WO1995023889A1 - Traitement de fibres, cosmetique, compose polymère a chaines laterales organopolysiloxane et procede de production d'un copolymere de silicone - Google Patents

Traitement de fibres, cosmetique, compose polymère a chaines laterales organopolysiloxane et procede de production d'un copolymere de silicone Download PDF

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Publication number
WO1995023889A1
WO1995023889A1 PCT/JP1995/000353 JP9500353W WO9523889A1 WO 1995023889 A1 WO1995023889 A1 WO 1995023889A1 JP 9500353 W JP9500353 W JP 9500353W WO 9523889 A1 WO9523889 A1 WO 9523889A1
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WIPO (PCT)
Prior art keywords
monomer
group
silicone
organopolysiloxane
copolymer
Prior art date
Application number
PCT/JP1995/000353
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English (en)
Japanese (ja)
Inventor
Yoshio Shimizu
Masahiro Takizawa
Masanori Isoda
Kenichiro Shibazaki
Kiyoshi Nakayama
Original Assignee
Lion Corporation
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Filing date
Publication date
Priority claimed from JP06033594A external-priority patent/JP3778369B2/ja
Priority claimed from JP7536994A external-priority patent/JPH07268778A/ja
Priority claimed from JP7536894A external-priority patent/JPH0770204A/ja
Priority claimed from JP16905994A external-priority patent/JPH0769828A/ja
Priority claimed from JP34024994A external-priority patent/JP3507925B2/ja
Application filed by Lion Corporation filed Critical Lion Corporation
Publication of WO1995023889A1 publication Critical patent/WO1995023889A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • 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
    • A61K8/73—Polysaccharides
    • 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
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
    • C07K1/107—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides
    • C07K1/1072—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides by covalent attachment of residues or functional groups
    • C07K1/1077—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides by covalent attachment of residues or functional groups by covalent attachment of residues other than amino acids or peptide residues, e.g. sugars, polyols, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15—Proteins or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon

Definitions

  • the present invention relates to a method for producing a polymer compound and a silicone-based copolymer having a fiber treating agent, a cosmetic, and an organopolysiloxane in a side chain.
  • the present invention relates to a method for producing a fiber treatment agent, a cosmetic, a high molecular compound having an organopolysiloxane in a side chain, and a silicone copolymer.
  • the fiber treating agent containing an organopolysiloxane chain is particularly excellent in performance
  • JP-A-58-26378 discloses that a butyl group-containing organopolysiloxane and Si—
  • a fiber treating agent comprising a copolymer of an H-containing organopolysiloxane and a Biel monomer is disclosed.
  • this fiber treatment agent does not provide a sufficiently satisfactory soft texture, development of a fiber treatment agent having both flexibility and resilience has been promoted, and Japanese Patent Application Laid-Open No. H11-68971 has been proposed.
  • Japanese Patent Application Laid-Open Nos. Hei 11-16872 and Hei 4-891313 disclose that an acryl monomer and a bur Mosomer are added to a high molecular weight organopolysiloxane having a radical reactive group.
  • a fiber treating agent comprising an emulsion of a copolymer obtained by graft copolymerization has been proposed.
  • These fiber treatment agents impart both flexibility and resilience to the fiber, but the treatment agent contains a high molecular weight organopolysiloxane structure in a cross-linked structure or main chain, and is used in water, alcohol, or a surfactant solution. Does not show sufficient solubility For this reason, when treating fibers with this treating agent, there are problems that the treating agent cannot be removed by washing, washing, or the like, or that the treating agent becomes dirty and accumulates.
  • a film-forming agent in cosmetics, it is widely used to incorporate a film-forming agent into the cosmetic.
  • a film forming agent poly (vinylpyrrolidone), poly (vinylpyrrolidone) acetate copolymer, acrylic copolymer and the like have been generally used.
  • a film formed with such a film-forming agent has a disadvantage that it absorbs moisture under high humidity, increases tackiness, and causes tackiness because of its high hygroscopicity.
  • a polymer containing an organopolysiloxane has been known as a film-forming agent having excellent water resistance and oil resistance, but the conventional one has not yet been satisfactory.
  • JP-A-2-254411 discloses a cosmetic containing a methacrylate polymer having dimethylpolysiloxane as a graft chain as a film-forming agent.
  • the film-forming agent in this case is insoluble in water, it is difficult to apply it to water-based cosmetics, and the film-removing property is poor.
  • For removing the film such as isoparaffin and low molecular weight silicone are used. There is a problem that the organic solvent must be used.
  • Japanese Patent Application Laid-Open Nos. 3-128311 and 3-128312 disclose acrylic acid / n-butyl methacrylate nopolymethyl as a film-forming agent in a hair care composition.
  • Siloxane mac mouth monomer copolymer, N, N-dimethylacrylamide / isobutyl methacrylate / polydimethyl It describes a blend of a copolymer having a polydimethylsiloxane as a graft chain, such as a monomer copolymer of siloxane.
  • the film-forming agent in this case it is difficult for the film-forming agent in this case to simultaneously satisfy the adhesiveness to hair and the like under high humidity and the film-removing property. If the film-removing agent has a high film-removing property, the adhesiveness becomes poor. On the other hand, those with high adhesion have poor film removal properties.
  • the above publication discloses polystyrene macromers as hydrophobic monomers copolymerizable with polydimethylsiloxane macromers. However, with the film-forming agent in this case, the resulting film is hard and whitened, has poor adhesion to hair and the like, and does not have satisfactory film removing properties.
  • a fiber treating agent comprising a polymer compound having an organopolysiloxane chain as a side chain, and soluble or dispersible in water and / or alcohol.
  • a fiber treating agent comprising a vinyl polymer having a first side chain composed of an organopolysiloxane chain and a second side chain composed of a water- and Z- or alcohol-soluble or hydrophobic polymer chain.
  • a method for treating fibers using a treatment liquid containing the treatment agent in a dissolved or dispersed state
  • a cosmetic comprising a polymer compound having an organopolysiloxane chain as a side chain, and a water- and / or alcohol-soluble or water-dispersible film-forming agent.
  • a cosmetic comprising a film forming agent comprising a first side chain comprising an organopolysiloxane chain and a butyl polymer having a second side chain comprising a water and / or alcohol-soluble or hydrophobic polymer chain. thing.
  • a fiber treating agent comprising a vinyl polymer having a side chain composed of an organopolysiloxane chain having 2 to 500 silicon atoms and having a weight average molecular weight of 5,000 to 5,000,000.
  • a first side chain consisting of an organopolysiloxane chain having 2 to 500 silicon atoms and a second side chain consisting of a water and / or alcohol soluble or hydrophobic polymer chain having a degree of polymerization of 5 to 500.
  • a fiber treatment agent consisting of 000 to 5,000 butyl polymer.
  • a fiber treating agent comprising an organopolysiloxane-containing polysaccharide compound comprising a main chain comprising a polysaccharide compound and a side chain comprising an organopolysiloxane.
  • a fiber treating agent comprising an organopolysiloxane-containing protein compound composed of a main chain composed of a protein compound and a side chain composed of an organopolysiloxane.
  • the weight ratio of the first silicone monomer (a) to the second silicone monomer (b) contained in the copolymer which is a radical copolymer of the bull monomer (c) (a) / (b) a fiber treating agent comprising a silicone-based copolymer in which the content of unreacted silicone-based monomer is in the range of 0 to 25%;
  • a method for treating a fiber comprising bringing the fiber into contact with a treatment liquid containing any of the above-mentioned fiber treatment agents in a dissolved or dispersed state.
  • the film-forming agent comprises a first side chain containing an organosiloxane polymer and a second side chain containing a water-soluble and / or alcohol-soluble polymer.
  • a hydrophilic copolymer having a weight average molecular weight in the range of 10,000 to 500,000, wherein the content of the organosiloxane polymer is 0.1 to 80 wt. /.
  • a water-soluble and / or alcohol-soluble polymer content in the range of 0.01 to 90 wt%.
  • the film-forming agent comprises a main chain comprising a hydrophilic segment having a repeating unit of a ⁇ -philic monomer and a hydrophobic segment having a repeating unit of a hydrophobic monomer.
  • a side chain ( ⁇ ) containing an organosiloxane polymer bonded to the main chain, the copolymer comprising the hydrophilic segment in the copolymer a cosmetic having a ratio of 1 to 95 wt%, a content of the hydrophobic segment in a range of 1 to 90 wt%, and a content of an organosiloxane polymer in a range of 1 to 80 wt%.
  • the film-forming agent comprises an organopolysiloxane-containing polysaccharide compound composed of a main chain composed of a polysaccharide compound and a side chain composed of an organopolysiloxane.
  • the film forming agent comprises an organopolysiloxane-containing protein compound composed of a main chain composed of a protein compound and a side chain composed of an organopolysiloxane. Cosmetics characterized by the thing.
  • the film-forming agent comprises a first silicone-based monomer (a) represented by the following general formula (S-1) and the following general formula (S-2) ), A radical copolymer of a hydrophilic silicone monomer (c) and a first silicone monomer (a) contained in the copolymer.
  • the weight ratio (a) / (b) of the second silicone-based monomer (b) is within the range of 10-1 to 1Z4, and the content of the unreacted silicone-based monomer is within the range of 0 to 25%.
  • An organopolysiloxane-containing polysaccharide compound comprising a main chain composed of a polysaccharide compound and a side chain composed of an organopolysiloxane.
  • An organopolysiloxane-containing protein compound comprising a main chain composed of a protein compound and a side chain composed of an organopolysiloxane.
  • the weight ratio (a) of the first silicone monomer (a) and the second silicone monomer (b) contained in the copolymer of the radical copolymer of the water-soluble monomer (c) ) / (b) is 10Z1 or more: a silicone copolymer characterized by having an unreacted silicone monomer content in the range of LZ4 and 0 to 25%.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group or an aryl group having 1 to 10 carbon atoms
  • R 3 is an alkyl group or an aryl group having 1 to 10 carbon atoms
  • p is! Number of ⁇ 20, q is 0 ⁇ : number of 19, r is number of 0 ⁇ 19, h is 0
  • CH 2 C— COO— (CH 2 ), — (O), — (S i 0) n — S -R ((S- 2)
  • the first fiber treatment agent of the present invention is a compound comprising an organopolysiloxane chain. It consists of a vinyl polymer having a chain. In the organopolysiloxane chain constituting the side chain, the number of silicon atoms is 2 to 500, preferably 5 to 500, and more preferably 10 to 300.
  • the resulting fiber treatment agent will be unsatisfactory in terms of flexibility, resilience, lubricity, shape retention and the like. If the amount is more than the above range, the obtained fiber treating agent becomes unsatisfactory in terms of solubility in water and / or alcohol, solubility in a surfactant solution, and the like.
  • a preferred organopolysiloxane chain in the fiber polymer having an organopolysiloxane chain, which is the fiber treating agent of the present invention (hereinafter, also simply referred to as a "bule polymer”), can be represented by the following general formula (1).
  • A represents a bonding group to a carbon atom in the main chain of the bullet polymer.
  • —CO—O— —NH—
  • one CO—NH—, —CO—, —O—CO — — NH—CO—O—
  • O—CO—NH— —(C RaR 2 ) a-(R x> R 2 : lower alkyl group, a: number of 1 to 6), ⁇ O—, ⁇ S—
  • B is a linking group and can be a divalent aliphatic group.
  • divalent aliphatic examples include an alkylene group, an alkylene group having a hetero atom such as an oxygen atom, a nitrogen atom, and a zeo atom in the main chain; an alkylene group including an arylene group such as a phenylene group in the main chain; Examples thereof include an alkylene group containing a carbonyloxy group or an oxycarbonyl group in the chain.
  • the terminal atom of the aliphatic group can be a hetero atom such as oxygen, nitrogen, and zeo atom in addition to carbon.
  • these aliphatic groups may have a hydroxy group, an alkoxy group, an alkyl group or the like as a substituent.
  • ⁇ 1 ⁇ ! ⁇ 5 represents an aliphatic group or an aromatic group.
  • Preferred examples of the aliphatic group include a lower alkyl group such as a methyl group, an ethyl group and a propyl group, and a lower alkoxy group such as a methoxy group and an ethoxy group.
