WO2014125687A1 - オルガノポリシロキサングラフトポリマー - Google Patents
オルガノポリシロキサングラフトポリマー Download PDFInfo
- Publication number
- WO2014125687A1 WO2014125687A1 PCT/JP2013/080464 JP2013080464W WO2014125687A1 WO 2014125687 A1 WO2014125687 A1 WO 2014125687A1 JP 2013080464 W JP2013080464 W JP 2013080464W WO 2014125687 A1 WO2014125687 A1 WO 2014125687A1
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- WIPO (PCT)
- Prior art keywords
- organopolysiloxane
- group
- mass
- less
- graft polymer
- Prior art date
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- BARWIPMJPCRCTP-UHFFFAOYSA-N oleic acid oleyl ester Natural products CCCCCCCCC=CCCCCCCCCOC(=O)CCCCCCCC=CCCCCCCCC BARWIPMJPCRCTP-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 229940101267 panthenol Drugs 0.000 description 1
- 235000020957 pantothenol Nutrition 0.000 description 1
- 239000011619 pantothenol Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229940097156 peroxyl Drugs 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229950001046 piroctone Drugs 0.000 description 1
- BTSZTGGZJQFALU-UHFFFAOYSA-N piroctone olamine Chemical compound NCCO.CC(C)(C)CC(C)CC1=CC(C)=CC(=O)N1O BTSZTGGZJQFALU-UHFFFAOYSA-N 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- 229940071139 pyrrolidone carboxylate Drugs 0.000 description 1
- 229940079889 pyrrolidonecarboxylic acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 102200116936 rs72549407 Human genes 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000002316 solid fats Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 150000003408 sphingolipids Chemical class 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229940042585 tocopherol acetate Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001256 tonic effect Effects 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D7/00—Processes of waving, straightening or curling hair
- A45D7/06—Processes of waving, straightening or curling hair combined chemical and thermal
-
- 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
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/148—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95
Definitions
- the present invention relates to an organopolysiloxane graft polymer, and more particularly to an organopolysiloxane graft polymer useful as a hair cosmetic.
- organopolysiloxane Since organopolysiloxane has many excellent features, various forms of organopolysiloxane have been used as a touch improver contained in shampoos, hair conditioners and the like.
- Patent Document 1 gives a soft feel and a natural finish to hair, firmly fixes the hairstyle, and provides a hairstyle against external factors (such as passing fingers through hair, wind, vibration, etc.).
- a hair cosmetic containing a poly (N-acylalkylenimine) -modified organopolysiloxane has been disclosed for the purpose of providing a hair styling method that can be maintained for a long time without breaking down and can be restyled. .
- this invention after applying the said cosmetics to hair and shaping hair at a hair temperature of 50 ° C.
- Patent Document 2 discloses a cosmetic composition containing a vinyl-silicone graft or block copolymer having a specific structure.
- Patent Document 3 discloses a personal care product including an anionic polyorganosiloxane graft polymer-treated powder and a cosmetic using the same.
- Patent Document 4 discloses a cosmetic containing a grafted silicone polymer containing a polymerization product of a radically polymerizable monomer component containing a mercapto-modified silicone polymer and (meth) acrylic acid and / or (meth) acrylic acid alkyl ester. ing.
- Patent Document 5 discloses a graft type in which a structural unit composed of a polysiloxane group and a structural unit composed of a polymer of an unsaturated monomer containing an unsaturated monomer having an anionic group are bonded via a sulfide bond. Or the temporary colorant composition for hair containing the anionic resin which is an alternating block type copolymer, and a pigment is disclosed.
- Patent Document 6 discloses a method for producing a silicone-vinyl copolymer in which a mercapto functional silicone compound and a free radical polymerizable monomer are polymerized.
- the present invention relates to an organopolysiloxane having a copolymer segment derived from an unsaturated monomer containing an organopolysiloxane segment as a main chain and a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain.
- a graft polymer In the organopolysiloxane graft polymer, the content of the organopolysiloxane segment is 35% by mass or more and 59% by mass or less, and the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 4% by mass or more.
- Repeating unit derived from an unsaturated monomer (excluding an unsaturated monomer having a carboxylic acid or a salt thereof) having a glass transition point of 150 ° C. or higher when a homopolymer is formed and is 17% by mass or less Is an organopolysiloxane graft polymer in which the number average molecular weight of the organopolysiloxane segment is 8000 or more and 200,000 or less.
- Example 1 The result of hair set property evaluation in Example 1 and Comparative Example 1 (Polymers A and J) is shown.
- the result of hair setting property evaluation in Comparative Examples 5 and 6 (Polymers N and O) is shown.
- the results of set retention evaluation under high humidity in Examples 3 to 6 (Polymers C to F) and Comparative Example (Polymer R) are shown.
- Patent Document 1 discloses an organopolysiloxane graft polymer having an anionic group. After shaping the hair at a hair temperature of 50 ° C. or higher, the hair temperature is cooled to below 50 ° C. It cannot be used in a hair styling method for fixing the attached hairstyle (for example, when setting hair using a hair iron or a dryer).
- the object of the present invention is excellent in water dispersibility, and after shaping the hair at a hair temperature of 50 ° C. or higher, by cooling the hair temperature to below 50 ° C., the shaped hairstyle can be fixed under high humidity.
- the present invention relates to an organopolysiloxane compound having excellent set retention and hair feel after being set.
- the present invention relates to the following organopolysiloxane graft polymer, production method thereof, hair cosmetic, use in hair cosmetic, and hair cosmetic method.
- Organopolysiloxane having a copolymer segment derived from an unsaturated monomer comprising an organopolysiloxane segment as a main chain and a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain
- the content of the organopolysiloxane segment is 35% by mass or more and 59% by mass or less
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 4% by mass or more.
- Repeating unit derived from an unsaturated monomer (excluding an unsaturated monomer having a carboxylic acid or a salt thereof) having a glass transition point of 150 ° C. or higher when a homopolymer is formed and is 17% by mass or less Is an organopolysiloxane graft polymer in which the number average molecular weight of the organopolysiloxane segment is 8000 or more and 200,000 or less.
- An organopolysiloxane graft having an unsaturated monomer-derived copolymer segment containing an organopolysiloxane segment as a main chain and a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain A method for producing a polymer comprising: In the presence of the radical reactive organopolysiloxane represented by the following general formula (4) or (5), an unsaturated monomer including an unsaturated monomer having a carboxylic acid or a salt thereof is polymerized, In the obtained organopolysiloxane graft polymer, the content of the organopolysiloxane segment is 35% by mass or more and 59% by mass or less, and the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 4% by mass.
- R 11 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 12 represents an alkyl group having a radical reactive functional group
- p Re represents a number of 2 or more and 4000 or less
- q represents a number of 2 or more and 250 or less.
- the coupling mode of p repeating units and q repeating units is such that each repeating unit is connected in a block shape. Or may be connected randomly.
- the organopolysiloxane graft polymer of the present invention is excellent in water dispersibility, and after shaping the hair at a hair temperature of 50 ° C or higher, the shaped hairstyle can be fixed by cooling the hair temperature to less than 50 ° C (Hereinafter also referred to as “setting force”), which has a high set holding force even when placed under high humidity (hereinafter also referred to as “set holding property under high humidity”), and is free of stickiness and stickiness (hereinafter referred to as “setting power”). It is also known as “hair feel”.
- the organopolysiloxane graft polymer of the present invention (hereinafter also referred to as “the graft polymer of the present invention”) is a repeating unit derived from an unsaturated monomer having an organopolysiloxane segment as a main chain and a carboxylic acid or a salt thereof as a side chain.
- the content of the repeating unit derived from the unsaturated monomer having an acid or a salt thereof is 14% by mass or less
- the organo The number average molecular weight of polysiloxane segments is more than 8000 to 200,000.
- two or more side chains are bonded to any silicon atom of the organopolysiloxane segment constituting the main chain via an alkylene group containing a hetero atom. More preferably, it is bonded to one or more silicon atoms excluding the terminal via the alkylene group, and more preferably, it is bonded to two or more silicon atoms excluding both terminals via the alkylene group.
- the graft polymer of the present invention has an organopolysiloxane segment as the main chain.
- the chemical structure of the organopolysiloxane segment is not particularly limited, but a preferred specific example is a modified organopolysiloxane segment represented by the following general formula (1) or (2).
- R 1 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R 2 contains a hetero atom.
- R 2 represents an optionally substituted alkylene group.
- p represents a number of 2 to 4000
- q represents a number of 2 to 250.
- the coupling mode of p repeating units and q repeating units may be such that each repeating unit is connected in a block shape or in a random shape.
- examples of the alkyl group represented by R 1 include a linear, branched, or cyclic alkyl group, and the carbon number of the alkyl group represented by R 1 is From the viewpoint of water dispersibility of the graft polymer of the present invention, it is preferably 1 or more and 10 or less, more preferably 6 or less, and still more preferably 3 or less.
- alkyl group represented by R 1 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, nonadecyl group, eicosyl group, docosyl group and the like.
- the water dispersibility of the graft polymer is a property that allows the graft polymer to be stably dispersed in a composition containing water as a main component.
- the solvent contains water as a main component. It is preferable because it can be blended in the hair cosmetics to be made and the hair washability is also improved.
- the number of carbon atoms of the aryl group represented by R 1 is preferably 6 or more and 12 or less, more preferably 9 or less, from the viewpoint of water dispersibility of the graft polymer of the present invention.
- R 1 Specific examples of the aryl group represented by R 1 include phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group and the like.
- R 1 is a linear or branched alkyl having 1 to 6 carbon atoms from the viewpoint of water dispersibility of the graft polymer of the present invention and the setting power after setting hair with a hair cosmetic.
- Group is preferable, a linear or branched alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is more preferable.
- p represents a number of 2 to 4000
- q represents a number of 2 to 250.
- p is preferably 50 or more, more preferably 60 or more, more preferably from the viewpoint of setting power after setting the hair with the hair cosmetic composition of the present invention, set retention under high humidity, and feel of the hair after setting.
- the number is preferably 80 or more, more preferably 100 or more, and from the viewpoint of the water dispersibility of the graft polymer of the present invention and the feel of the hair after setting, it is preferably 1500 or less, more preferably 1300.
- the number is more preferably 900 or less, still more preferably 500 or less, and still more preferably 200 or less.
- q is preferably a number of 3 or more from the viewpoint of the water dispersibility of the graft polymer, and is preferably 150 or less, more preferably from the viewpoint of the set power of the hair cosmetic of the present invention and the set retention under high humidity.
- the number is 110 or less, more preferably 70 or less, more preferably 20 or less, and still more preferably 10 or less.
- part or all of the alkylene group (R 2 ) that may contain a hetero atom is bonded to the main chain and the copolymer segment derived from the unsaturated monomer.
- the alkylene group that may contain the heteroatom is a main chain and a hydrogen atom. Is combined with.
- the number of carbon atoms of the alkylene group which may contain a hetero atom is preferably 2 or more, more preferably 3 or more, from the viewpoint of availability of raw materials when producing the graft polymer of the present invention. From the viewpoint of water dispersibility of the graft polymer of the present invention, it is preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.
- the alkylene group which may contain a hetero atom is one or more atoms or functional groups selected from an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR 3 CO—. It may be divided by a group. That is, the alkylene group which may contain a hetero atom may have a structure of “— (alkylene group moiety 1) — (the above atom or functional group) — (alkylene group moiety 2) —”.
- the carbon number of the alkylene group means the sum of the carbon number of the alkylene group part 1 and the carbon number of the alkylene group part 2.
- R 3 is an alkyl group having 1 to 3 carbon atoms.
- the alkylene group which may contain a hetero atom includes a hydroxyl group, an amino group, an alkyl (C1 or more and 3 or less) amino group, a dialkyl (C1 or more and 3 or less) amino group, an amino group and a carbon number.
- One or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (having 1 to 3 carbon atoms) ester group obtained by dehydration condensation of 2 to 4 fatty acids may be substituted.
- the carbon number of the alkylene group which may contain a hetero atom does not include the carbon number of the substituent.
- the alkylene group which may contain a hetero atom is selected from an acetamido group, an alkyl (C1 or more and 3 or less) amino group, and an amino group. It is preferable that one or more monovalent groups to be substituted are substituted.
- the alkylene group which may contain a heteroatom is a divalent heteroatom selected from —O—, —S—, —NH—, —NR 14 —, and —COO—, or a heteroatom.
- a divalent group containing may be substituted.
- R 14 is an alkyl group (having 1 to 3 carbon atoms) which may be substituted by a dimethylamino group.
- the heteroatom or a divalent group containing a heteroatom serves as a linking group with a polymer segment derived from an unsaturated monomer
- the alkylene group that may contain a heteroatom is an unsaturated monomer. It is bound to the polymer segment derived from the body.
- the alkylene group which may contain a hetero atom is preferably substituted with —S—.
- the alkylene group (R 2 ) which may contain a hetero atom is a polymer segment derived from an unsaturated monomer via the hetero atom, preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a sulfur atom. It is preferable that it is couple
- the “alkylene group optionally containing a hetero atom” represented by R 2 includes (i) an unsubstituted alkylene group, (ii) an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO.
- alkylene group that may contain a hetero atom in the present invention include the following formulas (i) to (xii). Of these, the following formulas (xi) and (xii) are preferred from the viewpoint of ease of production of the graft polymer of the present invention.
- X 1 is one or more selected from —O—, —OCO—, —COO—, —CONH—, and —NHCO—, from the viewpoint of ease of production of the graft polymer of the present invention— CONH- or -NHCO- is preferable, and -NHCO- is more preferable.
- R 4 represents a hydroxyl group, an amino group, an alkyl (C 1 or more and 3 or less) amino group, a dialkyl (C 1 or more and 3 or less) amino group, an amino group and a C 2-4 carbon atom. It is an alkylene group which may be substituted with one or more monovalent groups selected from an amide group, a carboxy group and an alkyl (having 1 to 3 carbon atoms) ester group obtained by dehydration condensation of a fatty acid.
- the substituent is preferably an acetamido group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group from the viewpoint of availability of raw materials during production.
- the number of carbon atoms of the alkylene group represented by R 4 is preferably 2 or more, more preferably 3 or more from the viewpoint of ease of production of the graft polymer of the present invention, and the water dispersibility of the graft polymer of the present invention. In view of the above, it is preferably 10 or less, more preferably 6 or less.
- R 4 include the following formulas (xiii) to (xiv).
- the content of the organopolysiloxane segment in the graft polymer of the present invention is 35% by mass or more, preferably 38% by mass or more, more preferably from the viewpoint of hair feel after setting with the hair cosmetic composition of the present invention. Is 40% by mass or more, more preferably 45% by mass or more. Also, from the viewpoint of water dispersibility of the graft polymer of the present invention, setting power after setting hair with hair cosmetics, set retention under high humidity From this viewpoint, it is 59% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less.
- the content of the organopolysiloxane segment in the graft polymer of the present invention is determined so that "the radical reactive organopolysiloxane introduced at the time of production"
- the total mass (c) ”and“ the total mass (d) of unsaturated monomers added during production ” can be obtained.
- the graft polymer of the present invention has an unsaturated monomer-derived copolymer segment containing a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain.
- the repeating unit derived from an unsaturated monomer refers to a repeating unit formed when the unsaturated monomer is polymerized.
- the content of the copolymer segment derived from the unsaturated monomer in the graft polymer of the present invention is determined from the viewpoint of water dispersibility of the graft polymer of the present invention and the setting power after setting the hair with a hair cosmetic, high humidity From the viewpoint of set retention below, it is 41% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, and the hair is prepared with a hair cosmetic containing the organopolysiloxane graft polymer of the present invention. From the viewpoint of the feel of the hair after setting, it is 65% by mass or less, preferably 62% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof in the graft polymer of the present invention is 4 masses from the viewpoint of the water dispersibility of the graft polymer and the feel of the hair after setting. % Or more, preferably 4.5% by mass or more, more preferably 8% by mass or more. Further, from the viewpoint of setting power after setting the hair with the hair cosmetic composition of the present invention and set retention under high humidity, it is 17% by mass or less, preferably 14% by mass or less, more preferably 11% by mass or less. More preferably, it is 9 mass% or less.
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof in the copolymer segment derived from the unsaturated monomer depends on the water dispersibility of the graft polymer and the hair after setting. From the viewpoint of feel, the amount is 6% by mass or more, preferably 10% by mass or more, and more preferably 17% by mass or more. Further, from the viewpoint of setting power after setting the hair with the hair cosmetic composition of the present invention and set retention under high humidity, it is 41% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less. More preferably, it is 18% by mass or less.
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof in the graft polymer of the present invention or in the copolymer segment derived from the unsaturated monomer is as follows. In the case of production from radical-reactive organopolysiloxane, “total mass of radical-reactive organopolysiloxane introduced during production (c)”, “total mass of unsaturated monomer introduced during production (d ) "And” the total mass of unsaturated monomers having a carboxylic acid or a salt thereof added during production ".
- the unsaturated monomer having a carboxylic acid or a salt thereof include, for example, unsaturated carboxylic acid monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and crotonic acid. Etc. Among these, (meth) acrylic acid and maleic acid are preferable from the viewpoint of availability, and (meth) acrylic acid is more preferable.
- the repeating unit derived from the unsaturated monomer having a carboxylic acid may be an acid or may be partially or wholly neutralized.
- the base compound used for neutralization include, for example, alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; ammonia; mono-, di-, or triethanolamine, triethylamine, morpholine And amine compounds such as aminomethylpropanol and aminoethylpropanediol.
- alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide
- ammonia mono-, di-, or triethanolamine, triethylamine, morpholine And amine compounds such as aminomethylpropanol and aminoethylpropanediol.
- a monomer that can be copolymerized with an unsaturated monomer having a carboxylic acid or a salt thereof, and other than an unsaturated monomer having a carboxylic acid or a salt thereof in particular Although there is no limitation, it is preferable that it is an unsaturated monomer which does not have an ionic group, for example, an olefin, halogenated olefin, vinyl ester, (meth) acrylic acid ester, (meth) acrylamide, etc. are mentioned.
- olefins include ethylene, propylene, and isobutylene.
- halogenated olefin include vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride.
- vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate.
- (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) Octyl acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene (meth) acrylate And glycol and (meth) acrylic acid polyethylene glycol monomethyl ether.
- (meth) acrylamides include (meth) acrylamide, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, Examples include diacetone (meth) acrylamide, N-cyclohexyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N-methylol (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide.
- These repeating units derived from the comonomer may be present in the graft polymer of the present invention only one kind or plural kinds.
- the above-mentioned (meth) acrylamides and (meth) acrylic are used as the comonomer.
- One or more monomers selected from acid esters are preferred, and Nt-butyl (meth) acrylamide, Ni-butyl (meth) acrylamide, polyethylene glycol (meth) acrylate (9) monomethyl ether, (meth ) Polyethylene glycol acrylate (2) monomethyl ether, (meth) acrylic acid polyethylene glycol (4) monomethyl ether, (meth) acrylic acid polyethylene glycol (23) monomethyl ether, (meth) acrylic acid polyethylene glycol (90) monomethyl ether, (Meth) acrylic acid polyethylene Glycol (2), polyethylene glycol (meth) acrylate (4.5), polyethylene glycol (meth) acrylate (8), polyethylene glycol (meth) acrylate (10), dodecyl (meth)
- the copolymer segment derived from an unsaturated monomer containing a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof may be a random copolymer or a block copolymer. Also good.
- the content of the repeating unit derived from the comonomer is preferably in the graft polymer of the present invention from the viewpoint of setting power after setting the hair with the hair cosmetic composition of the present invention and set retention under high humidity. It is preferably 24% by mass or more, more preferably 28% by mass or more, and preferably 61% by mass or less, more preferably 55% by mass from the viewpoint of hair feel after setting and the water dispersibility of the graft polymer. It is as follows.
- the repeating unit derived from the comonomer is a copolymer derived from an unsaturated monomer from the viewpoint of setting power after setting the hair with the hair cosmetic of the present invention and set retention under high humidity.
- it is preferably 59% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and still more preferably 82% by mass or more.
- From the viewpoint of water dispersibility of the polymer it is preferably 94% by mass or less, more preferably 90% by mass or less, and still more preferably 83% by mass or less.
- the content of the repeating unit derived from the comonomer in the graft polymer of the present invention or in the copolymer segment derived from the unsaturated monomer is such that the graft polymer of the present invention is derived from the radical reactive organopolysiloxane described later.
- “total mass of radical reactive organopolysiloxane charged during production (c)”, “total mass of unsaturated monomer introduced during production (d)” and “total production charged during production” The total mass of comonomer to be obtained "can be obtained.
- the comonomer is a monomer copolymerizable with an unsaturated monomer having a carboxylic acid or a salt thereof, and an unsaturated monomer having a carboxylic acid or a salt thereof.
- the glass transition point (Tg) is 150.
- Tg when the unsaturated monomer forms a homopolymer is “polymer handbook” 4th edition published by Wiley-Interscience, 1st edition. Tg described in Volume VI / 193-VI / 277.
