WO2011062210A1 - 整髪方法 - Google Patents
整髪方法 Download PDFInfo
- Publication number
- WO2011062210A1 WO2011062210A1 PCT/JP2010/070531 JP2010070531W WO2011062210A1 WO 2011062210 A1 WO2011062210 A1 WO 2011062210A1 JP 2010070531 W JP2010070531 W JP 2010070531W WO 2011062210 A1 WO2011062210 A1 WO 2011062210A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hair
- group
- organopolysiloxane
- component
- segment
- Prior art date
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- 0 C*(C)*(C)[N+](*)[O-] Chemical compound C*(C)*(C)[N+](*)[O-] 0.000 description 1
Classifications
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Definitions
- the present invention relates to a hair styling method.
- hair cosmetics are used depending on the purpose, such as the desired performance and the desired hairstyle.
- hair cosmetics used to prepare a hairstyle and hold the hairstyle for a certain period of time 1) A hair cosmetic that fixes a hairstyle with a film of a film-forming resin, 2) Hair cosmetics that fix hairstyles with adhesive strength, 3) Three types of hair cosmetics are known in which hair is shaped by hydrogen bonds that are cut and reformed in the process of water penetration and drying into the hair.
- Aerosol hair cosmetics are known as hair cosmetics that fix hairstyles with the film of the film-forming resin 1) (for example, Patent Document 1).
- This type of hair cosmetic has a fixing power enough to maintain a once made hairstyle for a whole day.
- the film formed on the surface of the hair is strong but fragile, so it is stiff, and if an external force is applied to the hairstyle once made, the film is destroyed and the hairstyle collapses.
- re-hairdressing There is a problem that it is impossible to perform. Therefore, hair styling with this type of hair cosmetic is performed, for example, by applying the hair cosmetic after preparing the hairstyle while heating with a dryer. During or after application of this type of hair cosmetic, care is taken not to apply external force to the hairstyle, and no dryer is applied. Therefore, the temperature of the hair returns to about room temperature when the hair cosmetic is applied.
- Patent Documents 2 and 3 As a hair cosmetic that fixes a hairstyle with the adhesive force of 2), one that obtains adhesive force by using a film-forming resin and a plasticizer in combination is known (for example, Patent Documents 2 and 3). Although this type of hair cosmetic is capable of re-styling, there is a problem that when the power for fixing the hairstyle is increased, it becomes sticky, and when it is suppressed, the power for fixing the hairstyle becomes insufficient. In addition, with this type of hair cosmetic, it is difficult to obtain a fixing force enough to maintain a once made hairstyle for a whole day.
- hair styling performed while heating with a drier is generally intended for hair in a state where the type of hair cosmetics such as 1) and 2) is not applied.
- the hair cosmetic 3) is applied to wet hair or dry hair, and then is subjected to hair shaping while heating with a dryer or drying with cold air.
- the main purpose of this type of hair cosmetic is to improve the way of combs and brushes, and the hair shaping with these hair cosmetics is very weak compared to the types 1) and 2) above. is there. Some of them contain supplementary film-forming resin, but when there are many film-forming resins, the film is destroyed by fingers, combs, brushes, etc. When the amount of the forming resin is small, the fixing force itself is small, and in any case, it is difficult to obtain a fixing force enough to maintain the made hairstyle for a whole day.
- Patent Document 4 discloses a poly (N-acylalkylenimine) -modified organopolysiloxane that does not break or plastically deform within a certain range of elongation. It is disclosed as a hair setting agent.
- this organopolysiloxane is superior in hair setting ability and retention, can give the hair after hair styling soft and has a good feeling without tingling, and is easily washed away by washing the hair. It has an excellent performance of being able to.
- this hair cosmetic composition containing an organopolysiloxane is used, a fixing force sufficient to maintain a once made hairstyle for a whole day cannot be obtained.
- the physical properties of this organopolysiloxane hardly change by heating, it is not suitable for the purpose of styling hair while heating.