  • the aromatic group include an aryl group such as a phenyl group and a tolyl group, an aralkyl group such as a benzyl group, and an aryloxy group such as a phenoxy group. These aryl, aralkyl, and aryloxy groups may have a substituent such as a hydroxy group, an alkoxy group, or an amino group on the aromatic ring.
  • n represents the degree of polymerization, and is a number of 2 to 500, preferably 5 to 500, and more preferably 10 to 300.
  • Specific examples of the linking group B include, for example, the following. (1) - (CH 2) x-
  • b represents 0 or 1; s, V, w, X, and y represent 0 to 12; and z represents an integer of 0 to 8.
  • R, R 6 , R 7 and R 8 represent hydrogen or an alkyl group having 2 carbon atoms, and L represents a divalent linking group selected from the formulas (1) and (6).
  • the organopolysiloxane content in the vinyl polymer is from 0.01 to 60% by weight, preferably 0.50 weight%, more preferably 0.30% by weight. If the content of the organopolysiloxane in the vinyl polymer is reduced by 0.1% by weight, the fiber treatment effect of the vinyl polymer becomes unsatisfactory. Does not improve the fiber treatment effect.
  • the weight average molecular weight of the BULL polymer is 50,000 to 500,000, preferably 50,000 to 300,000, and more preferably 50,000 to 200,000.
  • the main chain of the vinyl polymer can be composed of a water and / or alcohol soluble monomer, a hydrophobic monomer, or both. If the main chain is composed mainly of water and alcohol- or alcohol-soluble monomer, a water- and Z- or alcohol-soluble vinyl polymer can be obtained as a whole. With this configuration, a water-dispersible vinyl polymer can be obtained as a whole. In addition, there are various types of these monomer as described below. Preferred monomer which is soluble in water and Z or alcohol is polyacrylic acid or methacrylic acid, and hydrophobic monomer is butyl acetate or methacrylic acid. ) Atylic acid ⁇ ⁇ 8 -valent aliphatic alcohol ester.
  • Such a fiber treatment agent composed of a vinyl polymer is excellent in the ability to precipitate (deposit) on the fiber surface from the solution or dispersion liquid to form a thin film, and furthermore, the surface of the film has an organopolysiloxane chain.
  • the fiber treated with the fiber treating agent of the present invention provides a fiber treated material which is flexible, rich in repellency or shape retention, and excellent in lubricity.
  • the second fiber treatment agent of the present invention comprises a first side chain composed of an organopolysiloxane having 1 to 500 silicon atoms, and a water and / or alcohol soluble or hydrophobic polymer having a degree of polymerization of 5 to 500. And a weight average molecular weight of 5,000 to 5,000,000.
  • the vinyl polymer has an organopolysiloxane having a second side chain. Since it has the effect of accelerating the phase separation of siloxane chains, it exhibits a high fiber treatment effect even when the content of organopolysiloxane is low.
  • the second side chain may be derived from a hydrophobic monomer, but is preferably derived from water and a monomer soluble in alcohol or alcohol.
  • the polymer constituting the second side chain has a polymerization degree of 5 to 500, preferably 10 to 300, and more preferably 20 to 100. Further, the content of the polymer constituting the second side chain is 0.01 to 50% by weight, preferably 0.1 to 50% by weight, and preferably 0.1 to 40% by weight, based on the whole polymer. It is. If the content of the second side chain is less than the above range, the effect of promoting the phase separation of the organopolysiloxane chain by the second side chain cannot be obtained. On the other hand, if the amount is larger than the above range, problems such as a reduction in the fiber treatment effect occur, so it is not preferable.
  • the preferable second side chain can be represented by the following general formula (2).
  • a and B have the same meanings as those described with respect to the general formula (1).
  • P is a number of 0 or 1.
  • F is 1S-, 1O- or a divalent linking group represented by the following formula (3).
  • m is a number of 0 or 1.
  • G is one or more monomers.
  • q indicates the degree of polymerization and is a number of 5 to 500, preferably 10 to 300, and more preferably 20 to 100.
  • the following are specific examples of the monomer G.
  • the (meth) acryl shown below means that both acryl and methacryl are contained.
  • maleic acid or its neutralized product maleic anhydride and its semi-esters or its neutralized product; crotonic acid or its neutralized product; itaconic acid or its neutralized product Substance; diaryldimethylammonium mouth lid; aliphatic unsaturated lower phenols such as aryl alcohol and butyl alcohol; butyl ethers; maleimide; bulyl groups such as butylpyrrolidone, vinylpyridine, vinylimidazole and the like.
  • Heterocyclic compounds having the following: vinylinoleprotatatam; styrene; styrene derivatives such as ⁇ -methinolestyrene, t-butylinostyrene, vinylinolenorlene, styrene snolephonate, and 2-methoxystyrene; bullet esters such as butyl acetate; Part of the hydrolyzate: ethylene, butadiene, cyclohexadiene And other unsaturated hydrocarbons; ethylene oxide; and others.
  • particularly preferred monomers include (meth) acrylic acid or its Cids-valent aliphatic alcohol ester, butyl acetate, ethylenoxide, butyl alcohol, butylpyrrolidone and the like.
  • J in the general formula (2) represents a termination terminal of the polymerization reaction. This terminal group was derived from a chain transfer agent, polymerization initiator, monomer, solvent, etc. The specific structure of the terminal group in relation to the chain transfer agent is as follows. -(1) When a chain transfer agent represented by the following general formula (4) is used:
  • R alkylene group having 1 to 4 carbon atoms
  • R alkylene group having 1 to 4 carbon atoms
  • R—CO—SH 10
  • R—SH (12) R: alkyl group with 1 to 18 carbon atoms
  • d represents an integer of 0 to 5
  • e represents an integer of 0 to 1
  • ⁇ represents an integer of 0 to 5
  • g represents an integer of 0 to 5.
  • P is H, CH 3 or OCH 3
  • Q is H, CH 3 , CN or COOCH 3 ;
  • T is CN ⁇ ⁇ >, H, 3 ⁇ 4, CO OH, OH, CH 3 , or — CJ
  • the vinyl polymer having an organopolysiloxane chain can be obtained by radically polymerizing a polymerization material composed of a vinyl monomer having an organopolysiloxane chain and another vinyl monomer.
  • the vinyl polymer having a second side chain composed of another polymer together with the first side chain composed of an organopolysiloxane chain is composed of a vinyl monomer having an organopolysiloxane chain, a vinyl monomer having another polymer chain, and optionally It can be obtained by radically polymerizing a raw material for polymerization composed of ordinary low-molecular-weight monomer which is added in advance.
  • radical polymerization methods polymerization is carried out by subjecting a polymerization raw material composed of raw material monomers to a polymerization reaction in the presence of a radical polymerization initiator.
  • the radical polymerization methods include bulk polymerization, solution polymerization, and suspension polymerization. Polymerization, emulsion polymerization, microsuspension polymerization and the like.
  • the polymerization reaction is performed in a solvent or a dispersion medium under an atmosphere of an inert gas such as nitrogen.
  • the reaction temperature is 30 to 100 ° C, preferably 50 to 90 ° C, and the reaction time is 1 to 10 hours.
  • the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxyethoxy).
  • the solvent may be used in the form of a mixture with water.
  • the polar organic solvent include ethanol, propanol, acetone, ethyl acetate and the like.
  • the polymerization raw material is polymerized by an emulsion polymerization method
  • the polymerization raw material is polymerized in the presence of a protective colloid and an emulsifier.
  • the protective colloid include a polymer obtained by completely or partially saponifying a homopolymer or copolymer of vinyl acetate, processed starch, hydroxyshethyl cellulose, hydroxypropynolecellulose, methylcellulose, and cationization. Examples thereof include cellulose and cationized starch, and one or a mixture of two or more of these protective colloids may be used. The amount of these protective colloids added is based on the total weight of the reactor contents.
  • It is 0.1 to 20% by weight, preferably 0.5 to 20% by weight.
  • the emulsifier examples include non-emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene phenol phenol phenol, polyoxyethylene phenol phenol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and sucrose fatty acid ester.
  • Ionic surfactants such as sodium lauryl sulfate, polyoxyethylene sodium dodecyl sulfate, and nonylphenyl ether phosphate
  • monoalkyltrimethyl Cationic surfactants such as ammonium chloride, dialkyldimethylammonium chloride, and trialkylbenzyl ammonium chloride.
  • the amount of emulsifier added is 0.1 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the reactor contents.
  • a conventionally known silicone-based macromonomer can be used as the vinyl monomer having an organopolysiloxane chain.
  • examples of such a macromonomer include those represented by the following general formula (16). Then, by copolymerizing the monomer with another bullet monomer, a bullet polymer having an organopolysiloxane chain as a side chain can be obtained.
  • A, B,! ⁇ 1 ⁇ ! ⁇ 5 , p, m and n have the same meanings as those of the above-mentioned general formula (1).
  • a conventionally known non-silicone-based Mac mouth monomer can be used as the bullet monomer having a polymer chain.
  • macromonomers include those represented by the following general formula (17) (
  • D is the same as D in the general formula (16), and A, B, F, G, p, m, q and J are the same as those in the general formula (2) Means something.
  • the macromonomer represented by the general formula (17) is reacted with a silicone-based macromonomer and a normal low-molecular-weight vinyl monomer which is added as required, to thereby form a first side comprising an organopolysiloxane chain.
  • a bullet polymer having a second side chain consisting of a chain and a polymer chain is provided.
  • Byuruporima one consisting Bulle monomer (X) and low molecular weight Bulle monomer (gamma) with organopolysiloxane chain
  • the content of Byurumono mer (X) is 0.0 1-50 weight 0/0, preferably 0. 1-50 weight 0/0
  • Yo Li preferably from 0.1 to 30 weight 0/0.
  • the properties of such a vinyl polymer can be adjusted to water and / or alcohol-soluble or water-soluble properties by appropriately selecting the type and content of the vinyl monomer (Y). It can be dispersible.
  • a water and Z or alcohol-soluble vinyl monomer is used as the vinyl monomer (Y).
  • the content of the butyl monomer is preferably set to a sufficiently high value.
  • the content is usually 10% by weight or more, preferably 40 to 100% by weight.
  • butyl monomers are (meth) acrylic acid, quaternary salt of dimethylaminoethyl (meth) acrylate, crotonic acid, and itacone. Acids, butyl alcohol and the like.
  • a hydrophobic beer monomer is used as the bullet monomer (Y).
  • examples of such butyl monomers include alkyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, butyl sulfonate, methyl styrene, t-butyl styrene, butadiene, cyclohexadiene, and the like.
  • examples include ethylene and butyl toluene. One or a combination of two or more of these may be used, but the use of vinyl acetate or acrylate is particularly preferred.
  • the hydrophobic vinyl monomer can be used in combination with the above-mentioned water- or alcohol-soluble vinyl monomer.
  • the content of these hydrophobic butyl monomers is from 10 to 99.9% by weight, preferably from 40 to 99.9% by weight, and more preferably from 70 to 99.9% by weight.
  • a bullet monomer (X .) the content of 0 0 1-5 0 weight 0/0, preferably from 0:.! ⁇ 5 0 weight 0/0, Yo Li is preferably 0 to 3 0 wt 0/0..
  • Byurumono 'content of mer (Y) is from 0 to 99.99% by weight, preferably from 40-9 9.9 wt 0/0, Yo Li preferably from 70 to 99.9 weight 0/0.
  • a water and / or alcohol-soluble vulmonomer is used as the vul monomer (Z).
  • a monomer include a macromonomer represented by the general formula (17), wherein the polymer chain (G) q is a homopolymer or a copolymer derived from water and Z or an alcohol-soluble monomer.
  • G polymer chain
  • Y low molecular weight monomer
  • the content of the vinyl monomer (Z) is usually 0.01% by weight or more, preferably 0.1% by weight or more. 40 wt%, more preferred properly good that a 0.1 to 30 weight 0/0.
  • Bulle containing Yuritsu monomer (Y) is 0-9 9.9 9 wt 0/0, preferably from 40 to 99.9 weight 0/0, yo Li preferably 70-9 9.9% by weight.
  • the above-mentioned bullet polymer having an organopolysiloxane chain is obtained by a combination of a radical polymerization method and a functional group reaction method in addition to the above-mentioned radical polymerization method.