- the unsaturated monomer having an Tg of 150 ° C. or higher include, for example, adamantyl acrylate, adamantyl crotonic acid, Crotonic acid 3,5-dimethyladamantyl, ferrocenylethyl acrylate, ferrocenylmethyl acrylate, pentabromobenzyl acrylate, acrylamide, N-methyl, N-phenylacrylamide, adamantyl methacrylate, cyanophenyl methacrylate, methacryl 3,5-dimethyladamantyl acid, ferrocenylmethyl methacrylate, isobonyl methacrylate, N-tert-butylmethacrylamide, N-carboxyphenylmethacrylamide, 3- (4-biphenylyl) styrene, 4- (4-biphenylyl) Styrene, 2-car Boxy
- the content of the repeating unit derived from the unsaturated monomer having a glass transition point (Tg) of 150 ° C. or higher is determined by the radical of the graft polymer of the present invention described later.
- Tg glass transition point
- the mass ratio (a / b) between the organopolysiloxane segment (a) and the unsaturated monomer-derived copolymer segment (b) is preferably 35/65 or more, more preferably 38/62 or more, and even more preferably. Is 40/60 or more, more preferably 45/55 or more, preferably 59/41 or less, more preferably 55/45 or less, and still more preferably 50/50 or less.
- the mass ratio (a / b) is “a radical-reactive organopolyester introduced at the time of production”.
- the ratio (c / d) between the “total mass of siloxane (c)” and the “total mass (d) of unsaturated monomers added during production” is considered to be the same (the following formula (I)).
- graft polymer of the present invention is produced from a radical reactive organopolysiloxane described later, an organopolysiloxane graft polymer and a copolymer derived from an unsaturated monomer that is not bonded to the organopolysiloxane graft polymer.
- this mixture is used as an organopolysiloxane graft polymer.
- the number average molecular weight (MNg) of the organopolysiloxane segment between adjacent unsaturated monomer-derived copolymer segments (hereinafter sometimes referred to as “molecular weight between graft points”) is the organopolysiloxane of the present invention.
- MNg number average molecular weight of the organopolysiloxane segment between adjacent unsaturated monomer-derived copolymer segments.
- the “organopolysiloxane segment between adjacent unsaturated monomer-derived copolymer segments” means an organopolysiloxane segment of an unsaturated monomer-derived copolymer segment as shown in the following formula: A portion surrounded by a broken line between two points from the bond point (bond point A) to the bond point (bond point B) of the copolymer segment derived from the unsaturated monomer adjacent thereto, A segment composed of one R 1 SiO unit, one R 2 , and y + 1 R 12 SiO units.
- each R 1 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 2 represents an alkylene group which may contain a hetero atom
- —W -R 5 represents a copolymer segment derived from an unsaturated monomer
- R 5 represents a residue of a polymerization initiator or a hydrogen atom
- y represents a positive number.
- the molecular weight between graft points can be determined by the method described in Examples.
- the molecular weight between graft points is an average value of the molecular weight of the portion surrounded by a broken line in the above formula, and the mass of the organopolysiloxane segment per mole of the copolymer segment derived from the unsaturated monomer (g / mol) Can be understood.
- the molecular weight between graft points is the case where the graft polymer of the present invention is produced from the radical reactive organopolysiloxane described later, and all radical reactive functional groups and copolymers derived from unsaturated monomers are present. In the case of bonding, it corresponds to the reciprocal value of the number of moles of the radical reactive functional group (mol / g) present per unit mass of the radical reactive organopolysiloxane.
- the number average molecular weight (MNx) of the organopolysiloxane segment constituting the main chain is the setting force when the hair is set with the hair cosmetic containing the organopolysiloxane graft polymer of the present invention, and the set retention under high humidity From the viewpoint of the properties and feel of the hair after setting, it is 8000 or more, preferably 10,000 or more, more preferably 11000 or more, and further preferably 12000 or more. MNx is 200,000 or less, preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000, from the viewpoint of the water dispersibility of the graft polymer of the present invention and the feel of the hair after setting. It is as follows.
- the MNx is radical reactive because the organopolysiloxane segment has a common skeleton with the radical reactive organopolysiloxane. It is substantially the same as the number average molecular weight of the organopolysiloxane and is regarded as the same in the present invention.
- the number average molecular weight of radical reactive organopolysiloxane is measured by GPC under the measurement conditions described in the Examples, and is converted to polystyrene.
- the number average molecular weight (MNy) of the copolymer segment derived from each unsaturated monomer in the organopolysiloxane graft polymer of the present invention is the setting force when the hair is set with the hair cosmetic of the present invention under high humidity. From the viewpoint of set retention and the feel of the hair after setting, it is preferably 500 or more, more preferably 1000 or more, still more preferably 1500 or more. Also, from the viewpoint of ease of production of the present invention and after setting From the viewpoint of hair feel, it is preferably 50000 or less, more preferably 30000 or less, and still more preferably 6000 or less. In addition, MNy is calculated
- the number average molecular weight (MNt) of the graft polymer of the present invention is determined by the setting power when the hair is set with the hair cosmetic containing the organopolysiloxane graft polymer of the present invention, the set retention under high humidity, and after setting. From the viewpoint of the feel of hair, it is preferably 10,000 or more, more preferably 14,000 or more, still more preferably 20,000 or more, and from the viewpoint of water dispersibility of the graft polymer of the present invention, preferably 300. 50,000 or less, more preferably 250,000 or less, still more preferably 100,000 or less, and even more preferably 50,000 or less.
- MNt is the number average molecular weight of the radical reactive organopolysiloxane that is the raw material compound and the aforementioned mass ratio (a / b). It asks from.
- the graft polymer of the present invention preferably has an organopolysiloxane segment content of 45 mass% or more and 59 mass% or less in the graft polymer.
- the content of the repeating unit derived from the unsaturated monomer having an acid or a salt thereof is 4% by mass or more and 9% by mass or less, and the content of the repeating unit derived from the copolymer monomer is 32% by mass or more and 51% by mass.
- the content of the organopolysiloxane segment is 50% by mass or more and 59% by mass or less, and the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 5% by mass or more and 7% by mass.
- the content of the repeating unit derived from the copolymer monomer is 34% by mass or more and 45% by mass or less.
- the graft polymer of the present invention preferably has an organopolysiloxane segment content in the graft polymer of 45% by mass or more and 59% by mass or less, and has an unsaturated carboxylic acid or salt thereof.
- the content of the repeating unit derived from the monomer is 8% by mass or more and 17% by mass or less, and the content of the repeating unit derived from the copolymer monomer is 24% by mass or more and 47% by mass or less, more preferably organo.
- the content of the polysiloxane segment is 50% by mass or more and 59% by mass or less
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 10% by mass or more and 15% by mass or less
- the copolymer The content of the monomer-derived repeating unit is 26% by mass or more and 40% by mass or less.
- the method for producing the graft polymer of the present invention is not particularly limited.
- an organopolysiloxane having a reactive functional group, a carboxylic acid having a functional group capable of reacting with the reactive functional group, or a carboxylic acid thereof A graft-onto method (polymer reaction method) in which a copolymer segment derived from an unsaturated monomer containing a repeating unit derived from an unsaturated monomer having a salt is reacted;
- a radical-reactive organopolysiloxane described later Graft-from method in which an unsaturated monomer containing an unsaturated monomer having a carboxylic acid or a salt thereof is radically polymerized in the presence of Among these, from the viewpoint of reducing the load during production, (ii) radical polysiloxane having a reactive functional group, a carboxylic acid having a functional group capable of reacting with the reactive functional group, or a carboxylic acid thereof is reacted;
- the graft polymer of the present invention can be produced by radical polymerization of an unsaturated monomer in the presence of a radical reactive organopolysiloxane represented by the following general formula (4) or (5).
- each R 11 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 12 represents an alkyl group having a radical reactive functional group (hereinafter referred to as “radical reaction”). Also referred to as a functional group-containing alkyl group).
- a preferred embodiment of R 11 is the same as the preferred embodiment of R 1 in the general formulas (1) and (2).
- p and q have the same meanings as p and q in the general formulas (1) and (2), respectively, and preferable modes are the general formulas (1) and (2), respectively.
- p and q In the preferred embodiments of p and q.
- the radical reactive functional group means a functional group capable of generating a radical, and examples thereof include an ethylenically unsaturated group, a halogeno group such as a chloro group and a bromo group, and a sulfanyl group (mercapto group). It is done. Among these, a sulfanyl group is preferable from the viewpoint of reactivity with an unsaturated monomer and molecular weight control.
- the radical-reactive group-containing alkyl group represented by R 12 is a hydroxyl group, an amino group, an alkyl (1 to 3 carbon atoms) amino group, a dialkyl (1 to 3 carbon atoms).
- One or more monovalent groups selected from an amino group, an amide group obtained by dehydration condensation of an amino group and a fatty acid having 2 to 4 carbon atoms, a carboxy group, and an alkyl (1 to 3 carbon atoms) ester group May be substituted.
- an acetamido group, an alkyl (C 1 or more and 3 or less) amino group, or an amino group is preferable from the viewpoint of easy availability of raw materials when producing radical-reactive organopolysiloxane.
- the number of carbon atoms of the radical-reactive group-containing alkyl group represented by R 12 is preferably 2 or more, more preferably from the viewpoint of easy availability of the radical-reactive organopolysiloxane. Is 3 or more, and from the viewpoint of water dispersibility of the graft polymer of the present invention, it is preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.
- the number of carbon atoms of the radical reactive functional group-containing alkyl group does not include the number of carbon atoms of the radical reactive functional group even when the radical reactive functional group has carbon. Also when the containing alkyl group is the above-described monovalent group substituted, the carbon number of the monovalent group is not included.
- the radical-reactive group-containing alkyl group represented by R 12 includes an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR 13 CO—. It may be interrupted by one or more selected atoms or functional groups.
- R 13 is an alkyl group having 1 to 3 carbon atoms.
- radical-reactive group-containing alkyl group in the present invention include the following formulas (xvii) to (xx). Among these, from the viewpoint of easy production of a radical-reactive organopolysiloxane or the following formula, (Xix) or (xx) is preferred. X 11 and R 14 in formula (xx) and preferred embodiments thereof are the same as X 1 and R 4 in formula (xii) and preferred embodiments thereof.
- the number average molecular weight of the radical-reactive organopolysiloxane is considered to be the same as that of MNx in the present invention. Therefore, the preferred embodiment is the same as the preferred embodiment of MNx.
- the number average molecular weight of the radical-reactive organopolysiloxane is measured by GPC under the measurement conditions described in the examples and is converted to polystyrene.
- the number of moles of radical-reactive functional groups present per unit mass of the radical-reactive organopolysiloxane is the setting force when the hair is set with a hair cosmetic containing the organopolysiloxane graft polymer of the present invention, and high humidity. From the standpoint of set retention below, it is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1/1000 mol / g or less, and still more preferably 1/1500 mol / g or less.
- the graft polymer of the present invention preferably 1 / 30,000 mol / g or more, more preferably 1/2000 mol / g or more, still more preferably 1/1000 mol / g or more, more More preferably, it is 1/4000 mol / g or more.
- the radical-reactive organopolysiloxane can also be obtained by reacting an organopolysiloxane having a reactive functional group represented by the following general formula (6) or (7) with a radical reactivity-imparting agent.
- Organopolysiloxanes having reactive functional groups represented by the general formulas (6) and (7) are commercially available in various structures and are easily available.
- each R 21 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 22 represents an alkyl group having a reactive functional group (hereinafter referred to as “reactive group-containing”). Also referred to as an “alkyl group”.
- p and q are respectively synonymous with p and q of the general formulas (4) and (5), and preferable modes are the same as the preferable modes of p and q in the general formulas (4) and (5), respectively. is there.
- a preferred embodiment of R 21 is the same as the preferred embodiment of R 11 in the general formulas (4) and (5).
- the reactive functional group means a hydroxyl group, an amino group, a carboxy group, or an epoxy group.
- the organopolysiloxane having a reactive functional group has one or more substituents selected from a hydroxyl group, an amino group, a carboxy group, and an epoxy group.
- a hydroxyl group, an amino group, or an epoxy group is preferable from the viewpoint of availability, and an amino group is preferable from the viewpoint of reactivity and handleability.
- the number of carbon atoms of the reactive group-containing alkyl group represented by R 22 is preferably 2 or more from the viewpoint of easy availability of the organopolysiloxane having a reactive functional group. More preferably, it is 3 or more, and from the viewpoint of water dispersibility of the graft polymer of the present invention, it is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.
- the reactive group-containing alkyl group in the present invention include the following formulas (xxi) to (xxviii), and one or more selected from the following formulas (xxi) to (xxiv) are preferable from the viewpoint of availability, From the viewpoint of reactivity, the following formula (xxiv) is more preferable.
- the number average molecular weight (MNxm) of the organopolysiloxane having a reactive functional group is determined based on the set power when the hair is set with a hair cosmetic containing the organopolysiloxane graft polymer of the present invention, set retention under high humidity, and From the viewpoint of the feel of the hair after setting, it is preferably 8000 or more, more preferably 10,000 or more, still more preferably 11000 or more, still more preferably 12000 or more, and the water dispersibility viewpoint of the graft polymer of the present invention. From the viewpoint of the feel of the hair after setting, it is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, and even more preferably 30,000 or less. In the present invention, MNxm is measured by GPC under the measurement conditions described in the examples and converted to polystyrene.
- the number of moles of the reactive functional group present per unit mass of the organopolysiloxane having a reactive functional group is higher than the setting force when the hair is set with the hair cosmetic containing the organopolysiloxane graft polymer of the present invention. From the viewpoint of set retention under humidity, it is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1/1000 mol / g or less, and still more preferably 1/1500 mol / g or less.
- the graft polymer of the present invention is preferably 1 / 30,000 mol / g or more, more preferably 1/2000 mol / g or more, still more preferably 1/1000 mol / g or more, More preferably, it is 1/4000 mol / g or more.
- the radical reactivity imparting agent is an agent that reacts with a reactive functional group of an organopolysiloxane having a reactive functional group to add a radical reactive functional group to the organopolysiloxane having a reactive functional group.
- the radical reactivity imparting agent a radical reactive functional group in the molecule, a carboxy group capable of reacting with the reactive functional group of the organopolysiloxane having the reactive functional group, an ester group, an epoxy group, a hydroxyl group, and
- the reactive functional group of the organopolysiloxane having the reactive functional group is a hydroxyl group, an amino group, or an epoxy group
- Thiolactones which may have a substituent can be used.
- the radical reactive functional group of the radical reactivity imparting agent and its preferred mode are the same as the radical reactive functional group of the radical reactive organopolysiloxane and its preferred mode.
- the radical reactivity imparting agent preferably has a sulfanyl group (mercapto group) as a radical reactive functional group, for example, a sulfanyl group such as 3-mercaptopropionic acid.
- a compound having a carboxy group in the molecule lactones having a sulfanyl group such as ⁇ -butyrolactone thiol, and the like.
- the thiolactone which may have a substituent include ⁇ -thiobutyrolactone, N-acetyl-DL-homocysteine thiolactone, DL-homocysteine thiolactone hydrochloride and the like.
- N-acetyl-DL-homocysteine thiolactone is more preferable from the viewpoint of reactivity with the reactive organopolysiloxane and reactivity during polymerization.
- the amount of radical reactivity imparting agent used is preferably 0.8 equivalents or more, more preferably 0.9 equivalents, from the viewpoint of reactivity with respect to the total amount of reactive functional groups of the organopolysiloxane having a reactive functional group. From the viewpoint of reducing the unreacted radical reactivity imparting agent after the reaction, it is preferably 1.2 equivalents or less, more preferably 1.1 equivalents or less.
- a solvent In the reaction between the radical reactivity imparting agent and the organopolysiloxane having a reactive functional group, a solvent may be used.
- Solvents include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, ethers such as diethyl ether and tetrahydrofuran. , Aromatic compounds such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform. From the viewpoint of reducing environmental burden, it is preferable not to use a solvent.
- the reaction temperature is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of reactivity, and preferably 200 ° C. or lower, from the viewpoint of chemical stability of the resulting radical reactive polysiloxane. Preferably it is 150 degrees C or less, More preferably, it is 120 degrees C or less.
- the reaction time is preferably 1 hour or more, more preferably 2 hours or more from the viewpoint of sufficiently proceeding the reaction, and preferably 10 hours or less, more preferably 5 hours or less from the viewpoint of productivity. .
- the conversion of at least one of the reactive functional group of the organopolysiloxane having a reactive functional group and the radical reactivity imparting agent is 80% or more. It is preferable to carry out until it becomes, and it is more preferable to carry out until it becomes 90% or more.
- the method for measuring the conversion rate varies depending on the reactive functional group of the organopolysiloxane having a reactive functional group used for the reaction and the radical reactivity imparting agent, and any of them can be measured by a known method.
- the conversion rate of the amino group is “a total base number test method for petroleum products ( Perchloric acid method) ”(JIS K 2501), and the conversion rate of thiolactones can be determined by gas chromatography.
- the method for polymerizing the unsaturated monomer in the presence of the radical-reactive organopolysiloxane is not particularly limited, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method, etc. can be adopted, but a solution polymerization method is particularly preferable. .
- the amount of radical reactive organopolysiloxane used as a raw material is selected from the viewpoint of hair feel after setting with the hair cosmetic of the present invention, and the radical reactive organopolysiloxane used as a raw material and the unsaturated monomer used as a raw material. Is preferably 35% by mass or more, more preferably 38% by mass or more, still more preferably 40% by mass or more, and still more preferably 45% by mass or more, and the water dispersibility of the graft polymer of the present invention.
- the amount of the unsaturated monomer used as a raw material is determined from the viewpoint of the water dispersibility of the graft polymer of the present invention, the setting force after setting hair with a hair cosmetic, and the viewpoint of set retention under high humidity. Preferably, it is 41% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total amount of the radical-reactive organopolysiloxane and the unsaturated monomer as a raw material.
- the hair cosmetic containing the organopolysiloxane graft polymer of the present invention is preferably 65% by mass or less, more preferably 62% by mass or less, and still more preferably 60% by mass or less. More preferably, it is 55 mass% or less.
- the unsaturated monomer as a raw material contains an unsaturated monomer having a carboxylic acid or a salt thereof.
- the use amount of the unsaturated monomer having a carboxylic acid or a salt thereof is the water dispersibility of the graft polymer of the present invention relative to the total amount of the radical reactive organopolysiloxane as a raw material and the unsaturated monomer as a raw material.
- it is preferably 4.0% by mass or more, more preferably 4.5% by mass or more, and further preferably 8% by mass or more.
- the unsaturated monomer as a raw material contains a copolymerizable monomer in addition to the unsaturated monomer having a carboxylic acid or a salt thereof.
- Specific examples of the comonomer contained in the raw material unsaturated monomer, and preferred ranges thereof, are shown in the section ⁇ Copolymer segment derived from unsaturated monomer>. These are the same as the specific examples and preferred ranges thereof. There may be only one kind of comonomer, or a plurality of kinds may be present.
- the amount of the comonomer used is the radical reactive organopolysiloxane used as a raw material and the raw material from the viewpoint of the setting power after setting the hairstyle with the hair cosmetic of the present invention and the set retention under high humidity. It is preferably 24% by mass or more, and more preferably 28% by mass or more, based on the total amount of unsaturated monomers, and the hair feel and graft after setting the hairstyle with the hair cosmetic composition of the present invention From the viewpoint of water dispersibility of the polymer, it is 61% by mass or less, preferably 55% by mass or less.
- the unsaturated monomer as a raw material contains an unsaturated monomer having a Tg of 150 ° C. or higher (excluding an unsaturated monomer having a carboxylic acid or a salt thereof), the amount is 50 ° C. at the hair temperature. From the viewpoint of ease of shaping the hair in the above, it is 14% by mass or less, preferably 12% by mass or less, more preferably based on the total amount of the radical reactive organopolysiloxane as the raw material and the unsaturated monomer as the raw material. Is 10% by mass or less, more preferably 5% by mass or less. The lower limit is 0% by mass. Specific examples of unsaturated monomers having an unsaturated monomer having a Tg of 150 ° C. or higher (excluding unsaturated monomers having a carboxylic acid or a salt thereof) This is the same as the specific example of the unsaturated monomer having a Tg of 150 ° C. or higher shown in the item “Unified Segment>”.
- the graft polymer of the present invention is preferably based on the total amount of the radical reactive organopolysiloxane as a raw material and the unsaturated monomer as a raw material from the viewpoint of the feel of the hair after setting with the hair cosmetic of the present invention. Is 45 mass% or more and 59 mass% or less of radical reactive organopolysiloxane, 4 mass% or more and 9 mass% or less of carboxylic acid or its unsaturated monomer and 32 mass% or more and 51 mass% or less.
- the graft polymer of the present invention is preferably 45% by mass or more and 59% by mass with respect to the total amount of the radical reactive organopolysiloxane as a raw material and the unsaturated monomer as a raw material.
- the following radical-reactive organopolysiloxane, an unsaturated monomer having a carboxylic acid of 8% by mass or more and 17% by mass or less or a salt thereof, and a copolymerization monomer of 24% by mass or more and 47% by mass or less are reacted.