- the poly (N-acylalkylenimine) -modified organopolysiloxane described in Patent Document 5 has excellent extensibility, and is excellent in solubility and dispersibility in water and lower alcohols. Therefore, hair cosmetics containing this can provide a good feel, flexibility that does not break the hairstyle against external factors (such as passing fingers through hair, wind, vibration, etc.) and a natural finish. It is. However, since this organopolysiloxane has excellent extensibility, it is not suitable for firmly fixing the hairstyle made.
- this organopolysiloxane change somewhat by heating, the physical properties between room temperature and 220 ° C are generally soft, so if you try to shape your hair while heating, it will adhere to the tool. Therefore, it is not suitable for the purpose of styling hair while being heated because it does not have the performance to fix the hairstyle firmly even when it returns to room temperature.
- Patent Document 6 describes a hair cosmetic containing a specific branched fatty acid or a salt thereof and the organopolysiloxane described in Patent Document 5.
- a hair modification method using the hair cosmetic it is described that the hair cosmetic is heated after being applied to the hair.
- the heating is performed only for the purpose of modifying the hair, such as the smoothness of the hair and its durability, and not for preparing the hairstyle.
- the organopolysiloxane described in Patent Document 5 is not suitable for the purpose of styling hair while heating.
- a hair cosmetic containing the following component (A) is applied to hair, and after shaping the hair at a hair temperature of 50 ° C. or higher, the hair temperature is cooled to less than 50 ° C.
- a hair styling method for fixing a hairstyle is provided.
- the number average molecular weight of the poly (N-acylalkylenimine) segment is 1,200-5,500
- the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-acylalkyleneimine) segment (b) is 35/65 to 60/40
- the weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1,300-5,500
- the weight average molecular weight of the organopolysiloxane segment constituting the main chain is 7,000 to 100,000.
- the present invention provides the following general formula (1) through an alkylene group containing a hetero atom in at least two silicon atoms of the organopolysiloxane segment constituting the main chain:
- the number average molecular weight of the poly (N-acylalkylenimine) segment is 1600-3500
- the mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkylenimine) segment (b) is 42/58 to 58/42
- the weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1600-3500
- the weight average molecular weight of the organopolysiloxane segment constituting the main chain is 7,000 to 100,000.
- the present invention provides a hair cosmetic containing an organopolysiloxane
- the present invention gives the hair a soft touch and a natural finish, firmly fixes the hairstyle, and does not break the hairstyle against external factors (such as passing fingers through the hair, wind, vibration, etc.)
- the present invention relates to a hair styling method that satisfies all of the various performances such as being able to maintain for a long time and re-styling, and a hair cosmetic containing an organopolysiloxane that can be suitably used for the hair styling method.
- the inventors of the present invention have a specific range of organopolysiloxanes having the same structure as the organopolysiloxanes described in Patent Documents 4 to 6, giving hair a soft feel and a natural finish, and a hairstyle. It can be firmly fixed, and can be maintained for a long time against external factors (such as passing fingers through hair, wind, vibration, etc.) without breaking the hairstyle, and it is also soluble and dispersible in water and lower alcohols. It has been found that it exhibits excellent performance as a hair styling polymer, such as being excellent in hair.
- the present inventors can satisfy all of the above requirements by using a hair cosmetic containing the organopolysiloxane and taking a specific method of use, and the hair cosmetic can be easily washed away by washing the hair. I found out that I can do it.
- a hair cosmetic containing component (A) is applied to the hair, and after shaping the hair at a hair temperature of 50 ° C. or higher, the hair temperature is cooled to less than 50 ° C. This is by fixing the shaped hairstyle.
- the means of application (application) of hair cosmetics containing component (A) to the hair is not uniform depending on the type of the dosage form, but usually by spraying such as spray or by hand Application and a combination of both may be used.
- the hair cosmetic containing the component (A) it is preferable to apply water to the hair before applying the hair cosmetic containing the component (A) to the hair, so that the hair cosmetic can be easily adapted to the whole hair.