  • a vinyl monomer having a reactive group such as a hydroxyl group, an amino group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, or a mixture of the same with another vinyl monomer is subjected to radical polymerization.
  • the obtained butyl polymer (homopolymer or copolymer) is reacted with an organopolysiloxane having a reactive group Y at one end.
  • the reactive group Y located at one end of the organopolysiloxane is a group capable of reacting with the reactive group X introduced into the polymer.
  • the reactive group X is a reactive group having an active hydrogen atom such as a hydroxyl group, an amino group, an imino group, and a carboxyl group
  • the reactive group Y includes an epoxy group, a halogen atom, an isocyanate group, and the like. To be elected.
  • the reactive group X is an epoxy group, a halogen atom, an isocyanate group, or the like
  • a reactive group having an active hydrogen atom such as a hydroxyl group, an amino group, an imino group, or a carboxyl group is selected. .
  • the number of organopolysiloxane chains introduced into the polymer can be controlled by the number of reactive groups X in the polymer and the number of moles of the organopolysiloxane having a reactive group Y to be reacted therewith.
  • the organopolysiloxane having the reactive group Y those represented by the following general formula (18) can be used. Y— (B) p- (0) flourish- !! (18)
  • Y represents a reactive group such as a hydroxyl group, an amino group, an imino group, a carboxyl group, an epoxy group, an isocyanate group, and a halogen atom.
  • ⁇ , 1 to R 5 , p, m and n mean the same as those of the above-mentioned general formula (1).
  • the fiber treating agent (Bulle polymer) of the present invention can be used in the form of a solution in which it is dissolved in a medium such as water, alcohol, alcohol / water mixture and the like.
  • a medium such as water, alcohol, alcohol / water mixture and the like.
  • the alcohol lower alcohols such as methanol, ethanol, isopropanol and butanol are used.
  • Fiber treatment in solution The concentration of the agent is 0.1 to 40% by weight, preferably 0.1 to 20% by weight. '
  • the first fiber treatment agent of the present invention is made of a bur polymer, its production is easy.
  • the second fiber treatment agent of the present invention comprises an organopolysiloxane-containing polysaccharide compound composed of a main chain composed of a polysaccharide compound and a side chain composed of an organopolysiloxane.
  • polysaccharide compounds include various types of conventionally known compounds, for example, woody polysaccharides such as cellulose and hemicellulose; mucilage of plant such as arabia gum, tragacanth gum, and trolley mallow; Polysaccharides derived from the same; Leguminous polysaccharides such as guar gum, locust bean gum, tamarind gum, quince gum, etc .; Seaweed polysaccharides such as alginic acid, carrageenan, agar, etc .; Animal-derived polysaccharides such as chitin, chitosan, hyaluronic acid, and chondroitin sulfate; water-soluble derivatives of the polysaccharides, for example, carboxymethylation, sulfation, phosphorylation, methylation, ethylene glycol addition, and ethylene oxide. ⁇ Propylene oxide Various derivatives obtained by the treatment of alkylene oxide addition, hydroxypropylation, acylation, c
  • the weight average molecular weight of the polysaccharide compound is usually 1 ⁇ 10 3 to 5 ⁇ 10 6 , preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 . ⁇
  • an organopolysiloxane compound may be reacted with the polysaccharide compound directly or via a spacer compound.
  • the organopolysiloxane compound has a reactive group at its terminal, and for example, a compound represented by the following general formula (21) can be used.
  • a ′ is a reactive group capable of reacting with a polysaccharide compound directly or via a spacer compound.
  • a reactive group include an epoxy group, an isocyanate group, a vinyl group, a butyl ether group, a butyl ester group, a (meth) acryloyl group, a (meth) acryloyloxy group, an amino group, an imino group, a hydroxyl group, Examples include a mercapto group and a sulfoxyl group.
  • B represents a divalent aliphatic group.
  • the aliphatic group include an alkylene group, an alkylene group having an oxygen atom, a nitrogen atom, a zirconium atom and the like in the main chain, an alkylene group having an arylene group such as a phenylene group in the main chain, and a carboxy group in the main chain.
  • examples include an alkylene group containing a niloxy group or an oxycarbonyl group.
  • the terminal atom of the aliphatic group can be a hetero atom such as oxygen, nitrogen, and zeo atom.
  • these aliphatic groups can have a hydroxy group, an alkoxy group, an alkyl group, or the like as a substituent.
  • b is 0 or 1; p is 1 to 8; s is 0 to: L2; V is 0 to 12; w is 0 to 12; Is 2; y is! Shows an integer of ⁇ 12.
  • R, R 6 and R 7 represent hydrogen or an alkyl group having 2 carbon atoms.
  • L represents any divalent aliphatic group selected from the formulas (1) and (6).
  • RR 2 , R 3 , R 4 and R 5 in the general formula (21) may be the same or different and represent an aliphatic group or an aromatic group.
  • the aliphatic group includes a lower alkyl group such as a methyl group, an ethyl group, a methoxy group and an ethoxy group, and a lower alkoxy group.
  • the aromatic group includes an aryl group such as a phenyl group, a tolyl group, a benzyl group, a phenoxy group and a benzyloxy group, an arylalkyl group, an aryloxy group, an arylalkoxy group and the like. Also this These substituents may have a substituent such as an alkyl group or an alkoxy group.
  • p is 0 or 1
  • m is 0 or 1
  • n is a number of '2 to 500'.
  • the above-mentioned organopolysiloxane compound can be reactively bonded to the polysaccharide compound via the reactive group A,.
  • A is a group reactive with active hydrogen such as an epoxy group or an isocyanate group, it binds to a reactive group such as a hydroxyl group, a carboxyl group, an amino group, or an imino contained in a polysaccharide compound. Reacting with active hydrogen to bind to the polysaccharide compound.
  • the reaction in this case can be performed in water or a polar organic solvent using an acid or a base as a catalyst.
  • a ′ is a basic reactive group such as an amino group or a diamino group
  • it can be bound to the polysaccharide compound by a reaction with an epoxy group or a diisocyanate group contained in the polysaccharide compound.
  • a ′ is a hydroxyl group, a mercapto group, or a carboxyl group
  • it can be bound to the polysaccharide compound by reacting with a carboxyl group, an epoxy group, an isocyanate group, a halogen group, an aldehyde group, etc. contained in the polysaccharide compound. it can.
  • A is a reactive group having a polymerizable double bond such as a vinyl group, a vinyl ether group, a butyl ester group, a (meth) acryloyl group, a (meth) acryloyloxy group, etc.
  • the graft copolymerization method is used. Can be reactively bonded to a polysaccharide compound.
  • This graft copolymerization reaction can be carried out at 20 to 60 ° C. under acidic conditions using a cerium salt such as cerium ammonium nitrate as a catalyst.
  • This graft copolymerization reaction is described in detail in “Industrial Chemistry Magazine”, Vol. 64, pp. 21-218 (1961). This dara In the foot copolymerization reaction, hydrogen atoms are mainly extracted from the polysaccharide compound, and the organosiloxane compound having a polymerizable double bond is graft-polymerized there.
  • a non-polymerizable compound in the general formula (21), A 'is a reactive group having no polymerizable double bond] is added to the organopolysiloxane compound.
  • an organopolysiloxane chain represented by the following general formula (22) binds to a polysaccharide compound as a side chain.
  • A is a divalent bonding group derived from the reactive group A ′ in the general formula (21), and examples thereof include a bonding group derived from an epoxy group, a bonding group derived from an isocyanate group, a bonding group derived from an amino group, A bonding group derived from an imino group, a bonding group derived from a hydroxyl group, a bonding group derived from a mercapto group, a bonding group derived from a carboxyl group, and the like.
  • an imino group reacts with an epoxy group, an isocyanate group, a halogen group, an aldehyde group or the like in the polysaccharide compound to form a linking group: 1 NR— (R: an alkyl group).
  • R an alkyl group
  • a hydroxyl group it reacts with a carboxyl group in the polysaccharide compound to form a linking group: 1 O—.
  • a mercapto group it reacts with an epoxy group, an isocyanate group, a halogen group, a bur group and the like in the polysaccharide compound to form a bonding group: —S—.
  • a ′ is a reactive group containing a polymerizable double bond
  • an organopolysiloxane chain represented by the following general formula (23) binds to a polysaccharide compound as a side chain.
  • D is a residue obtained by removing a carbon-carbon double bond from a polymerizable compound, and is represented by one COO—, one CO_, one O—, -OCO P h-(P h phenyl group) and the like.
  • Xi is hydrogen, an alkyl group, one COOR (R: Alkyl group), a phenyl group, a cyano group and the like.
  • X 2 represents a terminating end of the radical polymerization reaction, and is hydrogen, a hydroxyl group, an alkoxy group, a polymerization initiator residue, or the like.
  • d Indicates an integer of ⁇ 300.
  • B,! ⁇ To 5 , p, m, and n are the same as those described for the general formula (21).
  • X 2 Represents a solvent residue, and is hydrogen or a hydroxyl group when the solvent is water.
  • R represents hydrogen, a lower alkyl group, a hydroxyalkyl group, a phenyl group, a substituted phenyl group, etc.
  • a desired reactive group can be introduced into the polysaccharide compound via a spacer compound in advance so that the polysaccharide compound can easily react with the organopolysiloxane compound.
  • a spacer compound a compound having a reactive group capable of binding to the polysaccharide compound and a reactive group capable of binding to the reactive group of the organopolysiloxane compound is used.
  • the spacer compound examples include epoxy compounds such as epichlorohydrin glycidol, glycidyl (meth) acrylate, and aryl glycidyl ether; alkylene oxides such as ethylene oxide and propylene oxide; and cyanogen bromide. Acid halide having a polymerizable double bond such as cyanogen halide; (meth) acrylic acid chloride.
  • epichlorohydrin is used as a spacer compound, active hydrogen contained in a reactive group such as a hydroxyl group, a carboxyl group, an amino group, or a sulfone group in the polysaccharide compound reacts with an epoxy group or a chlorine atom to form a chlorine atom or an epoxy group.
  • Cy groups are introduced into the polysaccharide compound.
  • a second spacer having two or more amino groups, hydroxyl groups, and mercapto groups in the molecule may be further bonded.
  • second spacer compounds include ethylene diamine, hexamethylene diamine, ethylene glycol, propylene glycol, hexamethylene glycol, ethylene mercaptan, hexmethylene mercaptan, aminoethanol, and the like.
  • active hydrogen in the polysaccharide compound reacts with an epoxy group to introduce a hydroxyl group.
  • a carboxyl group, a mercapto group, an amino group, or the like in the polysaccharide compound reacts with an oxysilane ring to introduce a hydroxyl group into the polysaccharide compound.
  • the active hydrogen in the polysaccharide compound reacts with the Hagen atom of the spacer compound to introduce a cyano group into the polysaccharide compound, and the cyano group is hydrolyzed. Can be changed to a carboxyl group.
  • the reaction contained in the polysaccharide compound It has higher reactivity than the group.
  • the spacer compound has a lower molecular weight than the organopolysiloxane compound, and reacts more easily with the polysaccharide compound than the organopolysiloxane compound.
  • the reactive group introduced into the polysaccharide compound is reacted with an organopolysiloxane compound having a reactive group having a reactivity with the reactive group at the terminal to obtain a polysaccharide having a side chain composed of an organopolysiloxane.
  • a compound can be obtained.
  • an organopolysiloxane compound having a polymerizable double bond at the double bond [A ′ in the general formula (21) is a polymerizable double bond]
  • a reactive group having a heavy bond] an organopolysiloxane chain can be introduced into the polysaccharide compound.
  • the radical polymerization reaction can be performed according to a conventionally known method.
  • the weight average molecular weight of the polysaccharide compound having an organopolysiloxane chain 2 X 1 0 3 ⁇ : LX 1 0 7, preferably 2 X 1 0 3 ⁇ 2 X 1 0 6.
  • the content of the organopolysiloxane chain contained in the polysaccharide compound is from 0.01 to 50% by weight, preferably from 0.05 to 40% by weight.
  • the content of organopolysiloxane chain is the content of organopolysiloxane represented by the following general formula (26).
  • the fourth fiber treatment agent of the present invention comprises an organopolysiloxane-containing protein compound composed of a main chain composed of a protein compound and a side chain composed of an organopolysiloxane.