- a radical-reactive organopolysiloxane More preferably 50% by mass or more and 59% by mass or less of a radical-reactive organopolysiloxane, 10% by mass or more and 15% by mass or less of a carboxylic acid or a salt thereof, and 26 It is obtained by reacting a comonomer that is not less than 40% by mass and not more than 40% by mass.
- the solvent used is a solution of the raw material radical-reactive organopolysiloxane, the unsaturated monomer, and the resulting graft polymer of the present invention.
- the solvent include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, diethyl ether and tetrahydrofuran.
- ethers such as benzene, toluene and the like, and halogenated hydrocarbons such as dichloromethane and chloroform. These may be used alone or in combination of two or more.
- alcohols having 1 to 8 carbon atoms such as water, ethanol and isopropanol, and having 2 or more carbon atoms such as ethyl acetate and butyl acetate.
- solvents selected from ethers of 8 or less, diethyl ether, and ethers of 2 to 8 carbon atoms such as tetrahydrofuran.
- the graft polymer of the present invention is used for hair cosmetics, It is more preferable to use one or more selected from alcohols having 1 to 3 carbon atoms, such as water and ethanol, from the viewpoint of bringing a solvent into the graft product during the production of the graft polymer.
- alcohols having 1 to 3 carbon atoms such as water and ethanol
- the amount of the solvent used is not particularly limited as long as all of the radical-reactive organopolysiloxane, the unsaturated monomer, and the resulting organopolysiloxane graft polymer are dissolved or uniformly dispersed. From the viewpoint of productivity, it is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass with respect to the total amount of radical-reactive organopolysiloxane and unsaturated monomer added at the time of production.
- % Or more more preferably 100% by mass or more, and from the viewpoint of reactivity, it is preferably 1000% by mass or less, more preferably 900% by mass or less, still more preferably 400% by mass or less, still more preferably 300%. It is below mass%.
- polymerization initiator examples include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), and peroxyl such as lauroyl peroxide and benzoyl peroxide. Examples thereof include oxide initiators and persulfate initiators such as ammonium persulfate. Further, polymerization may be initiated by generating radicals by light irradiation or the like. As the polymerization initiator, 2,2'-azobis (2,4-dimethylvaleronitrile) is preferable from the viewpoint of reactivity.
- the amount of the polymerization initiator used is not particularly limited, but is preferably 10% by mass or less, more preferably from the viewpoint of obtaining an organopolysiloxane graft polymer having a desired molecular weight based on the total mass of unsaturated monomers to be added. Is 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and from the viewpoint of reactivity, it is preferably 0.001% by mass or more, more preferably 0.01% by mass. As mentioned above, More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more.
- the temperature during the polymerization reaction can be appropriately selected depending on the polymerization initiator used, the type of solvent, and the like, but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of the polymerization reaction rate. Moreover, it is preferable to make it react at normal pressure for the equipment load reduction used for polymerization reaction, and from the viewpoint of making it react below the boiling point of a solvent, the temperature at the time of polymerization reaction becomes like this. is there.
- the polymerization reaction is preferably performed until the conversion rate of the unsaturated monomer is 80% or more, and more preferably 90% or more.
- the conversion rate of the unsaturated monomer can be determined by nuclear magnetic resonance ( 1 H-NMR) analysis. Specific operations are described in the examples.
- the polymerization reaction time is usually from 0.1 hours to 60 hours, and from the viewpoint of operability, it is preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 2 hours or more, and even more preferably 4 hours. From the viewpoint of productivity, it is preferably 30 hours or less, more preferably 20 hours or less, and even more preferably 10 hours or less.
- the polymerization reaction time includes the dropping time.
- the time for the polymerization reaction can be controlled by changing the polymerization reaction temperature.
- the radical-reactive organopolysiloxane and unsaturated monomer, solvent, polymerization initiator, etc. that are the raw materials may be added all at once, and the polymerization reaction may be carried out.
- a reaction may be performed.
- a solvent is added A method in which a radically reactive organopolysiloxane, an unsaturated monomer, and an initiator are separately or mixed and dissolved in a solvent, and the solution is added dropwise to the heated place;
- radical reactive organopolysiloxane, unsaturated monomer There is a method in which a part of a saturated monomer and a solvent are mixed and heated, and a solution in which the initiator and the remainder of the unsaturated monomer are dissolved is added
- purification or reduction of unreacted unsaturated monomers may be performed as required by a known method.
- unreacted unsaturated monomers and other impurities may be reduced by adding a polymerization initiator and heating, membrane purification, steam distillation, adsorbent treatment, or the like.
- organopolysiloxane graft polymer of the present invention can be produced by the above-described method, the organopolysiloxane graft polymer of the present invention can also be produced by the method for producing the organopolysiloxane graft polymer of the present invention.
- an organopolysiloxane graft polymer having a copolymer segment derived from an unsaturated monomer containing an organopolysiloxane segment as a main chain and a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain
- An unsaturated monomer comprising an unsaturated monomer having a carboxylic acid or a salt thereof in the presence of a radical reactive organopolysiloxane represented by the following general formula (4) or (5)
- the content of the organopolysiloxane segment is 35% by mass or more and 59% by mass or less
- the content of repeating units derived from an unsaturated monomer having a carboxylic acid or a salt thereof Is 4 mass% or more and 17 mass% or less, and when a homopolymer is formed, the glass transition point is 150 ° C.
- the content of the repeating unit derived from the unsaturated monomer is 14% by mass or less, and the number average molecular weight of the organopolysiloxane segment is 8000 to 20 It can be produced by a method for producing an organopolysiloxane graft polymer that is 10,000 or less.
- R 11 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 12 represents an alkyl group having a radical reactive functional group
- p Re represents a number of 2 or more and 4000 or less
- q represents a number of 2 or more and 250 or less.
- the coupling mode of p repeating units and q repeating units is such that each repeating unit is connected in a block shape. Or may be connected randomly.
- the radical reactive organopolysiloxane is preferably obtained by reacting an organopolysiloxane having a reactive functional group represented by the following general formula (6) or (7) with a radical reactivity imparting agent. .
- each R 21 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms;
- R 22 represents an alkyl group having a reactive functional group; Represents a number of 2 or more and 4000 or less, and q represents a number of 2 or more and 250 or less, and the bonding mode of p repeating units and q repeating units may be such that each repeating unit is connected in a block shape. , May be connected randomly.
- the hair cosmetic composition of the present invention contains the graft polymer of the present invention (hereinafter also referred to as “component (A)”).
- the content of the component (A) is determined from the viewpoint of the hair setting power of the hair cosmetic composition of the present invention, the set retention property under high humidity, the feel of the hair, and the water dispersibility of the graft polymer of the present invention. Based on the total mass, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably Is 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less.
- solvent in the hair cosmetic composition of the present invention, from the viewpoint of hair setting power, good usability, and operability when preparing the hair cosmetic composition, water, a straight chain or branched chain having 1 to 3 carbon atoms is used as a solvent.
- a straight chain or branched chain having 1 to 3 carbon atoms is used as a solvent.
- One or more selected from saturated or unsaturated alcohols can be contained.
- 1 or more types chosen from water, ethanol, and isopropanol are preferable, and 1 or more types chosen from water and ethanol are especially preferable.
- the hair cosmetic composition of the present invention has an effect of improving the elasticity and stiffness of the hair, an effect of improving the softness and cohesion of the hair, and an improvement effect (improvement of elasticity, improvement of moisture resistance, etc.) as well as component (A)
- component (B) From the viewpoint of improving the setting power of the hair by making it compatible with the organic solvent, it further contains an organic solvent selected from the following (b1) to (b5) (hereinafter referred to as “component (B)”) as a preferable component.
- component (B) organic solvent selected from the following (b1) to (b5) (hereinafter referred to as “component (B)”) as a preferable component.
- (B1) Compound represented by general formula (8) [Wherein R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group R 7 —Ph—R 8 — (R 7 ; a hydrogen atom, a methyl group or a methoxy group, R 8 ; a bond or carbon A saturated or unsaturated divalent hydrocarbon group (Ph; paraphenylene group) having a number of 1 or more and 3 or less, A represents a bond or a divalent saturated hydrocarbon group of 1 to 4 carbon atoms, Y 2 and Z each independently represent a hydrogen atom or a hydroxyl group, and r and s each independently represent an integer of 0 or more and 5 or less.
- R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group R 7 —Ph—R 8 — (R 7 ; a hydrogen atom, a methyl group or a methoxy group, R 8 ; a
- (b1) includes, as butanol, isobutanol and the like, straight chain or branched aliphatic alcohols having 4 to 6 carbon atoms, ethylene glycol, propylene glycol, dipropylene glycol, 1 , 3-butanediol, benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carb Tall, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether and the like.
- (B2) includes N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like.
- (B3) includes ethylene carbonate, propylene carbonate, and the like.
- polypropylene glycol having a number average molecular weight of 200 to 1,000 those having a number average molecular weight of 300 to 500 are preferred.
- the number average molecular weight refers to a polystyrene-equivalent number average molecular weight measured by GPC.
- R 9 and R 10 in the general formulas (9) to (11) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups, and phenyl groups.
- a sulfoalkyl group, an alkyl phosphate group, a carboxyalkyl group and the like are preferable, and among them, a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Is preferred.
- R 9 or R 10 may be an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxy group or the acidic group. It is preferred to have a substituted alkyl group.
- examples of the lactone include ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -heptanolactone, and the like, from the viewpoint of lactone stability.
- ⁇ -lactone, particularly ⁇ -butyrolactone and ⁇ -caprolactone are preferred.
- examples of the cyclic ketone include cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcycloheptanone and the like.
- the component (B) used by this invention is a liquid at 25 degreeC from a viewpoint of the penetration promotion of a component (B).
- ClogP of component (B) is preferably ⁇ 2 or more, more preferably ⁇ 1 or more, and preferably 3 or less, more preferably 2 or less.
- ClogP is a calculated value of the octanol-water-partition coefficient (logP) defined by the following formula (II), which is a scale representing the distribution of substances between the octanol phase and the water phase.
- ClogP of the main component (B) is shown by dipropylene glycol ( ⁇ 0.67), 1,3-butanediol ( ⁇ 0.29), benzyl alcohol (1.1), 2-benzyloxy Ethanol (1.2), 2-phenylethanol (1.2), 1-phenoxy-2-propanol (1.1), polypropylene glycol 400 (0.9), propylene carbonate (-0.41), ⁇ - Butyrolactone ( ⁇ 0.64).
- benzyl alcohol and 2-benzyloxyethanol are preferred.
- the component (B) may be used in combination of two or more, and the total content thereof is an effect of improving the elasticity and stiffness of the hair, an effect of improving the softness and cohesiveness of the hair, an improvement effect (improving elasticity, From the viewpoint of improving the setting power of the hair by being compatible with the component (A) in addition to improvement in moisture resistance, etc., in the hair cosmetic, preferably 0.1% by mass or more, more preferably 0.5% by mass. % Or more, more preferably 1% by mass or more, preferably 40% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
- the hair cosmetic used in the present invention has the effect of improving the internal hair (such as cavity repair), improving the elasticity and stiffness of the hair, improving the softness and cohesion of the hair, From the viewpoint of improving the setting power of the hair by being compatible with the component (A), an organic carboxylic acid or a salt thereof (hereinafter referred to as “component (C)”) which may have a hydroxy group is contained. Can do.
- preferred components (B) include dipropylene glycol, 1,3-butanediol, benzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, propylene carbonate and polypropylene glycol (The number average molecular weight is preferably 300 or more and 500 or less, more preferably 400).
- the organic carboxylic acid of component (C) is preferably an organic carboxylic acid having 2 to 8 carbon atoms from the viewpoint of promoting penetration of component (C).
- Specific examples of the organic carboxylic acid of component (C) include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; poly Examples include polycarboxylic acids such as glutamic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; acidic amino acids such as glutamic acid and aspartic acid.
- a hydroxycarboxylic acid having 2 to 6 carbon atoms is preferable, and lactic acid and malic acid are particularly preferable.
- salts of these organic carboxylic acids include salts with alkali metals, alkaline earth metals, ammonia, and organic amine compounds.
- Two or more kinds of these components (C) may be used in combination, and the total content thereof is an effect of improving internal hair (such as cavity repair), an effect of improving hair firmness and stiffness, and an effect of improving the softness and cohesion of hair.
- the hair cosmetic preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably It is 0.5 mass% or more, preferably 30 mass% or less, more preferably 20 mass% or less, and still more preferably 10 mass% or less.
- the mass ratio ((C) :( B)) of the organic carboxylic acid of component (C) or a salt thereof and the organic solvent of component (B) is the effect of internal reforming of hair (such as cavity repair), In order to effectively exhibit the effect of improving the stiffness, the softness of the hair and the improvement of the cohesiveness, it is preferably in the range of 10: 1 to 1: 7, more preferably in the range of 4: 1 to 1: 3.
- the hair cosmetic of the present invention may further contain a set polymer (hereinafter referred to as “component (D)”) as necessary.
- component (D) a set polymer
- Examples of the set polymer of component (D) include those shown in the following 1) to 8), and these can be used alone or in combination of two or more.
- Vinylpyrrolidone-based polymer Polyvinylpyrrolidone Examples of commercially available products include “Rubicol K12”, “Rubicol K30” (above, manufactured by BASF), “PVP K15”, “PVP K30” (above, made by Ashland), and the like. It is done.
- Vinyl pyrrolidone / vinyl acetate copolymer Commercially available products include “Lubicol VA28”, “Rubicol VA73” (above, manufactured by BASF), “PVP / VA E-735”, “PVP / VA S-630” (above , Manufactured by Ashland).
- Vinyl pyrrolidone / vinyl acetate / vinyl propionate terpolymer As a commercial product, “Lubicol VAP343” (manufactured by BASF) and the like can be mentioned.
- Vinylpyrrolidone / alkylaminoacrylate copolymer “Rubiflex” (manufactured by BASF), “copolymer 845”, “copolymer 937”, “copolymer 958” (manufactured by Ashland) and the like can be mentioned as commercially available products.
- Vinylpyrrolidone / acrylate / (meth) acrylic acid copolymer Commercially available products include “Rubiflex VBM35” (manufactured by BASF).
- Vinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer As a commercial product, “copolymer VC-713” (manufactured by Ashland) and the like can be mentioned.
- Acidic polyvinyl acetate polymer Vinyl acetate / crotonic acid copolymer
- Commercially available products include “Resin 28-1310” (manufactured by Akzo Nobel) and “Rubiset CA66” (manufactured by BASF).
- Vinyl acetate / crotonic acid / vinyl neodecanoate copolymer Commercially available products include “Resin 28-2930” (manufactured by Akzo Nobel).
- Vinyl acetate / crotonic acid / vinyl propionate copolymer “Rubiset CAP” (manufactured by BASF) and the like are mentioned as commercial products.
- Acidic acrylic polymer (Meth) acrylic acid / (meth) acrylic acid ester copolymer Commercially available “Plus Size L53P” (manufactured by Kyoyo Chemical Industry Co., Ltd.), “Diahold” (Mitsubishi Chemical Corporation) Holdings).
- Acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymer examples include “Ultrahold 8” (manufactured by BASF) and “Amformer V-42” (manufactured by Akzo Nobel).
- Amphoteric acrylic polymer (meth) acrylethylbetaine / (meth) acrylic acid alkyl ester copolymer
- Acrylic acid alkyl ester / butylaminoethyl methacrylate / octylamide acrylate copolymer For example, octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer and the like are exemplified. Etc.).
- Cellulose Derivative Cationic Cellulose Derivative examples include “Cellcoat H-100” and “Cellcoat L-200” (manufactured by Akzo Nobel).
- Carboxymethyl chitin, carboxymethyl chitosan, chitosan and monovalent acids such as pyrrolidone carboxylic acid, lactic acid, glycolic acid or divalent acids such as adipic acid, succinic acid, etc.
- pyrrolidone carboxylic acid lactic acid, glycolic acid or divalent acids
- adipic acid succinic acid
- Kitomer PC pyrrolidone carboxylate
- Kitemer L lactate
- a set polymer selected from acrylic polymers and vinylpyrrolidone polymers is particularly preferable.
- the content of the set polymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more, based on the total mass of the hair cosmetic. Is 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
- the hair cosmetic used in the present invention may contain a conditioning component selected from oils and silicones (excluding the component (A) of the present invention).
- Oil is used to improve the feeling of hair unity after drying.
- Oils include hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, ⁇ -olefin oligomer, liquid paraffin, cycloparaffin; castor oil, cacao oil, mink oil, avocado oil, olive oil, etc.
- Glycerides such as beeswax, whale wax, lanolin, microcrystalline wax, ceresin wax, carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; myristic acid Octyldodecyl, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, iso Esters such as tridecyl nanate; higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; cholesterol, petrolatum, Examples thereof include solid fats such as cholesteryl is
- the content of the oil agent is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.5% by mass in the hair cosmetic from the viewpoint of good unity and no stickiness. % Or more, preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
- Silicones include dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, polyglycerin-modified silicone, fat Aromatic alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone and the like are exemplified. Of these, dimethylpolysiloxane, polyether-modified silicone, and amino-modified silicone are preferable.
- Dimethylpolysiloxane can give good lubricity to hair
- polyether-modified silicone can give smoothness to hair
- amino-modified silicone can give moist feeling to hair.
- various silicones can be used alone or in combination of two or more depending on the desired performance.
- dimethylpolysiloxane those having a viscosity of about 5 mm 2 / s can be used depending on the desired feel, and those having a viscosity of about 10 million mm 2 / s, which are often supplied as emulsions.
- the viscosity of dimethylpolysiloxane is preferably 5,000 mm 2 / s or more, more preferably 50,000 mm 2 / s or more, and preferably 10 million mm 2 / s or less, more preferably 1,000. 10,000 mm 2 / s.
- the said viscosity is a viscosity in 25 degreeC.
- the polyether-modified silicone may be any silicone having a polyoxyalkylene group, and examples of the group constituting the polyoxyalkylene group include an oxyethylene group and an oxypropylene group.
- examples of commercially available products include “KF-6015”, “KF-945A”, “KF-6005”, “KF-6609”, “KF-6013”, “KF-6019”, “KF-6029”, “ KF-6017, KF-6043, KF-353A, KF-354A, KF-355A (manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-2404, SS-2805 ”,“ FZ-2411 ”,“ FZ-2412 ”,“ SH3771M ”,“ SH3772M ”,“ SH3773M ”,“ SH3775M ”,“ SH3749 ”,“ SS-280X series ”,“ BY22-008M ”,“ BY11- ” 030 ",” BY25-337 "(manufactured by
- amino-modified silicone those described in the third edition of the CTFA Dictionary (US, Cosmetic Ingredient Dictionary) under the name of Amodimethicone having an average molecular weight of about 3,000 to 100,000 are preferable.
- Commercially available products include “SM 8704C” (manufactured by Toray Dow Corning), “DC 929” (manufactured by Dow Corning), “KT 1989” (manufactured by Momentive Performance Materials Japan), “ 8500 Conditioning Agent ",” DOW CORNING TORAY SS-3588 “,” DOW CORNING TORAY SILSTYLE 104 "(manufactured by Toray Dow Corning Co., Ltd.).
- the content of silicones is preferably 0.05% by mass or more in the hair cosmetic composition of the present invention, from the viewpoint of fingering property and lack of stickiness. More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more, Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.
- the hair cosmetic composition of the present invention may contain a surfactant from the viewpoints of system stability including solubilization and dispersibility of the solvent, and improvement in touch.
- a surfactant any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and an anionic surfactant can be used.
- Examples of the cationic surfactant include an ammonium salt or a quaternary ammonium salt represented by the following general formula (12).
- R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously a hydrogen atom, a benzyl group or a lower alkyl group having 1 to 3 carbon atoms, or Except for a combination of these.
- An- represents an ammonium or quaternary ammonium counter ion.
- one of R 15 and R 16 is preferably an alkyl group having 16 to 24 carbon atoms, more preferably an alkyl group having 22 carbon atoms, and a straight chain alkyl group having 22 carbon atoms. Preferably there is.
- the other is preferably a lower alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
- Examples of An- include ethyl sulfate ion, methyl sulfate ion, chloride ion, iodide ion, sulfate ion, p-toluenesulfonate ion, and perchlorate ion.
- cationic surfactant mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, and alkylbenzalkonium chloride. Trimethylammonium or behenyltrimethylammonium chloride is preferred.
- Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether or polyoxyethylene / polyoxypropylene alkyl ether is more preferable.
- amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.
- betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are preferable, and fatty acid amidopropyl betaine is more preferable.
- the fatty acid amidopropyl betaine is preferably one having an acyl group having 8 to 18 carbon atoms, more preferably one having an acyl group having 10 to 16 carbon atoms, lauric acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine. More preferred is coconut oil fatty acid amidopropyl betaine.
- Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include ⁇ -sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters.
- Counter ions of the anionic residue of the surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms Alkanolamine (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.) having 1 or more and 3 or less.