- the hair cosmetic containing component (A) after applying the hair cosmetic containing component (A) to the hair, before shaping the hair at a hair temperature of 50 ° C. or higher, the hair is dried, and the shaping process can be completed in a short time. Therefore, it is possible to reduce the time required for the entire hair styling, which is preferable. Drying after applying the hair cosmetic can be performed by natural drying, heating, or the like.
- ⁇ Shaping at a hair temperature of 50 ° C. or higher In order to heat the hair temperature to 50 ° C. or higher, a hair iron, a dryer, a heater, a iron, a curler, a hot curler, or the like can be used.
- the temperature is preferably 50 to 220 ° C, more preferably 60 to 200 ° C, and even more preferably 80 to 180 ° C.
- “shaping” the hair means changing the shape of the hair itself. Specifically, adding curls or waves to straight hair, straightening curled or waved hair, changing the curl or wave of curled or waved hair, etc. Although it is included in “shaping”, simply shaping a disordered hairstyle by simply passing a comb or brush through the hair is not included in “shaping” because the shape of the hair itself has not changed. Examples of tools used for “shaping” include hair irons, hair dryers with combs, irons, curlers, hot curlers, combs, and brushes.
- the timing of the “shaping” process and the heating process may be the same or may be slightly different.
- ⁇ Make the shape first with a curler and heat with a dryer.
- ⁇ Shape with a comb while heating with a dryer.
- shape with a comb before the temperature drops).
- -Heat and shape with an iron almost simultaneously.
- ⁇ Shape while heating with a hot curler. Any of these embodiments may be used. In short, it is sufficient that shaping is performed at a hair temperature of 50 ° C or higher.
- the timing of applying the hair cosmetic containing the component (A) to the hair is not particularly limited as long as the hair cosmetic is applied to the hair when the hair is shaped at 50 ° C. or higher.
- -After applying the hair cosmetic containing component (A), shape with curlers, etc., and then heat before releasing curlers, etc.
- After shaping with curlers (before releasing curlers, etc.) apply hair cosmetic containing component (A) and heat to 50 ° C or higher. Any of these may be used.
- shaping and heating may be performed after applying the hair cosmetic containing component (A). preferable.
- Cooling is a concept including not only lowering the temperature consciously (for example, applying cool air) but also lowering the temperature naturally by the ambient temperature.
- the force to shape the hair may be “before releasing”, “simultaneously with releasing”, or “after releasing” .
- ⁇ Cool to below 50 °C without releasing the shaping force and then release the shaping force (such as treatment with curlers).
- ⁇ Cooling to less than 50 ° C at the same time as releasing the shaping force for example, releasing the winding with an iron set to 50 ° C will release the force and cooling to less than 50 ° C almost simultaneously. ).
- After releasing the shaping force cool it to less than 50 °C (in this case, if the time elapsed after release is too long, the bent shape may be destroyed, so cool immediately after release.
- the temperature may be kept at 50 ° C. or more for a short time after releasing the shaping force.
- “immediately” means preferably within 30 seconds, more preferably within 15 seconds, more preferably within 5 seconds, more preferably within 3 seconds.
- ⁇ Re-styling Component (A) organopolysiloxane used in the hair styling method of the present invention has a characteristic thermoplasticity that it becomes soft when heated to 50 ° C. or higher and immediately recovers its elasticity when cooled. Even after, you can easily re-hair it again and again. Therefore, even if a hairstyle once made fails, it can be easily corrected, and a hairstyle that can be easily satisfied even by a person who is not used to it can be obtained.
- the re-styling may be performed by shaping the hair that has been stipulated by the hair styling method of the present invention at a hair temperature of 50 ° C. or higher and then cooling the hair to below 50 ° C.
- the hair cosmetic containing the component (A) may be additionally applied to the hair, but since the hair cosmetic containing the component (A) has already been applied at the time of the first hair styling, the additional application is performed. You can re-hair it without it.