  • organopolysiloxane-containing protein compound will be described in detail.
  • protein compounds include gelatin, disaccharide, casein, soy protein, collagen, keratin, fibrin, anolebumin, protamine, globulin, prolamin, gluterin, histone, glycoprotein, lysoprotein, and lipoprotein.
  • Water-soluble derivatives of the above-mentioned protein compounds such as carboxymethylation, sulfation, phosphorylation, methylation, ethylene glycol addition, alkylene oxide addition, hydroxypropylation, acylation, cationization, and low-molecularization. Derivatives and the like obtained by the treatment can be given.
  • These protein compounds contain one or more amino groups, imino groups, hydroxyl groups, hydroxyl groups, etc., depending on the type of the protein compound.
  • the weight average molecular weight of the protein compound is 1 ⁇ 10 3 to 5 ⁇ 10 6 , preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 .
  • the protein compound may be reacted with the organopolysiloxane compound directly or via a spacer compound.
  • the organopolysiloxane compound has a reactive group at a terminal, and the compound represented by the general formula (21) can be used.
  • the organopolysiloxane compound represented by the general formula (21) can be reactively bonded to a protein compound via the reaction group A ′.
  • the method of reacting the organopolysiloxane compound the same method as in the above-described method of reacting the polysaccharide compound with the organopolysiloxane compound can be employed.
  • the weight average molecular weight of the protein compound having an organopolysiloxane chain is 2 ⁇ 10 3 to 1 ⁇ 10 7 , preferably 2 ⁇ 10 3 to 2 ⁇ 10 6 .
  • the content of the organopolysiloxane contained in the protein compound is 0.01 to 50% by weight, preferably 0.05 to 40% by weight.
  • the fifth fiber treatment agent of the present invention comprises a first silicone monomer (a) represented by the general formula (S-1) and a second silicone monomer represented by the general formula (S-2)
  • a first silicone monomer (a) and a second silicone monomer (b) contained in the copolymer which are composed of a radical copolymer of a hydrophilic monomer (c) and a hydrophilic monomer (c)
  • the weight ratio of (a) / (b) is in the range of 10/1 to 1Z4, and the content of unreacted silicone monomer is in the range of 0 to 25%. is there.
  • R 1 is hydrogen or a lower alkyl group, preferably a lower alkyl group. is there. Examples of the lower alkyl group include those having 4 or less carbon atoms, for example, methyl, ethyl, propyl, and butyl.
  • R 2 and R 3 are an alkyl group or an aryl group having 1 to 10 carbon atoms, preferably an alkyl group.
  • Preferred alkyl groups are lower alkyl groups having 1 to 4 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl and the like.
  • Examples of the aryl group include phenyl, trinole, and xylyl.
  • the range of P, q and r is from 1 to 20, preferably from 3 to 20.
  • h ranges from 0 to 6, but is preferably 1 to 4.
  • m is 0 or 1, but is preferably 0.
  • the range of p + q + r is 1 to 20, preferably 3 to 20, and more preferably 3 to 10.
  • p + q + r exceeds 20, the amount of unreacted silicone-based monomer contained in the copolymer increases, which is not preferable.
  • R 5 and R 6 are an alkyl group or aryl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
  • aryl groups include phenyl, tolyl, and xylyl.
  • n average degree of polymerization
  • the range of n is from 20 to 500, preferably from 40 to 500, and more preferably from 40 to 300. If n is less than 20, copolymer-based properties such as lubricity, gloss, and mold release properties of the silicone-based monomer will be lost. The amount of the unreacted monomer contained in the polymer increases.
  • First silicone monomer (a) and second silicone monomer (b) The weight ratio (a) / (b) ranges from 101 to 1/4, preferably from 8 to ⁇ . However, it is preferably 5 1 to 1 Z 1. If the weight ratio a Zb is too large, the properties of the copolymer, such as lubricity, gloss, and releasability, are impaired.
  • silicone type monomer amount of unreacted increases (c) contained in the polymer a hydrophilic group, for example, a hydroxyl group, a carboxyl group, an amino group, an amino-de-group, imide group It is a vinyl monomer containing a sulfonic acid group, a pyrrolidone group, a pyridine group, an imidazole group and the like.
  • the acidic monomers such as (meth) acrylic acid and maleic acid are alkali and dimethylaminomethyl (meth) acrylic so that the hydrophilic vinyl monomer (C) has good solubility in water or surfactant.
  • Amine monomers such as acrylate and dimethylaminoethyl (meth) acrylate can be partially or completely neutralized with an acid, and can be neutralized before or after polymerization.
  • Amine-based monomers are partially or completely quaternized using a quaternizing agent such as methyl sulfide or benzyl sulfide in order to have good solubility in water or surfactants,
  • a partial or complete amphoteric treatment may be carried out using an amphoteric agent such as monochloroacetic acid or monochloropropionic acid.
  • the quaternization or amphoteric treatment may be performed before or after the polymerization.
  • the toluene-based monomer imparts water solubility or surfactant solubility to the obtained copolymer.
  • hydrophilic bubble-based monomers may be used.By using two or more hydrophilic monomers, the properties of the copolymer can be improved, and the solubility in water or a surfactant is not impaired. If it is within the range, the following hydrophobic vinyl monomers may be used in combination.
  • P 1 to 23 phenoxy polyethylene glycol (meth) acrylate, linear or branched C 1 to 18 alcohol (meth) acrylate, benzyl (meth) acrylate, ( (Meth) cyclohexyl acrylate, butyl acetate, (meth) 2-methoxyl acrylate, oligo (meth) acrylic acid ester of C1-C4 alcohol having a radically polymerizable functional group at the terminal [(meth) Acrylic acid ester macromono Mer], styrene, ⁇ -methinolestyrene, t-butynolestyrene, vinylinoletoluene, butylcaprolactam, oligostyrenes having a radically polymerizable functional group at the terminal (styrene macromonomer), and the like.
  • (meth) acrylic acid means acrylic acid or methacrylic acid, or a mixture of both.
  • the proportion of the first silicone-based monomer (a) contained in the copolymer of the present invention is from 0.1 to 50% by weight, preferably from 1 to 50% by weight, more preferably from 1 to 30% by weight. %. Proportion of the monomer increases the percentage of 0.1 weight 0/0 Yo Li small the Most unreacted silicon corn-based monomer, more than 5 0 weight 0/0, solubility in the copolymer in water or a surfactant Gets worse.
  • the proportion of the second silicone-based monomer (b) is 0.1 to 30% by weight, preferably 1 to 30% by weight, and more preferably 1 to 20% by weight. If the proportion of the monomer is as low as 0.1% by weight, the properties of the copolymer such as lubricity, luster and release properties are not sufficient. The solubility of the coalesced water or surfactant becomes poor.
  • the first silicone monomer (a), the second silicone monomer (b) and the hydrophilic vinyl monomer (c) are combined,
  • Polymerization is carried out by a known polymerization method such as luk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or microsuspension polymerization.
  • Solution polymerization is preferred from the viewpoint of easy polymerization operation and easy control of the molecular weight of the resulting copolymer.
  • Preferred solvents used in the solution polymerization include, for example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and aromatic hydrocarbon solvents such as benzene and toluene.
  • Alcohols such as methanol, ethanol, n-propanol and isopropanol, as well as cyclohexane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and water.
  • Preferred are ethanol, isopropanol and ethyl acetate, and most preferred is isopropanol. These solvents can be used alone or in combination of two or more.
  • radical polymerization initiator examples include 2,2,1-azobisisobutyronitrile, 2,2,1-azobis (2,4-dimethylvale-tolyl), and 2,2′-azobis (4-methoxyethoxy).
  • 2,4-Dimethylvaleronitrile dimethyl 2,2,1-azobisisobutylate, 2,2,1-azobis (2-methinolevbutyronitrile), 1,1, -azobis (1-cyclohexane) Azo-based compounds such as 2,2'-azobis (2-amidinob pan) hydrochloride, 2,2,1-azobis (N, N-dimethyleneiso-peptidoamidine) salt, acid salt, etc .
  • t Peroxides such as monobenzyl acetate, dicumylperoxide, di-t-butylperoxide, dibenzoylperenoside, hydrogen peroxide, and t-butylhydroperoxide; calcium persulfate, ammonium persulfate
  • a chain transfer agent can be used, if necessary, for adjusting the molecular weight and viscosity.
  • mercaptoacetic acid, mercaptopropionic acid, dodecylmercaptan, thiophenol and the like can be used.
  • the copolymer obtained by the radical copolymerization has a low content of unreacted silicone-based monomer, and its content is usually 0 to 25% by weight.
  • the copolymer obtained in the copolymerization step can be used as it is without using a special purification step for removing unreacted silicone monomer.
  • the first to fifth fiber treatment agents according to the present invention can be used in the form of a solution in which they are dissolved in a medium such as water, alcohol, or a mixture of alcohol and Z water.
  • a medium such as water, alcohol, or a mixture of alcohol and Z water.
  • alcohol lower alcohols such as methanol, ethanol, isopropanol and butanol are used.
  • concentration of the fiber treating agent in the solution is 0.1 to 40% by weight, preferably 0.1 to 20% by weight.
  • the fiber treating agent of the present invention can be used in the form of a dispersion (aqueous emulsion) in which it is dispersed in water or an alcohol-water mixture.
  • a surfactant or a protective colloid can be added to the dispersion (the concentration of the fiber treating agent in the dispersion is 0.01 to 90% by weight, preferably 0.1 to 70% by weight).
  • Fiber-treating agent of the present invention, the solution or dispersion, dimethyl ether and C o 2 it is Rukoto used as aerosol compositions' containing a combination of propellants such as liquefied petroleum gas.
  • the fiber treating agent of the present invention may be brought into contact with the fiber in the above-described form.
  • the contact treatment method is, for example, a dipping method, a coating method, a spray method, or a treatment method in a washing machine.
  • the fibers can be in various forms such as yarns, woven fabrics, nonwoven fabrics, sheet fiber products, clothing, and other products.
  • the treatment agent contained in the treatment liquid precipitates on the fiber surface, and a thin polymer film is formed.
  • the fiber treating agent of the present invention since the organopolysiloxane chain is excellent in the precipitation property on the fiber surface from the treating solution, the thin polymer on the fiber surface even from a low concentration treating solution. The formation of a coating is possible.
  • the fiber treated with the fiber treating agent of the present invention has excellent flexibility and resilience or shape retention, and also has excellent lubricity (slipperiness). It is shown.
  • the fiber treatment agent of the present invention is applied to impart the above-mentioned flexibility, resilience, lubricity, shape retention, etc. to the fibers, and also to improve the slipperiness of the yarn during the sewing process. It is applied as a fiber treatment agent.
  • the first cosmetic of the present invention is characterized in that the film-forming agent contained therein is soluble in water-soluble and / or alcohol-containing first side chains containing an organosiloxane polymer.
  • the copolymer constituting the film-forming agent is obtained by radically copolymerizing a silicone macromonomer having a vinyl group at one end and a water-soluble and z- or alcohol-soluble Macmouth monomer having a butyl group at one end. Can be obtained.
  • the silicone-based mac-mouth monomer is conventionally known, and a monomer represented by the following general formula (31) can be used.
  • This silicone-based macromonomer provides a side chain composed of an organosiloxane polymer.
  • CH 2 CD
  • E indicates one COO—, one CO—, or —O—.
  • the B represents a divalent organic group.
  • the divalent organic group include an alkylene group, an alkylene group having a hetero atom such as an oxygen atom, a nitrogen atom, and a zeo atom in a main chain; an alkylene group including an arylene group such as a phenylene group in a main chain; Various aliphatic groups such as an alkylene group containing a carbonyloxy group or an oxycarbonyl group in the chain are included.
  • one or both terminal atoms of the organic group can be hetero atoms such as oxygen, nitrogen, and zeo atoms in addition to carbon.
  • these organic groups may have a hydroxy group ⁇ alkoxy group, an alkyl group, or the like as a substituent. The following can be illustrated as specific examples of the divalent organic group B.
  • b is 0 or 1; P is 1 to 8; S is 0 to 12; v is 0 to 12; w is 0 to 12; X is 0 to: L 2; The numbers 0 to 12 are indicated.