- alkali metal ions such as sodium ion and potassium ion
- alkaline earth metal ions such as calcium ion and magnesium ion
- ammonium ion alkanol group having 2 or 3 carbon atoms
- Alkanolamine for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc. having 1 or more and 3 or less.
- cationic surfactants and nonionic surfactants are preferred from the viewpoint of feel when the hair cosmetic composition of the present invention is used.
- Surfactant can be used individually or in combination of 2 or more types.
- the content of the surfactant is the stability of the system including the viewpoint of feel when the hair cosmetic composition of the present invention is used, and the solubilization and emulsification of the solvent and oil agent when the solvent and oil agent are blended. In terms of hair cosmetics, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less.
- the hair cosmetic used in the present invention may contain a polyhydric alcohol other than the component (B).
- the polyhydric alcohol contributes to the solubilization and stable dispersion of the component (B), and works synergistically with the component (B) to promote the improvement of gloss and hair modification effects.
- the polyhydric alcohol include glycerin and sorbitol, and glycerin is preferable.
- a polyhydric alcohol can be used individually or in combination of 2 or more types.
- the content of the polyhydric alcohol in the hair cosmetic is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less. It is.
- the components used in normal hair cosmetics can be appropriately blended in the hair cosmetic used in the present invention according to the purpose, application, dosage form, and the like.
- Such components include, for example, anti-dandruff agents such as zinc pyrithione and octopirox; vitamin agents; fungicides such as triclosan and trichlorocarban; anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate; methylparaben, butylparaben and the like Preservatives; chelating agents; moisturizers such as panthenol; colorants such as dyes and pigments; viscosity modifiers such as hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, clay minerals; pH of organic acids, sodium hydroxide, potassium hydroxide, etc. Conditioning agents; plant extracts; pearlizing agents; fragrances; dyes; ultraviolet absorbers; antioxidants; and others described in ENCYCLO
- the hair cosmetic used in the present invention can be prepared in various dosage forms according to a conventional method, for example, not only liquid compositions such as mist, lotion, tonic, but also gel, paste, cream, wax, etc.
- the semi-solid composition can be obtained.
- the hair cosmetic composition of the present invention may be an aerosol type hair cosmetic composition containing a propellant.
- the propellant is not particularly limited as long as it is usually used in aerosol-type cosmetics.
- lower saturated hydrocarbons such as propane, butane or a mixture thereof (including liquefied petroleum gas), Ethers such as dimethyl ether, nitrogen gas, carbon dioxide gas, nitrous oxide gas and the like can be used. These can be used alone or in combination of two or more.
- the content of the propellant is preferably 0.01% by mass or more, more preferably 10% by mass or more, and preferably 100% by mass with respect to the hair cosmetic composition of the present invention (excluding the propellant). Hereinafter, it is more preferably 40% by mass or less.
- the hair cosmetic composition of the present invention can be made into a non-aerosol hair cosmetic composition by filling a foam discharge container with a composition containing the organopolysiloxane of component (A).
- the foam discharge container is not particularly limited as long as the composition is mixed with air and discharged as a foam state.
- a squeeze foamer used by pressing the body of a soft container with fingers. Examples include a pump former and a trigger type that are used by pressing the head of a cap equipped with a pump mechanism with fingers.
- Examples of the squeeze former include those described in Japanese Utility Model Publication Nos. 62-042785, 62-042786, 62-042787, and equivalent pump pump formers. Examples thereof include those described in Kaihei 7-315463, JP-A-08-230961, and the like. In order to improve the foam quality, these containers are often equipped with a mesh body at the discharge part, and among them, one having one or two mesh bodies of 100 mesh or more and 300 mesh or less is preferred.
- Such a hair cosmetic is preferably used as a hair styling agent, hair conditioning agent, etc., and as its dosage form, pump spray, aerosol spray, pump foam, aerosol foam, gel, lotion, mist, cream, etc. are preferable. . Among these, pump spray, pump foam, and aerosol foam are more preferable.
- the present invention further discloses the following organopolysiloxane graft polymers, hair cosmetics containing the same, and the like.
- organopolysiloxane graft having a copolymer segment derived from an unsaturated monomer containing an organopolysiloxane segment as a main chain and a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain A polymer,
- the content of the organopolysiloxane segment is 35% by mass or more and 59% by mass or less
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 4% by mass or more.
- Repeating unit derived from an unsaturated monomer (excluding an unsaturated monomer having a carboxylic acid or a salt thereof) having a glass transition point of 150 ° C. or higher when a homopolymer is formed and is 17% by mass or less Is an organopolysiloxane graft polymer in which the number average molecular weight of the organopolysiloxane segment is 8000 or more and 200,000 or less.
- the number average molecular weight of the organopolysiloxane segment is preferably 10,000 or more, more preferably 11,000 or more, still more preferably 12,000 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably Is an organopolysiloxane graft polymer as described in ⁇ 1> above, which is 30,000 or less.
- the number average molecular weight (MNg) of the organopolysiloxane segment between the copolymer segments derived from adjacent unsaturated monomers in the organopolysiloxane segment is preferably 500 or more, more preferably 700 or more, still more preferably. Is 1000 or more, preferably 30,000 or less, more preferably 20,000 or less, and still more preferably 4000 or less, the organopolysiloxane graft polymer according to ⁇ 1> or ⁇ 2>.
- organopolysiloxane graft according to any one of ⁇ 1> to ⁇ 3>, wherein the organopolysiloxane segment is a modified organopolysiloxane segment represented by the following general formula (1) or (2): polymer.
- R 1 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 2 includes a hetero atom.
- R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms.
- the organopolysiloxane graft polymer according to ⁇ 4> which is a group, more preferably a methyl group.
- p is preferably a number of 50 or more, more preferably 60 or more, still more preferably 80 or more, still more preferably 100 or more, and preferably 1500.
- q is preferably a number of 3 or more, and is preferably 150 or less, more preferably 110 or less, more preferably 70 or less, more preferably 20
- the alkylene group (R 2 ), which may contain a hetero atom preferably has 2 or more carbon atoms, more preferably 3 or more, and preferably The organopolysiloxane graft polymer according to any one of ⁇ 4> to ⁇ 7>, which is 20 or less, more preferably 10 or less, and still more preferably 8 or less.
- the organopolysiloxane graft polymer according to any one of ⁇ 4> to ⁇ 8> which is bonded to a polymer segment derived from an unsaturated monomer through an intermediate.
- ⁇ 10> A group selected from the following formulas (i) to (xii) as an alkylene group (R 2 ) which may contain a hetero atom in the general formulas (1) and (2), preferably the following formula (xi) And the organopolysiloxane graft polymer according to any one of ⁇ 4> to ⁇ 9>, which is a group selected from (xii).
- * represents a site bonded to a silicon atom in the general formula (1) or (2)
- ** represents a copolymer segment derived from an unsaturated monomer. Represents the binding site.
- X 1 is one or more selected from —O—, —OCO—, —COO—, —CONH—, —NHCO—
- R 2 represents a hydroxyl group, an amino group , An alkyl group (1 to 3 carbon atoms) amino group, a dialkyl (1 to 3 carbon atoms) amino group, an amide group, a carboxy group and an alkyl group obtained by dehydration condensation of an amino group and a fatty acid having 2 to 4 carbon atoms ( 1 or more and 3 or less carbon atoms)
- An alkylene group which may be substituted with one or more monovalent groups selected from ester groups.
- organopolysiloxane graft polymer according to any one of ⁇ 10> to ⁇ 12>, wherein in the formula (xii), R 2 is a group selected from the following formulas (xiii) to (xiv).
- the repeating unit derived from an unsaturated monomer having the carboxylic acid or a salt thereof is selected from the group consisting of (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and crotonic acid.
- Repeating units derived from one or more unsaturated monomers preferably repeating units derived from one or more unsaturated monomers selected from the group consisting of (meth) acrylic acid and maleic acid, more preferably (meth) acrylic
- the content of the organopolysiloxane segment in the organopolysiloxane graft polymer is preferably 38% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and more preferably 55% by mass.
- the content of the copolymer segment derived from the unsaturated monomer in the organopolysiloxane graft polymer is 41% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more,
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof in the organopolysiloxane graft polymer is preferably 4.5% by mass or more, more preferably 8% by mass or more.
- the organopolysiloxane graft polymer according to any one of ⁇ 1> to ⁇ 16> which is preferably 14% by mass or less, more preferably 11% by mass or less, and still more preferably 9% by mass or less.
- the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof in the copolymer segment derived from the unsaturated monomer is preferably 6% by mass or more, more preferably 10% by mass. More preferably, it is 17% by mass or more, preferably 41% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 18% by mass or less.
- the organopolysiloxane graft polymer according to any one of 1> to ⁇ 17>.
- ⁇ 19> Derived from an unsaturated monomer (excluding an unsaturated monomer having a carboxylic acid or a salt thereof) having a glass transition point of 150 ° C. or higher when a homopolymer is formed in an organopolysiloxane graft polymer
- the organopolysiloxane graft polymer according to ⁇ 20> which is a repeating unit derived from one or more unsaturated monomers selected from (meth) acrylic acid esters.
- the content of the repeating unit derived from the unsaturated monomer copolymerizable with the unsaturated monomer having the carboxylic acid or a salt thereof in the organopolysiloxane graft polymer is preferably 24% by mass or more.
- the content of the repeating unit derived from an unsaturated monomer copolymerizable with the unsaturated monomer having the carboxylic acid or a salt thereof is preferable.
- organopolysiloxane graft polymer according to ⁇ 20> to ⁇ 22>, more preferably 83% by mass or less.
- the mass ratio (a / b) of the organopolysiloxane segment (a) and the copolymer segment (b) derived from the unsaturated monomer is preferably 35/65 or more, more preferably 38 / 62 or more, more preferably 40/60 or more, still more preferably 45/55 or more, preferably 59/41 or less, more preferably 55/45 or less, and even more preferably 50/50 or less,
- the organopolysiloxane graft polymer according to any one of ⁇ 1> to ⁇ 23>.
- the ⁇ 25> number average molecular weight (MNt) is preferably 10,000 or more, more preferably 14,000 or more, still more preferably 20,000 or more, and preferably 300,000 or less, more preferably 250,000.
- the number average molecular weight (MNy) of the copolymer segment derived from the ⁇ 26> unsaturated monomer is preferably 500 or more, more preferably 1000 or more, still more preferably 1500 or more, and preferably 50000 or less.
- ⁇ 27> The above-mentioned ⁇ 1> to ⁇ 26> obtained by radical polymerization of an unsaturated monomer containing an unsaturated monomer having a carboxylic acid or a salt thereof in the presence of a radical-reactive organopolysiloxane
- ⁇ 28> The organopolysiloxane graft polymer according to ⁇ 27>, wherein the radical reactive organopolysiloxane is a radical reactive organopolysiloxane represented by the following general formula (4) or (5).
- R 11 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 12 represents a radical-reactive functional group.
- P represents a number of 2 to 4000
- q represents a number of 2 to 250.
- the bonding mode of p repeating units and q repeating units is as follows: (Each repeating unit may be connected in blocks, or may be connected in random.)
- each repeating unit may be connected in blocks, or may be connected in random.
- R 11 is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms.
- the organopolysiloxane graft polymer according to ⁇ 28> or ⁇ 29> which is a group, more preferably a methyl group.
- p is preferably a number of 50 or more, more preferably 60 or more, still more preferably 80 or more, still more preferably 100 or more, and preferably 1500.
- q is preferably a number of 3 or more, preferably 150 or less, more preferably 110 or less, more preferably 70 or less, more preferably 20 or less. More preferably, the organopolysiloxane graft polymer according to any one of ⁇ 28> to ⁇ 31>, wherein the number is 10 or less.
- the radical-reactive group-containing alkyl group represented by R 12 preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 20 or more.
- the radical-reactive group-containing alkyl group represented by R 12 is an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR
- the radical-reactive group-containing alkyl group represented by R 12 is a group selected from the groups represented by the following formulas (xvii) to (xx), preferably The organopolysiloxane graft polymer according to any one of ⁇ 28> to ⁇ 34>, which is a group represented by the following formula (xix) or (xx).
- X 11 is one or more selected from —O—, —OCO—, —COO—, —CONH—, —NHCO—
- R 14 represents a hydroxyl group, an amino Group, alkyl (1 to 3 carbon atoms) amino group, dialkyl (1 to 3 carbon atoms) amino group, amide group, carboxy group and alkyl obtained by dehydration condensation of amino group and C2-4 fatty acid (C1-C3)
- An alkylene group optionally substituted with one or more substituents selected from ester groups, preferably an acetamido group, an alkyl (C1-C3) amino group, or an amino group
- the number of moles of radical reactive functional groups present per unit mass of ⁇ 36> radical reactive organopolysiloxane is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, and still more preferably 1 / 1000 mol / g or less, more preferably 1/1500 mol / g or less, preferably 1 / 30,000 mol / g or more, more preferably 1/2000 mol / g or more, and still more preferably 1/10000.
- the number average molecular weight of ⁇ 37> radical reactive organopolysiloxane is 8000 or more, preferably 10,000 or more, preferably 11,000 or more, more preferably 12,000 or more, and 200,000 or less, preferably 100,000 or less, more preferably
- radical-reactive organopolysiloxane is a product obtained by reacting an organopolysiloxane having a reactive functional group with a radical reactivity-imparting agent.
- the radical-reactive organopolysiloxane obtained by reacting an organopolysiloxane having a reactive functional group represented by the following general formula (6) or (7) with a radical reactivity-imparting agent
- p represents a number of 2 or more and 4000 or less
- q represents a number of 2 or more and 250 or less, in which the bonding mode of p repeating units and q repeating units is as follows. (Repeating units may be connected in blocks or randomly.)
- ⁇ 40> The above ⁇ 38> or ⁇ 39, wherein the ⁇ 40> reactive functional group is a group selected from a hydroxyl group, an amino group, a carboxy group, and an epoxy group, preferably a hydroxyl group, an amino group, or an epoxy group, more preferably an amino group.
- R 21 is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms.
- the organopolysiloxane graft polymer according to ⁇ 39> or ⁇ 40> which is a group, more preferably a methyl group.
- p is preferably a number of 50 or more, more preferably 60 or more, still more preferably 80 or more, still more preferably 100 or more, and preferably 1500.
- q is preferably a number of 3 or more, preferably 150 or less, more preferably 110 or less, more preferably 70 or less, more preferably 20 or less. More preferably, the organopolysiloxane graft polymer according to any one of ⁇ 39> to ⁇ 42>, wherein the number is 10 or less.
- the reactive group-containing alkyl group represented by R 22 preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 15 or less carbon atoms.
- the reactive group-containing alkyl group represented by R 22 is a group selected from the formulas (xxi) to (xxviii), preferably the formula (xxi) to The organopolysiloxane graft polymer according to any one of ⁇ 39> to ⁇ 44>, wherein the group is selected from (xxiv), more preferably the formula (xxiv).
- the number average molecular weight of the organopolysiloxane having a ⁇ 46> reactive functional group is preferably 8000 or more, more preferably 10,000 or more, still more preferably 11,000 or more, still more preferably 12000 or less, and preferably 200,000.
- the number of moles of the reactive functional group present per unit mass of the organopolysiloxane having a reactive functional group is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, and still more preferably. 1/1000 mol / g or less, more preferably 1/1500 mol / g or less, preferably 1 / 30,000 mol / g or more, more preferably 1/2000 mol / g or more, still more preferably 1 / 1,000 mol / g or less.
- the organopolysiloxane graft polymer according to any one of ⁇ 38> to ⁇ 46>, which is 10,000 mol / g or more, more preferably 1/4000 mol / g or more.
- ⁇ 48> a compound having a radical reactivity imparting agent in the molecule having a radical reactive functional group and one or more functional groups selected from a carboxy group, an ester group, an epoxy group, a hydroxyl group, and a lactone, or a substituent
- the radical reactivity imparting agent is selected from 3-mercaptopropionic acid, ⁇ -butyrolactone thiol, ⁇ -thiobutyrolactone, N-acetyl-DL-homocysteine thiolactone, and DL-homocysteine thiolactone hydrochloride 1
- the amount of ⁇ 51> radical reactivity imparting agent is preferably 0.8 equivalents or more, more preferably 0.9 equivalents or more, and preferably 1.2 equivalents or less, more preferably 1.1 equivalents or less.
- the repeating unit derived from an unsaturated monomer having an organopolysiloxane segment content of 45 mass% or more and 59 mass% or less, and having a carboxylic acid or a salt thereof, preferably in the graft polymer.
- the content of the repeating unit derived from the copolymer monomer is 32 mass% or more and 51 mass% or less, more preferably the content of the organopolysiloxane segment is 50% by mass or more and 59% by mass or less, and the content of the repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof is 5% by mass or more and 7% by mass or less, and the repeating unit derived from a copolymer monomer.
- the organopolysiloxane graft polymer according to any one of ⁇ 1> to ⁇ 51>, wherein the content of is from 34% by mass to 45% by mass. Ma.
- the content of the repeating unit derived from the copolymer monomer is 24% by mass or more and 47% by mass or less, more preferably the content of the organopolysiloxane segment is 8% by mass or more and 17% by mass or less.
- the organopolysiloxane graft polymer is preferably 45% by mass or more and 59% by mass or less of the radical reactive organopolysiloxane based on the total amount of the radical reactive organopolysiloxane and the unsaturated monomer, and 4% by mass or more. It is obtained by reacting an unsaturated monomer having a carboxylic acid of 9% by mass or less or a salt thereof and a comonomer having a content of 32% by mass to 51% by mass, more preferably 50% by mass.
- the organopolysiloxane graft polymer according to any one of ⁇ 1> to ⁇ 51>, which is obtained by reacting a body. ⁇ 55>
- the organopolysiloxane graft polymer is preferably 45% by mass or more and 59% by mass or less of the radical reactive organopolysiloxane based on the total amount of the radical reactive organopolysiloxane and the unsaturated monomer, and 8% by mass or more.
- the amount of the radical-reactive organopolysiloxane used is preferably 35% by mass or more, more preferably 38% by mass, based on the total amount of the radical-reactive organopolysiloxane as the raw material and the unsaturated monomer as the raw material. % Or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and preferably 59% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less.
- the amount of the unsaturated monomer used is preferably 41% by mass or more, more preferably 45% by mass, based on the total amount of the radical reactive organopolysiloxane used as a raw material and the unsaturated monomer used as a raw material. Or more, more preferably 50% by mass or more, preferably 65% by mass or less, more preferably 62% by mass or less, still more preferably 60% by mass or less, and still more preferably 55% by mass or less.
- 56> to ⁇ 58> A method for producing an organopolysiloxane graft polymer according to any one of items 56 to 58.
- the amount of the unsaturated monomer having ⁇ 60> carboxylic acid or a salt thereof is preferably 4.0 mass based on the total amount of the radical reactive organopolysiloxane as a raw material and the unsaturated monomer as a raw material. % Or more, more preferably 4.5% by weight or more, still more preferably 8% by weight or more, preferably 17% by weight or less, more preferably 14% by weight or less, still more preferably 11% by weight or less, and still more.
- the amount of the ⁇ 61> comonomer used is preferably 24% by mass or more, more preferably 28% by mass, based on the total amount of the radical reactive organopolysiloxane as a raw material and the unsaturated monomer as a raw material.
- ⁇ 62> The amount of the unsaturated monomer having a Tg of 150 ° C.
- the radical-reactive organopolysiloxane and the raw material is used as a raw material for the radical-reactive organopolysiloxane and the raw material.
- it is 14 mass% or less with respect to the total amount of a saturated monomer, More preferably, it is 12 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, and a minimum is 0 mass%.
- the amount of radical-reactive organopolysiloxane used is preferably 45% by mass or more and 59% by mass or less, and has a carboxylic acid or a salt thereof.
- the amount of the unsaturated monomer used is 4% by mass or more and 9% by mass or less, and the amount of the comonomer used is 32% by mass or more and 51% by mass or less, more preferably a radical reactive organopolysiloxane is used.
- the amount used is 50% by weight to 59% by weight, the amount of the unsaturated monomer having a carboxylic acid or a salt thereof is 5% by weight to 7% by weight, and the amount of the comonomer used is 34% by weight.
- the amount of radical-reactive organopolysiloxane used is preferably 45% by mass or more and 59% by mass or less, and has a carboxylic acid or a salt thereof.
- the amount of the unsaturated monomer used is 8% by mass or more and 17% by mass or less, and the amount of the comonomer used is 24% by mass or more and 47% by mass or less, more preferably a radical reactive organopolysiloxane is used.
- the amount of the unsaturated monomer having a carboxylic acid or a salt thereof is 10% by weight to 15% by weight, and the amount of the comonomer used is 26% by weight.
- the solvent is at least one solvent selected from water, an alcohol having 1 to 8 carbon atoms, an ester having 2 to 8 carbon atoms, and an ether having 2 to 8 carbon atoms, preferably water and carbon number.
- the amount of the solvent used is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, based on the total amount of the radical-reactive organopolysiloxane and the unsaturated monomer.