- the organopolysiloxane of component (A) used in the hair styling method of the present invention is an organopolysiloxane in which a poly (N-acylalkylenimine) segment comprising a repeating unit represented by the general formula (1) constitutes the main chain It is bonded to at least two silicon atoms of the segment through an alkylene group containing a hetero atom, and becomes soft when heated to a temperature range that can withstand hair, such as 50-220 ° C. It has a characteristic thermoplasticity that immediately restores elasticity.
- the poly (N-acylalkylenimine) segment can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom, except for both ends. It is preferable that it is bonded to the above silicon atom via the alkylene group, and it is more preferable that it is bonded to two or more silicon atoms excluding both ends via the alkylene group.
- the alkylene group containing a hetero atom functions as a linking group for the poly (N-acylalkylenimine) segment.
- Examples of such an alkylene group include an alkylene group having 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms, or sulfur atoms, and is represented by any of the following formulas (i) to (viii). And a group represented by any one of the following formulas (i) to (iii) is more preferable.
- An - represents a counter ion of the quaternary ammonium salts, for example, ethyl sulfate ion, methyl sulfate ion, chloride ion, iodide ion, sulfate ion, p- toluenesulfonate ion, perchlorate ion Is exemplified.
- the alkyl group having 1 to 22 carbon atoms in R 1 for example, straight-1 to 22 carbon atoms
- Examples include chain, branched or cyclic alkyl groups, and specifically include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, and cyclohexyl groups.
- Examples include xyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, nonadecyl, eicosyl, docosyl and the like.
- alkyl groups having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further 1 to 3 carbon atoms are preferable from the viewpoint of high solubility in water and lower alcohols.
- aralkyl group examples include aralkyl groups having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group. Among them, an aralkyl group having 7 to 14 carbon atoms, and more preferably 7 to 10 carbon atoms is preferable.
- aryl group examples include an aryl group having 6 to 14 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.
- An aryl group having 6 to 12 carbon atoms, more preferably 6 to 9 carbon atoms is preferable.
- R 1 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.
- the mass ratio (a / b) between the organopolysiloxane segment (a) and the poly (N-acylalkyleneimine) segment (b) is 35 / 65-60 / 40, but it is soluble and dispersed in the solvent. From the viewpoint of making it particularly suitable for the hair styling method of the present invention by having a good balance of the properties, ease of shaping at the time of hair styling, the feel of the hair after hair styling, and the setting power to hold the hair that has been styled for a long time
- the ratio is preferably 42/58 to 58/42, more preferably 45/55 to 55/45, and still more preferably 47/53 to 53/47.
- the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of the present invention in deuterated chloroform and analyzing it by nuclear magnetic resonance ( 1 H-NMR) analysis.
- the weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments (hereinafter sometimes referred to as “molecular weight between graft points”) is 1300-5500, preferably Is from 1600 to 3500, more preferably from 1800 to 3200, still more preferably from 2,000 to 3,000.
- an organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments means an organopolysiloxane of a poly (N-acylalkyleneimine) segment as shown in the following formula (2): A portion surrounded by a broken line between two points from a bonding point (bonding point ⁇ ) to a segment to a bonding point (bonding point ⁇ ) of a poly (N-acylalkyleneimine) segment adjacent thereto. A segment composed of an R 2 SiO unit, one R 6 , and y + 1 (R 2 ) 2 SiO units.
- the “poly (N-acylalkylenimine) segment” refers to —W—R 7 bonded to R 6 .
- each R 2 independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group
- R 6 represents an alkylene group containing a hetero atom
- —W—R 7 represents poly (N— An acylalkylenimine) segment
- R 7 represents a residue of a polymerization initiator
- y represents a positive number.
- the molecular weight MWg between graft points is the molecular weight of the portion surrounded by the broken line in the general formula (2), but the mass of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment (g / mol) Can be understood.
- the functional group of the modified organopolysiloxane which is a raw material compound, is 100% substituted with poly (N-acylalkylenimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.
- the molecular weight (MWox) of the poly (N-acylalkylenimine) segment can be calculated from the molecular weight of N-acylalkylenimine units and the degree of polymerization, or can be measured by gel permeation chromatography (GPC) measurement method described later. However, in the present invention, it means the number average molecular weight measured by the GPC measurement method.