  • R, R 6 and RR 8 represent hydrogen or an alkyl group having 1 to 12 carbon atoms.
  • L represents any divalent aliphatic group selected from the formulas (1) to (6).
  • RR 2 , R 3 , R 4 and R 5 may be the same or different and represent a methyl group, an optionally substituted phenyl group or an alkoxy group.
  • the portion represented by represents an organosiloxane polymer.
  • the water-soluble and / or alcohol-soluble Macguchi monomers are well known in the art.
  • the method for synthesizing such a macromonomer is described in detail in, for example, “Chemistry and Industry of Macromonomer” (IPS Publishing Division), pp. 39-71.
  • As the alcohol-soluble macromonomer those represented by the following general formula (34) can be preferably used.
  • This alcohol-soluble macromonomer provides a side chain consisting of an alcohol-soluble polymer.
  • A, B, p, and m have the same meanings as those described for the general formula (31). Having.
  • F represents —S—, —O—, or a divalent organic group represented by the following formula. ⁇ NN (35)
  • (G) q represents a water-soluble and Z- or alcohol-soluble polymer, and G represents a water-soluble and Z- or alcohol-soluble polymerizable monomer. q represents a number of 5 to 500.
  • the monomer G in particular, (meth) esterolinole acetic acid, vinylinole acetate, ethylene oxide, (meth) acrylic acid, bul alcohol, bulpyrrol
  • (meth) esterolinole acetic acid vinylinole acetate, ethylene oxide, (meth) acrylic acid, bul alcohol, bulpyrrol
  • (meth) acrylic acid bul alcohol, bulpyrrol
  • J in the general formula (34) represents a terminal group for terminating the polymerization reaction.
  • This terminal group is derived from a chain transfer agent, a polymerization initiator, a monomer, a solvent, and the like. Specific structures of such terminal groups are represented by the formulas (4) to (14) shown with respect to the general formula (2).
  • the film-forming agent used in the present invention is obtained by radically copolymerizing the silicone-based macromonomer with a water-soluble or Z- or alcohol-soluble mac-mouth monomer. If the amount is small, or if necessary, other copolymerizable ethylenically unsaturated monomers can be copolymerized.
  • the copolymer is hydrophilic.
  • the water-soluble ethylenically unsaturated monomer to be copolymerized include (meth) acrylic acid, N, N-dimethyl (meth) atarylamide, dimethylaminoethyl (meth) acrylate methyl chloride, and the like.
  • Grade salts dimethylaminoethyl (meth) atalylate monochrome mouth acetate, hydroxyxetil (meth) atalylate, atalylamide and the like.
  • the weight average molecular weight of the copolymer used as a film-forming agent in the present invention is 10,000 to 500,000, preferably 10,000 to 100,000.
  • the proportion of the monomer components constituting the copolymer is as follows: silicone macromonomer: 0.1 to 80 wt%, preferably 0.1 to 50 wt%, a water-soluble and / or alcohol-soluble Mac mouth monomer : 0.01 to 90 wt%, preferably 1 to 70 wt%. If the content of the silicone-based macromonomer (organosiloxane polymer) in the copolymer is less than the above range, the oil resistance and moisture resistance of the film formed from the copolymer will be insufficient and the lubricity will be low.
  • the copolymer film will have poor removability, and will not be dissolved in shampoo or soap solution. If the content of the water-soluble and / or alcohol-soluble macromonomer (water-soluble and / or alcohol-soluble polymer) is less than the above range, the film-forming property of the copolymer will be poor, while the content will be more than the above range. If so, a copolymer film satisfying both oil resistance and moisture resistance cannot be obtained.
  • the second side chain The water-soluble and / or alcohol-soluble polymer used as the polymer can be used to efficiently form the organosiloxane polymer, which is the first side chain, on the solid surface when the copolymer is applied from the cosmetic to the solid surface to form a film. It has the effect of separating. Therefore, even if the water-soluble and / or alcohol-soluble polymer chain has a low content of the organosiloxane polymer chain, the surface characteristics (moisture resistance, water resistance, oil resistance, lubricity, lubricity, lubricity) of the organosiloxane polymer are low. , Etc.).
  • the content of the organosiloxane polymer can be varied over a wide range according to the type of the solvent of the cosmetic, and the content is specified to be 50% by weight or less.
  • the content is specified to be 50% by weight or less.
  • the coating on the solid surface formed of such a copolymer can be easily removed from the solid surface by a cleaning agent such as soap shampoo.
  • the copolymer of the present invention When the copolymer of the present invention is blended into an aqueous-based cosmetic, it is preferable to use a copolymer having high solubility in water as the copolymer.
  • the content of the organosiloxane polymer in the copolymer is preferably set in the range of 0.1 to 50 wt%.
  • a water-soluble monomer such as methacrylic acid or acrylic acid, a sodium salt or a potassium salt thereof be contained as a copolymer component in the main chain of the copolymer.
  • the content of the water-soluble butyl monomer in the copolymer is preferably in the range of 20 to 99.9 wt%, more preferably 40 to 99.9 wt%.
  • the copolymer used as a film-forming agent in the present invention can be produced by a usual radical polymerization method. Examples of the radical polymerization method in this case include solution polymerization, suspension polymerization, and emulsion polymerization, and the solution polymerization method can be advantageously used.
  • a polar organic solvent can be used in the form of a mixture with water. Examples of the polar organic solvent include ethanol, propanol, acetone, and ethyl acetate.
  • a radical polymerization initiator is used.
  • 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-Dimethylvaleronitriol), 2,2,1-azobis (4-methoxy-1,2,4-dimethylinovaleronol relonitrile, dimethinole 2,2'azobisisobutyrate, 2,2'-azobis Azo compounds such as —methylbutyronitrile) and 1,1′—azobis (1-cyclohexanecarbonitrile) are also suitable, and organic peroxides such as t-dibenzoylperoxide are used. may be. these initiators to the total monomers of all, 0.
  • the polymerization reaction is preferably carried out at 30 to 100 ° C., preferably 50 to 90 ° C., for 1 to 10 hours under an atmosphere of an inert gas such as nitrogen. It is appropriately selected according to the type of the polymerization initiator and the type of the monomer solvent.
  • the second cosmetic of the present invention is characterized in that the film-forming agent contained therein comprises a hydrophilic segment (AJ and a hydrophobic monomer) having a hydrophilic monomer as a repeating unit.
  • a copolymer comprising a main chain (A) comprising a hydrophobic segment (A 2 ) having one repeating unit and a side chain (B) containing an organosiloxane polymer bonded to the main chain. It becomes.
  • the side chain (B) can bind to one or both of the segments (A and (A 2 ).
  • hydrophilic monomer forming the hydrophilic segment various types of conventionally known hydrophilic monomers are used. Specific examples of such a material include, for example, the various water-soluble monomers described above for the first film-forming agent.
  • the hydrophilic monomers are used alone or in the form of a mixture of two or more.
  • the polymerization degree of the hydrophilic monomer is 5 to 700, preferably 5 to 500.
  • Examples of preferred hydrophilic monomers are as follows.
  • (Meth) acrylic acid or its alkali neutralized product N, N-dimethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl Methyl chloride quaternary salts of dialkylaminoalkyl (meth) acrylates such as (meth) acrylates or acetate salts thereof; maleic acid or a neutralized product thereof; maleic anhydride or a salt thereof Neutralized product; (meth) acrylamide; vinylinoleanol, bulpyrrolidone, maleimide, bulpyridine, and the like.
  • hydrophobic monomer that forms the hydrophobic segment various types of conventionally known monomers can be used. Specific examples of such are linear or branched Alkyl (meth) acrylates having 1 to 18 carbon atoms, styrene, vinylinole acetate, polymethylstyrene, t-butylinolestyrene, butadiene, cyclohexadiene, ethylene, vinylinolenolene, Silicon macromonomer and the like can be mentioned.
  • a (meth) acrylate of a lower alcohol having 1 to 4 carbon atoms is particularly preferred.
  • the degree of polymerization of the hydrophobic monomer is from 5 to 70,000, preferably from 5 to 5000.
  • the organosiloxane polymer forming the side chain (B) is one that binds to the main chain (A) via a binding group.
  • the degree of polymerization n of the organosiloxane polymer is from 2 to 500, preferably from 10 to 300.
  • the side chain (B) containing the organosiloxane polymer one represented by the following general formula (36) can be used.
  • X is a bonding group, —COO—, one CRiR 2 — (Ri and R 2 represent hydrogen or a lower alkyl group), one NH—, —CONH—, one NHCO—, one CO— , One OCO—, one NHCOO—, one OCONH— and the like.
  • B, RR 2 , R 3 , R 4 , P, m and n have the same meanings as those described for the general formula (31) representing the silicone macromonomer.
  • the weight average molecular weight of the copolymer is from 5,000 to 5,000,000, preferably from 10,000 to 100,000.
  • the ratio of the organosiloxane polymer is 1 to 80 wt%, preferably 1 to 5 wt%, and the hydrophilic segment (the ratio of A is 1 to 95 wt%, preferably 1 to 95 wt%. 0-90 wt%, the proportion of the hydrophobic segment (A 2 ) is 1-90 wt%, preferably:!-70 wt%.
  • the proportion of the side chain (B) containing the organosiloxane polymer in the copolymer is less than the above range, the oil resistance and the moisture resistance of the film formed from the copolymer become insufficient and the lubricity
  • the amount is more than the above range, the removability of the copolymer film will be poor, and the copolymer film will not be dissolved in shampoo or soap solution.
  • the proportion of the hydrophilic segment (AO is less than the above range, the removal of the copolymer film becomes poor, and when the copolymer film is removed in shampoo, soap, etc., the removal is performed smoothly.
  • the copolymer can be produced by various conventionally known methods, and the method is described below.
  • the polymerization reaction in this case can be represented by the following formula.
  • A is a bullet monomer
  • B is a silicone macromonomer
  • R is an alkyl group
  • n and m indicate the number of moles of each monomer polymerized.
  • the terminal of the copolymer is changed to a mercapto group (-SH) by transesterifying the copolymer obtained as described above with alcohol (RiOH) in the presence of an acid or alkali ( Reaction 2).
  • the reaction in this case is represented by the following equation.
  • reaction product obtained above was added to a monomer having a property opposite to that of the monomer used in Reaction 1, for example, the monomer used in Reaction 1 was added. If is hydrophilic, use the hydrophobic vinyl monomer in reaction 1 In the case where the prepared butyl monomer is a hydrophobic butyl monomer, a hydrophilic butyl monomer is added, and if necessary, a silicone macromonomer is added to carry out a polymerization reaction (reaction 3).
  • the silicone macromonomer does not necessarily need to be added in the step of the reaction 1, but can be added and reacted in the step of the reaction 3.
  • a copolymer of a water-soluble butyl monomer and a hydrophobic butyl monomer is obtained in the same manner as in the first method without using a silicone macromonomer (reaction 1).
  • a water-soluble monomer having a reactive functional group such as a hydroxyl group, an amino group, an imino group, a carboxyl group, an epoxy group, or an isocyanate group is used.
  • a functional group having reactivity with the reactive functional group contained in the copolymer for example, an epoxy group, an isocyanate group, a hydroxyl group, an amino group,
  • An organosiloxane polymer having an imino group, a carboxyl group, or the like at one end is reacted to bind the organosiloxane polymer-containing group represented by the general formula (36) (reaction 2).
  • Macroazo initiators (Akira Ueda et al., Polymers, 33, 131-140 (19776)) in the presence of radical monomers and silicone macromonomer radical polymerization (reaction 1)
  • the macroazo initiator is an azo-type polymer polymerization initiator having a plurality of azo groups in a polymer chain.
  • Makuroazo initiator relative to the total monomers, 0. 0 0 1 to 2.0 moles 0/0, preferably used is 0. 0 1 to 1.0 at a ratio of moles 0/0.
  • a vinyl monomer having the opposite property to that of the vinyl monomer obtained in Reaction 1 is added to the obtained copolymer, and if necessary, a silicone macromonomer is added to perform a radical polymerization reaction.
  • a copolymer of a hydrophilic butyl monomer and a hydrophobic butyl monomer is obtained in the same manner as in the third method without adding a silicone macromonomer (reaction 1).