- Polymerization initiator preferably a polymerization initiator selected from azo initiators, peroxide initiators, and persulfuric acid initiators, more preferably 2,2′-azobisisobutyronitrile , 2,2′-azobis (2,4-dimethylvaleronitrile), lauroyl peroxide, benzoyl peroxide, and ammonium persulfate, more preferably 2,2′-azobis (2,4-dimethyl)
- the amount of the polymerization initiator used is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, and more preferably based on the total mass of the unsaturated monomers to be added. It is preferably 1% by mass or less, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, and still more preferably 0.5% by mass or more.
- the method for producing an organopolysiloxane graft polymer according to any one of ⁇ 56> to ⁇ 67>.
- the polymerization reaction is performed until the conversion rate of the unsaturated monomer is 80% or more, preferably 90% or more, wherein the organopolysiloxane graft polymer according to any one of the above ⁇ 56> to ⁇ 68> is used.
- Production method. ⁇ 70> Polymerization reaction time is 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, further preferably 2 hours or longer, still more preferably 4 hours or longer, and 60 hours.
- the reaction time of the organopolysiloxane having a reactive functional group and the radical reactivity imparting agent is preferably 1 hour or more, more preferably 2 hours or more, and preferably 10 hours or less, more preferably
- the method for producing an organopolysiloxane graft polymer according to ⁇ 71> which is 5 hours or less.
- the reaction temperature between the organopolysiloxane having a reactive functional group and the radical reactivity imparting agent is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and preferably 200 ° C. or lower, more preferably
- the reaction between the organopolysiloxane having a reactive functional group and the radical reactivity-imparting agent is obtained by converting at least one of the reactive functional group of the organopolysiloxane having a reactive functional group and the radical reactivity-imparting agent.
- An organopolysiloxane graft having an unsaturated monomer-derived copolymer segment containing an organopolysiloxane segment as a main chain and a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a side chain A method for producing a polymer, comprising: In the presence of the radical reactive organopolysiloxane represented by the following general formula (4) or (5), an unsaturated monomer including an unsaturated monomer having a carboxylic acid or a salt thereof is polymerized, In the obtained organopolysiloxane graft polymer, the content of the organopolysiloxane segment is 35% by mass or more and 59% by mass or less, and the content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof is 4% by mass.
- R 11 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 12 represents an alkyl group having a radical reactive functional group
- p Re represents a number of 2 or more and 4000 or less
- q represents a number of 2 or more and 250 or less.
- the coupling mode of p repeating units and q repeating units is such that each repeating unit is connected in a block shape. Or may be connected randomly.
- the radical-reactive organopolysiloxane is obtained by reacting an organopolysiloxane having a reactive functional group represented by the following general formula (6) or (7) with a radical reactivity-imparting agent.
- each R 21 independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms
- R 22 represents an alkyl group having a reactive functional group
- q represents a number of 2 or more and 250 or less
- the bonding mode of p repeating units and q repeating units may be such that each repeating unit is connected in a block shape.
- % means “% by mass” unless otherwise specified.
- the amount of amino groups of the mixture containing the sulfanyl group-modified organopolysiloxane was measured by using the mixture containing the sulfanyl group-modified organopolysiloxane as a sample. The measurement was performed in the same manner as the measurement of the base amount.
- ⁇ (%) [1 ⁇ ⁇ a1 ⁇ (f + g) / (a0 ⁇ f) ⁇ ] ⁇ 100 (IV)
- a0 and a1 are respectively the number of moles of amino groups per unit mass of the side chain primary aminopropyl-modified organopolysiloxane and the amino acid per unit mass in the reaction mixture after the reaction with the radical reactivity imparting agent. This represents the number of moles of the group
- f is the total charged mass of the side chain primary aminopropylorganopolysiloxane
- g is the total charged mass of the radical reactivity imparting agent.
- a 0.05 mM ethanol solution of 5,5′-dithiobis (2-nitrobenzoic acid) (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as Solution A.
- a 4 to 10% by mass ethanol solution of the organopolysiloxane graft polymer obtained in the examples was prepared as Solution B.
- 100 ⁇ L of borate pH standard solution (pH 9.18) (manufactured by Wako Pure Chemical Industries, Ltd.), 5 mL of solution A, and 1 mL of solution B were added to a 10 mL screw tube, and the lid was covered and shaken for 5 seconds.
- the conversion rate of the unsaturated monomer during the polymerization reaction was determined by measuring the unreacted unsaturated monomer under the following conditions using nuclear magnetic resonance ( 1 H-NMR) analysis.
- the organopolysiloxane graft polymer was dissolved in 2% by mass in deuterated chloroform and measured using a nuclear magnetic resonance ( 1 H-NMR) apparatus “Mercury 400” (manufactured by Varian).
- the measurement conditions were Proton 1D as the measurement mode, room temperature as the measurement temperature, and 32 times of integration.
- the conversion rates of MAA, tBuAA, and PEGMA are as follows.
- ⁇ Number average molecular weight (MNy) of copolymer segment derived from unsaturated monomer> From the graft point molecular weight and the mass ratio (a / b) between the organopolysiloxane segment (a) and the unsaturated monomer-derived copolymer segment (b), the molecular weight is determined as follows. Number average molecular weight of copolymer segment derived from unsaturated monomer molecular weight between graft points ⁇ b / a
- Synthesis example 1 Synthesis of radical reactive organopolysiloxane ⁇
- a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was attached to a side chain primary aminopropyl-modified organopolysiloxane (manufactured by Toray Dow Corning Co., Ltd., moles of amino groups per unit mass; 1 / 1970 mol / g, number average molecular weight 14000) 200 g and N-acetyl-DL-homocysteine thiolactone 16 g. Under a nitrogen atmosphere, the temperature was raised to 100 ° C.
- Synthesis Examples 2-4 In Synthesis Example 1, except that the side chain primary aminopropyl modified organopolysiloxane in which the number of moles of amino groups per unit mass of the side chain primary aminopropyl modified organopolysiloxane and the number average molecular weight were changed to the conditions shown in Table 1 was used. Were subjected to the same operations as in Synthesis Example 1 to obtain radical reactive organopolysiloxanes ⁇ to ⁇ .
- Example 1 ⁇ Synthesis of organopolysiloxane graft polymer A> 17 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device. While stirring under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) were respectively added to separate dropping funnels and dropped simultaneously over 3 hours. Then, after stirring for 1 hour while refluxing ethanol, the following solution (c) was added dropwise over 1 hour.
- MAA methacrylic acid
- tBuAA N-tert-butylacrylamide
- PEGMA polyethylene glycol methacrylate
- 110 g of ethanol ethanol
- the mixture was stirred for 1 hour while refluxing ethanol, and the conversion rates of MAA, tBuAA and PEGMA were measured and found to be 99%, 95% and 99%, respectively.
- the reaction solution was allowed to cool to room temperature, and 4.7 g of aminomethylpropanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a neutralizing agent.
- the reaction time is 6 hours in total. Ethanol was removed from the reaction mixture at room temperature (25 ° C.) under reduced pressure (20 kPa) over 4 hours to obtain a mixture containing the organopolysiloxane graft polymer A as a white solid.
- Example 2 Comparative Examples 1 to 4, 7, 8 ⁇ Synthesis of organopolysiloxane graft polymers B to I and J to M, P and Q>
- Example 1 the same procedure as in Example 1 was performed, except that the type of radical-reactive organopolysiloxane, the amount charged, the type of unsaturated monomer, and the amount charged were changed to the conditions shown in Table 2.
- a mixture comprising polysiloxane graft polymers B to I and J to M, P, Q was obtained.
- surface shows the preparation mass part of each component when the preparation total mass of a radical reactive organopolysiloxane and an unsaturated monomer is 100 mass parts.
- the radical reactive organopolysiloxane ⁇ is a commercially available radical reactive organopolysiloxane “KF-2001” (manufactured by Shin-Etsu Chemical Co., Ltd. An average molecular weight of 6700) was used.
- Table 3 shows the physical properties of the resulting organopolysiloxane graft polymers of Examples 1 to 9 and Comparative Examples 1 to 9.
- An ethanol or ethyl acetate solution (50% by mass) of an organopolysiloxane graft polymer was cast into a petri dish made of polytetrafluoroethylene and dried at room temperature under a nitrogen flow for 3 to 5 days. Thereafter, it was dried under reduced pressure at 80 ° C. for 3 to 8 hours to obtain a pale yellow transparent film having a thickness of about 1 mm. The obtained film was cut and used as a sample for elastic modulus measurement.
- Measuring device Dynamic viscoelasticity measuring device “DVA-225” (made by IT Measurement Control Co., Ltd.) Measurement mode: Shear mode Strain: 0.01-0.1% Frequency: 1Hz Sample size: (0.6 to 1.5) x (7 to 10) x (5 to 6) mm Measurement temperature: -50 to 200 ° C The elastic modulus at room temperature (20 ° C.) and the elastic modulus at high temperature (140 ° C.) were measured. The results are shown in Table 4.
- the softening point was defined as the temperature at which the elastic modulus at 20 ° C. decreased by 45% or more in the measurement result of the elastic modulus.
- the hair bundle was sufficiently wetted with water and then towel-dried, and 1.2 g of a 5% by mass ethanol solution of each organopolysiloxane graft polymer was applied, and the hair was alternately combed five times from the front side and the back side.
- the root of the hair bundle is sandwiched with a flat iron “CREATE ION” (manufactured by CREATS Co., Ltd.) at 150 to 160 ° C., and the iron is slid toward the hair tip as it is.
- CREATE ION manufactured by CREATS Co., Ltd.
- the action of extending the hair bundle was repeated three times, and then the same treatment was repeated twice with further combing.
- This series of treatments was completed and cooled to room temperature to obtain a hair bundle for evaluation.
- the hair setting property was evaluated by the following measurement method.
- the width of the hair bundle (the linear distance between the leftmost hair and the rightmost hair) at a position 5 cm above the hair tips (hereinafter also referred to as “C part” in the figure) is measured.
- the setting property is good, that is, the width of the hair bundle of part A is 3.0 to 4.5 cm, the width of the hair bundle of part B is 3.0 to 4.0 cm, and the hair bundle of part C is It means that the width is in the range of 2.5 to 3.8 cm.
- UV visible light spectrophotometer UV-3300 manufactured by Hitachi, Ltd.
- Measurement mode transmittance Measurement wavelength: 660 nm
- Optical path length 1 cm
- Tables 4 and 5 compare the evaluation results of organopolysiloxane graft polymers having different number average molecular weights of organopolysiloxane segments.
- the organopolysiloxane graft polymer having a number average molecular weight of 8000 or more of the organopolysiloxane segments of Examples 1, 2, and 6 is the number of the organopolysiloxane segments of Comparative Examples 7 and 8.
- the hair setting property and feel are excellent.
- the hair bundles shaped with the organopolysiloxane graft polymers A to I of the examples all have the widths of the hair bundles of the A part, the B part, and the C part within the above range.
- the polysiloxane graft polymers A to I had good hair setting properties.