- the MWox of component (A) is 1,200 to 5,500, preferably 1,600 to 3,500, more preferably 1,800 to 3,200, and still more preferably 2,000 to 3,000. As a result, it is sufficiently softened at 50 ° C. or higher and is in a state suitable for hair shaping, and has both hardness and good touch sufficient to maintain the hairstyle at less than 50 ° C., preferably at room temperature. Become.
- the molecular weight MWg between graft points can be determined by the following formula (I) using the content (Csi) of the organopolysiloxane segment constituting the main chain.
- the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 7,000 to 100,000. From the viewpoint of solubility in polar solvents such as water and ease of handling after dissolution, preferably 10,000 to 80,000, More preferably, it is 20,000 to 60,000, and further preferably 30,000 to 50,000. Since MWsi has a common skeleton with the modified organopolysiloxane that is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane that is the raw material compound.
- the average molecular weight of the modified organopolysiloxane that is a raw material compound is measured by GPC under the following measurement conditions and is converted to polystyrene.
- the weight average molecular weight (MWt) of the component (A) organopolysiloxane is preferably 7000 to 100,000, more preferably 20000 to 60000, and still more preferably 30000 to 50000. Thereby, a good touch can be imparted to the hair, and in addition, solubility in polar solvents such as water becomes excellent. Moreover, both styling of set property and set sustainability can be further improved.
- MWt can be determined from the weight average molecular weight of the modified organopolysiloxane that is the raw material compound and the above-mentioned mass ratio (a / b).
- the organopolysiloxane of the present invention is, for example, the following general formula (3)
- R 2 is as defined above, and R 3 and R 4 each represent the same group as R 2 , or the following formulas (ix) to (xiv)
- R 5 represents a monovalent group represented by the above formulas (ix) to (xiv), d represents an integer of 89 to 1332, and e represents 2 Indicates an integer of ⁇ 77.
- cyclic imino ether (4) a terminal reactive poly (N-acylalkylenimine) obtained by ring-opening polymerization of a cyclic imino ether represented by the following formula (hereinafter referred to as “cyclic imino ether (4)”).
- the functional group equivalent is preferably 1,700 to 3,500, more preferably 1,800 to 3,200, still more preferably 2,000 to 3,000, and the weight average molecular weight is preferably 7,000 to 100,000, more preferably It is desirable to use 10,000 to 80,000, more preferably 30,000 to 50,000.
- the weight average molecular weight of the modified organopolysiloxane (3) as the raw material is substantially the same as the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain.
- the terminal reactive poly (N-acylalkylenimine) is preferably adjusted to have a molecular weight of 1,200 to 5,500, preferably 1,600 to 3,500, more preferably 1,800 to 3,200, and even more preferably 2,000 to 3,000. This is substantially the same as the molecular weight (MWox) of the aforementioned poly (N-acylalkylenimine) segment.
- a polymerization initiator can be used for the ring-opening polymerization of the cyclic iminoether (4).
- a compound having strong electrophilic reactivity for example, a strong acid such as benzenesulfonic acid alkyl ester, p-toluenesulfonic acid alkyl ester, trifluoromethanesulfonic acid alkyl ester, trifluoroacetic acid alkyl ester, sulfuric acid dialkyl ester, etc.
- Alkyl esters can be used, and among them, dialkyl sulfate is preferably used.
- the amount of the polymerization initiator used is usually 1 mol of the polymerization initiator with respect to 2 to 100 mol of the cyclic imino ether (4).
- the polymerization solvent examples include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, acetonitrile. , Nitrile solvents such as benzonitrile, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc., among which acetates are preferred Is done.
- the amount of the solvent used is usually 20 to 2,000 parts by mass with respect to 100 parts by mass of the cyclic imino ether (4).
- the polymerization temperature is usually 30 to 170 ° C., preferably 40 to 150 ° C., and the polymerization time is usually 1 to 60 hours although it is not uniform depending on the polymerization temperature.