  • organosiloxane polymer having a reactive functional group having a reactivity with the reactive functional group at one end thereof is reacted with the reactive functional group contained in the copolymer to obtain the compound represented by the general formula
  • the organosiloxane polymer-containing group represented by (36) is bonded (reaction 2).
  • the radical polymerization in the first method to the fourth method is performed by a conventionally known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Good.
  • a conventionally known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.
  • examples of the organic solvent include ethanol, propanol, acetone, ethyl acetate, dioxane and the like. In particular, use of ethanol, propanol, acetone and dioxane is preferred. Also, an appropriate amount of water can be added to the organic solvent.
  • the radical polymerization initiator and the polymerization reaction conditions The ones shown above can be adopted.
  • the third cosmetic of the present invention is characterized in that the film-forming agent contained therein comprises an organopolysiloxane-containing polysaccharide compound composed of a main chain composed of a polysaccharide compound and a side chain composed of an organopolysiloxane. It becomes.
  • an organopolysiloxane-containing polysaccharide compound has already been described in detail in the description of the third fiber treating agent.
  • the fourth cosmetic of the present invention is characterized in that the film-forming agent contained in the cosmetic comprises an organopolysiloxane-containing protein compound composed of a main chain composed of a protein compound and a side chain composed of an organopolysiloxane. It is.
  • organopolysiloxane-containing protein compound has already been described in detail in the description of the fourth fiber treatment agent.
  • the film-forming agent is a first silicone-based monomer (a) represented by the general formula (S-1) and a general formula (S-2) It consists of a radical copolymer of a second silicone monomer (b) and a hydrophilic butyl monomer (c), and the first silicone monomer (a) and the second silicone monomer (a) contained in the copolymer.
  • (a) / (b) is in the range of 10/1 to 1 Z4, and the content of unreacted silicone monomer is in the range of 0 to 25%. It is composed of a silicone-based copolymer.
  • the content of the polymer compound containing an organosiloxane as a side chain in the cosmetic is 0.01. To 40 wt%, preferably 0.1 to 20 wt%.
  • Cosmetic products are water-based, ethanol-based, water / ethanol-based, water-Z multivalent alcohol (eg glycerin, alkylene glycol, etc.), organic solvents
  • the cosmetic according to the present invention has excellent film-forming properties because it contains the special polymer as a film-forming agent, and the polymer film formed by using the cosmetic is water-soluble and ethanol-soluble. Because of its properties, it has excellent film-removability and can be washed and removed with shampoo, soap, etc. In addition, this polymer film has excellent properties such as moisture resistance, adhesion, and lubricity. In particular, when the cosmetic of the present invention is used as a hair cosmetic, it is possible to give the hair an excellent feel after use, and to impart the hair with a comb-shaping power, a set holding power, a lubricating property, etc. it can.
  • the film-forming agent used in the present invention has excellent viscosity, it can be incorporated into cosmetics in the form of various creams and gels. Further, since the film-forming agent has water solubility and ethanol solubility, the cosmetic of the present invention is blended with various types of base cosmetics such as an aqueous base, an ethanol base and a water ethanol base. be able to.
  • the cosmetics of the present invention include shampoos, rinses, hair sprays, set forms, set lotions, genoles, mayukiyukia, mascara, and creams.
  • As an eyeliner or the like it can be applied in the form of a water-soluble, aqueous alcoholic solution, emulsion, cream, gel or the like. .
  • the organopolysiloxane-containing polysaccharide compound and the organopolysiloxane-containing protein compound according to the present invention have good film-forming properties, water repellency, lubricity, and gloss imparting properties unique to organopolysiloxanes. It has lubricity (smoothness, smoothness, etc.) that siloxane does not have, and has no shortcomings of the coating, which is a drawback of organopolysiloxane, and can be used advantageously as a fiber treatment agent. It is suitable as a film-forming agent. In addition, since it is made of natural products, it has excellent biodegradability and does not impair the natural environment.
  • the treatment agent contained in the treatment liquid precipitates on the fiber surface, and a thin polymer film is formed.
  • the formation of a thin polymer film on the fiber surface can be achieved even from a low-concentration processing solution because the organopolysiloxane chain is excellent in the deposition property on the fiber surface from the processing solution. It is possible.
  • the fiber treated with the organopolysiloxane-containing polymer compound has excellent flexibility and resilience or shape retention, and also has excellent lubricity (slipperiness), and excellent texture and feel. It shows.
  • the organopolysiloxane-containing polymer compound according to the present invention is used for imparting the above-mentioned flexibility, resilience, lubricity, shape-retaining property, etc. to the fibers, and also for the yarn slipping during the sewing process. It is applied as a fiber treatment agent for improving the resilience.
  • the cosmetic containing a polysaccharide compound or a protein compound containing an organopolysiloxane according to the present invention has the following features. .
  • the compound When adding a synthetic silicone graft polymer such as an ataryl-butyl compound to cosmetics, the compound is added in an amount of 10% by weight or more (preferably 20% by weight or more) in order to sufficiently exhibit the properties of the compound. Although it is necessary to add the compound of the present invention, sufficient addition effect can be obtained even if it is added at less than 0.5% by weight. Therefore, the solubility, the solution physical properties, the feeling of use in a solution state, etc. of the natural polymer are not sufficient. It maintains excellent properties and can exhibit excellent properties unique to silicone when forming a film after drying.
  • a synthetic silicone graft polymer such as an ataryl-butyl compound
  • the silicone copolymer according to the present invention since the amount of the unreacted silicone-based monomer contained therein is small, bleeding of the unreacted silicone-based monomer from the coating film hardly occurs. That series There is an advantage that a special purification step for removing the corn monomer is not required.
  • the copolymer of the present invention since the copolymer of the present invention is soluble in water or a surfactant, a coating film containing the copolymer can be easily removed by the water or the surfactant.
  • the organopolysiloxane-containing polymer compound of the present invention includes: hair cosmetics such as shampoos, rinses, conditioners, mousses, and mist; skin cosmetics such as body shampoos and creams; It can be advantageously used as a film-forming component such as, for example, and is also advantageously applied as a coating agent for various solid surfaces such as paper, metal, wood, glass, fiber, and plastic.
  • IPA isopropanol
  • A has a mixture of 0.5 parts of 2,2'-azobis (2-methylbutyronitrile) and 30 parts of IPA in B.
  • This vinyl polymer had a weight-average molecular weight of about 130,000 and was soluble in alcohols (ethanol and isopanol).
  • the structural formula of the silicone macromonomer A is as shown in the following formula (41).
  • CH 2 C CH;
  • the vinyl polymer thus obtained had a weight average molecular weight of about 250,000 and was soluble in water and alcohol.
  • the structural formulas of the silicone macromonomer (B) and the polybutyl acrylate monomer used as raw materials are as follows.
  • the weight average molecular weight of the obtained vinyl polymer was about 300,000, and this vinyl polymer was soluble in anolecol.
  • the structural formulas of the silicone macromonomer (C) and polyethyl methacrylate monomer used in the raw materials are as follows.
  • Silicone-based macromonomer (D) (Molecular weight about 1,000) 30 parts, polymethyl acrylate macromonomer (Molecular weight about 6,000) 20 parts, Acrylic acid 50 parts, Reference example except that toluene was used as solvent The experiment was performed as in 1.
  • the weight average molecular weight of the vinyl polymer thus obtained was about 68,000, which was soluble in water and alcohol.
  • the structural formulas of the silicone macromonomer (D) and polymethyl acrylate macromonomer used as raw materials are as follows.
  • the structural formulas of the silicone macromonomer (F) and the poly (methyl methacrylate) used as raw materials are as follows.
  • a mixture of 30 parts of butyl methacrylate, 20 parts of methacrylic acid and 20 parts of hydroxyshethyl and 50 parts of acrylic acid was used as a raw material to be dropped from the dropping port B, and the amount of the solvent (IPA) used was 200 parts.
  • a bullet polymer was produced in exactly the same manner as in Example 1.
  • a mixture of 7 parts of sodium hydroxide and 10 parts of water is added to the bull polymer to dissolve uniformly, and a silicone compound (G) having a molecular weight of about 10,000 represented by the following formula (46) is added to the solution. ) 6 parts were added, the reaction temperature was set to 50 ° C, and the mixture was reacted with stirring for 7 hours.
  • REFERENCE EXAMPLE 10'Purified water (233 parts) was placed in the same reactor as used in Reference Example 1, and 8 parts of the carotinated starch was dissolved therein. The air was replaced with nitrogen.
  • 1.1 parts of 2,2-azobis (N, N-dimethyleneisobutyrodiamidine) hydrochloride and a silicon-based macromonomer having a weight average molecular weight of about 200,000 [formula (41)] N 266 in the above) 26 parts was dissolved in 148 parts of butyl acetate to obtain a uniform liquid.
  • An aqueous emulsified dispersion was prepared by dispersing and emulsifying the above-mentioned homogeneous solution in 70 parts of purified water using a homomixer with 1 part of polyethylene dalicol monooleyl ether having a polymerization degree of 23 as an emulsifier.
  • the aqueous solution in which the cationized starch was dissolved was kept at 80 ° C. with stirring, and the aqueous emulsified dispersion was dropped from the dropping funnel over 4 hours, and the temperature was kept at 80 ° C. after completion of the dropping.
  • the polymerization was continued with stirring for 2 hours. After a lapse of 2 hours, the liquid temperature was raised to room temperature to terminate the polymerization reaction. As a result, an aqueous dispersion in which a butyl polymer having an organopolysiloxane oxane side chain was dispersed was obtained.
  • An aqueous emulsified dispersion was prepared.
  • cationized cellulose was used instead of cationized starch for the protective colloid.
  • an aqueous dispersion was prepared in exactly the same manner as in Reference Example 10. The behavior of the contents of the reactor during the polymerization reaction and the state of the generated aqueous dispersion were the same as those of Reference Example 10. there were.
  • the weight average molecular weight of the bullet polymer dispersed therein was about 1.8 million, and the content of the polymer in the dispersion was 37%.
  • a commercially available fiber treatment agent of Comparative Example 1 was prepared by diluting commercially available bulemarjion acetate (manufactured by Kanebo, trade name: Odozol, polybutyl acetate content: 40%) with purified water to 2%.
  • Example 1 An aerosol product was prepared by filling an aerosol can with various stock solutions containing 2 g of a fiber treating agent in a solvent of 60 milliliters per liter together with a propellant. In this case, the stock solution ratio was 60 Z The aerosol product contained 2 g of a fiber treating agent (polymer) of 100 milliliters per volume of the stock solution and the propellant. Table 2 shows the contents of the manufactured aerosol products.
  • Test cloth A Acryl
  • Test cloth B Tetron Z cotton blend
  • Test cloth C Nylon
  • Test cloth D Cotton broad (# 60)
  • test cloths A to C were used after pre-treating 1 kg of the cloth with 10 milliliters of perchlorethylene for 30 minutes using a dry cleaning tester (manufactured by Tester Sangyo Co., Ltd.).
  • test cloth D 1 kg of cloth was washed with 25 g of powder detergent (HITOP: manufactured by Lion) using a household washing machine, and this was used as test cloth.
  • HITOP powder detergent
  • Cationized starch (addition reaction of glycidyltrimethylammonium chloride to starch) 20 g of water, 20 g of water, 0.3 g of sodium hydroxide, and 8 Og of isopropyl alcohol (IPA) After dispersing in the resulting solution, the mixture was stirred at 75 to 80 ° C for 30 minutes. Next, this liquid was cooled to 50 ° C, 8 g of an organopolysiloxane represented by the following formula (51) was added, and the mixture was stirred for 7 hours to obtain a dispersion, which was cooled to room temperature. Then, the mixture was neutralized, and the solid content was recovered by filtration. This solid content is washed with IPA and dried, and the organopolysiloxane groups are graft-bonded via the hydroxyl groups in the starch. The resulting cationized starch was obtained.
  • IPA isopropyl alcohol
  • the weight average molecular weight of the cationized starch containing the organopolysiloxane was about 50,000, and the content of the organopolysiloxane was 1.0%.
  • the compound was soluble in water.
  • Reference Example 22 The experiment was carried out in the same manner as in Reference Example 21 except that hydroxyxethyl starch was used instead of the cationized starch.