- each of the hair bundles shaped by the organopolysiloxane graft polymers J, L, and M of Comparative Examples 1, 3, and 4 has a width of the hair bundle of the A part, the B part, and the C part within the specified range.
- the hair setting properties of the organopolysiloxane graft polymers J, L and M were insufficient.
- Fig. 1 shows a hair bundle shaped using organopolysiloxane graft polymers A and J.
- the setting force was evaluated in the same manner as described above using the 5 mass% ethanol solutions of the organopolysiloxane graft polymers N and O obtained in Comparative Examples 5 and 6, respectively.
- the appearance of the hair bundle treated with the organopolysiloxane graft polymer N or O is shown in FIG.
- the organopolysiloxane graft polymers N and O had insufficient setting power.
- organopolysiloxane graft polymer R of Comparative Example 9 was evaluated for set retention under high humidity in the same manner as described above. The results are shown in FIG. As shown in FIG. 3, as compared with the polymer R, the organopolysiloxane graft polymers C to F of the present invention are all excellent in set retention under high humidity.
- the organopolysiloxane graft polymer of the present invention has excellent water dispersibility, and after shaping the hair at a hair temperature of 50 ° C. or higher, the hair is cooled to less than 50 ° C. to fix the shaped hairstyle. It is most suitable for the method, is excellent in the feel of the hair after setting, and the set retention under high humidity, and is useful as a hair cosmetic.
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Abstract
Description
例えば、特許文献1には、毛髪に柔軟な感触と自然な仕上がり感を与え、髪形を強固に固定し、外的要因(手指を髪に通す、風、振動等)に対してもヘアスタイルを崩すことなく、長時間維持することができ、また再整髪もできる整髪方法を提供することを目的として、ポリ(N-アシルアルキレンイミン)変性オルガノポリシロキサンを含有する毛髪化粧料が開示されている。この発明では、上記化粧料を毛髪に適用し、毛髪温度50℃以上において毛髪を形付けした後、毛髪の温度を50℃未満に冷却することにより、形付けした髪形を固定する整髪方法が開示されている。
特許文献2には、特定の構造を有するビニル-シリコーングラフト又はブロック共重合体を含む化粧品組成物が開示されている。
特許文献3には、アニオン基を有するオルガノポリシロキサングラフトポリマー処理粉体、及びそれを用いた化粧品を含むパーソナルケア製品が開示されている。
特許文献4には、メルカプト変性シリコーンポリマーと(メタ)アクリル酸及び/又は(メタ)アクリル酸アルキルエステルを含むラジカル重合性モノマー成分の重合生成物を含むグラフト化シリコーンポリマーを含有する化粧品が開示されている。
特許文献5には、ポリシロキサン基よりなる構成単位とアニオン性基を有する不飽和単量体を含む不飽和単量体の重合体よりなる構成単位とがスルフィド結合を介して結合されたグラフト型又は交互ブロック型共重合体であるアニオン樹脂と顔料を含む毛髪用一時着色料組成物が開示されている。
特許文献6には、メルカプト官能シリコーン化合物とフリーラジカル重合性モノマーを重合させるシリコーン-ビニル共重合体の製造方法が開示されている。
該オルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、該オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマー、に関する。
本発明の課題は、水分散性に優れ、髪温度50℃以上において毛髪を形付けした後、毛髪の温度を50℃未満に冷却することにより、形付けした髪形を固定可能で、高湿度下におけるセット保持性及びセットした後の毛髪の感触に優れるオルガノポリシロキサン化合物に関する。
[1]主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む、不飽和単量体由来の共重合体セグメントを有するオルガノポリシロキサングラフトポリマーであって、
該オルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、該オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマー。
[2]主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを有するオルガノポリシロキサングラフトポリマーの製造方法であって、
下記一般式(4)又は(5)で表されるラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含む不飽和単量体を重合させ、
得られるオルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマーの製造方法。
[3]前記[1]に記載のオルガノポリシロキサングラフトポリマーを含有する毛髪化粧料。
[4]前記[1]に記載のオルガノポリシロキサングラフトポリマーの毛髪化粧料への使用。
[5]前記[1]に記載のオルガノポリシロキサングラフトポリマーを毛髪に適用する毛髪化粧方法。
本発明のオルガノポリシロキサングラフトポリマー(以下「本発明のグラフトポリマー」ともいう)は、主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む、不飽和単量体由来の共重合体セグメントを有し、該オルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、該オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である。
本発明のグラフトポリマーは、主鎖としてオルガノポリシロキサンセグメントを有する。
オルガノポリシロキサンセグメントの化学構造は特に限定されないが、好ましい具体例としては、下記一般式(1)又は(2)で表される変性オルガノポリシロキサンセグメントである。
R1で表されるアリール基の炭素数は、本発明のグラフトポリマーの水分散性の観点から好ましくは6以上12以下、より好ましくは9以下である。R1で表されるアリール基の具体例としては、フェニル基、トリル基、キシリル基、ナフチル基、ビフェニル基、アントリル基、フェナントリル基等が挙げられる。
これらの中でも、R1としては、本発明のグラフトポリマーの水分散性の観点及び毛髪化粧料で毛髪をセットした後のセット力の観点から炭素数1以上6以下の直鎖又は分岐状のアルキル基が好ましく、炭素数1以上3以下の直鎖又は分岐状のアルキル基がより好ましく、メチル基が更に好ましい。
pは、本発明の毛髪化粧料で毛髪をセットした後のセット力及び高湿度下におけるセット保持性及びセットした後の毛髪の感触の観点から、好ましくは50以上、より好ましくは60以上、更に好ましくは80以上、より更に好ましくは100以上の数であり、また、本発明のグラフトポリマーの水分散性の観点及びセットした後の毛髪の感触の観点から、好ましくは1500以下、より好ましくは1300以下、より好ましくは900以下、更に好ましくは500以下、より更に好ましくは200以下の数である。
qは、グラフトポリマーの水分散性の観点から、好ましくは3以上の数であり、本発明の毛髪化粧料のセット力及び高湿度下におけるセット保持性の観点から好ましくは150以下、より好ましくは110以下、より好ましくは70以下、より好ましくは20以下、更に好ましくは10以下の数である。
本発明において、ヘテロ原子を含んでいてもよいアルキレン基の炭素数は、本発明のグラフトポリマー製造時の原料の入手性の観点から、好ましくは2以上、より好ましくは3以上であり、また、本発明のグラフトポリマーの水分散性の観点から、好ましくは20以下、より好ましくは10以下、更に好ましくは8以下である。
本発明のグラフトポリマーの製造の容易性の観点から、ヘテロ原子を含んでいてもよいアルキレン基は、-S-が置換していることが好ましい。
ヘテロ原子を含んでいてもよいアルキレン基(R2)は、該ヘテロ原子、好ましくは窒素原子、酸素原子、又は硫黄原子、より好ましくは硫黄原子を介して不飽和単量体由来の重合体セグメントと結合していることが好ましい。
したがって、R2で表される「ヘテロ原子を含んでいてもよいアルキレン基」は、(i)無置換のアルキレン基、(ii)酸素原子、硫黄原子、-NH-、-COO-、-NHCO-、及び-NR3CO-から選ばれる1つ以上の原子又は官能基によって分断されたアルキレン基、(iii)水酸基、アミノ基、アルキル(炭素数1以上3以下)アミノ基、ジアルキル(炭素数1以上3以下)アミノ基、アミノ基と炭素数2~4の脂肪酸が脱水縮合して得られるアミド基、カルボキシ基及びアルキル(炭素数1以上3以下)エステル基から選ばれる1つ以上の1価の基が置換しているアルキレン基、(iv)-O-、-S-、-NH-、-NR14-及び-COO-から選ばれる2価のヘテロ原子、又はヘテロ原子を含む2価の基が置換したアルキレン基の他、上記(ii)、(iii)、(iv)の組合せからなるアルキレン基が該当する。
式(xii)中、X1は-O-、-OCO-、-COO-、-CONH-、-NHCO-から選ばれる一種以上であり、本発明のグラフトポリマーの製造の容易性の観点から-CONH-又は-NHCO-が好ましく、-NHCO-がより好ましい。
本発明のグラフトポリマー中におけるオルガノポリシロキサンセグメントの含有量は、本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合には、「製造時に投入されるラジカル反応性オルガノポリシロキサンの総質量(c)」と、「製造時に投入される不飽和単量体の総質量(d)」から求めることができる。
本発明のグラフトポリマーは、側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを有する。本発明において、不飽和単量体由来の繰返し単位とは、該不飽和単量体を重合した場合に形成される繰返し単位をいう。
これらカルボン酸を有する不飽和単量体由来の繰返し単位は、酸のままであってもよいし、一部又は全部が中和されたものであってよい。中和に使用する塩基化合物の具体例としては、例えば、水酸化リチウム、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物;アンモニア;モノ-、ジ-、もしくはトリエタノールアミン、トリエチルアミン、モルホリン、アミノメチルプロパノール、アミノエチルプロパンジオール等のアミン化合物等がある。このうち、本発明のグラフトポリマーの水分散性の観点から、一部又は全部が中和されていることが好ましい。
共重合単量体としては、カルボン酸又はその塩を有する不飽和単量体と共重合可能な単量体であって、且つカルボン酸又はその塩を有する不飽和単量体以外であれば特に限定は無いが、イオン性の基を持たない不飽和単量体であることが好ましく、例えばオレフィン、ハロゲン化オレフィン、ビニルエステル、(メタ)アクリル酸エステル、(メタ)アクリルアミド類等が挙げられる。
(メタ)アクリルアミド類の具体例としては、(メタ)アクリルアミド、N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、N-シクロヘキシル(メタ)アクリルアミド、N-t-オクチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミドが挙げられる。
これら共重合単量体由来の繰返し単位は、本発明のグラフトポリマー中、ただ1種存在していてもよいし、複数種存在していてもよい。
共重合単量体由来の繰返し単位の含有量は、本発明の毛髪化粧料で毛髪をセットした後のセット力及び高湿度下におけるセット保持性の観点から、本発明のグラフトポリマー中、好ましくは24質量%以上、より好ましくは28質量%以上であり、また、セットした後の毛髪の感触の観点及びグラフトポリマーの水分散性の観点から、好ましくは61質量%以下、より好ましくは55質量%以下である。
本発明のグラフトポリマー中、あるいは不飽和単量体由来の共重合体セグメント中における共重合単量体由来の繰返し単位の含有量は、本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合には、「製造時に投入されるラジカル反応性オルガノポリシロキサンの総質量(c)」、「製造時に投入される不飽和単量体の総質量(d)」及び「製造時に投入される共重合単量体の総質量」から求めることができる。
本発明のグラフトポリマーにおいて、ホモポリマーを形成した場合にはガラス転移点(Tg)が150℃以上となる不飽和単量体由来の繰返し単位の含有量は、本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合には、「製造時に投入されるラジカル反応性オルガノポリシロキサンの総質量(c)」、「製造時に投入される不飽和単量体の総質量(d)」及び「製造時に投入されるTgが150℃以上の不飽和単量体の総質量」から求めることができる。
なお、本明細書において、前記質量比(a/b)は、本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合には、「製造時に投入されるラジカル反応性オルガノポリシロキサンの総質量(c)」と、「製造時に投入される不飽和単量体の総質量(d)」との比(c/d)と同一であるとみなす(下式(I))。
a/b = c/d (I)
なお、本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合には、オルガノポリシロキサングラフトポリマーとオルガノポリシロキサングラフトポリマーに結合していない不飽和単量体由来の共重合体との混合物になる場合があるが、本発明においては、この混合物をオルガノポリシロキサングラフトポリマーとする。
ここで、「隣接する不飽和単量体由来の共重合体セグメント間におけるオルガノポリシロキサンセグメント」とは、下記式に示すように、不飽和単量体由来の共重合体セグメントのオルガノポリシロキサンセグメントに対する結合点(結合点A)から、これに隣接する不飽和単量体由来の共重合体セグメントの結合点(結合点B)までの2点間において破線で囲まれた部分であって、1つのR1SiO単位と、1つのR2と、y+1個のR12SiO単位とから構成されるセグメントをいう。
グラフト点間分子量は、上記式において破線で囲まれた部分の分子量の平均値であって、不飽和単量体由来の共重合体セグメント1モル当たりのオルガノポリシロキサンセグメントの質量(g/mol)と解することができる。グラフト点間分子量は、本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合であって、かつすべてのラジカル反応性官能基と不飽和単量体由来の共重合体とが結合している場合には、ラジカル反応性オルガノポリシロキサンの単位質量当たりに存在するラジカル反応性官能基モル数(mol/g)の逆数の値と一致する。
本発明のオルガノポリシロキサングラフトポリマーが、後述のラジカル反応性オルガノポリシロキサンから製造される場合には、オルガノポリシロキサンセグメントはラジカル反応性オルガノポリシロキサンと共通の骨格を有するため、MNxはラジカル反応性オルガノポリシロキサンの数平均分子量と略同一であり、本発明においては同一と見なす。なお、ラジカル反応性オルガノポリシロキサンの数平均分子量は、実施例に記載の測定条件によるGPCで測定し、ポリスチレン換算したものである。
本発明のグラフトポリマーが後述のラジカル反応性オルガノポリシロキサンから製造される場合には、MNtは、原料化合物であるラジカル反応性オルガノポリシロキサンの数平均分子量と、前述の質量比(a/b)とから求める。
次に、本発明のグラフトポリマーの製造方法について説明する。本発明のグラフトポリマーの製造方法としては特に制限はないが、例えば(i)反応性官能基を有するオルガノポリシロキサンと、該反応性官能基と反応しうる官能基を末端に有するカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを反応させるgraft-onto法(高分子反応法)、(ii)後述のラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含有する不飽和単量体をラジカル重合させるgraft-from法等があげられる。これらの中では製造時の負荷低減の観点から、(ii)ラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含有する不飽和単量体をラジカル重合させるgraft-from法が好ましい。
以下graft-from法による本発明のグラフトポリマーの製造方法に関して説明する。
本発明のグラフトポリマーは、下記一般式(4)又は(5)で示されるラジカル反応性オルガノポリシロキサンの存在下、不飽和単量体をラジカル重合することにより製造することができる。
前記一般式(4)及び(5)中、R11の好ましい様態は、前記一般式(1)及び(2)中、R1の好ましい様態と同様である。
前記一般式(4)及び(5)中のp及びqは、それぞれ一般式(1)及び(2)のp及びqと同義であり、好ましい様態は、それぞれ前記一般式(1)及び(2)中のp及びqの好ましい様態と同様である。
なお、本発明において、ラジカル反応性基含有アルキル基の炭素数には、ラジカル反応性官能基が炭素を有する場合であってもラジカル反応性官能基の炭素数は含まれず、またラジカル反応性基含有アルキル基が前述の1価の基が置換したものであった場合も、該1価の基の炭素数は含まれない。
なお、本発明においてラジカル反応性オルガノポリシロキサンの数平均分子量は、実施例に記載の測定条件によるGPCで測定し、ポリスチレン換算したものである。
またラジカル反応性オルガノポリシロキサンは、下記一般式(6)又は(7)で示される反応性官能基を有するオルガノポリシロキサンと、ラジカル反応性付与剤とを反応させて得ることもできる。一般式(6)及び(7)で示される反応性官能基を有するオルガノポリシロキサンは、種々の構造のものが市販されており、入手が容易である。
一般式(6)及び(7)中の、R21の好ましい様態は、一般式(4)及び(5)におけるR11の好ましい様態と同様である。
反応性官能基を有するオルガノポリシロキサンは、水酸基、アミノ基、カルボキシ基、エポキシ基から選ばれる1種以上の置換基を有している。
反応性官能基としては、入手性の観点から、水酸基、アミノ基、又はエポキシ基が好ましく、反応性及び取扱い性の観点から、アミノ基が好ましい。
なお、本発明においてMNxmは、実施例に記載の測定条件によるGPCで測定し、ポリスチレン換算したものである。
本発明においてラジカル反応性付与剤とは、反応性官能基を有するオルガノポリシロキサンの反応性官能基と反応して、反応性官能基を有するオルガノポリシロキサンにラジカル反応性官能基を付加する剤をいう。
ラジカル反応性付与剤のラジカル反応性官能基及びその好ましい様態は、前記ラジカル反応性オルガノポリシロキサンのラジカル反応性官能基及びその好ましい様態と同様である。中でも、重合時の反応性の観点から、ラジカル反応性付与剤はラジカル反応性官能基として、スルファニル基(メルカプト基)を有しているものが好ましく、例えば、3-メルカプトプロピオン酸等のスルファニル基とカルボキシ基を分子内に有する化合物、γ-ブチロラクトンチオール等のスルファニル基を有するラクトン類等が挙げられる。また、置換基を有していてもよいチオラクトンとしては、γ-チオブチロラクトン、N-アセチル-DL-ホモシステインチオラクトン、DL-ホモシステインチオラクトン塩酸塩等が挙げられる。これらの内、ラジカル反応性付与剤としては、反応性オルガノポリシロキサンとの反応性、重合時の反応性の観点からN-アセチル-DL-ホモシステインチオラクトンがより好ましい。
ラジカル反応性付与剤と反応性官能基を有するオルガノポリシロキサンとの反応では、溶媒を用いてもよい。
溶媒としては水、メタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、ヘキサン、シクロヘキサン等の炭化水素類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ベンゼン、トルエン等の芳香族化合物、ジクロロメタン、クロロホルム等のハロゲン化炭化水素等が挙げられる。
環境負荷低減の観点から、溶媒は用いないことが好ましい。
反応時間は、反応を十分に進行させる観点から、好ましくは1時間以上、より好ましくは2時間以上であり、また、生産性の観点から、好ましくは10時間以下、より好ましくは5時間以下である。
反応は、得られるラジカル反応性オルガノポリシロキサンの反応性の観点から、反応性官能基を有するオルガノポリシロキサンの反応性官能基とラジカル反応性付与剤の少なくとも一方の転化率が、80%以上となるまで行うことが好ましく、90%以上となるまで行うことがより好ましい。
転化率の測定法は、反応に用いる反応性官能基を有するオルガノポリシロキサンの反応性官能基、及びラジカル反応性付与剤によって異なるが、いずれも公知の方法によって測定できる。例えば反応性官能基を有するオルガノポリシロキサンの反応性官能基がアミノ基であり、ラジカル反応性付与剤がチオラクトン類である場合には、アミノ基の転化率は「石油製品全塩基価試験方法(過塩素酸法)」(JIS K 2501)によって求められ、またチオラクトン類の転化率は、ガスクロマトグラフ法を用いて求めることができる。
ラジカル反応性オルガノポリシロキサンの存在下、不飽和単量体を重合させる方法は特に限定されず、バルク重合法、溶液重合法、懸濁重合法等を採用しうるが、特に溶液重合法が好ましい。
溶媒の具体例としては、水、メタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、ヘキサン、シクロヘキサン等の炭化水素類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ベンゼン、トルエン等の芳香族化合物、ジクロロメタン、クロロホルム等のハロゲン化炭化水素等が挙げられる。これらは単独で又は2種以上を組み合わせて使用してよい。
これらの中で、より均一な側鎖分子量分布を有する本発明のグラフトポリマー得る観点から、水、エタノール、イソプロパノール等の炭素数1以上8以下のアルコール、酢酸エチル、酢酸ブチル等の炭素数2以上8以下のエステル、ジエチルエーテル、及びテトラヒドロフラン等の炭素数2以上8以下のエーテルから選ばれる1種以上の溶媒を用いることが好ましく、本発明のグラフトポリマーを毛髪化粧料用途等に用いる場合、化粧料製品へのグラフトポリマー製造時の溶媒の持ち込みの観点から水、エタノール等の炭素数1以上3以下のアルコールから選ばれる1種以上を用いることがより好ましい。
不飽和単量体の転化率は、核磁気共鳴(1H-NMR)分析により求めることができる。具体的な操作については、実施例に記載する。
重合反応時間は通常0.1時間以上60時間以下であり、操作性の観点から、好ましくは0.5時間以上、より好ましくは1時間以上、更に好ましくは2時間以上、より更に好ましくは4時間以上であり、また、生産性の観点から、好ましくは30時間以下、より好ましくは20時間以下、更に好ましくは10時間以下である。重合反応を、原料を滴下して行う場合、重合反応時間は、滴下時間を含む。重合反応の時間は、重合反応温度を変えることにより制御することができる。
また重合反応終了後に必要に応じて公知の方法によって精製や、未反応の不飽和単量体の低減等を行ってもよい。例えば、重合開始剤を添加して加熱することや膜精製、水蒸気蒸留、吸着剤処理等による未反応の不飽和単量体やその他不純物の低減を行ってもよい。
すなわち、主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを有するオルガノポリシロキサングラフトポリマーの製造方法であって、下記一般式(4)又は(5)で表されるラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含む不飽和単量体を重合させ、得られるオルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマーの製造方法によって製造することができる。
(本発明のグラフトポリマー(成分(A)))
本発明の毛髪化粧料は、本発明のグラフトポリマー(以下「成分(A)」ともいう)を含有する。これにより、柔軟な感触と、手指を髪に通してもヘアスタイルが崩れないセット特性と、より自然な仕上がりが得られる。
その他、本発明の毛髪化粧料においては、毛髪のセット力、使用感の良さ、毛髪化粧料を調製する際の操作性の観点から、溶媒として水、炭素数1以上3以下の直鎖若しくは分岐の飽和若しくは不飽和アルコールから選ばれる1種以上を含有させることができる。中でも、溶媒としては、水、エタノール、及びイソプロパノールから選ばれる1種以上が好ましく、水、エタノールから選ばれる1種以上が特に好ましい。
また、本発明の毛髪化粧料は、毛髪のハリ及びコシ向上効果、毛髪の柔らかさやまとまり性改善効果、改質効果の促進(弾性の向上、耐湿性の向上等)のほか、成分(A)と相溶させることで毛髪のセット力を向上させる観点から、更に、次の(b1)~(b5)から選ばれる有機溶剤(以下、「成分(B)」という)を好ましい成分として含有することができる。
(b2)窒素原子に炭素数1以上18以下のアルキル基又はアルケニル基が結合したN-アルキルピロリドン又はN-アルケニルピロリドン
(b3)炭素数2以上4以下のアルキレンカーボネート
(b4)数平均分子量200以上1,000以下のポリプロピレングリコール
(b5)一般式(9)、(10)又は(11)で表されるラクトン又は環状ケトン
(b5)のうち、ラクトンとしては、γ-ブチロラクトン、γ-カプロラクトン、γ-バレロラクトン、δ-バレロラクトン、δ-カプロラクトン、δ-ヘプタノラクトン等が挙げられるが、ラクトンの安定性の点から、γ-ラクトン、特にγ-ブチロラクトン、γ-カプロラクトンが好ましい。
(b5)のうち、環状ケトンとしては、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、4-メチルシクロヘプタノン等が挙げられる。
また成分(B)の浸透促進の観点から、成分(B)のClogPが、好ましくは-2以上、より好ましくは-1以上であり、また、好ましくは3以下、より好ましくは2以下である。ここで、ClogPとは、オクタノール相と水相の間での物質の分配を表す尺度である、下記式(II)で定義されるオクタノール-水-分配係数(logP)の計算値をいい、ケミカルレビューズ,71巻,6号(1971)にその例が記載されている。