- Examples of the method for linking poly (N-acylalkylenimine) and the organopolysiloxane segment include the following methods.
- the method 1) can easily control the degree of polymerization by the amount of the cyclic iminoether (4) and the polymerization initiator used as shown in the following theoretical formula (II), and moreover than ordinary radical polymerization. It is most effective in that a substantially monodispersed poly (N-acylalkylenimine) having a narrow molecular weight distribution can be obtained.
- the organopolysiloxane of component (A) at least two silicon atoms of the organopolysiloxane segment having a predetermined molecular weight have poly (N-acylalkyleneimine) segments at predetermined intervals via an alkylene group containing a hetero atom, In addition, it has a unique structure combined at a predetermined ratio. As a result, it softens moderately at 50 ° C or higher, has a setting power to hold the hairstyle for a long time at less than 50 ° C, preferably near normal temperature, and has a good feel and a natural finish that does not collapse even when subjected to external force. It has the physical properties suitable for use in the hair styling method of the present invention. Moreover, it can be dissolved in polar solvents such as water and lower alcohols.
- organopolysiloxane of component (A) include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, poly (N-propionylethyleneimine) organosiloxane, and the like. .
- the hair cosmetic used in the present invention contains the above-described component (A) organopolysiloxane.
- A organopolysiloxane
- the organopolysiloxane of component (A) can be used alone or in combination of two or more, and the content thereof is a hair cosmetic from the viewpoint of hair setability, set durability, and washability by shampooing. Is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, still more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 10% by mass. Moreover, by setting it as this content, when using the organic solvent mentioned later and an organic acid or its salt together, set property and without disturbing the hair modification effect (a unity improvement etc.) by an organic acid and an organic solvent. Both styling of set sustainability can be further improved.
- the hair cosmetic composition of the present invention may further contain an organic solvent selected from the following (b1) to (b5) (hereinafter referred to as “component (B)”) as a preferred component.
- component (B) an organic solvent selected from the following (b1) to (b5) (hereinafter referred to as “component (B)”) as a preferred component.
- R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group R 9 —Ph—R 10 — (R 9 ; hydrogen atom, methyl group or methoxy group, R 10 ; bond or carbon number 1 to 3 saturated or unsaturated divalent hydrocarbon group, Ph (paraphenylene group),
- A represents a bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms
- Y and Z are Each independently represents a hydrogen atom or a hydroxyl group
- p and q each independently represents an integer of 0 to 5.
- X represents a methylene group or an oxygen atom
- R 11 and R 12 represent different substituents
- a and b each independently represent 0 or 1.
- (b1) includes C 4 to C 6 linear or branched aliphatic alcohols such as butanol and isobutanol, 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 carbitol , Triethylene glycol monoethyl ether, triethylene glycol monobutyl ether and the like.
- C 4 to C 6 linear or branched aliphatic alcohols such as butanol and isobutanol, ethylene glycol, propylene glycol, dipropylene glycol, 1, 3-butanediol, benzyl alcohol, cinnamyl alcohol, phenethyl
- (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 100 to 1,000 is preferably a number average molecular weight of 300 to 500.
- the number average molecular weight refers to the number average molecular weight in terms of polystyrene measured by GPC.
- R 11 and R 12 in the general formulas (6) to (8) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups, 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. preferable.
- R 11 or R 12 has an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxy group, or an alkyl group substituted with these. Is preferred.
- 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 in the present invention is preferably liquid at 25 ° C., and ClogP is preferably ⁇ 2 to 3, more preferably ⁇ 1 to 2 from the viewpoint of promoting penetration. preferable.
- ClogP is a calculated value of the octanol-water-partition coefficient (logP) defined by the following formula (III), which is a measure representing the distribution of substances between the octanol phase and the aqueous phase.
- ClogP of the main component (B) is shown by dipropylene glycol (-0.67), 1,3-butanediol (-0.29), benzyl alcohol (1.1), 2-benzyloxyethanol (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.