  • the weight average molecular weight of the obtained organopolysiloxane-containing hydroxyshethyl starch was about 100,000, and the organopolysiloxane content was 2.0%.
  • the compound was soluble in water and a 50% aqueous ethanol solution.
  • the weight average molecular weight of the obtained organopolysiloxane-containing guar gum was about 250,000, and the organopolysiloxane content was 4.5%.
  • the compound was soluble in water and an aqueous solution of 15% lauryl polyoxyethylene sulfate sodium salt.
  • the weight average molecular weight of the obtained organopolysiloxane-containing chitosan was about 120,000, and the organopolysiloxane content was 15%.
  • the compound was soluble in water and an aqueous solution of 15% lauryl polyoxyethylene ester sodium salt.
  • Dissolve 20 g of gelatin produced by the acid treatment method (weight average molecular weight: about 150,000, isoelectric point pH: 7 to 9) and 0.5 g of sodium hydroxide in 50 g of water at 40 ° C.
  • 50 g of water was mixed, and 500 milliliters of IPA was added to reprecipitate the polymer.
  • This reprecipitation operation was repeated twice, followed by washing with IPA and drying to obtain gelatin in which an organopolysiloxane group was graft-bonded via an amino group.
  • the weight average molecular weight of the organopolysiloxane-containing gelatin was about 170,000, and the organopolysiloxane content was 11%.
  • the compound was soluble in ethanol and dissolved in water at a temperature of 35 ° C or less without gelation. Therefore, this is useful as a non-gelling gelatin.
  • Hydrolyzed collagen (weight average molecular weight: about 150, 000, isoelectric point pH: 7 to 9) is used instead of gelatin, and has the same structure as the compound of formula (51) shown in Reference Example 21.
  • the weight average molecular weight of the thus obtained organopolysiloxane-containing collagen was about 17,000, and the organopolysiloxane content was 10% by weight.
  • the compound was soluble in water and 5% aqueous ethanol.
  • the organopolicy The weight-average molecular weight of the hydroxypropyl starch containing oxane was about 1,000,000, and its organopolysiloxane content was 8%.
  • the compound was soluble in water and a 50% aqueous ethanol solution.
  • the hydroxyl group in the starch molecule reacts with the chlorine atom and a part of the epoxy group in the epichlorohydrin molecule to synthesize starch having an epoxy group as a reactive group and a partial chlorine atom in the molecule.
  • 20 g of water, 80 g of IPA and 6 g of an organopolysiloxane having the following structure (compounds A to H) were added to the solid, and the mixture was stirred at 50 ° C for 5 hours. The solid was recovered by filtration, washed with IPA and dried. In this way, the organopolysiloxane group is interposed through the spacer compound.
  • Table 5 shows the molecular weight, etc., of the products grafted to the hydroxyl groups in the starch.
  • the mixture was cooled to room temperature, neutralized with dilute hydrochloric acid, mixed with about 2 liters of IPA, and the precipitated solid was washed with IPA and dried.
  • an organopolysiloxane-containing cationized starch having an organopolysiloxane group graft-bonded via a hydroxyl group in the cationized starch was obtained.
  • the weight average molecular weight of this organopolysiloxane-containing cationized starch was about 30,000, and the organopolysiloxane content was 0.2%.
  • cationized guar gum obtained by adding glycidyltrimethylammonium chloride to guar gum and 0.3 g of sodium hydroxide were dispersed in 105 g of an 80% IPA aqueous solution.
  • 0.5 g of a polysiloxane having the same structure as that used in the above and having a molecular weight of about 30,000 (n 403) was mixed and stirred at 50 ° C. for 2 hours. The mixture was cooled to room temperature, neutralized with dilute hydrochloric acid, filtered to remove the liquid, and the solid was washed 5 times with about 100 milliliters of IPA and dried.
  • organopolysiloxane-containing guar gum in which the organopolysiloxane groups were graft-bonded via the hydroxyl groups in the guar gum was obtained.
  • This Olga The guar gum containing nopolysiloxane has an average molecular weight of about 250,000, and its organopolysiloxane content is 0.05. /. Met. ⁇ Reference example 3 1
  • Table 6 shows the molecular weight and the organopolysiloxane content of the reaction product obtained by graft-bonding the organopolysiloxane group to the hydroxyl group in the starch via the spacer compound.
  • a fiber treatment agent of Comparative Example 21 was prepared by diluting commercially available bulemarjion acetate [manufactured by Kanebo, trade name: Dodozol, polyvinyl acetate content: 40%] to 2% with purified water.
  • a 40% aqueous dispersion of 311—200 was used as the fiber treating agent of Comparative Example 23.
  • SH-200 is dimethylpolysiloxane made by Torre's silicone.
  • An aerosol can was prepared by filling an aerosol can with various stock solutions containing 2 g of a fiber treating agent together with a propellant at 60 milliliters of solvent.
  • the stock solution Z propellant ratio was set at 60 to 40 (volume ratio).
  • This aerosol product contained 2 g of a fiber treatment agent (polymer), 100 ml of the stock solution and the propellant volume. Table 7 shows the contents of the aerosol products produced in this way.
  • the aerosol product was sprayed uniformly on the following test cloths (20 cm x 20 cm) for 4 seconds, and then placed in a thermo-hygrostat at a temperature of 25 ° C and a relative humidity of 50% for 6 hours and dried.
  • Table 8 shows the results of sensory evaluation of the test cloth treated in this manner.
  • Test cloth A Acryl
  • Test cloth B Tetron / cotton blend
  • Test cloth c Nail
  • Test cloth D Cotton broad (# 60)-Of the test cloths, for test cloths A to C, use a dry cleaning tester (manufactured by Tester Sangyo Co., Ltd.) and weigh 1 kg of cloth with 10 milliliters of perchlor ethylene. It was pretreated for 30 minutes before use.
  • test cloth D 1 kg of cloth was washed with 25 g of powder detergent (HITOP: manufactured by Lion) using a household washing machine, and this was used as test cloth. After being air-dried, each test cloth was cut into 20 cm ⁇ 20 cm before use.
  • the sensory evaluation of the treated test cloth was performed according to the following criteria for two items: rigidity, ironing, and texture.
  • the average molecular weight of the copolymer obtained as described above was about 110,000 in terms of weight average molecular weight.
  • CH 2 C CH 3 CH 3
  • Macromonomer (II) (Molecular weight about 30,000) 48 parts by weight,
  • the weight average molecular weight of the copolymer thus obtained was about 350,000.
  • CH 2 C CH 3 CH 3
  • PDMS macromonomer (III) (molecular weight about 1,000) 30 parts by weight, polymethyl acrylate macromonomer (molecular weight about 6,000) 20 parts by weight, acrylic acid 50 parts by weight, except that toluene was used as a solvent An experiment was performed in the same manner as in Reference Example 41.
  • the weight average molecular weight of the copolymer thus obtained was about 68,000.
  • the structural formulas of the PDMS macromonomer (III) and the polymethyl acrylate macromonomer are as follows.
  • CH 2 C CH 3 CH 3
  • a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer was charged with 95 parts by weight of isopropanol, and after introducing nitrogen gas, the flask was heated and heated, and replaced with nitrogen for one hour. I do.
  • 0.5 parts by weight of poly (hexamethylene 'azobiscyananopentanoic acid) and 30 parts by weight of isopropanol were placed in a dropping funnel (referred to as dropping funnel A), and ethyl acrylate was added to another dropping funnel (referred to as dropping funnel B). 5 parts by weight and 15 parts by weight of a silicone mac mouth monomer having the following structure were added.
  • the contents of the dropping funnel AB were dropped over 1 hour to polymerize.
  • the reaction was terminated by cooling to room temperature, and the reaction mixture was poured into a Teflon coat pan and dried under vacuum to remove unreacted monomer with isopropanol. Dissolve this in 95 parts by weight of isopropanol again
  • the temperature of the flask is increased by heating and the atmosphere is replaced with nitrogen for 1 hour.
  • 80 parts by weight of methacrylic acid and 30 parts by weight of isopropanol were placed in a dropping funnel (referred to as dropping funnel C), and the mixture was dropped and polymerized over 2 hours.
  • the average molecular weight by weight of the copolymer thus obtained was about 37,000, and it was confirmed that this copolymer exhibited water solubility and ethanol solubility.
  • Reference Example 45 95 parts by weight of isopropanol was charged into a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer.After introducing nitrogen gas, the flask was heated and heated. Replace with nitrogen for 1 hour. Meanwhile, dripping 0.5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) and 30 parts by weight of isopropanol are placed in a funnel (referred to as dropping funnel A), and dimethylamino is added to another dropping funnel (referred to as dropping funnel B).
  • dropping funnel A a funnel
  • dropping funnel B dimethylamino is added to another dropping funnel
  • dropping funnel C a dropping funnel
  • the average weight molecular weight of the copolymer thus obtained was about 180,000, and it was confirmed that this copolymer exhibited water solubility and ethanol solubility.
  • the contents of the dropping funnels A and B were added dropwise over 2 hours and polymerized.
  • the reaction was terminated by cooling to room temperature, and the reaction mixture was poured into a Tef-N-neck pan and dried under vacuum to remove unreacted monomer with isopropanol. This was re-dissolved in 95 parts by weight of ethanol and 5 parts by weight of purified water, 0.5 parts by weight of p-toluenesulfonic acid was added, and the mixture was heated at 70 ° C for 1 hour. After introducing nitrogen gas, the flask is heated and heated, and nitrogen is replaced for 1 hour.
  • dropping funnel C 5 parts by weight of methyl methacrylate and 30 parts by weight of ethanol were placed in a dropping funnel (referred to as dropping funnel C), and the mixture was dropped and polymerized over 2 hours. Further, 10 parts by weight of a polysiloxane having the following structure was added, and the mixture was heated at 70 ° C. for 1 hour.
  • the average molecular weight of the copolymer obtained in this way was about 320,000, and it was confirmed that this copolymer exhibited water solubility and ethanol solubility, CH 2 CH 2
  • Reference example 4 7 Charge 95 parts by weight of isopropanol to a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer. After the introduction of nitrogen gas, the temperature of the flask is increased by heating, and nitrogen replacement is performed for 1 hour. On the other hand, 0.5 parts by weight of poly (hexamethylene 'azobiscyananopentanoic acid) and 30 parts by weight of isopropanol were placed in a dropping funnel (referred to as dropping funnel A), and methyl acrylate was added to another dropping funnel (referred to as dropping funnel B).
  • dropping funnel A a dropping funnel
  • dropping funnel B methyl acrylate was added to another dropping funnel
  • a silicone macromonomer having the following structure.
  • the contents of the dropping funnels A and B were added dropwise over 1 hour to carry out polymerization.
  • the reaction was terminated by cooling to room temperature, and the reaction mixture was poured into a Teflon coat pan and dried under vacuum to remove unreacted monomer with isopropanol. This was dissolved again in 95 parts by weight of isopropanol, and after introducing nitrogen gas, the flask was heated and heated and replaced with nitrogen for 1 hour. 80 parts by weight of bulpyrrolidone was added to a dropping funnel (referred to as dropping funnel C).
  • Copolymer A of the present invention (Reference Example 41) 0% cetyl alcohol 5% stearyl alcohol 0% stearyl trimethylammonium chloride 07% glycerin 30% fragrance
  • Copolymer A of the present invention (Reference Example 41) 80% liquid paraffin 50% polyoxyethylene hydrogenated castor oil
  • Copolymer of the present invention C (Reference Example 43) 100% Nitrocellulose 100% Ethyl acetate 200% butyl acetate 150% Ethinoleanoreconore 50% Toluene 350% Pigment
  • Copolymer D of the present invention (Reference Example 45) 0% cetyl alcohol 5% stearyl alcohol, 0% stearyl trimethylammonium chloride 07% glycerin 30% fragrance
  • Copolymer D of the present invention (Reference Example 45) 8.0% liquid paraffin 5.0% polyoxyethylene hydrogenated castor oil
  • the hair foams shown in the above Examples 23 and 28 and the commercially available film-forming resin for hair styling agents were used as follows. Evaluation by feeling was performed.