logP=log([物質]Octanol/[物質]Water) (II)
〔式中、[物質]Octanolは1-オクタノール相中の物質のモル濃度を、[物質]Waterは水相中の物質のモル濃度を示す。〕
また、本発明で使用する毛髪化粧料には、成分(B)とともに、毛髪の内部改質(空洞補修など)効果、毛髪のハリ及びコシ向上効果、毛髪の柔らかさやまとまり性改善効果のほか、成分(A)と相溶させることで毛髪のセット力を向上させる観点から、ヒドロキシ基を有していてもよい有機カルボン酸又はその塩(以下、「成分(C)」という)を含有させることができる。この場合、成分(C)の浸透促進の観点から、好ましい成分(B)としては、ジプロピレングリコール、1,3-ブタンジオール、ベンジルアルコール、フェノキシエタノール、2-ベンジルオキシエタノール、プロピレンカーボネート及びポリプロピレングリコール(数平均分子量が好ましくは300以上500以下、より好ましくは400)が挙げられる。
成分(C)の有機カルボン酸の具体例としては、酢酸、プロピオン酸等のモノカルボン酸;マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、フタル酸等のジカルボン酸;ポリグルタミン酸等のポリカルボン酸;グリコール酸、乳酸、ヒドロキシアクリル酸、グリセリン酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシカルボン酸;グルタミン酸、アスパラギン酸等の酸性アミノ酸等が挙げられる。中でも、成分(C)の浸透促進の観点から炭素数2以上6以下のヒドロキシカルボン酸が好ましく、とりわけ乳酸、リンゴ酸が好ましい。
これら有機カルボン酸の塩としては、例えば、アルカリ金属、アルカリ土類金属、アンモニア、有機アミン化合物との塩が挙げられる。
また、本発明の毛髪化粧料にセットポリマーである成分(A)に加え、更にセットポリマー(以下、「成分(D)」という)を必要に応じて、配合することもできる。
成分(D)のセットポリマーとしては、下記1)~8)に示すものが挙げられ、単独で又は2種以上を組み合わせて用いることができる。
ポリビニルピロリドン
市販品として、「ルビスコールK12」、「ルビスコールK30」(以上、BASF社製)、「PVP K15」、「PVP K30」(以上、Ashland社製)等が挙げられる。
市販品として、「ルビスコールVA28」、「ルビスコールVA73」(以上、BASF社製)、「PVP/VA E-735」、「PVP/VA S-630」(以上、Ashland社製)等が挙げられる。
市販品として、「ルビスコールVAP343」(BASF社製)等が挙げられる。
市販品として、「ルビフレックス」(BASF社製)、「コポリマー845」、「コポリマー937」、「コポリマー958」(Ashland社製)等が挙げられる。
市販品として、「ルビフレックスVBM35」(BASF社製)等が挙げられる。
市販品として、「コポリマーVC-713」(Ashland社製)等が挙げられる。
メチルビニルエーテル/無水マレイン酸アルキルハーフエステル共重合体
市販品として、「ガントレッツES-225」、「ガントレッツES-425」、「ガントレッツSP-215」(以上、Ashland社製)等が挙げられる。
酢酸ビニル/クロトン酸共重合体
市販品として、「レジン28-1310」(アクゾノーベル社製)、「ルビセットCA66」(BASF社製)等が挙げられる。
市販品として、「レジン28-2930」(アクゾノーベル社製)等が挙げられる。
市販品として、「ルビセットCAP」(BASF社製)等が挙げられる。
(メタ)アクリル酸/(メタ)アクリル酸エステル共重合体
市販品として、「プラスサイズL53P」(互応化学工業(株)製)、「ダイヤホールド」((株)三菱ケミカルホールディングス製)等が挙げられる。
市販品として、「ウルトラホールド8」(BASF社製)、「アンフォーマーV-42」(アクゾノーベル社製)等が挙げられる。
(メタ)アクリルエチルベタイン/(メタ)アクリル酸アルキルエステル共重合体
例えば、N-メタクリロイルオキシエチル-N,N-ジメチルアンモニウム-α-N-メチルカルボキシベタインと、(メタ)クリル酸アルキルエステルとの共重合体等が例示され、市販品としては「ユカフォーマーM-75」、「ユカフォーマーSM」(以上、(株)三菱ケミカルホールディングス製)等が挙げられる。
アミド共重合体
例えば、オクチルアクリルアミド/アクリレート/ブチルアミノエチルメタクリレートコポリマー等が例示され、市販品として、「アンフォーマー28-4910」(アクゾノーベル社製)等が挙げられる。
アクリルアミド・アクリルエステル系共重合体
例えば、特開平2-180911号公報、特開平8-291206号公報の実施例に記載されているもの等が挙げられる。
カチオン性セルロース誘導体
市販品として、「セルコートH-100」、「セルコートL-200」(アクゾノーベル社製)等が挙げられる。
ヒドロキシプロピルキトサン
市販品として、「キトフィルマー」(一丸ファルコス(株)製)等が挙げられる。
本発明で使用する毛髪化粧料には、コンディショニング効果の更なる向上のため、油剤及びシリコーン類(但し、本発明の成分(A)を除く)から選ばれるコンディショニング成分を含有させることができる。
ジメチルポリシロキサンとしては、求める感触に応じて5mm2/s程度の粘度のものから、エマルションとして供給される場合が多い1,000万mm2/s程度の粘度のものまで使用できる。ジメチルポリシロキサンの粘度は、好ましくは5,000mm2/s以上、より好ましくは5万mm2/s以上であり、また、好ましくは1,000万mm2/s以下、より好ましくは1,000万mm2/sである。なお、上記粘度は25℃における粘度である。
本発明の毛髪化粧料には、溶剤の可溶化、分散性等を含めた系の安定性、及び感触向上の点から、界面活性剤を含有させることができる。界面活性剤としては、カチオン界面活性剤、非イオン界面活性剤、両性界面活性剤及びアニオン界面活性剤のいずれをも使用できる。
界面活性剤の含有量は、本発明の毛髪化粧料を使用した際の感触の観点、及び溶剤や油剤を配合する場合の該溶剤や油剤の可溶化、乳化等を含めた系の安定性の点から、毛髪化粧料中、好ましくは0.01質量%以上、より好ましくは0.05質量%以上であり、また、好ましくは10質量%以下、より好ましくは5質量%以下である。
更に、本発明で使用する毛髪化粧料には、成分(B)以外の多価アルコールを含有させることができる。多価アルコールは、成分(B)の可溶化、安定分散に寄与し、また、成分(B)と相乗的に働き、ツヤや毛髪の改質効果の向上を促進する。多価アルコールとしては、グリセリン、ソルビトールなどが挙げられ、グリセリンが好ましい。
多価アルコールは、単独で又は2種以上を組み合わせて使用できる。
多価アルコールの含有量は、毛髪化粧料中、好ましくは0.1質量%以上、より好ましくは0.5質量%以上であり、また、好ましくは10質量%以下、より好ましくは5質量%以下である。
本発明で使用する毛髪化粧料には、上記成分のほか、通常の毛髪化粧料に用いられる成分を目的、用途、剤型等に応じて適宜配合できる。このような成分としては、例えば、ジンクピリチオン、オクトピロックス等の抗フケ剤;ビタミン剤;トリクロサン、トリクロロカルバン等の殺菌剤;グリチルリチン酸ジカリウム、酢酸トコフェロール等の抗炎症剤;メチルパラベン、ブチルパラベン等の防腐剤;キレート剤;パンテノール等の保湿剤;染料、顔料等の着色剤;ヒドロキシエチルセルロース、メチルセルロース、ポリエチレングリコール、粘土鉱物等の粘度調整剤;有機酸、水酸化ナトリウム、水酸化カリウム等のpH調整剤;植物エキス類;パール化剤;香料;色素;紫外線吸収剤;酸化防止剤;その他エンサイクロペディア・オブ・シャンプー・イングリーディエンツ〔ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS)〕に記載されている成分等が挙げられる。
本発明で使用する毛髪化粧料は、常法に従い各種剤型に調製することができ、例えば、ミスト、ローション、トニック等の液状組成物だけなく、ゲル状、ペースト状、クリーム状、ワックス状等の半固形状組成物とすることができる。
噴射剤の含有量は、本発明の毛髪化粧料(但し噴射剤を除く)に対して、好ましくは0.01質量%以上、より好ましくは10質量%以上であり、また、好ましくは100質量%以下、より好ましくは40質量%以下である。
該オルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、該オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマー。
<3>前記オルガノポリシロキサンセグメント中の隣接する不飽和単量体由来の共重合体セグメント間におけるオルガノポリシロキサンセグメントの数平均分子量(MNg)が好ましくは500以上、より好ましくは700以上、更に好ましくは1000以上であり、また、好ましくは3万以下、より好ましくは2万以下、更に好ましくは4000以下である、前記<1>又は<2>に記載のオルガノポリシロキサングラフトポリマー。
<5>前記一般式(1)及び(2)において、R1が炭素数1以上6以下の直鎖又は分岐状のアルキル基、好ましくは炭素数1以上3以下の直鎖又は分岐状のアルキル基、より好ましくはメチル基である、前記<4>に記載のオルガノポリシロキサングラフトポリマー。
<6>前記一般式(1)及び(2)において、pが好ましくは50以上、より好ましくは60以上、更に好ましくは80以上、より更に好ましくは100以上の数であり、また、好ましくは1500以下、より好ましくは1300以下、より好ましくは900以下、更に好ましくは500以下、より更に好ましくは200以下の数である、前記<4>又は<5>に記載のオルガノポリシロキサングラフトポリマー。
<7>前記一般式(1)及び(2)において、qが、好ましくは3以上の数であり、また、好ましくは150以下、より好ましくは110以下、より好ましくは70以下、より好ましくは20以下、更に好ましくは10以下の数である、前記<4>~<6>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<8>前記一般式(1)及び(2)において、ヘテロ原子を含んでいてもよいアルキレン基(R2)の炭素数が好ましくは2以上、より好ましくは3以上であり、また、好ましくは20以下、より好ましくは10以下、更に好ましくは8以下である、前記<4>~<7>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<9>前記一般式(1)及び(2)におけるヘテロ原子を含んでいてもよいアルキレン基(R2)のヘテロ原子、好ましくは窒素原子、酸素原子、又は硫黄原子、より好ましくは硫黄原子を介して不飽和単量体由来の重合体セグメントと結合している、前記<4>~<8>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
式(xii)中、X1は-O-、-OCO-、-COO-、-CONH-、-NHCO-から選ばれる一種以上であり、式(xii)中、R2は、水酸基、アミノ基、アルキル(炭素数1以上3以下)アミノ基、ジアルキル(炭素数1以上3以下)アミノ基、アミノ基と炭素数2~4の脂肪酸が脱水縮合して得られるアミド基、カルボキシ基及びアルキル(炭素数1以上3以下)エステル基から選ばれる1つ以上の1価の基が置換していてもよいアルキレン基である。)
<12>前記式(xii)において、R2がアセトアミド基、アルキル(炭素数1以上3以下)アミノ基、又はアミノ基で置換されていてもよいアルキレン基である、前記<10>又は<11>に記載のオルガノポリシロキサングラフトポリマー。
<13>前記式(xii)において、R2が下記式(xiii)~(xiv)から選ばれる基である、前記<10>~<12>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<15>オルガノポリシロキサングラフトポリマー中のオルガノポリシロキサンセグメントの含有量が、好ましくは38質量%以上、より好ましくは40質量%以上、更に好ましくは45質量%以上であり、より好ましくは55質量%以下、更に好ましくは50質量%以下である、前記<1>~<14>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<16>オルガノポリシロキサングラフトポリマー中の不飽和単量体由来の共重合体セグメントの含有量が、41質量%以上、好ましくは45質量%以上、より好ましくは50質量%以上であり、また、65質量%以下、好ましくは62質量%以下、より好ましくは60質量%以下、更に好ましくは55質量%以下である、前記<1>~<15>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<17>オルガノポリシロキサングラフトポリマー中の、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が、好ましくは4.5質量%以上、より好ましくは8質量%以上であり、また、好ましくは14質量%以下、より好ましくは11質量%以下、更に好ましくは9質量%以下である、前記<1>~<16>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<18>不飽和単量体由来の共重合体セグメント中におけるカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量は、好ましくは6質量%以上、より好ましくは10質量%以上、更に好ましくは17質量%以上であり、また、好ましくは41質量%以下、より好ましくは30質量%以下、更に好ましくは25質量%以下、より更に好ましくは18質量%以下である、前記<1>~<17>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<19>オルガノポリシロキサングラフトポリマー中の、ホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が好ましくは12質量%以下、より好ましくは10質量%以下、更に好ましくは5質量%以下である、前記<1>~<18>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<20>前記カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントが、カルボン酸又はその塩を有する不飽和単量体以外に、カルボン酸又はその塩を有する不飽和単量体と共重合可能な不飽和単量体由来の繰返し単位を含有する、前記<1>~<19>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<21>前記カルボン酸又はその塩を有する不飽和単量体と共重合可能な不飽和単量体由来の繰返し単位が、イオン性の基を持たない不飽和単量体由来の繰返し単位、好ましくはオレフィン、ハロゲン化オレフィン、ビニルエステル、(メタ)アクリル酸エステル、(メタ)アクリルアミド類からなる群より選ばれる1種以上の不飽和単量体由来の繰返し単位、より好ましくは(メタ)アクリルアミド類及び(メタ)アクリル酸エステルから選ばれる1種以上の不飽和単量体由来の繰返し単位である、前記<20>に記載のオルガノポリシロキサングラフトポリマー。
<22>前記オルガノポリシロキサングラフトポリマー中における、前記カルボン酸又はその塩を有する不飽和単量体と共重合可能な不飽和単量体由来の繰返し単位の含有量が、好ましくは24質量%以上、より好ましくは28質量%以上であり、また、好ましくは61質量%以下、より好ましくは55質量%以下である、前記<20>又は<21>に記載のオルガノポリシロキサングラフトポリマー。
<23>不飽和単量体由来の共重合体セグメント中における、前記カルボン酸又はその塩を有する不飽和単量体と共重合可能な不飽和単量体由来の繰返し単位の含有量が、好ましくは59質量%以上、より好ましくは65質量%以上、更に好ましくは70質量%以上、より更に好ましくは82質量%以上であり、また、好ましくは94質量%以下、より好ましくは90質量%以下、更に好ましくは83質量%以下である、前記<20>~<22>に記載のオルガノポリシロキサングラフトポリマー。
<24>前記オルガノポリシロキサンセグメント(a)と前記不飽和単量体由来の共重合体セグメント(b)との質量比(a/b)が、好ましくは35/65以上、より好ましくは38/62以上、更に好ましくは40/60以上、より更に好ましくは45/55以上であり、また、好ましくは59/41以下、より好ましくは55/45以下、更に好ましくは50/50以下である、前記<1>~<23>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<25>数平均分子量(MNt)が好ましくは10,000以上、より好ましくは14,000以上、更に好ましくは20,000以上であり、また、好ましくは300,000以下、より好ましくは250,000以下、更に好ましくは100,000以下、より更に好ましくは50,000以下である、前記<1>~<24>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<26>不飽和単量体由来の共重合体セグメントの数平均分子量(MNy)は、好ましくは500以上、より好ましくは1000以上、更に好ましくは1500以上であり、また、好ましくは50000以下、より好ましくは30000以下、更に好ましくは6000以下である、前記<1>~<25>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<28>前記ラジカル反応性オルガノポリシロキサンが、下記一般式(4)又は(5)で示されるラジカル反応性オルガノポリシロキサンである、前記<27>に記載のオルガノポリシロキサングラフトポリマー。
<29>ラジカル反応性官能基が、エチレン性不飽和基、ハロゲノ基、及びスルファニル基から選ばれる基、好ましくはスルファニル基である、前記<28>に記載のオルガノポリシロキサングラフトポリマー。
<30>前記一般式(4)及び(5)において、R11が炭素数1以上6以下の直鎖又は分岐状のアルキル基、好ましくは炭素数1以上3以下の直鎖又は分岐状のアルキル基、より好ましくはメチル基である、前記<28>又は<29>に記載のオルガノポリシロキサングラフトポリマー。
<31>前記一般式(4)及び(5)において、pが好ましくは50以上、より好ましくは60以上、更に好ましくは80以上、より更に好ましくは100以上の数であり、また、好ましくは1500以下、より好ましくは1300以下、より好ましくは900以下、更に好ましくは500以下、より更に好ましくは200以下の数である、前記<28>~<30>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<32>前記一般式(4)及び(5)において、qが好ましくは3以上の数であり、また、好ましくは150以下、より好ましくは110以下、より好ましくは70以下、より好ましくは20以下、更に好ましくは10以下の数である、前記<28>~<31>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<33>前記一般式(4)及び(5)において、R12で示されるラジカル反応性基含有アルキル基の炭素数が、好ましくは2以上、より好ましくは3以上であり、また、好ましくは20以下、より好ましくは10以下、更に好ましくは8以下である、前記<28>~<32>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<34>前記一般式(4)及び(5)において、R12で示されるラジカル反応性基含有アルキル基が、酸素原子、硫黄原子、-NH-、-COO-、-NHCO-、及び-NR13CO-から選ばれる1つ以上の原子又は官能基によって分断されている、前記<28>~<33>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<35>前記一般式(4)及び(5)において、R12で示されるラジカル反応性基含有アルキル基が、下記式(xvii)~(xx)で表される基から選ばれる基、好ましくは下記式(xix)又は(xx)で表される基である、前記<28>~<34>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<36>ラジカル反応性オルガノポリシロキサンの単位質量当たりに存在するラジカル反応性官能基のモル数が、好ましくは1/500mol/g以下、より好ましくは1/700mol/g以下、更に好ましくは1/1000mol/g以下、より更に好ましくは1/1500mol/g以下であり、また、好ましくは1/3万mol/g以上、より好ましくは1/2万mol/g以上、更に好ましくは1/1万mol/g以上、より更に好ましくは1/4000mol/g以上である、前記<27>~<35>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<37>ラジカル反応性オルガノポリシロキサンの数平均分子量が、8000以上、好ましくは10000以上、好ましくは11000以上、更に好ましくは12000以上であり、また、20万以下、好ましくは10万以下、より好ましくは5万以下、更に好ましくは3万以下である、前記<27>~<36>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<39>前記ラジカル反応性オルガノポリシロキサンが、下記一般式(6)又は(7)で示される反応性官能基を有するオルガノポリシロキサンと、ラジカル反応性付与剤とを反応させて得られた物である、前記<27>~<38>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<41>前記一般式(6)及び(7)において、R21が炭素数1以上6以下の直鎖又は分岐状のアルキル基、好ましくは炭素数1以上3以下の直鎖又は分岐状のアルキル基、より好ましくはメチル基である、前記<39>又は<40>に記載のオルガノポリシロキサングラフトポリマー。
<42>前記一般式(6)及び(7)において、pが好ましくは50以上、より好ましくは60以上、更に好ましくは80以上、より更に好ましくは100以上の数であり、また、好ましくは1500以下、より好ましくは1300以下、より好ましくは900以下、更に好ましくは500以下、より更に好ましくは200以下の数である、前記<39>~<41>ずれかに記載のオルガノポリシロキサングラフトポリマー。
<43>前記一般式(6)及び(7)において、qが好ましくは3以上の数であり、また、好ましくは150以下、より好ましくは110以下、より好ましくは70以下、より好ましくは20以下、更に好ましくは10以下の数である、前記<39>~<42>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<44>前記一般式(6)及び(7)において、R22で示される反応性基含有アルキル基の炭素数が、好ましくは2以上、より好ましくは3以上であり、また、好ましくは15以下、り好ましくは10以下、更に好ましくは5以下である、前記<39>~<43>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<45>前記一般式(6)及び(7)において、R22で示される反応性基含有アルキル基が、前記式(xxi)~(xxviii)から選ばれる基、好ましくは前記式(xxi)~(xxiv)から選ばれる基、より好ましくは前記式(xxiv)である、前記<39>~<44>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<46>反応性官能基を有するオルガノポリシロキサンの数平均分子量が、好ましくは8000以上、より好ましくは10000以上、更に好ましくは11000以上、より更に好ましくは12000以下であり、また、好ましくは20万以下、より好ましくは10万以下、更に好ましくは5万以下、より更に好ましくは3万以下である、前記<38>~<45>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<47>反応性官能基を有するオルガノポリシロキサンの単位質量当たりに存在する反応性官能基のモル数が、好ましくは1/500mol/g以下、より好ましくは1/700mol/g以下、更に好ましくは1/1000mol/g以下、より更に好ましくは1/1500mol/g以下であり、また、好ましくは1/3万mol/g以上、より好ましくは1/2万mol/g以上、更に好ましくは1/1万mol/g以上、より更に好ましくは1/4000mol/g以上である、前記<38>~<46>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<49>ラジカル反応性付与剤のラジカル反応性官能基が、エチレン性不飽和基、ハロゲノ基、及びスルファニル基から選ばれる基、好ましくはスルファニル基である、前記<48>に記載のオルガノポリシロキサングラフトポリマー。
<50>ラジカル反応性付与剤が、3-メルカプトプロピオン酸、γ-ブチロラクトンチオール、γ-チオブチロラクトン、N-アセチル-DL-ホモシステインチオラクトン、及びDL-ホモシステインチオラクトン塩酸塩から選ばれる1種以上の化合物、好ましくはN-アセチル-DL-ホモシステインチオラクトンである、前記<38>~<49>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<51>ラジカル反応性付与剤の使用量が、好ましくは0.8当量以上、より好ましくは0.9当量以上であり、また、好ましくは1.2当量以下、より好ましくは1.1当量以下である、前記<38>~<50>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<53>オルガノポリシロキサングラフトポリマーが、好ましくはグラフトポリマー中におけるオルガノポリシロキサンセグメントの含有量が45質量%以上59質量%以下、かつカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が8質量%以上17質量%以下、かつ共重合体単量体由来の繰返し単位の含有量が24質量%以上47質量%以下であり、より好ましくはオルガノポリシロキサンセグメントの含有量が50質量%以上59質量%以下、かつカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が10質量%以上15質量%以下、かつ共重合体単量体由来の繰返し単位の含有量が24質量%以上40質量%以下である、前記<1>~<51>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<54>オルガノポリシロキサングラフトポリマーが、ラジカル反応性オルガノポリシロキサンと不飽和単量体の総量に対して、好ましくは45質量%以上59質量%以下のラジカル反応性オルガノポリシロキサン、4質量%以上9質量%以下であるカルボン酸又はその塩を有する不飽和単量体及び32質量%以上51質量%以下である共重合単量体を反応させて得られるものであり、より好ましくは50質量%以上59質量%以下のラジカル反応性オルガノポリシロキサン、5質量%以上7質量%以下であるカルボン酸又はその塩を有する不飽和単量体及び34質量%以上45質量%以下である共重合単量体を反応させて得られるものである、前記<1>~<51>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<55>オルガノポリシロキサングラフトポリマーが、ラジカル反応性オルガノポリシロキサンと不飽和単量体の総量に対して、好ましくは45質量%以上59質量%以下のラジカル反応性オルガノポリシロキサン、8質量%以上17質量%以下であるカルボン酸又はその塩を有する不飽和単量体及び24質量%以上47質量%以下である共重合単量体を反応させて得られるものであり、より好ましくは50質量%以上59質量%以下のラジカル反応性オルガノポリシロキサン、10質量%以上15質量%以下であるカルボン酸又はその塩を有する不飽和単量体及び26質量%以上40質量%以下である共重合単量体を反応させて得られるものである、前記<1>~<51>のいずれかに記載のオルガノポリシロキサングラフトポリマー。