- Ingredient (B) may be used in combination of two or more, and the total content thereof is an effect of improving the firmness and stiffness after washing the hair, improving the softness and cohesion of the hair, promoting the modification effect (improving elasticity)
- it is preferably 0.1 to 40% by mass, and more preferably 0.5 to 10% by mass in hair cosmetics from the viewpoint of improving hair setability by being compatible with component (A). In particular, 1 to 5% by mass is preferable.
- water, C 1 -C 3 straight chain or a solvent are used from the viewpoint of hair setability, good feeling of use, and dissolution promotion when preparing the hair cosmetic.
- Branched saturated or unsaturated alcohols can be included. These can be used alone or in combination of two or more. Among these, water, ethanol, and isopropanol are preferable, and water and ethanol are particularly preferable.
- the total content of water and C 1 -C 3 alcohol is preferably 0.1 to 98% by mass, more preferably 1 to 90% by mass, and particularly preferably 5 to 60% by mass, based on the total mass of the hair cosmetic. is there.
- the hair cosmetic used in the present invention may contain an organic carboxylic acid or a salt thereof (hereinafter referred to as “component (C)”) optionally having a hydroxy group, together with the component (B). it can.
- component (C) organic carboxylic acid or a salt thereof
- particularly preferred components (B) include dipropylene glycol, 1,3-butanediol, benzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, propylene carbonate, and polypropylene glycol (number average molecular weight 300 to 500, particularly 400). Is mentioned.
- the organic carboxylic acid of component (C) is preferably one having 2 to 8 carbon atoms, specifically, monocarboxylic acids such as acetic acid and propionic acid; malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid Dicarboxylic acids such as fumaric acid and phthalic acid; polycarboxylic acids such as polyglutamic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; glutamic acid, aspartic acid, etc. Examples include acidic amino acids.
- hydroxycarboxylic acids having 2 to 6 carbon atoms are 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 internal reforming of hair (such as cavity repair), an effect of improving firmness and stiffness after shampooing, an improvement in softness and coherence of hair
- it is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, especially 0.5 to 10% by mass in the hair cosmetics from the viewpoint of improving the setability of the hair by being compatible with component (A).
- the mass ratio of the organic carboxylic acid of component (C) or salt thereof to the organic solvent of component (B) is the effect of internal modification of hair (such as cavity repair), the effect of improving the firmness and stiffness after washing, the softness of hair
- (C) :( B) 10: 1 to 1: 7, particularly 4: 1 to 1: 3.
- the hair cosmetic used in the present invention contains (D) a set polymer, the set holding power is further improved and the slipping feeling of the hair is improved.
- Examples of the set polymer of component (D) include those shown in the following 1) to 8), and they can be used alone or in combination of two or more.
- Vinylpyrrolidone-based polymer Polyvinylpyrrolidone Commercially available products include Rubiscol K12, K30 (above BASF), PVP K15, K30 (above GAF) and the like.
- Vinyl pyrrolidone / vinyl acetate copolymer Commercially available products include Rubiscol VA28, VA73 (above BASF), PVP / VA E-735, S-630 (above GAF).
- Vinyl pyrrolidone / alkylamino acrylate copolymer Commercially available products include rubiflex (manufactured by BASF), copolymers 845, 937 and 958 (manufactured by GAF).
- Vinylpyrrolidone / acrylate / (meth) acrylic acid copolymer Commercially available products include Rubyflex VBM35 (manufactured by BASF).
- Vinyl pyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer As a commercial product, copolymer VC-713 (manufactured by GAF) and the like can be mentioned.
- Acidic polyvinyl acetate polymer Vinyl acetate / crotonic acid copolymer
- Resin 28-1310 National Starch
- Ruby Set CA66 (BASF).
- Vinyl acetate / crotonic acid / vinyl neodecanoate copolymer Commercially available products include Resin 28-2930 (manufactured by National Starch).
- Vinyl acetate / crotonic acid / vinyl propionate copolymer Rubiset CAP (manufactured by BASF) and the like are listed as commercial products.
