耐候性、離型性、撥水性、生理的不活性に優れるため、プラスチック、繊維、塗料、化粧品、樹脂のコーティング等の様々な分野で使用されている。しかし、オルガノポリシロキサンの多くは疎水性であり、水やアルコール等への相溶性に乏しく、疎水性のオルガノポリシロキサンの乳化、相溶化、分散等を行うために、従来からノニオン界面活性剤が使用されてきた。 Organopolysiloxane is excellent in chemical stability, heat resistance, weather resistance, releasability, water repellency, and physiological inertness, so it is used in various fields such as plastics, fibers, paints, cosmetics, and resin coatings. ing. However, most of the organopolysiloxanes are hydrophobic and have poor compatibility with water, alcohol, etc., and nonionic surfactants have been conventionally used to emulsify, compatibilize and disperse hydrophobic organopolysiloxanes. Have been used.
　しかし、ノニオン界面活性剤による乳化物は、アルコールや塩に対して不安定であり、乳化物にアルコールや塩が添加されると分離や破壊を生じる可能性がある。化粧品は保湿剤や香料としてアルコール類が多く含まれ、また衣類等の柔軟剤にも香料であるアルコール類が多く含まれる。オルガノポリシロキサンは滑り性や柔軟性を付与できることから、化粧品や柔軟剤等の多くの製品に配合されているが、それらの製品に含まれるアルコール類によりオルガノポリシロキサンの乳化物の安定性が低下するという問題がある。そのため、アルコールに対して安定性の高いオルガノポリシロキサンの乳化物が求められていた。 However, emulsions with nonionic surfactants are unstable with respect to alcohols and salts, and if alcohols or salts are added to the emulsions, they may be separated or broken. Cosmetics contain a lot of alcohols as moisturizers and fragrances, and softeners such as clothes contain a lot of alcohols that are fragrances. Organopolysiloxane can be added to many products such as cosmetics and softeners because it can provide slipperiness and flexibility, but the stability of the emulsion of organopolysiloxane is reduced by the alcohols contained in these products. There is a problem of doing. Therefore, there has been a demand for an emulsion of organopolysiloxane that is highly stable against alcohol.
　また、高重合度のオルガノポリシロキサンの乳化物は、樹脂のコーティング剤やヘアケア製品に広く使用されているが、高重合度のオルガノポリシロキサン単独での乳化が困難であり、通常は高重合度のオルガノポリシロキサンと低重合度のオルガノポリシロキサンを混合して乳化している。そのような乳化物は高重合度のオルガノポリシロキサンを単独で乳化した乳化物と比べ滑り性やコーティング作用に違いがあるため、高重合度のオルガノポリシロキサン単独でも容易に乳化できる乳化剤もしくは乳化助剤の開発が求められていた。 Emulsions of organopolysiloxane with a high degree of polymerization are widely used in resin coating agents and hair care products, but it is difficult to emulsify with a high degree of polymerization of organopolysiloxane alone, and usually a high degree of polymerization is required. These organopolysiloxanes and low-polymerization organopolysiloxanes are mixed and emulsified. Since such emulsions differ in slipperiness and coating action compared to emulsions obtained by emulsifying high-polymerization degree organopolysiloxane alone, emulsifiers or emulsification aids that can be easily emulsified with high-polymerization degree organopolysiloxane alone. There was a need for the development of agents.
　なお、本発明に関連する公知文献としては、以下のものが挙げられる。
　即ち、特開２００７－１２６３５９号公報（特許文献１）は、ポリオキシアルキレングリセリルエーテル残基が結合する側鎖ポリエーテル変性シリコーンを含有する皮膚用化粧料であるが、６ｍｍ2／ｓのシリコーンオイルの乳化の例しか示されておらず、高重合度のオルガノポリシロキサンの乳化物については例示されていない。また、構造はポリグリセリルエーテルを付加させたポリオキシアルキレン変性オルガノポリシロキサンであり、本発明で記述するポリオキシアルキレン変性ジオルガノポリシロキサン化合物とは構造が異なる。 In addition, the following are mentioned as well-known literature relevant to this invention.
That is, Japanese Patent Application Laid-Open No. 2007-126359 (Patent Document 1) is a skin cosmetic containing a side-chain polyether-modified silicone to which a polyoxyalkylene glyceryl ether residue is bonded, but is a 6 mm 2 / s silicone oil. Only an emulsification example is shown, and an emulsion of an organopolysiloxane having a high polymerization degree is not exemplified. Further, the structure is a polyoxyalkylene-modified organopolysiloxane added with polyglyceryl ether, and the structure is different from the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
　特許第５１３６８４９号公報（特許文献２）は、側鎖ポリオキシアルキレン変性オルガノポリシロキサン化合物の水希釈品に窒素を吹き込み発泡した際の塩存在下での気泡安定性について例示している。側鎖ポリオキシアルキレン変性オルガノポリシロキサンは耐塩性を特徴としたものであり、高重合度のオルガノポリシロキサンの乳化を目的としたものではない。また、側鎖のポリオキシアルキレン変性オルガノポリシロキサン化合物であり、本発明で記述するポリオキシアルキレン変性ジオルガノポリシロキサン化合物とは構造が異なる。 Japanese Patent No. 513649 (Patent Document 2) exemplifies the bubble stability in the presence of salt when nitrogen is blown into a water-diluted product of a side-chain polyoxyalkylene-modified organopolysiloxane compound. The side chain polyoxyalkylene-modified organopolysiloxane is characterized by salt resistance and is not intended for emulsification of organopolysiloxane having a high degree of polymerization. Further, it is a side chain polyoxyalkylene-modified organopolysiloxane compound, which is different in structure from the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
　特許第４４８５１３４号公報（特許文献３）は、分岐ポリグリセロール変性シリコーンであるが、繊維等への吸着を目的に開発されたものであり、高重合度のポリシロキサンの乳化剤もしくは乳化助剤として開発されたものではない。また、構造は分岐ポリグリセロール変性シリコーンであり、本発明で記述するポリオキシアルキレン変性ジオルガノポリシロキサン化合物とは構造が異なる。 Japanese Patent No. 4485134 (Patent Document 3) is a branched polyglycerol-modified silicone, which was developed for the purpose of adsorption onto fibers and the like, and was developed as an emulsifier or emulsification aid for polysiloxane having a high degree of polymerization. It is not what was done. Further, the structure is branched polyglycerol-modified silicone, and the structure is different from the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
　国際公開第２０１１／０４９２４７号（特許文献４）は、シロキサンデンドロン構造を有する基及び親水性基を有する共変性オルガノポリシロキサンであり、化粧料に配合した場合には優れた感触や質感を付与し、また様々な油剤を安定的に乳化できる優れた乳化助剤又は乳化剤として働く。ジメチルポリシロキサンの２ｍｍ2／ｓや６ｍｍ2／ｓの乳化について例示しているが、高重合度のポリシロキサンについての例示はない。また、シロキサンデンドロン構造を有する基及び親水性基を有する共変性オルガノポリシロキサンは、本発明で記述するポリオキシアルキレン変性ジオルガノポリシロキサン化合物とは構造が異なる。 International Publication No. 2011/049247 (Patent Document 4) is a co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group, and imparts excellent feel and texture when blended in cosmetics. In addition, it works as an excellent emulsification aid or emulsifier that can stably emulsify various oils. Examples of emulsification of dimethylpolysiloxane at 2 mm 2 / s and 6 mm 2 / s are given, but there is no example of polysiloxane having a high degree of polymerization. The co-modified organopolysiloxane having a group having a siloxane dendron structure and a hydrophilic group has a structure different from that of the polyoxyalkylene-modified diorganopolysiloxane compound described in the present invention.
特開２００７－１２６３５９号公報JP 2007-126359 A 特許第５１３６８４９号公報Japanese Patent No. 5136849 特許第４４８５１３４号公報Japanese Patent No. 4485134 国際公開第２０１１／０４９２４７号International Publication No. 2011/049247
　本発明は上記事情に鑑みなされたもので、高重合度オルガノポリシロキサンとの相溶性に優れ、容易に高重合度オルガノポリシロキサンを乳化することができると共に、アルコールや塩の存在下においてもオルガノポリシロキサンを乳化することが可能で、界面活性能を十分に維持でき、乳化剤もしくは乳化助剤として好適に用いることができるポリオキシアルキレン変性ジオルガノポリシロキサン化合物、及びその製造方法を提供することを目的とする。また、耐溶剤性や耐塩性に優れ、特に化粧品、柔軟剤、コーティング剤、離型剤等として有効なオルガノポリシロキサン乳化組成物を提供することを他の目的とする。 The present invention has been made in view of the above circumstances, is excellent in compatibility with high-polymerization degree organopolysiloxane, can easily emulsify high-polymerization degree organopolysiloxane, and can also be used in the presence of alcohol or salt. To provide a polyoxyalkylene-modified diorganopolysiloxane compound capable of emulsifying polysiloxane, sufficiently maintaining the surface activity, and suitably used as an emulsifier or an emulsification aid, and a method for producing the same. Objective. Another object of the present invention is to provide an organopolysiloxane emulsion composition that is excellent in solvent resistance and salt resistance and is particularly effective as a cosmetic, a softening agent, a coating agent, a release agent and the like.
　本発明は、上記目的を達成するため、下記のポリオキシアルキレン変性ジオルガノポリシロキサン化合物及びその製造方法を提供する。
〔１〕
　下記一般式（１）で表されるポリオキシアルキレン基を有するシロキサン鎖が末端に結合し、かつ下記一般式（２）で表される構造単位を分子内に４０個以上有するポリオキシアルキレン変性ジオルガノポリシロキサン化合物。
Figure JPOXMLDOC01-appb-C000009
 ［式中、Ｒ及びＲ1はそれぞれ同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。Ｌは下記一般式（３）で表される２鎖型のポリオキシアルキレンアルキル基である。
Figure JPOXMLDOC01-appb-C000010
 （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又は、フェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）］
〔２〕
　下記一般式（４）で表される〔１〕記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物。
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ1、Ｌは上記の通りである。ｍは４０以上の整数である。）
〔３〕
　下記一般式（５）で表される〔１〕記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物。
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ1、Ｌは上記の通りである。Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。Ｘは炭素数２～２０のアルキレン基である。ｍ１＋ｍ２＋ｍ３＝ｍで、ｍは４０以上の整数である。）
〔４〕
　下記一般式（６）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと下記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物とをヒドロシリル化触媒により溶媒存在下又は非存在下で反応させる工程を含む〔２〕記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物の製造方法。
Figure JPOXMLDOC01-appb-C000013
 （式中、Ｒ1は同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。ｍは４０以上の整数である。）
Figure JPOXMLDOC01-appb-C000014
 （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又は、フェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）
〔５〕
　下記一般式（８）で表される両末端不飽和基含有ジオルガノポリシロキサンの両末端不飽和基のそれぞれに下記一般式（９）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの一方の末端ケイ素原子結合水素原子を付加反応させる工程、及びこの工程後、上記両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの他方の末端ケイ素原子結合水素原子に下記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物の不飽和基を付加反応させる工程を含む〔３〕記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物の製造方法。
Figure JPOXMLDOC01-appb-C000015
 （式中、Ｒ1は同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。ｎ１、ｎ２はそれぞれ０以上の整数であるが、ｎ１＋ｎ２＋ｎ２は４０以上の整数である。）
Figure JPOXMLDOC01-appb-C000016
 （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又は、フェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）
〔６〕
　〔１〕～〔３〕のいずれかに記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物とノニオン界面活性剤との混合物。
〔７〕
　（Ａ）〔１〕～〔３〕のいずれかに記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物：１～５０質量部、
（Ｂ）界面活性剤：０～５０質量部、
（Ｃ）上記（Ａ）成分を除くオルガノポリシロキサン：１００質量部、
（Ｄ）水：０～１０，０００質量部
を含有することを特徴とするオルガノポリシロキサン乳化組成物。
〔８〕
　（Ｃ）成分のオルガノポリシロキサンの粘度が、２５℃において５００，０００ｍＰａ・ｓ以上である〔７〕記載のオルガノポリシロキサン乳化組成物。
〔９〕
　（Ｃ）成分のオルガノポリシロキサンが、ジメチルポリシロキサン、ジメチルシロキサンとメチルフェニルシロキサンの共重合体、又は両末端ヒドロキシ変性ジメチルポリシロキサンである〔７〕又は〔８〕記載のオルガノポリシロキサン乳化組成物。
〔１０〕
　乳化物の平均粒径が１００μｍ以下である〔７〕～〔９〕のいずれかに記載のオルガノポリシロキサン乳化組成物。 In order to achieve the above object, the present invention provides the following polyoxyalkylene-modified diorganopolysiloxane compound and a method for producing the same.
[1]
A polyoxyalkylene-modified di having a siloxane chain having a polyoxyalkylene group represented by the following general formula (1) bonded to the terminal and having 40 or more structural units represented by the following general formula (2) in the molecule Organopolysiloxane compound.
Figure JPOXMLDOC01-appb-C000009
 [In the formula, R and R 1 may be the same or different and each is a substituted or unsubstituted linear or branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, polyoxy group having 1 to 20 carbon atoms. It is a monovalent hydrocarbon group having an alkylene group or a hydrogen atom. L is a two-chain polyoxyalkylene alkyl group represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000010
 (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = 1 to 150, t = 0 to 150)]]
[2]
[1] The polyoxyalkylene-modified diorganopolysiloxane compound represented by the following general formula (4):
Figure JPOXMLDOC01-appb-C000011
 (In the formula, R 1 and L are as described above. M is an integer of 40 or more.)
[3]
[1] The polyoxyalkylene-modified diorganopolysiloxane compound represented by the following general formula (5):
Figure JPOXMLDOC01-appb-C000012
 (Wherein R 1 and L are as defined above. R 3 may be the same or different and each represents a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group having 1 to 20 carbon atoms, A monovalent hydrocarbon group having an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, X is an alkylene group having 2 to 20 carbon atoms, m1 + m2 + m3 = m, and m is 40 or more. (It is an integer.)
[4]
A silicon-bonded hydrogen atom-containing diorganopolysiloxane represented by the following general formula (6) and an unsaturated group-containing polyoxyalkylene compound represented by the following general formula (7) in the presence of a solvent using a hydrosilylation catalyst Or the manufacturing method of the polyoxyalkylene modified diorganopolysiloxane compound of [2] including the process made to react in absence.
Figure JPOXMLDOC01-appb-C000013
 (Wherein R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group. A monovalent hydrocarbon group or a hydrogen atom, and m is an integer of 40 or more.)
Figure JPOXMLDOC01-appb-C000014
 (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = (1 to 150, t = 0 to 150)
[5]
A diorganopolysiloxane containing hydrogen atoms at both ends represented by the following general formula (9) in each unsaturated group at both ends of the diorganopolysiloxane containing unsaturated groups at both ends represented by the following general formula (8) The step of addition reaction of one terminal silicon atom-bonded hydrogen atom of siloxane, and after this step, the other terminal silicon atom-bonded hydrogen atom of the silicon atom-bonded hydrogen atom-containing diorganopolysiloxane has the following general formula (7) [3] The method for producing a polyoxyalkylene-modified diorganopolysiloxane compound according to [3], comprising a step of subjecting an unsaturated group of the unsaturated group-containing polyoxyalkylene compound to an addition reaction.