  • the hair foam of Example 3 After wetting a hair bundle of 18 cm in length and 1.5 g in weight with water, the hair foam of Example 3, the hair foam of Example 8, and a commercially available hair-forming agent film-forming resin Don / Butyl acetate copolymer) was applied in an amount of 2 g each, wound on a rod having a diameter of 2 cm, and air-dried. After drying, the rod was removed from the hair, and the sliding and setting power were evaluated by five expert panelists. The collapse of this set was observed. This tress was washed with shampoo and evaluated for ease of washing off.
  • 0 is added to another dropping funnel (dropping funnel C), and a predetermined amount by weight of a water-soluble and / or alcohol-soluble macromonomer (second macromonomer) shown in Table 10 and a solvent 40 parts by weight were added.
  • the first macromonomer, the second macromonomer, and the vinylinomer were blended so that the total amount would be 150 parts by weight.
  • the contents of the dropping funnels A, B, and C were added dropwise over 2 hours, and the polymerization reaction was further continued for 2 hours while stirring.
  • the reaction was terminated by cooling to room temperature, the reaction mixture was poured into a Teflon coat pan, and the solvent was removed by drying under reduced pressure. After dissolving the solid in ethanol, the solid was purified by reprecipitation with n-hexane.
  • Comparative Reference Example 21 A copolymer having a first macromonomer content of 1 wt% was obtained in the same manner as in Reference Example 10 except that the second macromonomer was not used. Comparative Reference Example 22 In the same manner as in Reference Example 11 except that the second macromonomer was not used, a copolymer having a first Mac mouth monomer content of 3 wt% was obtained. Types of solvents used in Reference Examples 48 to 55 and Comparative Reference Examples 21 and 22, parts by weight of a polymerization initiator, wt% of the first macromonomer, wt% of the second macromonomer, and Table 10 shows wt%.
  • Table 11 shows the content of the first side chain (organosiloxane polymer) contained in each of the copolymers obtained in Reference Examples 48 to 55 and Comparative Reference Examples 21 and 22.
  • 2 shows the content of side chains (water-soluble and alcohol-soluble or alcohol-soluble polymers) and the weight average molecular weight of the copolymer.
  • the specific contents of the first macromonomer and the second macromonomer indicated by reference numerals in Table 10 are as follows. (1st Mac mouth monomer) Structural formula
  • CH 2 C CH 3 CH 3
  • Example 30 Measurement of Coefficient of Friction of Polymer Film and Evaluation of Lubricity
  • Reference Examples 48 to 55 and Comparative Reference Examples 21 After dissolving the copolymers of 1 to 22 in predetermined solvents shown in Table 12 (Concentration 5 to 10 wt%), apply this solution to a glass plate (8 x 5 cm) using a coater so that the thickness becomes 100 im im, and maintain constant temperature and humidity (25 ° C, 50%) And dried all day and night.
  • the lubricity of the film was evaluated by rubbing the film surface with a finger.
  • the effect is recognized when the content of the first side chain in Tests 1 to 4 is (0.1) wt% or more.
  • Tests 2-4 and 5-6 clearly show the effect of the second side chain.
  • Tests 9 and 11 to 12 show that when a film is formed from an aqueous system, it is preferable that the content of the first side chain is smaller. 2 6 Table 1 2
  • the copolymer solution obtained by the solution copolymerization reaction was added to ethyl acetate, and the copolymer was purified by precipitation.
  • the silicone monomer content in the copolymer was determined from its NMR measurement values. Then, the graft efficiency [G] of the silicone-based monomer was determined according to the following equation.
  • the unreacted silicone monomer content [W] was calculated by the following equation.
  • the copolymer solution obtained by the solution polymer reaction is further diluted with water and adjusted to 5 wt%, and the solution is adjusted to a thickness of 100 ⁇ m using a glass plate (8 ⁇ 5 cm). And dried all day and night at constant temperature and humidity (25 ° C, 50%).
  • Surface tester Shinto Kagaku Kogyo Co., Ltd., HEIDON 3K-314 A
  • a vertical load of 100 g, a steel ball with a diameter of 10 mm as a contact, a stage speed of 100 mm / min, a temperature of 25 ° C, and a humidity of 50% were applied to a glass plate.
  • the coefficient of static friction of polymer film was measured.
  • the glass plate coated with the copolymer used for measuring the coefficient of static friction is immersed in a 20 cm diameter petri dish containing water and left for 24 hours. After the standing, if there is any residual residue visually, a general surfactant such as sodium alkylsulfate was added, and the mixture was further left for 24 hours, and then visually judged according to the following criteria. ⁇ : None remains on the glass plate
  • the copolymer solution obtained by the solution polymer reaction is further diluted with water and adjusted to 5 wt%, and the solution is adjusted to a thickness of 100 m using a glass plate (8 x 5 cm). And dried all day and night at constant temperature and humidity (25 ° C, 50%).
  • a surface tester Shinto Kagaku Kogyo Co., Ltd., HEIDON 3K-34 ⁇
  • vertical load 100 g, steel ball 10 mm in diameter as a contact, stage speed 100 mmZm in 25
  • the coefficient of static friction of the copolymer film coated on the glass plate was measured under the conditions of ° C and a humidity of 50%.
  • the glass plate coated with the copolymer used for measuring the coefficient of static friction is immersed in a 20 cm diameter petri dish containing water and left for 24 hours. After the standing, if there is any residual residue visually, a general surfactant such as sodium alkylsulfate was added, and the mixture was further left for 24 hours, and then visually judged according to the following criteria. ⁇ : None remains on the glass plate
  • CH 2 C CH: CH;
  • CH 2 C CH: CH:
  • Example 41 The experiment was carried out in the same manner as in Example 41 except that the weights of the monomer (a) and the monomer (b) were changed as shown in Table 15, to obtain a copolymer solution.
  • Example 41 An experiment was conducted in the same manner as in Example 41 except that the type of the monomer (a) was changed to a monomer having the following structure.
  • the characteristic values of the copolymer in this case were as follows: [G]: 40%, [W]: 60%, the coefficient of static friction: 0.30, and the solubility: ⁇ .
  • CH 2 C CH;
  • Example 41 The monomer used in Example 41 was placed in a 500 ml four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer.
  • Example 41 The monomer used in Example 41 was placed in a 50-mL four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube, and a stirrer.
  • Example 16 The experiment was carried out in the same manner as in Example 51 except that the monomers (a), (b) and (c) shown in Table 16 were used, and the solvents shown in Table 16 were used. Table 16 shows the characteristic values of the obtained copolymer.
  • Each of the silicone copolymers obtained as described above could be advantageously applied as a fiber treating agent and a film forming agent for cosmetics.

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Abstract

Traitement de fibres à l'aide d'un composé polymère à chaînes latérales organopolysiloxane et cosmétique contenant le composé précité comme agent filmogène. Composés polysaccharidiques protéiques présentant chacun des chaînes latérales organopolysiloxane, et copolymère de silicone à chaînes latérales organopolysiloxane, ainsi que son procédé de production.
PCT/JP1995/000353 1994-03-03 1995-03-03 Traitement de fibres, cosmetique, compose polymère a chaines laterales organopolysiloxane et procede de production d'un copolymere de silicone WO1995023889A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP6/60335 1994-03-03
JP06033594A JP3778369B2 (ja) 1994-03-03 1994-03-03 繊維処理剤
JP7536994A JPH07268778A (ja) 1994-03-22 1994-03-22 繊維処理剤
JP6/75368 1994-03-22
JP7536894A JPH0770204A (ja) 1993-06-30 1994-03-22 オルガノポリシロキサンを含有する多糖化合物及び蛋白質化合物
JP6/75369 1994-03-22
JP6/169059 1994-06-28
JP16905994A JPH0769828A (ja) 1993-06-30 1994-06-28 化粧料
JP34024994A JP3507925B2 (ja) 1994-12-29 1994-12-29 シリコーン系共重合体
JP6/340249 1994-12-29

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WO1995023889A1 true WO1995023889A1 (fr) 1995-09-08

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318939A (en) * 1996-11-01 1998-05-06 Richard James Harvey Infra-red identification device
US6280748B1 (en) * 1998-06-12 2001-08-28 Dow Corning Toray Silicone, Ltd. Cosmetic raw material cosmetic product and method for manufacturing cosmetic products
FR2818535A1 (fr) * 2000-12-22 2002-06-28 Oreal Composition cosmetique comprenant un polysaccharide greffe par un polysiloxane et une silicone soluble
EP1240888A1 (fr) * 2001-03-13 2002-09-18 L'oreal Composition capillaire comprenant un polysaccharide greffé par un polysiloxane et un polymére fixant
EP1240889A1 (fr) * 2001-03-13 2002-09-18 L'oreal Composition capillaire épaissie comprenant un polysaccharide greffé par un polysiloxane
EP1240887A1 (fr) * 2001-03-13 2002-09-18 L'oreal Dispositif aerosol contenant une composition capillaire comprenant un polysaccharide greffe par un polysiloxane
DE102007023828A1 (de) * 2007-05-21 2008-11-27 Henkel Ag & Co. Kgaa Farbschützendes Wasch- oder Reinigungsmittel
JP2009256660A (ja) * 2008-03-27 2009-11-05 Chisso Corp ジオルガノポリシロキサン化合物及びその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60190408A (ja) * 1984-03-12 1985-09-27 Shin Etsu Chem Co Ltd 撥水撥油性組成物
JPH02214791A (ja) * 1989-02-15 1990-08-27 Dainichiseika Color & Chem Mfg Co Ltd 撥水撥油剤
JPH0489813A (ja) * 1990-08-02 1992-03-24 Toray Dow Corning Silicone Co Ltd オルガノポリシロキサン―アクリル酸エステル系共重合体エマルジョン
JPH0593071A (ja) * 1991-10-02 1993-04-16 Asahi Chem Ind Co Ltd シリコーン含有高分子ラテツクス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60190408A (ja) * 1984-03-12 1985-09-27 Shin Etsu Chem Co Ltd 撥水撥油性組成物
JPH02214791A (ja) * 1989-02-15 1990-08-27 Dainichiseika Color & Chem Mfg Co Ltd 撥水撥油剤
JPH0489813A (ja) * 1990-08-02 1992-03-24 Toray Dow Corning Silicone Co Ltd オルガノポリシロキサン―アクリル酸エステル系共重合体エマルジョン
JPH0593071A (ja) * 1991-10-02 1993-04-16 Asahi Chem Ind Co Ltd シリコーン含有高分子ラテツクス

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318939A (en) * 1996-11-01 1998-05-06 Richard James Harvey Infra-red identification device
US6280748B1 (en) * 1998-06-12 2001-08-28 Dow Corning Toray Silicone, Ltd. Cosmetic raw material cosmetic product and method for manufacturing cosmetic products
FR2818535A1 (fr) * 2000-12-22 2002-06-28 Oreal Composition cosmetique comprenant un polysaccharide greffe par un polysiloxane et une silicone soluble
WO2002051365A1 (fr) * 2000-12-22 2002-07-04 L'oreal Composition cosmetique comprenant un polysaccharide greffe par un polysiloxane et une silicone soluble
EP1240888A1 (fr) * 2001-03-13 2002-09-18 L'oreal Composition capillaire comprenant un polysaccharide greffé par un polysiloxane et un polymére fixant
EP1240889A1 (fr) * 2001-03-13 2002-09-18 L'oreal Composition capillaire épaissie comprenant un polysaccharide greffé par un polysiloxane
EP1240887A1 (fr) * 2001-03-13 2002-09-18 L'oreal Dispositif aerosol contenant une composition capillaire comprenant un polysaccharide greffe par un polysiloxane
FR2822060A1 (fr) * 2001-03-13 2002-09-20 Oreal Composition capillaire comprenant un polysaccharide greffe par un polysiloxane et un polymere fixant
FR2822059A1 (fr) * 2001-03-13 2002-09-20 Oreal Composition capillaire epaissie comprenant un polysaccharide greffe par un polysiloxane
FR2822061A1 (fr) * 2001-03-13 2002-09-20 Oreal Dispositif aerosol contenant une composition capillaire comprenant un polysaccharide greffe par un polysiloxane
DE102007023828A1 (de) * 2007-05-21 2008-11-27 Henkel Ag & Co. Kgaa Farbschützendes Wasch- oder Reinigungsmittel
JP2009256660A (ja) * 2008-03-27 2009-11-05 Chisso Corp ジオルガノポリシロキサン化合物及びその製造方法

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