WO2016111225A1 - Composé de diorganoploysiloxane modifié par polyoxyalkylène, procédé de fabrication de celui-ci, et composition d'émulsion d'organopolysiloxane - Google Patents

Composé de diorganoploysiloxane modifié par polyoxyalkylène, procédé de fabrication de celui-ci, et composition d'émulsion d'organopolysiloxane 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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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.

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Abstract

L'invention concerne un composé de diorganopolysiloxane modifié par polyoxyalkylène comprenant une chaîne siloxane contenant un groupe polyoxyalkylène correspondant à la formule (1) liée à une extrémité de celui-ci, et comprenant au moins 40 unités structurelles correspondant à la formule (2) dans sa molécule. L est un groupe alkyle de polyoxyalkylène à chaîne double représenté par la formule (3). EO représente un groupe polyoxyéthylène, AO représente un groupe polyoxyalkylène C3-10, R2 représente un atome d'hydrogène, un groupe alkyle, un groupe carboxy, un groupe acyle ou un groupe phényle, r = 0 à 10, s = 1 à 150, et t = 0 à 150. )La présente invention possède une excellente compatibilité avec des organopolysiloxanes ayant un degré de polymérisation élevé. En utilisant ce composé de diorganopolysiloxane modifié par polyoxyalkylène en tant qu'émulsifiant ou d'une aide à l'émulsification, il est possible d'émulsifier facilement un organopolysiloxane ayant un degré de polymérisation élevé.
PCT/JP2015/086486 2015-01-09 2015-12-28 Composé de diorganoploysiloxane modifié par polyoxyalkylène, procédé de fabrication de celui-ci, et composition d'émulsion d'organopolysiloxane WO2016111225A1 (fr)

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WO2018029966A1 (fr) * 2016-08-10 2018-02-15 信越化学工業株式会社 Composition d'émulsion d'organopolysiloxane, et composition de résine
CN111356442A (zh) * 2017-11-02 2020-06-30 信越化学工业株式会社 免冲洗护发化妆品

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JP7306313B2 (ja) * 2020-04-21 2023-07-11 信越化学工業株式会社 （ポリ）チオフェン－（ポリ）シロキサンブロックコポリマー及びその製造方法
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WO2018029966A1 (fr) * 2016-08-10 2018-02-15 信越化学工業株式会社 Composition d'émulsion d'organopolysiloxane, et composition de résine
JPWO2018029966A1 (ja) * 2016-08-10 2018-12-27 信越化学工業株式会社 オルガノポリシロキサン乳化組成物及び樹脂組成物
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