Figure JPOXMLDOC01-appb-C000015
 (Wherein R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group. R 3 may be the same or different and is a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group having 1 to 20 carbon atoms And a monovalent hydrocarbon group having an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, n1 and n2 are each an integer of 0 or more, and n1 + n2 + n2 is an integer of 40 or more.)
Figure JPOXMLDOC01-appb-C000016
 (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = (1 to 150, t = 0 to 150)
[6]
A mixture of the polyoxyalkylene-modified diorganopolysiloxane compound according to any one of [1] to [3] and a nonionic surfactant.
[7]
(A) The polyoxyalkylene-modified diorganopolysiloxane compound according to any one of [1] to [3]: 1 to 50 parts by mass,
(B) Surfactant: 0 to 50 parts by mass,
(C) Organopolysiloxane excluding the component (A): 100 parts by mass,
(D) Water: An organopolysiloxane emulsion composition containing 0 to 10,000 parts by mass.
[8]
The organopolysiloxane emulsion composition according to [7], wherein the viscosity of the organopolysiloxane of component (C) is 500,000 mPa · s or more at 25 ° C.
[9]
The organopolysiloxane emulsion composition according to [7] or [8], wherein the organopolysiloxane of component (C) is dimethylpolysiloxane, a copolymer of dimethylsiloxane and methylphenylsiloxane, or both-end hydroxy-modified dimethylpolysiloxane. .
[10]
The organopolysiloxane emulsion composition according to any one of [7] to [9], wherein the average particle size of the emulsion is 100 μm or less.
　本発明のポリオキシアルキレン変性ジオルガノポリシロキサン化合物は、高重合度オルガノポリシロキサンとの相溶性に優れる。本発明のポリオキシアルキレン変性ジオルガノポリシロキサン化合物を乳化剤もしくは乳化助剤とすることで、容易に高重合度オルガノポリシロキサンの乳化ができる。また、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物はアルコールや塩の存在下においてもオルガノポリシロキサンを乳化することが可能であり、界面活性能を十分に維持できる。
　また、本発明のオルガノポリシロキサン乳化組成物は、耐溶剤性に優れるため、アルコール、ケトン、エステル等の極性溶剤に添加した場合でも分離や破壊を生じることなく安定である。また、耐塩性にも優れるため、塩化ナトリウムや硫酸ナトリウム等の塩が乳化組成物に配合されても、分離や破壊を生じることなく安定である。２鎖型のポリオキシアルキレンアルキル基を末端に有するポリオキシアルキレン変性ジオルガノポリシロキサン化合物を乳化剤もしくは乳化助剤とすることで、高重合度のオルガノポリシロキサンの乳化が容易にでき、そのような高重合度のオルガノポリシロキサン乳化組成物は、樹脂や毛髪へのコーティング効果に優れ、金型やプラスチックの離型の持続性に優れる。 The polyoxyalkylene-modified diorganopolysiloxane compound of the present invention is excellent in compatibility with a high degree of polymerization organopolysiloxane. By using the polyoxyalkylene-modified diorganopolysiloxane compound of the present invention as an emulsifier or an emulsification aid, the high-polymerization degree organopolysiloxane can be easily emulsified. Further, the polyoxyalkylene-modified diorganopolysiloxane compound can emulsify the organopolysiloxane even in the presence of alcohol or salt, and can sufficiently maintain the surface activity.
Moreover, since the organopolysiloxane emulsion composition of the present invention is excellent in solvent resistance, it is stable without causing separation or destruction even when added to a polar solvent such as alcohol, ketone or ester. Moreover, since it is excellent also in salt tolerance, even if salts, such as sodium chloride and sodium sulfate, are mix | blended with an emulsified composition, they are stable, without producing separation or destruction. By using a polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal as an emulsifier or an emulsification aid, emulsification of an organopolysiloxane having a high degree of polymerization can be facilitated. The highly polymerized organopolysiloxane emulsion composition is excellent in the coating effect on the resin and the hair, and is excellent in the mold and plastic mold release sustainability.
　本発明のポリオキシアルキレン変性ジオルガノポリシロキサン化合物は、下記一般式（１）で表されるポリオキシアルキレン基を有するシロキサン鎖が末端に結合し、かつ下記一般式（２）で表される構造単位を分子内に４０個以上有する。
Figure JPOXMLDOC01-appb-C000017
 ［式中、Ｒ及びＲ1はそれぞれ同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。Ｌは下記一般式（３）で表される２鎖型のポリオキシアルキレンアルキル基である。
Figure JPOXMLDOC01-appb-C000018
 （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又はフェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）］ The polyoxyalkylene-modified diorganopolysiloxane compound of the present invention has a structure in which a siloxane chain having a polyoxyalkylene group represented by the following general formula (1) is bonded to the terminal and is represented by the following general formula (2). It has 40 or more units in the molecule.
Figure JPOXMLDOC01-appb-C000017
 [In the formula, R and R 1 may be the same or different and each is a substituted or unsubstituted linear or branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, polyoxy group having 1 to 20 carbon atoms. It is a monovalent hydrocarbon group having an alkylene group or a hydrogen atom. L is a two-chain polyoxyalkylene alkyl group represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000018
 (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = 1. 150, t = 0 to 150)]]
　この場合、上記ポリオキシアルキレン変性ジオルガノポリシロキサン化合物としては、特に下記一般式（４）又は（５）で表されるものが好ましい。
Figure JPOXMLDOC01-appb-C000019
 （式中、Ｒ1、Ｌは上記の通りである。ｍは４０以上の整数である。）
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｒ1、Ｌは上記の通りである。Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。Ｘは炭素数２～２０のアルキレン基である。ｍ１＋ｍ２＋ｍ３＝ｍで、ｍは４０以上の整数である。） In this case, the polyoxyalkylene-modified diorganopolysiloxane compound is particularly preferably a compound represented by the following general formula (4) or (5).
Figure JPOXMLDOC01-appb-C000019
 (In the formula, R 1 and L are as described above. M is an integer of 40 or more.)
Figure JPOXMLDOC01-appb-C000020
 (Wherein R 1 and L are as defined above. R 3 may be the same or different and each represents a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group having 1 to 20 carbon atoms, A monovalent hydrocarbon group having an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, X is an alkylene group having 2 to 20 carbon atoms, m1 + m2 + m3 = m, and m is 40 or more. (It is an integer.)
　本発明のポリオキシアルキレン変性ジオルガノポリシロキサン化合物は、高重合度のオルガノポリシロキサンとの相溶性が高く、乳化剤もしくは乳化助剤とすることで、容易に高重合度のオルガノポリシロキサンを乳化することができる。その乳化物は耐溶剤性に優れるため、アルコール、ケトン、エステル等の極性溶剤に添加した場合でも分離や破壊を生じることなく安定である。更に、耐塩性にも優れるため、塩化ナトリウムや硫酸ナトリウム等の塩が乳化物に配合されても分離や破壊を生じることなく安定である。 The polyoxyalkylene-modified diorganopolysiloxane compound of the present invention is highly compatible with organopolysiloxane having a high degree of polymerization, and can easily emulsify organopolysiloxane having a high degree of polymerization by using an emulsifier or an emulsification aid. be able to. Since the emulsion is excellent in solvent resistance, it is stable without causing separation or destruction even when added to a polar solvent such as alcohol, ketone or ester. Furthermore, since salt tolerance is excellent, even if salts, such as sodium chloride and sodium sulfate, are mix | blended with an emulsion, it is stable, without producing a separation and destruction.
　本発明のポリオキシアルキレン変性ジオルガノポリシロキサン化合物は、具体的には下記の方法ｉ又はｉｉにより得られる。
＜方法ｉ＞
　下記一般式（６）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと下記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物とを反応させる。
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｒ1は同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。ｍは４０以上の整数である。）
Figure JPOXMLDOC01-appb-C000022
 （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又はフェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。） The polyoxyalkylene-modified diorganopolysiloxane compound of the present invention is specifically obtained by the following method i or ii.
<Method i>
A silicon-bonded hydrogen atom-containing diorganopolysiloxane represented by the following general formula (6) is reacted with an unsaturated group-containing polyoxyalkylene compound represented by the following general formula (7).
Figure JPOXMLDOC01-appb-C000021
 (Wherein R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group. A monovalent hydrocarbon group or a hydrogen atom, and m is an integer of 40 or more.)
Figure JPOXMLDOC01-appb-C000022
 (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = 1. 150, t = 0 to 150.)
　ここで、上記一般式（６）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンにおいて、Ｒ1は同一もしくは異なってもよく、炭素数１～２０の置換もしくは非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子であり、好ましくは炭素数１～２０の置換もしくは非置換の直鎖又は分岐のアルキル基、アリール基、又はアラルキル基であり、入手や合成の容易さ等から更に好ましくはメチル基もしくはフェニル基である。 Here, in the diorganopolysiloxane containing both ends of silicon atom-bonded hydrogen atoms represented by the general formula (6), R 1 may be the same or different, and is a substituted or unsubstituted straight chain having 1 to 20 carbon atoms. Or a branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, monovalent hydrocarbon group having a polyoxyalkylene group, or a hydrogen atom, preferably a substituted or unsubstituted straight chain having 1 to 20 carbon atoms. A chain or branched alkyl group, an aryl group, or an aralkyl group is preferred, and a methyl group or a phenyl group is more preferred from the standpoint of availability and synthesis.
　ｍは、ｍ≧４０であり、好ましくは５，０００≧ｍ≧１００であり、より好ましくは１，０００≧ｍ≧２００である。ｍが４０より小さい場合、ポリオキシアルキレン変性ジオルガノポリシロキサンを乳化剤もしくは乳化助剤としたオルガノポリシロキサンの乳化物の耐溶剤性や耐塩性は低下し、ｍが５，０００より大きい場合、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の乳化性は低下し、オルガノポリシロキサンの乳化が困難になる。２種類以上の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンを混合することも可能である。２種類以上の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンを混合する際は、混合したオイルの平均構造式が上述したｍの値の範囲を満たしていればよい。 M is m ≧ 40, preferably 5,000 ≧ m ≧ 100, and more preferably 1,000 ≧ m ≧ 200. When m is less than 40, the solvent resistance and salt resistance of the emulsion of organopolysiloxane using polyoxyalkylene-modified diorganopolysiloxane as an emulsifier or emulsification aid are reduced, and when m is greater than 5,000, The emulsifiability of the oxyalkylene-modified diorganopolysiloxane compound is lowered, making it difficult to emulsify the organopolysiloxane. It is also possible to mix two or more types of diorganopolysiloxanes having both ends of silicon-bonded hydrogen atoms. When two or more kinds of diorganopolysiloxanes having silicon atom-bonded hydrogen atoms at both terminals are mixed, it is only necessary that the average structural formula of the mixed oil satisfies the range of the value of m described above.
　一般式（６）で表されるジオルガノポリシロキサン成分としては、下記式で表されるものが挙げられるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000023
 （式中、Ｐｈはフェニル基であり、Ｒｆはトリフルオロプロピル基である。ｐ、ｑはそれぞれ０以上の整数であり、好ましくはｐ、ｑはそれぞれ１以上の整数であり、ｐ＋ｑは４０以上、好ましくは１００以上の整数である。） Examples of the diorganopolysiloxane component represented by the general formula (6) include, but are not limited to, those represented by the following formula.
Figure JPOXMLDOC01-appb-C000023
 (In the formula, Ph is a phenyl group and Rf is a trifluoropropyl group. P and q are each an integer of 0 or more, preferably p and q are each an integer of 1 or more, and p + q is 40 or more. , Preferably an integer of 100 or more.)
　また、上記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物において、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又はフェニル基を表す。好ましくは炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、又はヒドロキシ基であり、入手や合成の容易さからより好ましくはヒドロキシ基である。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。好ましくはｓ＝１～１００、ｔ＝０～１５０であり、より好ましくはｓ＝３～５０、ｔ＝３～５０である。ｓが１未満であると高重合度のポリシロキサンに対する乳化性が低く、ｓ、ｔが１５０より大きいと不飽和基含有ポリオキシアルキレン化合物の粘度が高くなりすぎて扱いにくくなる。ｒは上記の値を満たせばよいが、汎用性の観点からｒ＝１が最も好ましい。２種類以上の不飽和基含有ポリオキシアルキレン化合物を混合して使用することも可能である。 In the unsaturated group-containing polyoxyalkylene compound represented by the general formula (7), EO represents a polyoxyethylene group, and AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms. . R 2 may be the same or different and represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a carboxy group, an acyl group, or a phenyl group. A linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a hydroxy group is preferable, and a hydroxy group is more preferable from the viewpoint of availability and synthesis. r, s, and t may be the same or different, and r = 0 to 10, s = 1 to 150, and t = 0 to 150. Preferably, s = 1 to 100 and t = 0 to 150, more preferably s = 3 to 50 and t = 3 to 50. When s is less than 1, the emulsifiability with respect to polysiloxane having a high degree of polymerization is low, and when s and t are more than 150, the viscosity of the unsaturated group-containing polyoxyalkylene compound becomes too high and becomes difficult to handle. Although r should satisfy | fill said value, r = 1 is the most preferable from a versatility viewpoint. Two or more types of unsaturated group-containing polyoxyalkylene compounds may be used in combination.
　一般式（７）で表されるポリオキシアルキレン化合物成分としては、下記式で表されるものが挙げられるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000024
 Examples of the polyoxyalkylene compound component represented by the general formula (7) include, but are not limited to, those represented by the following formula.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
＜方法ｉｉ＞
　下記一般式（８）で表される両末端不飽和基含有ジオルガノポリシロキサンの両末端不飽和基のそれぞれに下記一般式（９）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの一方の末端ケイ素原子結合水素原子を付加反応させる工程、及びこの工程後、上記両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの他方の末端ケイ素原子結合水素原子に上記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物の不飽和基を付加反応させる。
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｒ1は上記の通りである。Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。ｎ１、ｎ２はそれぞれ０以上の整数であるが、ｎ１＋ｎ２＋ｎ２（ｎ１＋２×ｎ２）は４０以上の整数である。） <Method ii>
A diorganopolysiloxane containing hydrogen atoms at both ends represented by the following general formula (9) in each unsaturated group at both ends of the diorganopolysiloxane containing unsaturated groups at both ends represented by the following general formula (8) A step of addition reaction of one terminal silicon atom-bonded hydrogen atom of siloxane, and, after this step, the other terminal silicon atom-bonded hydrogen atom of the above-mentioned silicon atom-bonded hydrogen atom-containing diorganopolysiloxane has the above general formula (7) An unsaturated group of the unsaturated group-containing polyoxyalkylene compound represented by
Figure JPOXMLDOC01-appb-C000026
 (In the formula, R 1 is as described above. R 3 may be the same or different and is a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group having 1 to 20 carbon atoms. , An aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, and n1 and n2 are each an integer of 0 or more, but n1 + n2 + n2 (n1 + 2 × n2) is an integer of 40 or more. is there.)