<57>重合が、溶媒の存在下に行われる溶液重合である、前記<56>に記載のオルガノポリシロキサングラフトポリマーの製造方法。
<58>ラジカル反応性オルガノポリシロキサンの使用量が、原料となるラジカル反応性オルガノポリシロキサンと原料となる不飽和単量体の総量に対して、好ましくは35質量%以上、より好ましくは38質量%以上、更に好ましくは40質量%以上、更に好ましくは45質量%以上であり、また、好ましくは59質量%以下、より好ましくは55質量%以下、更に好ましくは50質量%以下である、前記<56>又は<57>に記載のオルガノポリシロキサングラフトポリマーの製造方法。
<59>不飽和単量体の使用量が、原料となるラジカル反応性オルガノポリシロキサンと原料となる不飽和単量体の総量に対して、好ましくは41質量%以上、より好ましくは45質量%以上、更に好ましくは50質量%以上であり、また、好ましくは65質量%以下、より好ましくは62質量%以下、更に好ましくは60質量%以下、より更に好ましくは55質量%以下である、前記<56>~<58>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<60>カルボン酸又はその塩を有する不飽和単量体の使用量は、原料となるラジカル反応性オルガノポリシロキサンと原料となる不飽和単量体の総量に対して、好ましくは4.0質量%以上、より好ましくは4.5質量%以上、更に好ましくは8質量%以上であり、また、好ましくは17質量%以下、より好ましくは14質量%以下、更に好ましくは11質量%以下、より更に好ましくは9質量%以下である、前記<56>~<59>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<61>共重合単量体の使用量は、原料となるラジカル反応性オルガノポリシロキサンと原料となる不飽和単量体の総量に対して、好ましくは24質量%以上、より好ましくは28質量%以上であり、また、61質量%以下、好ましくは質量55%以下である、前記<56>~<60>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<62>Tgが150℃以上の不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)の使用量が、原料となるラジカル反応性オルガノポリシロキサンと原料となる不飽和単量体の総量に対して、好ましくは14質量%以下、より好ましくは12質量%以下、更に好ましくは10質量%以下、より更に好ましくは5質量%以下であり、下限が0質量%である、前記<56>~<61>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<63>ラジカル反応性オルガノポリシロキサンと不飽和単量体の総量に対して、好ましくはラジカル反応性オルガノポリシロキサンの使用量が45質量%以上59質量%以下、かつカルボン酸又はその塩を有する不飽和単量体の使用量が4質量%以上9質量%以下、かつ共重合単量体の使用量が32質量%以上51質量%以下であり、より好ましくはラジカル反応性オルガノポリシロキサンの使用量が50質量%以上59質量%以下、かつカルボン酸又はその塩を有する不飽和単量体の使用量が5質量%以上7質量%以下、かつ共重合単量体の使用量が34質量%以上45質量%以下である、前記<56>~<62>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<64>ラジカル反応性オルガノポリシロキサンと不飽和単量体の総量に対して、好ましくはラジカル反応性オルガノポリシロキサンの使用量が45質量%以上59質量%以下、かつカルボン酸又はその塩を有する不飽和単量体の使用量が8質量%以上17質量%以下、かつ共重合単量体の使用量が24質量%以上47質量%以下であり、より好ましくはラジカル反応性オルガノポリシロキサンの使用量が50質量%以上59質量%以下、かつカルボン酸又はその塩を有する不飽和単量体の使用量が10質量%以上15質量%以下、かつ共重合単量体の使用量が26質量%以上40質量%以下である、前記<56>~<63>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<65>溶媒が、水、炭素数1以上8以下のアルコール、炭素数2以上8以下のエステル、及び炭素数2以上8以下のエーテルから選ばれる1種以上の溶媒、好ましくは水、炭素数1以上3以下のアルコールから選ばれる1種以上である、前記<56>~<64>に記載のオルガノポリシロキサングラフトポリマーの製造方法。
<66>溶媒の使用量が、ラジカル反応性オルガノポリシロキサン及び不飽和単量体の総量に対して、好ましくは20質量%以上、より好ましくは40質量%以上、更に好ましくは60質量%以上、より更に好ましくは100質量%以上であり、また、好ましくは1000質量%以下、より好ましくは900質量%以下、更に好ましくは400質量%以下、より更に好ましくは300質量%以下である、前記<56>~<65>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<68>重合開始剤の使用量が、投入する不飽和単量体の総質量に対して、好ましくは10質量%以下、より好ましくは5質量%以下、更に好ましくは2質量%以下、より更に好ましくは1質量%以下であり、好ましくは0.001質量%以上、より好ましくは0.01質量%以上、更に好ましくは0.1質量%以上、より更に好ましくは0.5質量%以上である、前記<56>~<67>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<69>重合反応を、不飽和単量体の転化率が80%以上、好ましくは90%以上になるまで行う、前記<56>~<68>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<70>重合反応時間が、0.1時間以上、好ましくは0.5時間以上、より好ましくは1時間以上、更に好ましくは2時間以上、より更に好ましくは4時間以上であり、また、60時間以下、好ましくは30時間以下、より好ましくは20時間以下、更に好ましくは10時間以下である、前記<56>~<69>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<71>ラジカル反応性オルガノポリシロキサンが、反応性官能基を有するオルガノポリシロキサンにラジカル反応性付与剤を反応させて得られる、前記<56>~<70>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<72>反応性官能基を有するオルガノポリシロキサンとラジカル反応性付与剤との反応時間が、好ましくは1時間以上、より好ましくは2時間以上であり、また、好ましくは10時間以下、より好ましくは5時間以下である、前記<71>に記載のオルガノポリシロキサングラフトポリマーの製造方法。
<73>反応性官能基を有するオルガノポリシロキサンとラジカル反応性付与剤との反応温度が、好ましくは70℃以上、より好ましくは90℃以上であり、また、好ましくは200℃以下、より好ましくは150℃以下、更に好ましくは120℃以下である、前記<71>又は<72>に記載のオルガノポリシロキサングラフトポリマーの製造方法。
<74>反応性官能基を有するオルガノポリシロキサンとラジカル反応性付与剤との反応を、反応性官能基を有するオルガノポリシロキサンの反応性官能基とラジカル反応性付与剤の少なくとも一方の転化率が、80%以上、好ましくは90%以上となるまで行う、前記<71>~<73>のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
<75>主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを有するオルガノポリシロキサングラフトポリマーの製造方法であって、
下記一般式(4)又は(5)で表されるラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含む不飽和単量体を重合させ、
得られるオルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマーの製造方法。
<76>ラジカル反応性オルガノポリシロキサンが、下記一般式(6)又は(7)で表される反応性官能基を有するオルガノポリシロキサンにラジカル反応性付与剤を反応させて得られるものである、<75>に記載のオルガノポリシロキサングラフトポリマーの製造方法。
<77>前記<1>~<55>のいずれかに記載のオルガノポリシロキサングラフトポリマーを含有する毛髪化粧料。
<78>前記<1>~<55>のいずれかに記載のオルガノポリシロキサングラフトポリマーの毛髪化粧料への使用。
<79>前記<1>~<55>のいずれかに記載のオルガノポリシロキサングラフトポリマーを毛髪に適用する毛髪化粧方法。
<反応性官能基を有するオルガノポリシロキサン、及びラジカル反応性オルガノポリシロキサンの数平均分子量のGPC測定条件>
カラム:「K-804L」(東ソー(株)製)2つを直列につないで使用
溶離液:1mMジメチルドデシルアミン/クロロホルム溶液
流量:1.0mL/min
カラム温度:40℃
検出器:RI
サンプル濃度及びサンプル量:5mg/mL、500μL
上記条件を用い、ポリスチレン換算で、反応性官能基を有するオルガノポリシロキサンの数平均分子量(MNxm)、又はラジカル反応性オルガノポリシロキサンの数平均分子量(MNx)を測定した。
側鎖一級アミノプロピル変性オルガノポリシロキサンの単位質量当たりのアミノ基量は、ASTM D 2073に準拠した方法で行った。具体的には、フラスコに試料(側鎖一級アミノプロピル変性オルガノポリシロキサン)を約10gはかりとり、エタノールを50mL加えて撹拌し、電位差滴定装置を用いて0.2mol/Lのエタノール性塩酸溶液で滴定し、同時にブランク試験を行って補正して測定した。
側鎖一級アミノプロピル変性オルガノポリシロキサンとラジカル反応性付与剤との反応により得られたスルファニル基変性オルガノポリシロキサン(ラジカル反応性オルガノポリシロキサン)を含む混合物のアミノ基量及び前記側鎖一級アミノプロピル変性オルガノポリシロキサンの単位質量当たりのアミノ基量から、反応により消費されたアミノ基量を測定した。スルファニル基変性オルガノポリシロキサンを含む混合物のアミノ基量の測定は、試料としてスルファニル基変性オルガノポリシロキサンを含む混合物を用いた他は、前記側鎖一級アミノプロピル変性オルガノポリシロキサンの単位質量当たりのアミノ基量の測定と同様に行った。
α(%)=[1-{a1×(f+g)/(a0×f)}]×100 (IV)
上式中、a0、a1は、それぞれ側鎖一級アミノプロピル変性オルガノポリシロキサンの単位質量当たりのアミノ基のモル数、及びラジカル反応性付与剤との反応後の反応混合物中の単位質量当たりのアミノ基のモル数を表し、fは側鎖一級アミノプロピルオルガノポリシロキサンの仕込み総質量、gはラジカル反応性付与剤の仕込み総質量を示す。
S(mol/g)=(a0×f×α/100)/[f+(a0×f×α/100)×h] (V)
上式中、a0、fは、それぞれ上記式(IV)中のa0、fと同じ意味を示し、hはラジカル反応性付与剤の分子量を表す。
5,5’-ジチオビス(2-ニトロ安息香酸)(和光純薬工業(株)製)0.05mMエタノール溶液を調製し、溶液Aとした。実施例で得られたオルガノポリシロキサングラフトポリマーの4~10質量%エタノール溶液を調製し、溶液Bとした。10mLスクリュー管にほう酸塩pH標準液(pH9.18)(和光純薬工業(株)製)100μL、溶液A 5mL、溶液B 1mLを加え、ふたをして5秒振り混ぜた。この溶液の412nmの吸光度から測定される残存スルファニル基量(S1)から、スルファニル基の残存率を算出し、更にスルファニル基の転化率を算出した。
UV測定装置:UV可視分光光度計((株)島津製作所製)
セルの光路長:1cm
残存スルファニル基量S1(mol/g)=(2350×I+0.0058)/1000
スルファニル基の残存率(%)=S1/S×(c+d)/c×100 (VI)
スルファニル基の転化率(%)=100-スルファニル基の残存率(%) (VII)
上式中、IはUV可視分光光度計により測定される412nmの吸光度を表し、Sはスルファニル基変性オルガノポリシロキサンの単位質量当たりのスルファニル基のモル数を表し、c、dはそれぞれ製造時に投入されるラジカル反応性オルガノポリシロキサンの総質量及び製造時に投入される不飽和単量体の総質量を表す。
重合反応時の不飽和単量体の転化率は核磁気共鳴(1H-NMR)分析を用い、以下の条件で未反応の不飽和単量体を測定し、転化率を算出した。
オルガノポリシロキサングラフトポリマーを重クロロホルム中に2質量%溶解させ、核磁気共鳴(1H-NMR)装置「Mercury 400」(Varian社製)を用いて測定した。測定条件は、測定モードをProton 1D、測定温度を室温、積算回数を32回とした。MAA、tBuAA、PEGMAの転化率は、それぞれのアルケニル基(5.5~6.3ppm)と、不飽和単量体由来の重合体セグメント中のアルキル基もしくはアルコキシ基(MAAのメチル基:0.8~1.5ppm付近、tBuAAのtert-ブチル基:1.0~1.4ppm、PEGMAのメトキシ基:3.0~3.4ppm付近)の積分比より求めた。
原料に用いたラジカル反応性オルガノポリシロキサンの単位質量当たりのスルファニル基のモル数及び前記<スルファニル基の残存率の測定方法>で得られたスルファニル基の残存率から、不飽和単量体と反応した単位質量当たりのスルファニル基のモル数を求め、その逆数からグラフト点間分子量を算出する。
ラジカル反応性オルガノポリシロキサンの数平均分子量と、オルガノポリシロキサンセグメント(a)と不飽和単量体由来の共重合体セグメント(b)との質量比(a/b)とから以下のように求める。
オルガノポリシロキサングラフトポリマーの数平均分子量 = ラジカル反応性オルガノポリシロキサンの数平均分子量 × (1 + b/a)
グラフト点間分子量とオルガノポリシロキサンセグメント(a)と不飽和単量体由来の共重合体セグメント(b)との質量比(a/b)とから以下のように求める。
不飽和単量体由来の共重合体セグメントの数平均分子量 = グラフト点間分子量 × b/a
(ラジカル反応性オルガノポリシロキサンαの合成)
還流冷却管、温度計、窒素導入管、撹拌装置を取り付けたセパラブルフラスコに側鎖一級アミノプロピル変性オルガノポリシロキサン(東レ・ダウコーニング(株)製、単位質量当たりのアミノ基のモル数;1/1970mol/g、数平均分子量14000)を200g、N-アセチル-DL-ホモシステインチオラクトンを16g仕込んだ。窒素雰囲気下で、100℃に昇温し、3時間撹拌し、スルファニル基を有するラジカル反応性オルガノポリシロキサンαを合成した。電位差滴定測定によりアミノ基の残存量を測定したところ、原料とした側鎖一級アミノイソプロピル変性オルガノポリシロキサンのアミノ基の99%がN-アセチル-DL-ホモシステインチオラクトンと反応していた(アミノ基転化率99%)。したがって、ラジカル反応性オルガノポリシロキサンαの単位質量当たりのスルファニル基のモル数は、1/2100mol/gとなる。GPC測定により求めたラジカル反応性オルガノポリシロキサンαの数平均分子量は、14000であった。
合成例1において、側鎖一級アミノプロピル変性オルガノポリシロキサンの単位質量当たりのアミノ基のモル数及び数平均分子量を表1に示す条件に変えた側鎖一級アミノプロピル変性オルガノポリシロキサンを用いた以外は、合成例1と同様の操作を行い、ラジカル反応性オルガノポリシロキサンβ~δを得た。
<オルガノポリシロキサングラフトポリマーAの合成>
還流冷却器、温度計、窒素導入管、撹拌装置を取り付けたセパラブルフラスコにエタノール17gを仕込んだ。窒素雰囲気下80℃の還流下で撹拌しながら、下記溶液(a)及び溶液(b)をそれぞれ別の滴下ロートに入れ、同時に3時間かけて滴下した。その後、エタノールを還流させながら1時間撹拌したのち、下記溶液(c)を1時間かけて滴下した。
溶液(a):メタクリル酸(和光純薬工業(株)製、以下「MAA」という)4.6g、N-tert-ブチルアクリルアミド(和光純薬工業(株)製、以下「tBuAA」という)27g、メタクリル酸ポリエチレングリコール(9)モノメチルエーテル(日本乳化剤(株)製、以下「PEGMA」という)14g、エタノール110gを混合した溶液。
溶液(b):上記合成例1にて合成したラジカル反応性オルガノポリシロキサンα 30g、2,2’-アゾビス(2,4-ジメチルバレロニトリル)「V-65B」(和光純薬工業(株)製、アゾ系重合開始剤)0.4g、エタノール30gを混合した溶液。
溶液(c):2,2’-アゾビス(2,4-ジメチルバレロニトリル)「V-65B」(和光純薬工業(株)製、アゾ系重合開始剤)0.4g、エタノール20gを混合した溶液。
得られた混合物中のオルガノポリシロキサングラフトポリマーの不飽和単量体由来の共重合体セグメントの数平均分子量(MNy)について前記の方法に従って測定したところ、2500であった。また、オルガノポリシロキサングラフトポリマーの数平均分子量MNtを算出したところ、3.1万であった。
<オルガノポリシロキサングラフトポリマーB~I及びJ~M、P、Qの合成>
実施例1において、ラジカル反応性オルガノポリシロキサンの種類、仕込み量、不飽和単量体の種類、仕込み量を表2に示す条件に変えた以外は、実施例1と同様の操作を行い、オルガノポリシロキサングラフトポリマーB~I及びJ~M、P、Qを含む混合物を得た。ここで、表中の数字は、ラジカル反応性オルガノポリシロキサン及び不飽和単量体の仕込み総質量を100質量部とした場合の各成分の仕込み質量部を示す。
なお、ラジカル反応性オルガノポリシロキサンεとしては、市販のラジカル反応性オルガノポリシロキサン「KF-2001」(信越化学工業(株)製、単位質量当たりのスルファニル基のモル数1/2000mol/g、数平均分子量6700)を使用した。
特表平10-512233号公報の実施例49に記載の方法に従って、オルガノポリシロキサングラフトポリマーNを得た。
特開2009-161598号公報の実施例5に記載の方法に従って、オルガノポリシロキサングラフトポリマーOを得た。
国際公開第2011/062210号の合成例1に記載の方法に従って、オルガノポリシロキサングラフトポリマーRを得た。
<弾性率>
実施例1~9及び比較例1~4、7、8で得られたオルガノポリシロキサングラフトポリマーを試料として用い、弾性率を下記の方法に従って測定した。なお、比較例5及び6で得られたオルガノポリシロキサングラフトポリマーについては、後述の毛髪セット性評価で劣る結果となったため弾性率測定を行わなかった。
測定装置:動的粘弾性測定装置「DVA-225」(アイティー計測制御(株)製)
測定モード:せん断モード
歪み:0.01~0.1%
周波数:1Hz
試料サイズ:(0.6~1.5)×(7~10)×(5~6)mm
測定温度:-50~200℃
室温(20℃)の弾性率及び高温(140℃)の弾性率を測定した。結果を表4に示す。
軟化点は、上記弾性率の測定結果において、20℃の弾性率が45%以上減少したときの温度と定義した。
実施例1~9及び比較例1~4、7,8で得られたオルガノポリシロキサングラフトポリマーを試料として用い、オルガノポリシロキサングラフトポリマー混合物の5質量%エタノール溶液を調製し、下記の方法に従って毛髪セット性評価を行った。
長さ30cm、重さ6gのコーカシアンカーリーの未化学処理毛の毛束(根元の毛束幅3cm)、を評価に用いた。この毛束を水で十分に濡らした後タオルドライし、各オルガノポリシロキサングラフトポリマーの5質量%エタノール溶液を1.2g塗布し、表側及び裏側から交互に5回くし通しを行った。次いで毛束をドライヤーで完全に乾燥させた後、150~160℃のフラットアイロン「CREATE ION」((株)クレイツ製)で毛束の根本をはさみ、そのまま毛先に向かってアイロンを滑らすようにして毛束を伸ばす行為を3回繰り返し、その後、同様の処理をさらにくしを添えて2回繰り返した。この一連の処理が完了し、室温まで冷却させ、評価用毛束を得た。評価用毛束を用いて、以下の測定方法により毛髪セット性の評価を行った。
実施例1~9及び比較例7で得られたオルガノポリシロキサングラフトポリマーを試料として用い、感触の評価を行った。なお、比較例1~4、8で得られたオルガノポリシロキサングラフトポリマーについては、毛髪セット性評価で劣る結果となったため感触評価を行わなかった。
毛髪セット性評価と同様に行って評価用毛束を得た。評価用毛束の形付けした部分を手で握ったときの感触(ごわつきやべとつきのなさ)について、実施例9を基準とした下記の判定基準により官能評価を行った。評価は3名の専門パネラーによる評価の平均値を示した。
(評価基準)
5 とても良い
4 良い
3 ふつう(実施例9)
2 悪い
1 とても悪い
実施例1、3、4、9得られたオルガノポリシロキサングラフトポリマーを試料として用いて、水分散性の評価を行った。
(評価条件)
撹拌子を入れた20mlスクリュー管に各ポリマー0.45g、エタノール0.55gを加え、均一溶液とした。その後、イオン交換水9gを一滴ずつ滴下し、ポリマーのイオン交換水-エタノール分散液とした。得られた液体の透過率(%)を下記条件で測定した。
値が大きいほど、水分散性に優れる。
装置:UV可視光分光光度計UV-3300(株式会社日立製作所製)
測定モード:透過率
測定波長:660nm
試料:4.5重量%イオン交換水-エタノール分散液
光路長:1cm
表4及び表5から明らかなように、実施例1、2及び6のオルガノポリシロキサンセグメントの数平均分子量が8000以上のオルガノポリシロキサングラフトポリマーは、比較例7及び8のオルガノポリシロキサンセグメントの数平均分子量が8000未満のオルガノポリシロキサングラフトポリマーに比べ、毛髪セット性及び感触に優れる。
なお、比較例5及び6で得られたオルガノポリシロキサングラフトポリマーN及びOそれぞれの5質量%エタノール溶液を用いて上記と同様の方法でセット力を評価した。オルガノポリシロキサングラフトポリマーN又はOで処理した毛束の外観を図2に示す。図2に示すように、オルガノポリシロキサングラフトポリマーN及びOは、いずれもセット力が不十分であった。
次に、セット力を有する実施例1~9のオルガノポリシロキサングラフトポリマーA~Iのうち、代表的なポリマーとして実施例3~6のオルガノポリシロキサングラフトポリマーC、D、E及びFについて、高湿度下におけるセット保持性を評価した。
温度25℃、相対湿度90%の環境下で、上記<毛髪セット性評価>に記載の方法と同様の形付けを行った毛束を、毛先を下にして吊るして放置した。1時間放置したとき、放置の前後での変化の度合いを高湿度下におけるセット保持性として評価した。結果を図3に示す。
また、比較例9のオルガノポリシロキサングラフトポリマーRについて、上記と同様にして高湿度下におけるセット保持性を評価した。結果を図3に示す。
図3に示すように、ポリマーRと比較して、本発明のオルガノポリシロキサングラフトポリマーC~Fはいずれも高湿度下におけるセット保持性に優れる。
Claims (17)
- 主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを有するオルガノポリシロキサングラフトポリマーであって、
該オルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、該オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマー。 - 前記オルガノポリシロキサンセグメント中の隣接する不飽和単量体由来の共重合体セグメント間におけるオルガノポリシロキサンセグメントの数平均分子量(MNg)が500以上3万以下である、請求項1に記載のオルガノポリシロキサングラフトポリマー。
- 前記不飽和単量体由来の共重合体セグメントが、更に(メタ)アクリルアミド類及び(メタ)アクリレート類から選ばれる1種以上の不飽和単量体由来の繰返し単位を含有する、請求項1又は2に記載のオルガノポリシロキサングラフトポリマー。
- 前記カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位が、(メタ)アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、クロトン酸からなる群より選ばれる1種以上の不飽和単量体由来の繰り返し単位である、請求項1~3のいずれかに記載のオルガノポリシロキサングラフトポリマー。
- 下記一般式(4)又は(5)で表されるラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含有する不飽和単量体をラジカル重合して得られる、請求項1~4のいずれかに記載のオルガノポリシロキサングラフトポリマー。
- 前記ラジカル反応性官能基が、エチレン性不飽和基、ハロゲノ基、及びスルフアニル基から選ばれる基である、請求項5に記載のオルガノポリシロキサングラフトポリマー。
- 前記ラジカル反応性オルガノポリシロキサンが、下記一般式(6)又は(7)で表される反応性官能基を有するオルガノポリシロキサンにラジカル反応性付与剤を反応させて得られた物である、請求項5又は6に記載のオルガノポリシロキサングラフトポリマー。
- 前記反応性官能基が、水酸基、アミノ基、カルボキシ基及びエポキシ基から選ばれる基である、請求項7に記載のオルガノポリシロキサングラフトポリマー。
- 主鎖としてオルガノポリシロキサンセグメント、及び側鎖としてカルボン酸又はその塩を有する不飽和単量体由来の繰返し単位を含む不飽和単量体由来の共重合体セグメントを有するオルガノポリシロキサングラフトポリマーの製造方法であって、
下記一般式(4)又は(5)で表されるラジカル反応性オルガノポリシロキサンの存在下、カルボン酸又はその塩を有する不飽和単量体を含む不飽和単量体を重合させ、
得られるオルガノポリシロキサングラフトポリマー中の、オルガノポリシロキサンセグメントの含有量が35質量%以上59質量%以下、カルボン酸又はその塩を有する不飽和単量体由来の繰返し単位の含有量が4質量%以上17質量%以下であり、かつホモポリマーを形成した場合にガラス転移点が150℃以上となる不飽和単量体(但しカルボン酸又はその塩を有する不飽和単量体を除く)由来の繰返し単位の含有量が14質量%以下であり、オルガノポリシロキサンセグメントの数平均分子量が8000以上20万以下である、オルガノポリシロキサングラフトポリマーの製造方法。
- 前記ラジカル反応性官能基が、エチレン性不飽和基、ハロゲノ基、及びスルフアニル基から選ばれる基である、請求項9に記載のオルガノポリシロキサングラフトポリマーの製造方法。
- 一般式(4)及び(5)においてR12で示されるラジカル反応性基含有アルキル基の炭素数が、2以上20以下である、請求項9又は10に記載のオルガノポリシロキサングラフトポリマーの製造方法。
- 前記ラジカル反応性オルガノポリシロキサンの単位質量当たりに存在するラジカル反応性官能基のモル数が、1/3万mol/g以上、1/500mol/g以下である 、請求項9~11のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
- ラジカル反応性オルガノポリシロキサンが、下記一般式(6)又は(7)で表される反応性官能基を有するオルガノポリシロキサンにラジカル反応性付与剤を反応させて得られるものである、請求項9~12のいずれかに記載のオルガノポリシロキサングラフトポリマーの製造方法。
- 前記反応性官能基が、水酸基、アミノ基、カルボキシ基及びエポキシ基から選ばれる基である、請求項13に記載のオルガノポリシロキサングラフトポリマーの製造方法。
- 請求項1~8のいずれかに記載のオルガノポリシロキサングラフトポリマーを含有する毛髪化粧料。
- 請求項1~8のいずれかに記載のオルガノポリシロキサングラフトポリマーの毛髪化粧料への使用。
- 請求項1~8のいずれかに記載のオルガノポリシロキサングラフトポリマーを毛髪に適用する毛髪化粧方法。
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