　ここで、上記一般式（８）で表される両末端不飽和基含有ジオルガノポリシロキサンにおいて、Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。好ましくは炭素数１～２０の直鎖又は分岐のハロゲン原子置換又は非置換のアルキル基、アリール基、アラルキル基であり、入手や合成の容易さ等からメチル基もしくはフェニル基であることが更に好ましい。 Here, in the diorganopolysiloxane having unsaturated groups at both ends represented by the general formula (8), R 3 may be the same or different, and is a linear or branched substituted or unsubstituted having 1 to 20 carbon atoms. A monovalent hydrocarbon group having an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group. Preferred is a linear or branched halogen atom-substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and a methyl group or a phenyl group is more preferred from the standpoint of availability and synthesis. .
　また、ｎ１＝０～１０，０００の整数である。好ましくはｎ１＝０～３，０００、より好ましくはｎ１＝０～１，０００である。ｎ１が１０，０００より大きいと合成したポリオキシアルキレン変性ジオルガノポリシロキサン化合物の粘度が高くなり、扱いにくくなる。また、疎水性が高く乳化力が低下する欠点もある。 Also, n1 is an integer from 0 to 10,000. Preferably n1 = 0 to 3,000, more preferably n1 = 0 to 1,000. When n1 is greater than 10,000, the synthesized polyoxyalkylene-modified diorganopolysiloxane compound has a high viscosity and is difficult to handle. In addition, there is a drawback that the emulsifying power is lowered due to the high hydrophobicity.
　一般式（８）で表されるジオルガノポリシロキサン成分としては、下記式で表されるものが挙げられるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｖｉはビニル基、Ｐｈはフェニル基、Ｒｆはトリフルオロプロピル基である。ｘ、ｙはそれぞれ０以上の整数である。） Examples of the diorganopolysiloxane component represented by the general formula (8) include, but are not limited to, those represented by the following formula.
Figure JPOXMLDOC01-appb-C000027
 (In the formula, Vi is a vinyl group, Ph is a phenyl group, and Rf is a trifluoropropyl group. X and y are each an integer of 0 or more.)
　上記両末端不飽和基含有ジオルガノポリシロキサンは、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の疎水性を調節することを目的に配合する原料であり、必要に応じて配合すればよい。２種類以上の不飽和基含有ジオルガノポリシロキサンを混合して使用することも可能である。 The above-mentioned diorganopolysiloxane containing unsaturated groups at both terminals is a raw material blended for the purpose of adjusting the hydrophobicity of the polyoxyalkylene-modified diorganopolysiloxane compound, and may be blended as necessary. Two or more kinds of unsaturated group-containing diorganopolysiloxanes can be mixed and used.
　一方、一般式（９）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンにおいて、Ｒ1は上記の通りである。また、ｎ２は０以上の整数であり、好ましくはｎ２＝５～１０，０００、より好ましくはｎ２＝９～１，０００である。この場合、一般式（９）で表されるジオルガノポリシロキサン成分としては、下記式で表されるものが挙げられるが、これらに限定されない。
　ここで、式（９）のジオルガノポリシロキサンは、その２分子が式（８）のジオルガノポリシロキサン１分子に付加するものである。
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｐｈはフェニル基であり、Ｒｆはトリフルオロプロピル基である。ｐ、ｑはそれぞれ０以上の整数である。） On the other hand, in the diorganopolysiloxane having silicon atom-bonded hydrogen atoms at both terminals represented by the general formula (9), R 1 is as described above. N2 is an integer of 0 or more, preferably n2 = 5 to 10,000, and more preferably n2 = 9 to 1,000. In this case, examples of the diorganopolysiloxane component represented by the general formula (9) include, but are not limited to, those represented by the following formula.
Here, the diorganopolysiloxane of the formula (9) is one in which two molecules are added to one molecule of the diorganopolysiloxane of the formula (8).
Figure JPOXMLDOC01-appb-C000028
 (In the formula, Ph is a phenyl group and Rf is a trifluoropropyl group. P and q are each an integer of 0 or more.)
　ここで、上記ｎ１＋ｎ２＋ｎ２は４０以上の整数である。好ましくは５，０００≧ｎ１＋ｎ２＋ｎ２≧１００であり、より好ましくは１，０００≧ｎ１＋ｎ２＋ｎ２≧２００である。ｎ１＋ｎ２＋ｎ２が４０より小さい、もしくはｎ１＋ｎ２＋ｎ２が５，０００より大きい場合、合成したポリオキシアルキレン変性ジオルガノポリシロキサン化合物の乳化性は低下し、高重合度のポリシロキサンの乳化が困難になる。
　なお、ｎ１＋ｎ２＋ｎ２＝ｍ（ｍ１＋ｍ２＋ｍ３）である。 Here, n1 + n2 + n2 is an integer of 40 or more. Preferably, 5,000 ≧ n1 + n2 + n2 ≧ 100, more preferably 1,000 ≧ n1 + n2 + n2 ≧ 200. When n1 + n2 + n2 is smaller than 40 or n1 + n2 + n2 is larger than 5,000, the emulsifiability of the synthesized polyoxyalkylene-modified diorganopolysiloxane compound is lowered, and it becomes difficult to emulsify polysiloxane having a high polymerization degree.
Note that n1 + n2 + n2 = m (m1 + m2 + m3).
　上記方法ｉ、ｉｉは、いずれもヒドロシリル化触媒を用いて、溶媒存在下又は非存在下で付加反応を行い、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物を製造する。 In each of the above methods i and ii, a polyoxyalkylene-modified diorganopolysiloxane compound is produced by performing an addition reaction in the presence or absence of a solvent using a hydrosilylation catalyst.
　更に詳述すると、上記方法ｉの場合、式（６）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサン及び式（７）の不飽和基含有ポリオキシアルキレン化合物をヒドロシリル化反応触媒下、ヒドロシリル化反応によりポリオキシアルキレン変性ジオルガノポリシロキサン化合物を合成する。不飽和基含有ポリオキシアルキレン化合物の不飽和基のモル数は、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンのケイ素原子結合水素原子のモル数と等しくなるような量、あるいは不飽和基のモル数が過剰となる量を反応させることが好ましい。ケイ素原子結合水素原子のモル数が多くヒドロシリル化反応後に水素原子が残存する場合はヘキセン、ヘプテン等のオレフィンを添加し更にヒドロシリル化反応させることにより、この残存ケイ素原子結合水素原子を少なくすることができる。 More specifically, in the case of the above-mentioned method i, the diorganopolysiloxane containing hydrogen atoms at both ends of the formula (6) and the polyoxyalkylene compound containing an unsaturated group of the formula (7) are hydrosilylated in a hydrosilylation reaction catalyst. A polyoxyalkylene-modified diorganopolysiloxane compound is synthesized by a conversion reaction. The number of moles of unsaturated groups in the unsaturated group-containing polyoxyalkylene compound is equal to the number of moles of silicon-bonded hydrogen atoms in the diorganopolysiloxane containing silicon-bonded hydrogen atoms at both ends, or the number of unsaturated groups. It is preferable to react with an amount in which the number of moles is excessive. When the number of moles of silicon-bonded hydrogen atoms is large and hydrogen atoms remain after the hydrosilylation reaction, the remaining silicon-bonded hydrogen atoms can be reduced by adding olefins such as hexene and heptene and further hydrosilylation reaction. it can.
　また、上記方法ｉｉの場合、上記式（９）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと式（８）の両末端不飽和基含有ジオルガノポリシロキサンをヒドロシリル化反応触媒下、ヒドロシリル化反応を行う。その際、式（９）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンのケイ素原子結合水素原子のモル数は、式（８）の両末端不飽和基含有ジオルガノポリシロキサンの不飽和基のモル数より多く、ケイ素原子結合水素原子を残存させておく必要がある。式（９）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンのケイ素原子結合水素原子のモル数と式（８）の両末端不飽和基含有ジオルガノポリシロキサンの不飽和基のモル数の比率（両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンのケイ素原子結合水素原子のモル数／両末端不飽和基含有ジオルガノポリシロキサンの不飽和基のモル数）は好ましくは１．１以上であり、より好ましくは１．３以上である。１．１より小さいと、合成するポリオキシアルキレン変性ジオルガノポリシロキサン化合物の親水性が低くなり、乳化性が低下する可能性がある。続いて、式（７）の不飽和基含有ポリオキシアルキレン化合物を加え、ヒドロシリル化反応によりポリオキシアルキレン変性ジオルガノポリシロキサン化合物を合成する。式（７）の不飽和基含有ポリオキシアルキレン化合物と式（８）の両末端不飽和基含有ジオルガノポリシロキサンを併せた不飽和基のモル数は、式（９）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンのケイ素原子結合水素原子のモル数と等しくなるような量、あるいは不飽和基のモル数が過剰となる量を反応させることが好ましい。ケイ素原子結合水素原子のモル数が不飽和基のモル数より多く、ヒドロシリル化反応後にケイ素原子結合水素原子が残存する場合は、ヘキセン、ヘプテン等のオレフィンを添加し更にヒドロシリル化反応させることにより、この残存ケイ素原子結合水素原子を少なくすることができる。また、不飽和基含有ポリオキシアルキレン化合物と不飽和基含有ジオルガノポリシロキサンのモル数の比（不飽和基含有ポリオキシアルキレン化合物／両末端不飽和基含有ジオルガノポリシロキサン）は０．１以上であることが望ましい。０．１未満であると、合成したポリオキシアルキレン変性ジオルガノポリシロキサン化合物の疎水性が高く、乳化力が低くなるおそれがある。 In the case of the above method ii, both ends of silicon atom-bonded hydrogen atom-containing diorganopolysiloxane of the above formula (9) and diorganopolysiloxane of both ends unsaturated group containing the formula (8) are hydrosilylated in a hydrosilylation reaction catalyst. Perform the chemical reaction. At that time, the number of moles of silicon atom-bonded hydrogen atoms in the diorganopolysiloxane having silicon atoms bonded to hydrogen atoms at both ends of formula (9) is the unsaturated group of diorganopolysiloxane having unsaturated groups at both ends of formula (8). It is necessary to leave silicon-bonded hydrogen atoms in excess of the number of moles. The number of moles of silicon atom-bonded hydrogen atoms in the diorganopolysiloxane containing both ends of silicon atom-bonded hydrogen atoms of formula (9) and the number of moles of unsaturated groups in the diorganopolysiloxane containing both ends unsaturated groups of formula (8) The ratio (number of moles of silicon atom-bonded hydrogen atoms in diorganopolysiloxane containing both ends of silicon atom-bonded hydrogen atoms / number of moles of unsaturated groups in diorganopolysiloxane containing both ends unsaturated groups) is preferably 1.1 or more. Yes, more preferably 1.3 or more. If it is smaller than 1.1, the hydrophilicity of the polyoxyalkylene-modified diorganopolysiloxane compound to be synthesized becomes low, and the emulsifiability may be lowered. Subsequently, an unsaturated group-containing polyoxyalkylene compound of the formula (7) is added, and a polyoxyalkylene-modified diorganopolysiloxane compound is synthesized by a hydrosilylation reaction. The number of moles of unsaturated groups in which the unsaturated group-containing polyoxyalkylene compound of formula (7) and the diorganopolysiloxane having unsaturated groups at both ends of formula (8) are combined is the silicon atom bond at both ends of formula (9). It is preferable to react the hydrogen atom-containing diorganopolysiloxane in an amount that is equal to the number of moles of silicon-bonded hydrogen atoms or an amount in which the number of unsaturated groups is excessive. When the number of moles of silicon-bonded hydrogen atoms is greater than the number of moles of unsaturated groups, and silicon-bonded hydrogen atoms remain after the hydrosilylation reaction, by adding an olefin such as hexene or heptene, the hydrosilylation reaction is further performed. This residual silicon atom-bonded hydrogen atom can be reduced. The ratio of the number of moles of the unsaturated group-containing polyoxyalkylene compound to the unsaturated group-containing diorganopolysiloxane (unsaturated group-containing polyoxyalkylene compound / both-terminal unsaturated group-containing diorganopolysiloxane) is 0.1 or more. It is desirable that If it is less than 0.1, the synthesized polyoxyalkylene-modified diorganopolysiloxane compound has high hydrophobicity and may have low emulsifying power.
　ヒドロシリル化触媒とは、ヒドロシリル化反応を促進するための触媒であり、白金系触媒、ロジウム系触媒、パラジウム系触媒が例示され、好ましくは、白金系触媒である。この白金系触媒としては、塩化白金酸、アルコール変性塩化白金酸、白金のオレフィン錯体、白金のケトン錯体、白金のビニルシロキサン錯体、四塩化白金、白金微粉末、アルミナ又はシリカの担体に固体状白金を担持させたもの、白金黒、白金のオレフィン錯体、白金のアルケニルシロキサン錯体、白金のカルボニル錯体が例示されるが、安定性や汎用性から、塩化白金酸もしくは白金のビニルシロキサン錯体が好ましい。触媒の含有量について有効量であれば特に限定されないが、式（６）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと式（７）の不飽和基含有ポリオキシアルキレン化合物の合計質量、或いは式（８）の両末端不飽和基含有ジオルガノポリシロキサンと式（９）の両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの合計質量、更には式（８）及び式（９）のジオルガノポリシロキサンと式（７）の不飽和基含有ポリオキシアルキレン化合物の合計質量に対して触媒金属が質量で０．１～１，０００ｐｐｍの範囲以内となるような量であることが好ましく、特に、０．５～１００ｐｐｍの範囲以内となる量であることが好ましい。 The hydrosilylation catalyst is a catalyst for promoting the hydrosilylation reaction, and examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferable. The platinum-based catalyst includes chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complex, platinum ketone complex, platinum vinylsiloxane complex, platinum tetrachloride, platinum fine powder, solid platinum on alumina or silica carrier , Platinum black, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes are exemplified, but chloroplatinic acid or platinum vinylsiloxane complexes are preferred from the standpoint of stability and versatility. Although it is not particularly limited as long as it is an effective amount with respect to the content of the catalyst, the total mass of the diorganopolysiloxane containing silicon atoms-bonded hydrogen atoms at both ends of formula (6) and the unsaturated group-containing polyoxyalkylene compound of formula (7), Or the total mass of the diorganopolysiloxane containing unsaturated groups at both ends of formula (8) and the diorganopolysiloxane containing silicon atoms-bonded hydrogen atoms at both ends of formula (9), as well as those of formulas (8) and (9) It is preferable that the amount of the catalyst metal is within the range of 0.1 to 1,000 ppm by mass with respect to the total mass of the diorganopolysiloxane and the unsaturated group-containing polyoxyalkylene compound of the formula (7), In particular, the amount is preferably within the range of 0.5 to 100 ppm.
　ヒドロシリル化反応に用いる溶媒としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ヘキサン、オクタン等の炭化水素系溶剤、ジブチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、メチルエチルケトン等のケトン系溶剤、エタノール、イソプロパノール、１－ブタノール、等のアルコール系溶剤、塩素化炭化水素系溶剤を挙げることができる。両末端ケイ素原子結合水素原子含有オルガノポリシロキサンと不飽和基含有ポリオキシアルキレンアルキルエーテルと不飽和基含有オルガノポリシロキサンの合計を１００質量部としたとき、溶媒の含有量は、０～１，０００質量部である。溶媒を配合する場合、好ましくは１０～１，０００質量部とすることがよい。溶媒の含有量が少ないとヒドロシリル化反応の進行が遅くなる場合があるが、一方で溶媒の含有量が多いと廃棄物が多くなるという問題がある。 Examples of the solvent used for the hydrosilylation reaction include aromatic hydrocarbon solvents such as toluene and xylene, hydrocarbon solvents such as hexane and octane, ether solvents such as dibutyl ether, dioxane, and tetrahydrofuran, ethyl acetate, and butyl acetate. And ester solvents such as methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol and 1-butanol, and chlorinated hydrocarbon solvents. When the total of the silicon atom-bonded hydrogen atom-containing organopolysiloxane, unsaturated group-containing polyoxyalkylene alkyl ether, and unsaturated group-containing organopolysiloxane is 100 parts by mass, the solvent content is 0 to 1,000. Part by mass. When a solvent is blended, the amount is preferably 10 to 1,000 parts by mass. If the content of the solvent is small, the progress of the hydrosilylation reaction may be slow. On the other hand, if the content of the solvent is large, there is a problem that waste increases.
　ヒドロシリル化反応の反応温度は、５０～１５０℃の範囲であることが望ましい。反応温度が５０℃より低いと反応速度が低下するおそれがあり、反応温度が１５０℃より高い場合は不飽和炭化水素が内部転移し、ヒドロシリル化反応が進行しなくなるおそれがある。 The reaction temperature of the hydrosilylation reaction is preferably in the range of 50 to 150 ° C. When the reaction temperature is lower than 50 ° C., the reaction rate may decrease. When the reaction temperature is higher than 150 ° C., the unsaturated hydrocarbon may undergo internal transfer and the hydrosilylation reaction may not proceed.
　一般式（６）又は（９）のＳｉ－Ｈの反応性基を完全に反応させるため、末端に二重結合を有する炭素数４～１６の炭化水素、具体的には１－ブテン、イソブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテンなどを追加して反応させることもできる。 In order to completely react the Si—H reactive group of the general formula (6) or (9), a hydrocarbon having 4 to 16 carbon atoms having a double bond at the end, specifically 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like can be added and reacted.
　アルコール系溶剤を使用する場合には、脱水素反応を防止乃至抑制するために、酢酸カリウム等のｐＨ調整剤（特公昭６２－３４０３９号公報）を用いるのが好ましい。 When an alcohol solvent is used, it is preferable to use a pH adjuster such as potassium acetate (Japanese Patent Publication No. 62-34039) in order to prevent or suppress the dehydrogenation reaction.
　ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の有機溶剤溶液は、公知の方法で製造することが可能である。
　より具体的に述べると、方法ｉの場合、窒素雰囲気下、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと不飽和基含有ポリオキシアルキレン化合物のイソプロピルアルコール溶剤にｐＨ調整剤として酢酸カリウムのエタノール溶液を加えた後、加熱し、内部温度を５０～８０℃とする。次いで、白金のビニルシロキサン錯体のトルエン溶液を加え、２～１２時間撹拌することで、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物を合成することができる。更に、加熱及び減圧をすることにより、イソプロピルアルコール溶剤を留去することができる。その際、加熱温度は１２０℃未満であることが望ましい。１２０℃より温度が高いとポリアルキルエーテル部位が酸化するおそれがある。 The organic solvent solution of the polyoxyalkylene-modified diorganopolysiloxane compound can be produced by a known method.
More specifically, in the case of the method i, ethanol of potassium acetate as a pH adjuster in a isopropyl alcohol solvent of a diorganopolysiloxane containing hydrogen atoms containing silicon atoms at both ends and an unsaturated group-containing polyoxyalkylene compound in a nitrogen atmosphere. After the solution is added, it is heated to bring the internal temperature to 50-80 ° C. Next, a polyoxyalkylene-modified diorganopolysiloxane compound can be synthesized by adding a toluene solution of a platinum vinylsiloxane complex and stirring for 2 to 12 hours. Furthermore, the isopropyl alcohol solvent can be distilled off by heating and reducing the pressure. At that time, the heating temperature is preferably less than 120 ° C. If the temperature is higher than 120 ° C., the polyalkyl ether moiety may be oxidized.
　次に、方法ｉｉの場合、窒素雰囲気下、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと両末端不飽和基含有ジオルガノポリシロキサンのイソプロピルアルコール溶剤にｐＨ調整剤として酢酸カリウムのエタノール溶液を加えた後、加熱し、内部温度を５０～８０℃とする。次いで、白金のビニルシロキサン錯体を加え、２～１２時間撹拌した後、不飽和基含有ポリオキシアルキレン化合物を加え、２～１２時間撹拌し、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物を合成する。 Next, in the case of method ii, an ethanol solution of potassium acetate is added as a pH adjuster to an isopropyl alcohol solvent of both ends of silicon atom-bonded hydrogen atom-containing diorganopolysiloxane and both ends of unsaturated group-containing diorganopolysiloxane in a nitrogen atmosphere. After the addition, it is heated to bring the internal temperature to 50-80 ° C. Next, platinum vinylsiloxane complex is added and stirred for 2 to 12 hours, and then an unsaturated group-containing polyoxyalkylene compound is added and stirred for 2 to 12 hours to synthesize a polyoxyalkylene-modified diorganopolysiloxane compound.
　更に、加熱及び減圧をすることにより、イソプロピルアルコール溶剤を留去することができる。その際、加熱温度は１２０℃未満であることが望ましい。１２０℃より温度が高いとポリアルキルエーテル部位が酸化するおそれがある。 Furthermore, the isopropyl alcohol solvent can be distilled off by heating and reducing the pressure. At that time, the heating temperature is preferably less than 120 ° C. If the temperature is higher than 120 ° C., the polyalkyl ether moiety may be oxidized.
　本発明のポリオキシアルキレン変性ジオルガノポリシロキサン化合物は固体状の場合がある。その際はポリオキシアルキレン変性ジオルガノポリシロキサン化合物の有機溶剤溶液のまま取り扱うことが可能である。更に、ノニオン界面活性剤に溶解して、使用することもできる。その際は、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の有機溶剤溶解品にノニオン界面活性剤を配合し、加熱及び減圧をすることにより、有機溶剤をノニオン界面活性剤に置換する。 The polyoxyalkylene-modified diorganopolysiloxane compound of the present invention may be solid. In that case, the organic solvent solution of the polyoxyalkylene-modified diorganopolysiloxane compound can be handled as it is. Furthermore, it can also be used by dissolving in a nonionic surfactant. In that case, a nonionic surfactant is mix | blended with the organic solvent melt | dissolution product of a polyoxyalkylene modified diorganopolysiloxane compound, and an organic solvent is substituted to a nonionic surfactant by heating and pressure reduction.
　更に、上記の方法では、ヒドロシリル化反応後に酸性物質によるアリルエーテル基の除去あるいは水素添加反応によるアルキル化によって無臭化を行ってもよい。また、得られたポリエーテル変性シリコーンに酸化防止剤としてトコフェロールやＢＨＴ（ジブチルヒドロキシトルエン）を添加してもよい。 Furthermore, in the above method, after the hydrosilylation reaction, no bromination may be performed by removal of the allyl ether group with an acidic substance or alkylation by a hydrogenation reaction. Moreover, you may add tocopherol and BHT (dibutylhydroxytoluene) as antioxidant to the obtained polyether modified silicone.
　溶剤を置換する際に使用するノニオン界面活性剤は、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物を溶解することができれば特に制限はないが、２５℃において液状のものが好ましく、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセリン脂肪酸エステルのようなノニオン界面活性剤等を挙げることができる。これらの界面活性剤を単独あるいは２種以上を併用して使用することができる。 The nonionic surfactant used when replacing the solvent is not particularly limited as long as it can dissolve the polyoxyalkylene-modified diorganopolysiloxane compound, but is preferably liquid at 25 ° C., for example, polyoxyethylene alkyl Nonionic surfactants such as ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester it can. These surfactants can be used alone or in combination of two or more.
　ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の有機溶剤溶解品をノニオン界面活性剤で置換する際は、ノニオン界面活性剤は留去されず有機溶剤のみが留去されるように、有機溶剤の蒸気圧より低い蒸気圧のノニオン界面活性剤を選択する。更に上記の界面活性剤のうち、より好ましいものはエチレンオキサイドの付加モル数が２～１２であり、ＨＬＢが７．５～１４．０のものである。そのようなノニオン系乳化剤は２５℃において液状であり、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の有機溶剤希釈品を乳化剤で容易に置換することができる。ＨＬＢはグリフィンの式による。 When a polyoxyalkylene-modified diorganopolysiloxane compound dissolved in an organic solvent is replaced with a nonionic surfactant, the nonionic surfactant is not distilled off, and only the organic solvent is distilled off. Choose a lower vapor pressure nonionic surfactant. Further, among the above surfactants, more preferable are those having an addition mole number of ethylene oxide of 2 to 12 and an HLB of 7.5 to 14.0. Such a nonionic emulsifier is liquid at 25 ° C., and the diluted organic solvent of the polyoxyalkylene-modified diorganopolysiloxane compound can be easily replaced with the emulsifier. HLB is according to the Griffin equation.
　ポリオキシアルキレン変性ジオルガノポリシロキサン化合物とノニオン界面活性剤の比率に指定はないが、質量比率（ポリオキシアルキレン変性ジオルガノポリシロキサン化合物／ノニオン界面活性剤）は０．１以上であることが望ましい。０．１未満であるとポリオキシアルキレン変性ジオルガノポリシロキサン化合物の界面活性剤溶液を高重合度のオルガノポリシロキサンの乳化剤もしくは乳化助剤として使用した際に、高重合度のオルガノポリシロキサンに対する乳化力の低下や乳化物の耐溶剤性、耐塩性の低下のおそれがある。 The ratio of the polyoxyalkylene-modified diorganopolysiloxane compound to the nonionic surfactant is not specified, but the mass ratio (polyoxyalkylene-modified diorganopolysiloxane compound / nonionic surfactant) is preferably 0.1 or more. . When the surfactant solution of the polyoxyalkylene-modified diorganopolysiloxane compound is less than 0.1 as an emulsifier or an emulsification aid for the organopolysiloxane having a high degree of polymerization, emulsification to the organopolysiloxane having a high degree of polymerization There is a risk of lowering the force and the solvent resistance and salt resistance of the emulsion.
　上記ポリオキシアルキレン変性ジオルガノポリシロキサン化合物は、このように高重合度オルガノポリシロキサン等の乳化に好適に用いられるもので、従って本発明は、下記のオルガノポリシロキサン乳化組成物を提供する。
（Ａ）上述したポリオキシアルキレン変性ジオルガノポリシロキサン化合物、
（Ｂ）界面活性剤、
（Ｃ）上記（Ａ）成分を除くオルガノポリシロキサン、
（Ｄ）水
　この場合、（Ｂ）、（Ｄ）成分は任意成分である。 The polyoxyalkylene-modified diorganopolysiloxane compound is thus suitably used for emulsification of high-polymerization degree organopolysiloxane and the like, and therefore the present invention provides the following organopolysiloxane emulsion composition.
(A) the polyoxyalkylene-modified diorganopolysiloxane compound described above,
(B) a surfactant,
(C) an organopolysiloxane excluding the component (A),
(D) Water In this case, the components (B) and (D) are optional components.
　この場合、（Ａ）成分として、上記の末端に２鎖型のポリオキシアルキレンアルキル基を有するポリオキシアルキレン変性ジオルガノポリシロキサン化合物を（Ｃ）成分のオルガノポリシロキサンの乳化助剤もしくは乳化剤とすることで、容易に高重合度のオルガノポリシロキサンの乳化ができる。（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物を含むことで（Ｃ）成分のオルガノポリシロキサン乳化組成物は耐溶剤性や耐塩性の効果を発現する。 In this case, as the component (A), the polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal is used as an emulsification aid or emulsifier for the component (C). Thus, it is possible to easily emulsify organopolysiloxane having a high degree of polymerization. By including the polyoxyalkylene-modified diorganopolysiloxane compound as the component (A), the organopolysiloxane emulsion composition as the component (C) exhibits the effects of solvent resistance and salt resistance.
　（Ｃ）成分のオルガノポリシロキサンに対する（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物の乳化力は（Ｃ）成分のオルガノポリシロキサンの重合度と（Ａ）の分子内の一般式（２）で表わされる構造単位数に関係する。（Ｃ）成分のオルガノポリシロキサンの重合度が低い場合は、（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物に含まれる一般式（２）の構造単位数がある程度小さいものでしか乳化ができない場合がある。一方で、（Ｃ）成分のオルガノポリシロキサンの重合度が高い場合は、（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物に含まれる一般式（２）の構造単位数がある程度大きくても乳化が可能である。 The emulsifying power of the polyoxyalkylene-modified diorganopolysiloxane compound (A) relative to the organopolysiloxane (C) is determined by the degree of polymerization of the organopolysiloxane (C) and the general formula (2) in the molecule (A). ). When the degree of polymerization of the component (C) organopolysiloxane is low, emulsification is possible only when the number of structural units of the general formula (2) contained in the polyoxyalkylene-modified diorganopolysiloxane compound (A) is small to some extent. There are cases where it is not possible. On the other hand, when the degree of polymerization of the organopolysiloxane of component (C) is high, the number of structural units of general formula (2) contained in the polyoxyalkylene-modified diorganopolysiloxane compound of component (A) is large to some extent. Emulsification is possible.
　ここで、（Ｃ）成分のオルガノポリシロキサンとは、２５℃において２～１００，０００，０００ｍＰａ・ｓの範囲のシリコーンオイル、シリコーンガム、シリコーン樹脂などである。コーティング用途やヘアケア用途では、５００，０００ｍＰａ・ｓ以上のものがよく、好ましくは５００，０００～１００，０００，０００ｍＰａ・ｓであり、より好ましくは７５０，０００～１００，０００，０００ｍＰａ・ｓである。５００，０００ｍＰａ・ｓより粘度が低いと、コーティング剤として使用した際に耐摩耗性等が低下するおそれがあり、１００，０００，０００ｍＰａ・ｓより粘度が高いと、乳化する際に装置に対して負荷が大きくかかるおそれがある。上記粘度は回転粘度計により２５℃で測定される絶対粘度である。 Here, the organopolysiloxane of component (C) is silicone oil, silicone gum, silicone resin, etc. in the range of 2 to 100,000,000 mPa · s at 25 ° C. For coating applications and hair care applications, those of 500,000 mPa · s or more are preferable, preferably 500,000 to 100,000,000 mPa · s, more preferably 750,000 to 100,000,000 mPa · s. . If the viscosity is lower than 500,000 mPa · s, there is a risk that the wear resistance and the like will be reduced when used as a coating agent. If the viscosity is higher than 100,000,000 mPa · s, the emulsification will be applied to the apparatus. There is a risk of heavy load. The viscosity is an absolute viscosity measured at 25 ° C. with a rotational viscometer.
　オルガノポリシロキサンとして、具体的には環状シロキサン、ジメチルポリシロキサン、ジメチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルトリフルオロプロピルポリシロキサン、高重合度のガム状ジメチルポリシロキサン、ガム状のジメチルシロキサン・メチルフェニルシロキサン共重合体等のシリコーン生ゴム、及びシリコーン生ゴムの環状シロキサン溶液、トリメチルシロキシケイ酸、トリメチルシロキシケイ酸の環状シロキサン溶液、アルキル変性シリコーン、アラルキル変性シリコーン、ビニル変性シリコーン、アミノ変性シリコーン、アミノ酸変性シリコーン、フッ素変性シリコーン、エポキシ変性シリコーン、（メタ）アクリル変性シリコーン、ヒドロキシ変性シリコーンが例示される。 Specific examples of organopolysiloxanes include cyclic siloxane, dimethylpolysiloxane, dimethylphenylpolysiloxane, methylhydrogenpolysiloxane, methyltrifluoropropylpolysiloxane, high degree of polymerization gum dimethylpolysiloxane, gum dimethylsiloxane Silicone raw rubber such as methylphenylsiloxane copolymer, cyclic siloxane solution of silicone raw rubber, trimethylsiloxysilicic acid, cyclic siloxane solution of trimethylsiloxysilicic acid, alkyl-modified silicone, aralkyl-modified silicone, vinyl-modified silicone, amino-modified silicone, amino acid Examples include modified silicone, fluorine-modified silicone, epoxy-modified silicone, (meth) acryl-modified silicone, and hydroxy-modified silicone.
　なお、上記（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物の含有量は、（Ｃ）成分のオルガノポリシロキサンの含有量を１００質量部としたとき、１～５０質量部である。好ましくは１０～４０質量部であり、より好ましくは２０～３５質量部である。ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の含有量が少なすぎると、乳化性の低下により（Ｃ）成分のオルガノポリシロキサンが乳化しない場合がある。また、耐溶剤性、耐塩性の低下が生じるおそれがある。一方で（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物が多すぎると、（Ｃ）成分のオルガノポリシロキサンの耐摩耗性等の特性を阻害する可能性がある。 The content of the polyoxyalkylene-modified diorganopolysiloxane compound as the component (A) is 1 to 50 parts by mass when the content of the organopolysiloxane as the component (C) is 100 parts by mass. The amount is preferably 10 to 40 parts by mass, and more preferably 20 to 35 parts by mass. If the content of the polyoxyalkylene-modified diorganopolysiloxane compound is too small, the organopolysiloxane of component (C) may not be emulsified due to a decrease in emulsification. Moreover, there exists a possibility that the solvent resistance and salt resistance may fall. On the other hand, if the amount of the polyoxyalkylene-modified diorganopolysiloxane compound (A) is too large, the properties such as the wear resistance of the organopolysiloxane (C) may be impaired.
　（Ｂ）成分の界面活性剤は、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤が挙げられる。ノニオン界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、グリセリン脂肪酸エステルのようなノニオン界面活性剤等を挙げることができる。これらの具体例としては、ポリオキシエチレンオクチルエーテル、ポリオキシエチレンポリオキシプロピレンオクチルエーテル、ポリオキシエチレンノニルエーテル、ポリオキシエチレンデシルエーテル、ポリオキシエチレンポリオキシプロピレンデシルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンポリオキシプロピレンラウリルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンポリオキシプロピレントリデシルエーテル、ポリオキシエチレンセチルエーテルなどが挙げられる。また、官能基を有する反応性の界面活性剤を使用することも可能である。 (B) Component surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and glycerin fatty acid ester. Such nonionic surfactants can be mentioned. Specific examples thereof include polyoxyethylene octyl ether, polyoxyethylene polyoxypropylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Examples thereof include oxyethylene polyoxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene polyoxypropylene tridecyl ether, and polyoxyethylene cetyl ether. It is also possible to use a reactive surfactant having a functional group.
　アニオン界面活性剤としては、ラウリルスルフェート等のアルキルスルフェート、アルキルベンゼンスルホン酸及びその塩、モノアルキルポリオキシエチレンエーテル類の硫酸エステル塩、モノアルキルポリオキシエチレンエーテル類の酢酸エステル塩、アルキルナフチルスルホン酸及びその塩、アルカリ金属スルホレシネート、アルカリ金属スルホサクシネート、アルキルリン酸及びその塩、モノアルキルポリオキシエチレンエーテル類のリン酸エステル塩、脂肪酸のスルホン化グリセリルエステル、アルキル硫酸アルカリ金属塩及び硫酸エステル類が挙げられる。これらの具体例としては、ラウリル硫酸、ラウリル硫酸ナトリウム、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル酢酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンスルホコハク酸ラウリル２ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルエーテルリン酸エステルナトリウム、アルキルナフタレンスルホン酸ナトリウムなどが挙げられる。また、官能基を有する反応性の界面活性剤を使用することも可能である。 Anionic surfactants include alkyl sulfates such as lauryl sulfate, alkylbenzene sulfonic acids and salts thereof, sulfate salts of monoalkyl polyoxyethylene ethers, acetate salts of monoalkyl polyoxyethylene ethers, alkyl naphthyl sulfones. Acids and salts thereof, alkali metal sulforesinates, alkali metal sulfosuccinates, alkyl phosphoric acids and salts thereof, phosphate esters of monoalkyl polyoxyethylene ethers, sulfonated glyceryl esters of fatty acids, alkali metal sulfates and sulfates of alkyl sulfates Kind. Specific examples thereof include lauryl sulfate, sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether acetate, sodium dodecylbenzenesulfonate, polyoxyethylenesulfosuccinic acid. Examples thereof include disodium lauryl, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl ether phosphate, sodium alkylnaphthalene sulfonate, and the like. It is also possible to use a reactive surfactant having a functional group.
　カチオン界面活性剤としては、アルキルアミン塩、第４級アンモニウム塩、スルホニウム塩、ホスホニウム塩及び酢酸塩等が挙げられる。これらの具体例としては、ステアリルアミンアセテート、ラウリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウム、ステアリルトリメチルアンモニウムクロライド、アルキルベンジルジメチルアンモニウムクロライドなどが挙げられる。 Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, sulfonium salts, phosphonium salts, and acetates. Specific examples thereof include stearylamine acetate, lauryltrimethylammonium chloride, cetyltrimethylammonium, stearyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride.
　両性界面活性剤としては、アルキルベタイン、アルキルイミダゾリン等を挙げることができる。これらの具体例としては、ラウリルジメチルアミノ酢酸ベタイン、ラウリルジメチルアミンオキサイド、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチルイミダゾリニウムベタインが挙げられる。 Examples of amphoteric surfactants include alkyl betaines and alkyl imidazolines. Specific examples thereof include lauryldimethylaminoacetic acid betaine, lauryldimethylamine oxide, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.
　アニオン界面活性剤やカチオン界面活性剤、両性界面活性剤は分子内に電荷をもっており、そのために用途が制限される場合がある。従って、好ましくはノニオン界面活性剤であり、乳化性の観点からより好ましくはポリオキシアルキレンアルキルエーテルもしくはポリオキシエチレンソルビタン脂肪酸エステルである。 Anionic surfactants, cationic surfactants, and amphoteric surfactants have a charge in the molecule, which may limit their use. Accordingly, nonionic surfactants are preferred, and polyoxyalkylene alkyl ethers or polyoxyethylene sorbitan fatty acid esters are more preferred from the viewpoint of emulsifying properties.
　本発明のオルガノポリシロキサン乳化組成物において、（Ｂ）成分の界面活性剤の含有量は、（Ｃ）成分のオルガノポリシロキサンの含有量を１００質量部としたとき、０～５０質量部である。好ましくは０～４０質量部であり、より好ましくは０～３５質量部である。（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物のみで（Ｃ）成分のオルガノポリシロキサンを乳化できる場合は、（Ｂ）成分の界面活性剤を配合しなくてもよい。（Ｂ）成分の界面活性剤が５０質量部より多いと、（Ｃ）成分のオルガノポリシロキサンの撥水性や耐摩耗性を阻害する可能性がある。なお、（Ｂ）成分を配合する場合、１質量部以上、特に５質量部以上であることが好ましい。 In the organopolysiloxane emulsion composition of the present invention, the content of the component (B) surfactant is 0 to 50 parts by mass when the content of the component (C) organopolysiloxane is 100 parts by mass. . The amount is preferably 0 to 40 parts by mass, and more preferably 0 to 35 parts by mass. When the organopolysiloxane of the component (C) can be emulsified only with the polyoxyalkylene-modified diorganopolysiloxane compound of the component (A), the surfactant of the component (B) may not be blended. When the amount of the component (B) surfactant is more than 50 parts by mass, the water repellency and wear resistance of the component (C) organopolysiloxane may be impaired. In addition, when mix | blending (B) component, it is preferable that it is 1 mass part or more, Especially 5 mass parts or more.
　本発明のオルガノポリシロキサン乳化組成物において、（Ｄ）成分の水は自己乳化型やエマルション型等の要求される製品の形態もしくは乳化性等の観点から必要に応じて添加され、従って（Ｄ）成分の水の含有量は、（Ｃ）成分のオルガノポリシロキサンの含有量を１００質量部としたとき、０～１０，０００質量部である。好ましくは０～５，０００質量部であり、より好ましくは０～１，０００質量部である。１，０００質量部より多いと安定性が低下し、大きく分離するおそれがある。（Ｄ）成分の水の含有量が上記の範囲内であれば、粒径は経時で変化することなく安定である。（Ｄ）成分の水を配合する場合、１質量部以上が好ましく、より好ましくは５質量部以上、更に好ましくは１０質量部以上である。 In the organopolysiloxane emulsion composition of the present invention, the water of component (D) is added as required from the viewpoint of the required product form such as self-emulsification type or emulsion type, or emulsification properties. Therefore, (D) The water content of the component is 0 to 10,000 parts by mass when the content of the organopolysiloxane of component (C) is 100 parts by mass. The amount is preferably 0 to 5,000 parts by mass, and more preferably 0 to 1,000 parts by mass. When the amount is more than 1,000 parts by mass, the stability is lowered and there is a risk of separation. If the water content of the component (D) is within the above range, the particle size is stable without changing over time. (D) When mix | blending the water of a component, 1 mass part or more is preferable, More preferably, it is 5 mass parts or more, More preferably, it is 10 mass parts or more.
　本発明のオルガノポリシロキサン乳化組成物には、界面活性剤の他に、保護コロイド剤ないし増粘剤としてポリビニルアルコール、メチルセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ポリビニルピロリドン、アルギン酸塩、キサンタンガム、アクリル酸重合体などの水溶性高分子を配合してもよい。更にオキサゾリン系化合物や芳香族カルボン酸塩等の抗菌剤ないし防腐剤、香料、酸化防止剤、防錆剤、染料、充填剤、硬化触媒、有機粉体、無機粉体などを配合してもよい。 In addition to the surfactant, the organopolysiloxane emulsion composition of the present invention includes polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl pyrrolidone, alginate, xanthan gum, acrylic acid polymer as a protective colloid agent or thickener. You may mix | blend water-soluble polymers, such as. Furthermore, antibacterial agents or antiseptics such as oxazoline compounds and aromatic carboxylates, fragrances, antioxidants, rust inhibitors, dyes, fillers, curing catalysts, organic powders, inorganic powders and the like may be blended. .
　本発明のオルガノポリシロキサン乳化組成物の具体的な乳化方法は以下の通りである。（Ｃ）成分のオルガノポリシロキサンに対して、（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物、必要により（Ｂ）成分の界面活性剤を添加し、ゲートミキサーにより転相させる。所定の粒径になるまで２～１８０分撹拌した後、必要に応じて更に界面活性剤及び／又は水を加えてゲートミキサー、Ｔ．Ｋ．ホモディスパー（プライミクス社製商品名）もしくはＴ．Ｋ．ホモミキサー（プライミクス社製商品名）により希釈する。また、転相させる際に（Ｄ）成分の水を配合させてもよい。転相させる際に水を添加することで、乳化物の粒径のコントロールが可能であり、また乳化しやすくなる場合がある。転相させる際に水を添加する場合の具体的な乳化方法は以下の通りである。（Ｃ）成分のオルガノポリシロキサンに対して、（Ａ）成分のポリオキシアルキレン変性ジオルガノポリシロキサン化合物、必要により（Ｂ）成分の界面活性剤、（Ｄ）成分の水を添加し、ゲートミキサーにより転相させる。所定の粒径になるまで２～１８０分撹拌した後、必要に応じて更に界面活性剤及び／又は水を加えてゲートミキサー、Ｔ．Ｋ．ホモディスパー（プライミクス社製商品名）もしくはＴ．Ｋ．ホモミキサー（プライミクス社製商品名）により希釈する。 The specific emulsification method of the organopolysiloxane emulsion composition of the present invention is as follows. The (A) component polyoxyalkylene-modified diorganopolysiloxane compound and, if necessary, the (B) surfactant are added to the organopolysiloxane of the component (C), and the phase is inverted by a gate mixer. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, a surfactant and / or water is further added as necessary, and a gate mixer, T.M. K. Homo disperse (trade name, manufactured by Primix) or T. K. Dilute with a homomixer (trade name, manufactured by Primics). Moreover, you may mix | blend the water of (D) component when making a phase inversion. By adding water at the time of phase inversion, it is possible to control the particle size of the emulsion, and it may be easy to emulsify. A specific emulsification method in the case of adding water at the time of phase inversion is as follows. To the organopolysiloxane (C), add the polyoxyalkylene-modified diorganopolysiloxane compound (A), the surfactant (B) if necessary, the water (D), and gate mixer. Phase inversion. After stirring for 2 to 180 minutes until a predetermined particle size is obtained, a surfactant and / or water is further added as necessary, and a gate mixer, T.M. K. Homo disperse (trade name, manufactured by Primix) or T. K. Dilute with a homomixer (trade name, manufactured by Primics).
　乳化物中の（Ｃ）成分のオルガノポリシロキサンの濃度は１～９０質量％の範囲であることが好ましい。１質量％未満では乳化物の安定性に問題があり、９０質量％より大きい場合では乳化物の粘度が高く、取り扱いにくくなる。 The concentration of the organopolysiloxane of component (C) in the emulsion is preferably in the range of 1 to 90% by mass. If it is less than 1% by mass, there is a problem in the stability of the emulsion, and if it is more than 90% by mass, the viscosity of the emulsion is high and handling becomes difficult.
　乳化する際の温度については、好ましくは０～８０℃、より好ましくは０～５０℃である。０℃未満もしくは８０℃より高い温度では乳化しなくなる場合や製造した乳化物が不安定になる可能性がある。乳化する際の圧力については、常圧だけでなく減圧もしくは加圧でもよい。減圧もしくは加圧の環境下で乳化する場合、泡が混入しにくくなり、効果的に乳化できることがある。減圧にする場合の圧力は、原料の蒸気圧より高くし、原料が揮発しないように注意する。 The temperature during emulsification is preferably 0 to 80 ° C., more preferably 0 to 50 ° C. If the temperature is less than 0 ° C. or higher than 80 ° C., the emulsion may not be emulsified or the produced emulsion may become unstable. About the pressure at the time of emulsification, not only a normal pressure but pressure reduction or pressurization may be sufficient. When emulsifying in a reduced pressure or pressurized environment, bubbles are less likely to be mixed and may be effectively emulsified. The pressure for reducing the pressure should be higher than the vapor pressure of the raw material so that the raw material does not volatilize.
　乳化には、必要に応じて、Ｔ．Ｋ．ホモミキサー（プライミクス社製商品名）、Ｔ．Ｋ．ホモディスパー（プライミクス社製商品名）、Ｔ．Ｋ．コンビミックス（プライミクス社製商品名）、アジホモミキサー（プライミクス社製商品名）、ホモミキサーとホモディスパーとアンカーミキサーを組み合わせた３軸型分散混練機コンビミックス（プライミクス社製商品名）、ハイビスディスパーミックス（プライミクス社製商品名）、Ｔ．Ｋ．ハイビスミックス（プライミクス社製商品名）、プラネタリーミキサー（井上製作所製商品名）、同方向スクリューもしくは異方向スクリューを有する２軸混合機であるＨＡＡＫＥ　Ｍｉｎｉ　Ｌａｂ　ＩＩ（Ｔｈｅｒｍｏ　ｓｃｉｅｎｔｉｆｉｃ社製商品名）やＭＣ１５、ＭＣ５（レオ・ラボ社製商品名）などを使用することも可能である。３軸型分散混練機コンビミックス（プライミクス社製商品名）やハイビスディスパーミックス（プライミクス社製商品名）を使用する場合はアンカーのみで乳化することも可能である。コロイドミルや高圧ホモジナイザーといった連続式の装置を使用し、乳化をすることも可能である。 For emulsification, if necessary, T.M. K. Homomixer (trade name, manufactured by Primics), T.M. K. Homo disperse (trade name, manufactured by Primics), T. K. Combimix (trade name, manufactured by Primix), Ajihomo mixer (trade name, manufactured by Primics), triaxial dispersion kneader combination mix (trade name, manufactured by Primics), a combination of homomixer, homodisper and anchor mixer, Hibis Disper Mix (trade name, manufactured by Primics), T.M. K. Hibismix (product name made by Primix), planetary mixer (product name made by Inoue Seisakusho), HAAKE Mini Lab II (product name made by Thermo scientific) or MC15, which is a twin screw mixer having the same direction screw or different direction screw. MC5 (trade name, manufactured by Leo Laboratories Inc.) can also be used. When using a triaxial dispersion kneader combination mix (trade name, manufactured by Primics) or Hibis Disper mix (trade name, manufactured by Primics), emulsification can be performed only with an anchor. It is also possible to emulsify using a continuous apparatus such as a colloid mill or a high-pressure homogenizer.
　本発明のオルガノポリシロキサン乳化組成物の平均粒径は１００μｍ以下であることが好ましい。１００μｍより平均粒径が大きい場合、乳化組成物の安定性が低下し、分離等が生じる可能性がある。本発明のオルガノポリシロキサン乳化組成物において、平均粒径が２μｍ以上のときはベックマンコールター社製Ｍｕｌｔｉｓｉｚｅｒ３により測定することができる。平均粒径が２μｍ未満のときは堀場製作所製ＬＡ９６０もしくはＬＡ９２０、又はベックマンコールター社製Ｎ４　ＰＬＵＳにより測定することができる。なお、平均粒径の下限は特に限定されないが、通常０．１μｍ以上、特に０．５μｍ以上である。 The average particle size of the organopolysiloxane emulsion composition of the present invention is preferably 100 μm or less. When the average particle size is larger than 100 μm, the stability of the emulsified composition is lowered, and separation or the like may occur. In the organopolysiloxane emulsion composition of the present invention, when the average particle size is 2 μm or more, it can be measured by Multisizer 3 manufactured by Beckman Coulter. When the average particle size is less than 2 μm, it can be measured with LA960 or LA920 manufactured by Horiba, Ltd., or N4 PLUS manufactured by Beckman Coulter. The lower limit of the average particle diameter is not particularly limited, but is usually 0.1 μm or more, particularly 0.5 μm or more.
　本発明のオルガノポリシロキサン乳化組成物は、２鎖型のポリオキシアルキレンアルキル基を末端に有するポリオキシアルキレン変性ジオルガノポリシロキサン化合物を乳化剤もしくは乳化助剤とした乳化組成物である。本発明のオルガノポリシロキサン乳化組成物はアルコール、ケトン、エステル等の極性溶剤に対して耐溶剤性があり、また塩化ナトリウムや硫酸ナトリウム等の塩に対して耐塩性もある。通常、化粧品などには香料や保湿剤であるアルコール類を配合しており、柔軟剤にも香料であるアルコール類が含まれている。本発明のオルガノポリシロキサン乳化組成物はそのような化粧品や柔軟剤製品にも安定に配合することができる。２鎖型のポリオキシアルキレンアルキル基を末端に有するポリオキシアルキレン変性ジオルガノポリシロキサン化合物を乳化剤もしくは乳化助剤とすることで、容易に高重合度のオルガノポリシロキサン乳化組成物が製造できる。そのため、本発明の乳化組成物はベースオイルとして高重合度のポリシロキサンを使用できる。そのような高重合度のオルガノポリシロキサン乳化組成物はコーティング効果が優れているため、樹脂のコーティング剤、ヘアケア製品、金型やプラスチックやタイヤ用の離型剤に有用である。 The organopolysiloxane emulsion composition of the present invention is an emulsion composition using a polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal as an emulsifier or an emulsification aid. The organopolysiloxane emulsion composition of the present invention is resistant to polar solvents such as alcohols, ketones and esters, and is also resistant to salts such as sodium chloride and sodium sulfate. Usually, cosmetics and the like are blended with alcohols that are perfumes and moisturizers, and softeners also contain alcohols that are perfumes. The organopolysiloxane emulsion composition of the present invention can be stably blended in such cosmetics and softener products. By using a polyoxyalkylene-modified diorganopolysiloxane compound having a two-chain polyoxyalkylene alkyl group at the terminal as an emulsifier or an emulsifying aid, an organopolysiloxane emulsion composition having a high degree of polymerization can be easily produced. Therefore, the emulsion composition of the present invention can use polysiloxane having a high degree of polymerization as the base oil. Such a highly polymerized organopolysiloxane emulsion composition has an excellent coating effect, and is therefore useful as a resin coating agent, hair care product, mold, plastic and tire release agent.
　以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、粘度はＢＭ型もしくはＢＨ型回転粘度計により測定した２５℃における値である。また、３０質量％トルエン溶液粘度とは対象となる化合物が３０質量％になるようトルエンで希釈した後にＢＭ型もしくはＢＨ型回転粘度計により測定した２５℃における絶対粘度の値である。また、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの粘度は２５℃におけるオストワルド粘度計で測定される動粘度である。ＧＰＣ（ＴＯＳＯＨ製、ＨＬＣ８２２０）はＴＨＦ溶媒のポリスチレン換算による重量平均分子量の値である。乳化物の平均粒径はベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３により２５℃で測定される体積基準の体積平均粒径である。 Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is a value at 25 ° C. measured with a BM type or BH type rotational viscometer. The 30% by mass toluene solution viscosity is a value of an absolute viscosity at 25 ° C. measured with a BM type or BH type rotational viscometer after dilution with toluene so that the target compound becomes 30% by mass. The viscosity of the diorganopolysiloxane containing silicon atoms bonded to hydrogen atoms at both ends is a kinematic viscosity measured with an Ostwald viscometer at 25 ° C. GPC (manufactured by TOSOH, HLC8220) is a value of weight average molecular weight in terms of polystyrene of THF solvent. The average particle diameter of the emulsion is a volume-based volume average particle diameter measured at 25 ° C. by a Multisizer 3 manufactured by Beckman Coulter.
［実施例１］
　窒素雰囲気下、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサン［一般式（６）］（ｍ＝４００、Ｒ1＝ＣＨ3、粘度２，２００ｍｍ2／ｓ、ケイ素原子に結合した水素原子の量０．００６ｍｏｌ／１００ｇ）８３質量部（８３ｇ）と不飽和基含有ポリオキシアルキレン化合物［一般式（７）］（ｒ＝１、ｓ＝２４、ｔ＝８、Ｒ2＝Ｈ）１７質量部（１７ｇ）とイソプロピルアルコール１００質量部（１００ｇ）にｐＨ調整剤として１０質量％酢酸カリウムのエタノール溶液１．０質量部（１．０ｇ）を加えた後、加熱し、内部温度を７５℃とした。次いで、白金のビニルシロキサン錯体のトルエン溶液を白金金属としてシロキサンに対して５ｐｐｍ加え、８時間撹拌することで、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物Ａを合成した（ＧＰＣによる重量平均分子量３７，０００）。これにノニオン界面活性剤サンノニックＳＳ－１２０（三洋化成社製、ポリオキシエチレンアルキルエーテル、ＨＬＢ１４．５）１００質量部（１００ｇ）を添加し、１０～１５ｍｍＨｇ、３５～４０℃の条件でイソプロピルアルコールを減圧留去し、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の界面活性剤溶解液Ａを得た。
　続いて、下記一般式（１０）
Figure JPOXMLDOC01-appb-C000029
 （ｋは下記粘度とする数を示す。）
で示される両末端ヒドロキシジメチルポリシロキサン（３０質量％トルエン溶液粘度１，４００ｍＰａ・ｓ）２７．５質量部（２７．５ｇ）、及びポリオキシアルキレン変性ジオルガノポリシロキサン化合物の界面活性剤溶解液Ａ１０質量部（１０ｇ）、サンノニックＳＳ－１２０（三洋化成社製、ポリオキシエチレンアルキルエーテル、ＨＬＢ１４．５）１２．５質量部（１２．５ｇ）をＴ．Ｋ．ホモディスパー（プライミクス社製）で５００～２，０００ｒｐｍで約１０分撹拌して乳化物Ａを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、２２．５μｍであった。 [Example 1]
Under nitrogen atmosphere, diorganopolysiloxane having hydrogen atoms containing silicon atoms bonded at both ends [general formula (6)] (m = 400, R 1 = CH 3 , viscosity 2,200 mm 2 / s, hydrogen atoms bonded to silicon atoms Amount 0.006 mol / 100 g) 83 parts by mass (83 g) and unsaturated group-containing polyoxyalkylene compound [general formula (7)] (r = 1, s = 24, t = 8, R 2 = H) 17 parts by mass (17 g) and 100 parts by mass (100 g) of isopropyl alcohol were added 1.0 parts by mass (1.0 g) of an ethanol solution of 10% by mass potassium acetate as a pH adjuster, and then heated to set the internal temperature to 75 ° C. . Next, 5 ppm of a platinum solution of platinum in a vinylsiloxane complex as platinum metal was added to the siloxane and stirred for 8 hours to synthesize a polyoxyalkylene-modified diorganopolysiloxane compound A (weight average molecular weight by GPC: 37,000). ). Nonionic surfactant Sannonic SS-120 (manufactured by Sanyo Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB14.5) 100 parts by mass (100 g) was added, and isopropyl alcohol was added under the conditions of 10 to 15 mmHg and 35 to 40 ° C. Depressurizingly distilled, the surfactant solution A of the polyoxyalkylene modified diorganopolysiloxane compound was obtained.
Subsequently, the following general formula (10)
Figure JPOXMLDOC01-appb-C000029
 (K indicates the number of the following viscosity)
27.5 parts by mass (27.5 g) of both ends hydroxydimethylpolysiloxane (30% by weight toluene solution viscosity 1,400 mPa · s) represented by the above, and surfactant solution A10 of polyoxyalkylene-modified diorganopolysiloxane compound 12.5 parts by mass (12.5 g) of Sannonic SS-120 (manufactured by Sanyo Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB 14.5) K. Emulsion A was obtained by stirring with a homodisper (Primix) at 500 to 2,000 rpm for about 10 minutes. The average particle diameter was measured with a Multisizer 3 manufactured by Beckman Coulter and found to be 22.5 μm.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
［実施例２］
　窒素雰囲気下、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサン［一般式（９）］（ｎ２＝１００、Ｒ1＝ＣＨ3、粘度１３０ｍｍ2／ｓ、ケイ素原子に結合した水素原子の量０．０３ｍｏｌ／１００ｇ）３３質量部（６６ｇ）、不飽和基含有ジオルガノポリシロキサン［一般式（８）］（ｎ１＝２００、Ｒ3＝ＣＨ3、粘度１，０００ｍｍ2／ｓ、１価オレフィン性不飽和基の量０．０１２ｍｏｌ／１００ｇ）３１質量部（６２ｇ）と不飽和基含有ジオルガノポリシロキサン［一般式（８）］（ｎ１＝４００、Ｒ3＝ＣＨ3、粘度５，０００ｍｍ2／ｓ、１価オレフィン性不飽和基の量０．００６３ｍｏｌ／１００ｇ）２０質量部（４０ｇ）及びイソプロピルアルコール３００質量部（６００ｇ）にｐＨ調整剤として１０質量％酢酸カリウムのエタノール溶液１．０質量部（２．０ｇ）を加えた後、加熱し、内部温度が７５℃になったら、白金のビニルシロキサン錯体のトルエン溶液を白金金属としてシロキサンに対して５ｐｐｍ加えて２時間撹拌した。次いで、不飽和基含有ポリオキシアルキレン化合物［一般式（７）］（ｒ＝１、ｓ＝２４、ｔ＝８、Ｒ2＝Ｈ）１７質量部（３４ｇ）及び白金のビニルシロキサン錯体のトルエン溶液を白金金属としてシロキサンに対して５ｐｐｍ加え、６時間撹拌し、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物Ｂを合成した（ＧＰＣによる重量平均分子量８１，０００）。得られたポリオキシアルキレン変性ジオルガノポリシロキサン化合物のイソプロパノール溶液１５０質量部（３００ｇ）に対してノニオン界面活性剤タージトールＴＭＮ－６（ダウケミカル社製、ポリオキシエチレンアルキルエーテル９０質量％水溶液、ＨＬＢ１３．１）１８．７５質量部（３７．５ｇ）を添加し、１０～１５ｍｍＨｇ、３５～４０℃の条件でイソプロピルアルコールを減圧留去し、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物の界面活性剤溶解液Ｂを得た。
　続いて、下記一般式（１１）
Figure JPOXMLDOC01-appb-C000031
 （ｋ’は下記粘度とする数を示す。）
で示される両末端ヒドロキシジメチルポリシロキサン（３０質量％トルエン溶液粘度４７，０００ｍＰａ・ｓ）１７．５質量部（３５ｇ）と合成したポリオキシアルキレン変性ジオルガノポリシロキサン化合物の界面活性剤溶解液Ｂ７．５質量部（１５ｇ）をＴ．Ｋ．ハイビスミックス（プライミクス社製）４０～５０ｒｐｍで２０分撹拌して乳化物Ｂを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、３．５μｍであった。 [Example 2]
Under a nitrogen atmosphere, silicon-bonded diorganopolysiloxane [general formula (9)] (n2 = 100, R 1 = CH 3 , viscosity 130 mm 2 / s, amount of hydrogen atoms bonded to silicon atoms 0 0.03 mol / 100 g) 33 parts by mass (66 g), unsaturated group-containing diorganopolysiloxane [general formula (8)] (n1 = 200, R 3 = CH 3, viscosity 1,000 mm 2 / s, monovalent olefinic Unsaturated group amount 0.012 mol / 100 g) 31 parts by mass (62 g) and unsaturated group-containing diorganopolysiloxane [general formula (8)] (n1 = 400, R 3 = CH 3 , viscosity 5,000 mm 2 / s Monovalent olefinically unsaturated group amount 0.0063 mol / 100 g) 20 parts by mass (40 g) and isopropyl alcohol 300 parts by mass (600 g) After adding 1.0 parts by mass (2.0 g) of an ethanol solution of potassium acetate and heating, when the internal temperature reaches 75 ° C., 5 ppm of a toluene solution of platinum vinylsiloxane complex as platinum metal is added to the siloxane. And stirred for 2 hours. Next, an unsaturated group-containing polyoxyalkylene compound [general formula (7)] (r = 1, s = 24, t = 8, R 2 = H) 17 parts by mass (34 g), and a toluene solution of a platinum vinylsiloxane complex Was added to the siloxane as platinum metal at 5 ppm and stirred for 6 hours to synthesize polyoxyalkylene-modified diorganopolysiloxane compound B (weight average molecular weight by GPC of 81,000). Nonionic surfactant Taditol TMN-6 (manufactured by Dow Chemical Co., polyoxyethylene alkyl ether 90% by mass aqueous solution, HLB13. With respect to 150 parts by mass (300 g) of an isopropanol solution of the obtained polyoxyalkylene-modified diorganopolysiloxane compound. 1) 18.75 parts by mass (37.5 g) was added, and isopropyl alcohol was distilled off under reduced pressure at 10 to 15 mmHg and 35 to 40 ° C. to obtain a surfactant solution of polyoxyalkylene-modified diorganopolysiloxane compound B was obtained.
Subsequently, the following general formula (11)
Figure JPOXMLDOC01-appb-C000031
 (K ′ represents the number of the following viscosity.)
A surfactant solution B7 of a polyoxyalkylene-modified diorganopolysiloxane compound synthesized with 17.5 parts by mass (35 g) of both ends hydroxydimethylpolysiloxane (30 mass% toluene solution viscosity 47,000 mPa · s) represented by formula (7). 5 parts by mass (15 g) of T.I. K. Hibismix (Primix) was stirred at 40-50 rpm for 20 minutes to obtain an emulsion B. The average particle diameter was 3.5 μm as measured by Multisizer 3 manufactured by Beckman Coulter.
Figure JPOXMLDOC01-appb-C000032
 （Ｌ1は上記の通りである。）
Figure JPOXMLDOC01-appb-C000032
 (L 1 is as described above.)
［実施例３］
　両末端ヒドロキシジメチルポリシロキサン［一般式（１１）］（３０質量％トルエン溶液粘度４７，０００ｍＰａ・ｓ）６９質量部（４４．５ｇ）と合成したポリオキシアルキレン変性ジオルガノポリシロキサンの界面活性剤溶解液Ｂ２９質量部（１８．７ｇ）、水２質量部（１．３ｇ）をＴ．Ｋ．ハイビスミックス（プライミクス社製）４０～５０ｒｐｍで２０分撹拌して乳化物Ｃを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、４．０μｍであった。 [Example 3]
Surfactant dissolution of polyoxyalkylene-modified diorganopolysiloxane synthesized with 69 parts by mass (44.5 g) of both ends hydroxydimethylpolysiloxane [general formula (11)] (30 mass% toluene solution viscosity 47,000 mPa · s) 29 parts by mass (18.7 g) of liquid B and 2 parts by mass (1.3 g) of water K. Emulsion C was obtained by stirring for 20 minutes at 40-50 rpm with Hibismix (Primix). The average particle size was 4.0 μm as measured by Multisizer 3 manufactured by Beckman Coulter.
［実施例４］
　両末端ヒドロキシジメチルポリシロキサン［一般式（１１）］（３０質量％トルエン溶液粘度４７，０００ｍＰａ・ｓ）５９．５質量部（４４．６ｇ）と合成したポリオキシアルキレン変性ジオルガノポリシロキサンの界面活性剤溶解液Ｂ２５．５質量部（１９．１ｇ）、水２質量部（１．５ｇ）をＴ．Ｋ．ハイビスミックス（プライミクス社製）４０～５０ｒｐｍで２０分撹拌した。更に、水１３質量部（９．８ｇ）を加えてＴ．Ｋ．ハイビスミックス（プライミクス社製）４０～５０ｒｐｍで２０分撹拌して乳化物Ｄを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、４．４μｍであった。 [Example 4]
Surface activity of polyoxyalkylene-modified diorganopolysiloxane synthesized with 59.5 parts by mass (44.6 g) of both ends hydroxydimethylpolysiloxane [general formula (11)] (30 mass% toluene solution viscosity 47,000 mPa · s) Agent solution B 25.5 parts by mass (19.1 g) and 2 parts by mass of water (1.5 g) K. Hibismix (Primics) was stirred at 40-50 rpm for 20 minutes. Further, 13 parts by mass of water (9.8 g) was added and T.W. K. Hibismix (Primics Co., Ltd.) was stirred at 40-50 rpm for 20 minutes to obtain Emulsion D. The average particle size was 4.4 μm as measured by Multisizer 3 manufactured by Beckman Coulter.
［比較例１］
　窒素雰囲気下、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサン［一般式（６）］（ｍ＝３０、Ｒ1＝ＣＨ3、粘度３０ｍｍ2／ｓ、ケイ素原子に結合した水素原子の量０．１ｍｏｌ／１００ｇ）２３質量部（２３ｇ）と不飽和基含有ポリオキシアルキレン化合物［一般式（７）］（ｒ＝１、ｓ＝２４、ｔ＝８、Ｒ2＝Ｈ）７７質量部（７７ｇ）とイソプロピルアルコール１００質量部（１００ｇ）にｐＨ調整剤として１０質量％酢酸カリウムのエタノール溶液１．０質量部（１．０ｇ）を加えた後、加熱し、内部温度を７５℃とした。次いで、白金のビニルシロキサン錯体のトルエン溶液を白金金属としてシロキサンに対して５ｐｐｍ加え、８時間撹拌することで、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物を合成した。次いで、１０～１５ｍｍＨｇ、３５～４０℃の条件でイソプロピルアルコールを減圧留去した。ポリオキシアルキレン変性ジオルガノポリシロキサン化合物ＣのＧＰＣによる重量平均分子量は６，０００である。
　続いて、合成したポリオキシアルキレン変性ジオルガノポリシロキサン化合物Ｃを１０質量部（１０ｇ）とノニオン界面活性剤ＴＥＲＧＩＴＯＬ－ＴＭＮ－６（ダウケミカル社製、ポリオキシエチレンアルキルエーテル９０質量％水溶液、ＨＬＢ１３．１）５．５質量部（５．５ｇ）と上記一般式（１０）の両末端ヒドロキシジメチルポリシロキサン（３０質量％トルエン溶液粘度１，４００ｍＰａ・ｓ）３５質量部（３５ｇ）をＴ．Ｋ．ハイビスミックス（プライミクス社製）４０～５０ｒｐｍで６０分撹拌して乳化物Ｅを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、２．９μｍであった。
Figure JPOXMLDOC01-appb-C000033
 （Ｌ1は上記の通りである。） [Comparative Example 1]
Under nitrogen atmosphere, diorganopolysiloxane having silicon atom-bonded hydrogen atoms at both ends [general formula (6)] (m = 30, R 1 = CH 3 , viscosity 30 mm 2 / s, amount of hydrogen atoms bonded to silicon atoms 0 .1 mol / 100 g) 23 parts by mass (23 g) and unsaturated group-containing polyoxyalkylene compound [general formula (7)] (r = 1, s = 24, t = 8, R 2 = H) 77 parts by mass (77 g ) And 100 parts by mass (100 g) of isopropyl alcohol were added 1.0 parts by mass (1.0 g) of a 10% by mass potassium acetate ethanol solution as a pH adjuster, followed by heating to an internal temperature of 75 ° C. Next, 5 ppm of a toluene solution of a platinum vinylsiloxane complex as platinum metal was added to the siloxane and stirred for 8 hours to synthesize a polyoxyalkylene-modified diorganopolysiloxane compound. Next, isopropyl alcohol was distilled off under reduced pressure under conditions of 10 to 15 mmHg and 35 to 40 ° C. The weight average molecular weight by GPC of the polyoxyalkylene-modified diorganopolysiloxane compound C is 6,000.
Subsequently, 10 parts by mass (10 g) of the synthesized polyoxyalkylene-modified diorganopolysiloxane compound C and nonionic surfactant TERGITOL-TMN-6 (manufactured by Dow Chemical Company, polyoxyethylene alkyl ether 90 mass% aqueous solution, HLB13. 1) 5.5 parts by mass (5.5 g) and 35 parts by mass (35 g) of both terminal hydroxydimethylpolysiloxane of the above general formula (10) (30 mass% toluene solution viscosity 1,400 mPa · s) K. Hibismix (Primix) was stirred at 40-50 rpm for 60 minutes to obtain Emulsion E. The average particle diameter was measured with a Multisizer 3 manufactured by Beckman Coulter and found to be 2.9 μm.
Figure JPOXMLDOC01-appb-C000033
 (L 1 is as described above.)
［比較例２］
　窒素雰囲気下、両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサン［一般式（６）］（ｍ＝６０、Ｒ1＝ＣＨ3、粘度７５ｍｍ2／ｓ、ケイ素原子に結合した水素原子の量０．０５ｍｏｌ／１００ｇ）５５質量部（５５ｇ）と不飽和基含有ポリオキシアルキレンアルキルエーテル（ＣＨ2＝ＣＨ（ＣＨ2）9Ｏ（ＣＨ2ＣＨ2Ｏ）21（ＣＨ2ＣＨＣＨ3Ｏ）7Ｈ）４５質量部（４５ｇ）とイソプロピルアルコール１００質量部（１００ｇ）にｐＨ調整剤として１０質量％酢酸カリウムのイソプロピルアルコール溶液１．０質量部（１．０ｇ）を加えた後、加熱し、内部温度を７５℃とした。次いで、白金のビニルシロキサン錯体のトルエン溶液を白金金属としてシロキサンに対して５ｐｐｍ加え、８時間撹拌することで、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物を合成した。窒素バブリングをしながら１１０～１２０℃、３０ｍｍＨｇ以下で減圧をして、イソプロパノールを留去し、ポリオキシアルキレン変性ジオルガノポリシロキサン化合物Ｄ（一般式（１２）、ＧＰＣによる重量平均分子量は９，５００）を得た。
　合成したポリオキシアルキレン変性ジオルガノポリシロキサン化合物Ｄ［一般式（１２）］１０質量部（１０ｇ）とノニオン界面活性剤ＴＥＲＧＩＴＯＬ－ＴＭＮ－６（ダウケミカル社製、ポリオキシエチレンアルキルエーテル９０質量％水溶液、ＨＬＢ１３．１）５．５質量部（５．５ｇ）と両末端ヒドロキシジメチルポリシロキサン［一般式（１１）］（３０質量％トルエン溶液粘度４７，０００ｍＰａ・ｓ）３５質量部（３５ｇ）をＴ．Ｋ．ハイビスミックス（プライミクス社製）４０～５０ｒｐｍで１５分撹拌して、乳化物Ｆを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、２．７μｍであった。 [Comparative Example 2]
Under nitrogen atmosphere, diorganopolysiloxane having silicon atom-bonded hydrogen atoms at both ends [general formula (6)] (m = 60, R 1 = CH 3 , viscosity 75 mm 2 / s, amount of hydrogen atoms bonded to silicon atoms 0 .05 mol / 100 g) 55 parts by mass (55 g) and unsaturated group-containing polyoxyalkylene alkyl ether (CH 2 ═CH (CH 2 ) 9 O (CH 2 CH 2 O) 21 (CH 2 CHCH 3 O) 7 H) To 45 parts by mass (45 g) and 100 parts by mass (100 g) of isopropyl alcohol, 1.0 part by mass (1.0 g) of a 10% by mass potassium acetate isopropyl alcohol solution was added as a pH adjuster, followed by heating to adjust the internal temperature. The temperature was 75 ° C. Next, 5 ppm of a toluene solution of a platinum vinylsiloxane complex as platinum metal was added to the siloxane and stirred for 8 hours to synthesize a polyoxyalkylene-modified diorganopolysiloxane compound. The pressure was reduced at 110 to 120 ° C. and 30 mmHg or less with nitrogen bubbling to distill off isopropanol, and the polyoxyalkylene-modified diorganopolysiloxane compound D (general formula (12), weight average molecular weight by GPC was 9,500). )
10 parts by mass (10 g) of the synthesized polyoxyalkylene-modified diorganopolysiloxane compound D [general formula (12)] and nonionic surfactant TERGITOL-TMN-6 (manufactured by Dow Chemical Co., Ltd., 90% by mass aqueous solution of polyoxyethylene alkyl ether , HLB13.1) 5.5 parts by mass (5.5 g) and 35 parts by mass (35 g) of both terminal hydroxydimethylpolysiloxane [general formula (11)] (30 mass% toluene solution viscosity 47,000 mPa · s) . K. Hibismix (Primix) was stirred at 40-50 rpm for 15 minutes to obtain Emulsion F. The average particle size was 2.7 μm as measured with Multisizer 3 manufactured by Beckman Coulter.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
［比較例３］
　窒素雰囲気下、ケイ素原子結合水素原子含有ジオルガノポリシロキサン［一般式（１３）］７７質量部（７７ｇ）と不飽和基含有ポリオキシアルキレンアルキルエーテル（ＣＨ2＝ＣＨＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）24（ＣＨ2ＣＨＣＨ3Ｏ）8Ｈを２３質量部（２３ｇ）とイソプロピルアルコール１５０質量部（１５０ｇ）及びｐＨ調整剤として１０質量％酢酸カリウムのイソプロピルアルコール溶液１．０質量部（１．０ｇ）を加えた後、加熱し、内部温度を７５℃とした。次いで、白金のビニルシロキサン錯体のトルエン溶液を白金金属としてシロキサンに対して５ｐｐｍ加え、８時間撹拌することで、ポリオキシアルキレン変性オルガノポリシロキサン化合物を合成した。サンノニックＳＳ－１２０（三洋化成社製、ポリオキシエチレンアルキルエーテル、ＨＬＢ１４．５）５０質量部（５０ｇ）を加えた後、窒素バブリングを行いながら３０～４５℃、１０～１５ｍｍＨｇに減圧してイソプロピルアルコールを留去し、ポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶液Ｅ（一般式（１４）、ＧＰＣによる重量平均分子量は５３，０００）を得た。
　合成したポリオキシアルキレン変性オルガノポリシロキサン化合物の界面活性剤溶液Ｅ１５質量部（１５ｇ）及び両末端ヒドロキシジメチルポリシロキサン［一般式（１１）］（３０質量％トルエン溶液粘度４７，０００ｍＰａ・ｓ）３５質量部（３５ｇ）を配合し、Ｔ．Ｋ．ホモディスパー（プライミクス社製）で５００～２，０００ｒｐｍで約１０分撹拌したが、両末端ヒドロキシジメチルポリシロキサンは乳化しなかった。 [Comparative Example 3]
Under nitrogen atmosphere, silicon-bonded hydrogen atom-containing diorganopolysiloxane [general formula (13)] 77 parts by mass (77 g) and unsaturated group-containing polyoxyalkylene alkyl ether (CH 2 ═CHCH 2 O (CH 2 CH 2 O) ) 24 (CH 2 CHCH 3 O) 8 H in 23 parts by mass (23 g), 150 parts by mass of isopropyl alcohol (150 g) and 1.0 part by mass of an isopropyl alcohol solution of 10% by mass potassium acetate as a pH adjuster (1.0 g ) And heated to an internal temperature of 75 ° C. Next, 5 ppm of a toluene solution of a platinum vinylsiloxane complex as platinum metal is added to the siloxane, and the mixture is stirred for 8 hours. A polysiloxane compound was synthesized, Sannonic SS-120 (manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene) Polyalkylene-modified organopolysiloxane by adding 50 parts by mass (50 g) of alkyl ether, HLB 14.5) and then depressurizing to 30 to 45 ° C. and 10 to 15 mmHg with nitrogen bubbling to distill off isopropyl alcohol. A surfactant solution E of the compound (general formula (14), weight average molecular weight by GPC of 53,000) was obtained.
15 parts by weight (15 g) of a surfactant solution E of the synthesized polyoxyalkylene-modified organopolysiloxane compound and 35 parts by weight of both terminal hydroxydimethylpolysiloxane [general formula (11)] (30% by weight toluene solution viscosity 47,000 mPa · s) Part (35 g). K. The mixture was stirred at 500 to 2,000 rpm for about 10 minutes with a homodisper (manufactured by Primics), but the both end hydroxydimethylpolysiloxane was not emulsified.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
［比較例４］
　ポリオキシアルキレン変性ジオルガノポリシロキサン化合物Ｄ［一般式（１２）］１０質量部（５ｇ）とノニオン界面活性剤サンノニックＳＳ－１２０（三洋化成社製、ポリオキシエチレンアルキルエーテル、ＨＬＢ１４．５）３５質量部（１７．５ｇ）と両末端ヒドロキシジメチルポリシロキサン［一般式（１０）］（３０質量％トルエン溶液粘度１，４００ｍＰａ・ｓ）５５質量部（２７．５ｇ）をＴ．Ｋ．ホモディスパー（プライミクス社製）５００～２，０００ｒｐｍで１０分撹拌して乳化物Ｇを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、４．４μｍであった。 [Comparative Example 4]
Polyoxyalkylene-modified diorganopolysiloxane compound D [general formula (12)] 10 parts by mass (5 g) and nonionic surfactant Sannonic SS-120 (manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene alkyl ether, HLB 14.5) 35 parts by mass Part (17.5 g) and 55 parts by mass (27.5 g) of both terminal hydroxydimethylpolysiloxane [general formula (10)] (30 mass% toluene solution viscosity 1,400 mPa · s). K. Emulsion G was obtained by stirring for 10 minutes at 500 to 2,000 rpm with homodisper (Primix). The average particle size was 4.4 μm as measured by Multisizer 3 manufactured by Beckman Coulter.
［比較例５］
　ノニオン界面活性剤サンノニックＳＳ－１２０（三洋化成社製、ポリオキシエチレンアルキルエーテル、ＨＬＢ１４．５）１０質量部（１０ｇ）と両末端ヒドロキシジメチルポリシロキサン［一般式（１０）］（３０質量％トルエン溶液粘度１，４００ｍＰａ・ｓ）５５質量部（５５ｇ）とイオン交換水７質量部（７ｇ）をＴ．Ｋ．ホモディスパー（プライミクス社製）５００～２，０００ｒｐｍで１０分撹拌し、更にイオン交換水２８質量部（２８ｇ）を加え、Ｔ．Ｋ．ホモミキサー（プライミクス社製）８００～４，０００ｒｐｍで撹拌して乳化物Ｈを得た。平均粒径をベックマンコールター社製のＭｕｌｔｉｓｉｚｅｒ３で測定したところ、４．３μｍであった。 [Comparative Example 5]
Nonionic surfactant Sannonic SS-120 (manufactured by Sanyo Chemical Co., Ltd., polyoxyethylene alkyl ether, HLB14.5) 10 parts by mass (10 g) and both ends hydroxydimethylpolysiloxane [general formula (10)] (30% by weight toluene solution Viscosity of 1,400 mPa · s) 55 parts by mass (55 g) and 7 parts by mass of ion-exchanged water (7 g) K. Homodisper (Primics Co., Ltd.) was stirred at 500 to 2,000 rpm for 10 minutes, and 28 parts by mass (28 g) of ion-exchanged water was added. K. Emulsion H was obtained by stirring at 800 to 4,000 rpm with a homomixer (Primics). The average particle size was 4.3 μm as measured by Multisizer 3 manufactured by Beckman Coulter.
［比較例６］
　ノニオン界面活性剤サンノニックＳＳ－１２０（三洋化成社製、ポリオキシエチレンアルキルエーテル、ＨＬＢ１４．５）１０質量部（１０ｇ）と両末端ヒドロキシジメチルポリシロキサン［一般式（１１）］（３０質量％トルエン溶液粘度４７，０００ｍＰａ・ｓ）５５質量部（５５ｇ）とイオン交換水７質量部（７ｇ）をＴ．Ｋ．ホモディスパー（プライミクス社製）５００～２，０００ｒｐｍで１０分撹拌したが、乳化できなかった。 [Comparative Example 6]
Nonionic surfactant Sannonic SS-120 (manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene alkyl ether, HLB14.5) 10 parts by mass (10 g) and both ends hydroxydimethylpolysiloxane [general formula (11)] (30% by weight toluene solution Viscosity of 47,000 mPa · s) 55 parts by mass (55 g) and 7 parts by mass of ion-exchanged water (7 g) K. Homodisper (Primix Co., Ltd.) was stirred at 500 to 2,000 rpm for 10 minutes, but could not be emulsified.
　上記実施例、比較例について、下記の乳化性及び耐アルコール性の評価を行った。結果を表１，２に示す。
乳化性：実施例１～４、比較例１～６による両末端ヒドロキシジメチルポリシロキサンの乳化の可否を、サンプル０．５ｇとイオン交換水９．５ｇをガラス瓶に入れて振とうし、外観を観察した。
　　○：水にサンプルの分散が可能
　　×：水にサンプルの分散が不可
　乳化物Ａ～Ｇに対して耐アルコール性試験を行った。
耐アルコール性：乳化物Ａ～Ｇ２．０ｇとイソプロピルアルコール８．０ｇをガラス瓶に入れて振とうし、溶液の状態を観察した。
　　○：オルガノポリシロキサンの析出がほとんどなく、乳化物がイソプロピルアルコールに分散した状態
　　×：イソプロピルアルコールにより乳化物が破壊され、オルガノポリシロキサンが析出した状態 About the said Example and comparative example, the following emulsifiability and alcohol-resistant evaluation were performed. The results are shown in Tables 1 and 2.
Emulsification: Whether or not both ends hydroxydimethylpolysiloxane can be emulsified in Examples 1 to 4 and Comparative Examples 1 to 6 was shaken in a glass bottle with 0.5 g of sample and 9.5 g of ion-exchanged water, and the appearance was observed. did.
○: Sample can be dispersed in water ×: Sample cannot be dispersed in water Emulsions A to G were subjected to an alcohol resistance test.
Alcohol resistance: 2.0 g of emulsions A to G and 8.0 g of isopropyl alcohol were placed in a glass bottle and shaken, and the state of the solution was observed.
○: There is almost no precipitation of the organopolysiloxane, and the emulsion is dispersed in isopropyl alcohol. X: The emulsion is broken by isopropyl alcohol, and the organopolysiloxane is precipitated.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037

Claims (10)

  1. 　下記一般式（１）で表されるポリオキシアルキレン基を有するシロキサン鎖が末端に結合し、かつ下記一般式（２）で表される構造単位を分子内に４０個以上有するポリオキシアルキレン変性ジオルガノポリシロキサン化合物。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ及びＲ1はそれぞれ同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。Ｌは下記一般式（３）で表される２鎖型のポリオキシアルキレンアルキル基である。
    Figure JPOXMLDOC01-appb-C000002
     （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又は、フェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）］     A polyoxyalkylene-modified di having a siloxane chain having a polyoxyalkylene group represented by the following general formula (1) bonded to the terminal and having 40 or more structural units represented by the following general formula (2) in the molecule Organopolysiloxane compound.
    Figure JPOXMLDOC01-appb-C000001
     [In the formula, R and R 1 may be the same or different and each is a substituted or unsubstituted linear or branched alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, polyoxy group having 1 to 20 carbon atoms. It is a monovalent hydrocarbon group having an alkylene group or a hydrogen atom. L is a two-chain polyoxyalkylene alkyl group represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = 1 to 150, t = 0 to 150)]]
  2. 　下記一般式（４）で表される請求項１記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ1、Ｌは上記の通りである。ｍは４０以上の整数である。）     The polyoxyalkylene-modified diorganopolysiloxane compound according to claim 1 represented by the following general formula (4).
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 1 and L are as described above. M is an integer of 40 or more.)
  3. 　下記一般式（５）で表される請求項１記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物。
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ1、Ｌは上記の通りである。Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。Ｘは炭素数２～２０のアルキレン基である。ｍ１＋ｍ２＋ｍ３＝ｍで、ｍは４０以上の整数である。）     The polyoxyalkylene-modified diorganopolysiloxane compound according to claim 1 represented by the following general formula (5).
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 1 and L are as defined above. R 3 may be the same or different and each represents a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group having 1 to 20 carbon atoms, A monovalent hydrocarbon group having an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, X is an alkylene group having 2 to 20 carbon atoms, m1 + m2 + m3 = m, and m is 40 or more. (It is an integer.)
  4. 　下記一般式（６）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンと下記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物とをヒドロシリル化触媒により溶媒存在下又は非存在下で反応させる工程を含む請求項２記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ1は同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。ｍは４０以上の整数である。）
    Figure JPOXMLDOC01-appb-C000006
     （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又は、フェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）     A silicon-bonded hydrogen atom-containing diorganopolysiloxane represented by the following general formula (6) and an unsaturated group-containing polyoxyalkylene compound represented by the following general formula (7) in the presence of a solvent using a hydrosilylation catalyst Or the manufacturing method of the polyoxyalkylene modified diorganopolysiloxane compound of Claim 2 including the process made to react in absence.
    Figure JPOXMLDOC01-appb-C000005
     (Wherein R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group. A monovalent hydrocarbon group or a hydrogen atom, and m is an integer of 40 or more.)
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = (1 to 150, t = 0 to 150)
  5. 　下記一般式（８）で表される両末端不飽和基含有ジオルガノポリシロキサンの両末端不飽和基のそれぞれに下記一般式（９）で表される両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの一方の末端ケイ素原子結合水素原子を付加反応させる工程、及びこの工程後、上記両末端ケイ素原子結合水素原子含有ジオルガノポリシロキサンの他方の末端ケイ素原子結合水素原子に下記一般式（７）で表される不飽和基含有ポリオキシアルキレン化合物の不飽和基を付加反応させる工程を含む請求項３記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ1は同一もしくは異なってもよく、炭素数１～２０の置換又は非置換の直鎖又は分岐のアルキル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、ポリオキシアルキレン基を有する１価炭化水素基、又は水素原子である。Ｒ3は同一もしくは異なってもよく、炭素数１～２０の直鎖又は分岐の置換又は非置換のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、ヒドロキシ基、アルコキシ基、又はポリオキシアルキレン基を有する１価炭化水素基である。ｎ１、ｎ２はそれぞれ０以上の整数であるが、ｎ１＋ｎ２＋ｎ２は４０以上の整数である。）
    Figure JPOXMLDOC01-appb-C000008
     （式中、ＥＯはポリオキシエチレン基を表し、ＡＯは炭素数３～１０の直鎖又は分岐のポリオキシアルキレン基を表す。Ｒ2は同一でも異なってもよく、水素原子、炭素数１～１０の直鎖もしくは分岐の置換又は非置換のアルキル基、カルボキシ基、アシル基、又は、フェニル基を表す。ｒ、ｓ、ｔはそれぞれ同一もしくは異なってもよく、ｒ＝０～１０、ｓ＝１～１５０、ｔ＝０～１５０である。）     A diorganopolysiloxane containing hydrogen atoms at both ends represented by the following general formula (9) in each unsaturated group at both ends of the diorganopolysiloxane containing unsaturated groups at both ends represented by the following general formula (8) The step of addition reaction of one terminal silicon atom-bonded hydrogen atom of siloxane, and after this step, the other terminal silicon atom-bonded hydrogen atom of the silicon atom-bonded hydrogen atom-containing diorganopolysiloxane has the following general formula (7) The manufacturing method of the polyoxyalkylene modified diorganopolysiloxane compound of Claim 3 including the process of carrying out the addition reaction of the unsaturated group of the unsaturated group containing polyoxyalkylene compound represented by these.
    Figure JPOXMLDOC01-appb-C000007
     (Wherein R 1 may be the same or different and each represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group. R 3 may be the same or different and is a linear or branched substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group having 1 to 20 carbon atoms And a monovalent hydrocarbon group having an aralkyl group, a hydroxy group, an alkoxy group, or a polyoxyalkylene group, n1 and n2 are each an integer of 0 or more, and n1 + n2 + n2 is an integer of 40 or more.)
    Figure JPOXMLDOC01-appb-C000008
     (In the formula, EO represents a polyoxyethylene group, AO represents a linear or branched polyoxyalkylene group having 3 to 10 carbon atoms, R 2 may be the same or different, and may be a hydrogen atom, 1 to 10 represents a linear or branched substituted or unsubstituted alkyl group, carboxy group, acyl group, or phenyl group, and r, s, and t may be the same or different, and r = 0 to 10, s = (1 to 150, t = 0 to 150)
  6. 　請求項１～３のいずれか１項記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物とノニオン界面活性剤との混合物。 A mixture of the polyoxyalkylene-modified diorganopolysiloxane compound according to any one of claims 1 to 3 and a nonionic surfactant.
  7. 　（Ａ）請求項１～３のいずれか１項記載のポリオキシアルキレン変性ジオルガノポリシロキサン化合物：１～５０質量部、
    （Ｂ）界面活性剤：０～５０質量部、
    （Ｃ）上記（Ａ）成分を除くオルガノポリシロキサン：１００質量部、
    （Ｄ）水：０～１０，０００質量部
    を含有することを特徴とするオルガノポリシロキサン乳化組成物。     (A) The polyoxyalkylene-modified diorganopolysiloxane compound according to any one of claims 1 to 3: 1 to 50 parts by mass,
    (B) Surfactant: 0 to 50 parts by mass,
    (C) Organopolysiloxane excluding the component (A): 100 parts by mass,
    (D) Water: An organopolysiloxane emulsion composition containing 0 to 10,000 parts by mass.
  8. 　（Ｃ）成分のオルガノポリシロキサンの粘度が、２５℃において５００，０００ｍＰａ・ｓ以上である請求項７記載のオルガノポリシロキサン乳化組成物。 The organopolysiloxane emulsion composition according to claim 7, wherein the viscosity of the organopolysiloxane of component (C) is 500,000 mPa · s or more at 25 ° C.
  9. 　（Ｃ）成分のオルガノポリシロキサンが、ジメチルポリシロキサン、ジメチルシロキサンとメチルフェニルシロキサンの共重合体、又は両末端ヒドロキシ変性ジメチルポリシロキサンである請求項７又は８記載のオルガノポリシロキサン乳化組成物。 The organopolysiloxane emulsion composition according to claim 7 or 8, wherein the organopolysiloxane of component (C) is dimethylpolysiloxane, a copolymer of dimethylsiloxane and methylphenylsiloxane, or hydroxy-modified dimethylpolysiloxane at both ends.
  10. 　乳化物の平均粒径が１００μｍ以下である請求項７～９のいずれか１項記載のオルガノポリシロキサン乳化組成物。 The organopolysiloxane emulsion composition according to any one of claims 7 to 9, wherein the average particle size of the emulsion is 100 µm or less.
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