- Acid acrylic polymer (Meth) acrylic acid / (meth) acrylic ester copolymer Commercially available products include Plus Size L53P (manufactured by Kyoyo Chemical Co., Ltd.), Diamond (Mitsubishi Yuka Co., Ltd.), etc. Can be mentioned.
- Acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymer examples include Ultrahold 8 (manufactured by BASF) and Amphomer V-42 (manufactured by National Starch).
- Amphoteric acrylic polymer (meth) acrylethyl betaine / (meth) acrylic acid alkyl ester copolymer
- N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine and (meth) examples thereof include copolymers with alkyl crylate and the like, and commercially available products include Yuka Former M-75, SM (manufactured by Mitsubishi Yuka Co., Ltd.) and the like.
- Acrylic acid alkyl ester / butyl aminoethyl methacrylate / octyl amide acrylate copolymer For example, octyl acrylamide / acrylate / butyl aminoethyl methacrylate copolymer and the like are exemplified, and as a commercial product, Anformer 28-4910 (National Starch Co., Ltd.) Manufactured) and the like.
- Cellulose derivative Cationic cellulose derivative examples of commercially available products include Cellcoat H-100 and L-200 (manufactured by National Starch).
- monovalent acids such as pyrrolidone carboxylic acid, lactic acid and glycolic acid or salts with divalent acids such as adipic acid and succinic acid.
- Kitemer L lactate
- Union Carbide manufactured by Union Carbide
- a set polymer selected from acrylic polymers and vinylpyrrolidone polymers is particularly preferable.
- the content of the set polymer is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.3 to 5% by mass based on the total mass of the hair cosmetic.
- the hair cosmetic used in the present invention may contain a conditioning component selected from oils and silicones other than the organopolysiloxane of component (A) for further improving the conditioning effect.
- 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 and 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, isononanoic acid Esters such as tridecyl; 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, cholesteryl iso Examples thereof include solid
- the content of the oil agent is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 5% by mass in the hair cosmetic from the viewpoint of good unity and no stickiness.
- silicones dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic Examples thereof include silicone and alkyl-modified silicone. Of these, dimethylpolysiloxane, polyether-modified silicone, and amino-modified silicone are preferable.
- Dimethylpolysiloxane can impart good lubricity to hair, polyether-modified silicone can impart smoothness to hair, and amino-modified silicone can impart moist feeling to hair.
- various silicones can be used alone or in combination of two or more depending on the desired performance.
- Dimethylpolysiloxanes can be used from those with a viscosity of about 5 mm 2 / s to those with a viscosity of about 10 million mm 2 / s, which are often supplied as emulsions, depending on the desired feel.
- mm 2 / s particularly 50,000 to 10 million mm 2 / s is preferable.
- 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. More specifically, for example, KF-6015, KF-945A, KF-6005, KF-6009, KF-6013, KF-6019, KF-6029, KF-6017, KF-6043, KF-353A, KF- 354A, KF-355A (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 (above, Toray Dow Corning).
- amino-modified silicone those described in the third edition of the CTFA Dictionary (USA, 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 (Toray Dow Corning), DC 929 (Dow Corning), KT 1989 (GE Toshiba Silicone), 8500 Conditioning Agent, DOW CORNING TORAY SS-3588, DOW CORNING TORAY SILSTYLE 104 (Toray ⁇ Dow Corning).
- the content of the silicone is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoints of fingering and non-stickiness. Is preferred.
- the hair cosmetic used in the present invention may contain a surfactant from the viewpoints of system stability including solubilization and dispersibility of the solvent, and improvement in feel.
- 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 a quaternary ammonium salt represented by the following general formula (9).
- R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms, or a benzyl group, and at the same time, a hydrogen atom, a benzyl group, a lower alkyl group having 1 to 3 carbon atoms, or these Except when combined.
- An ⁇ represents a counter ion of a quaternary ammonium salt.
- one of R 13 and R 14 is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, particularly a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms, particularly A methyl group is preferred.
- 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 specifically, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylbenzalkonium chloride and the like. In particular, stearyltrimethylammonium chloride and behenyltrimethylammonium chloride are preferable.
- 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 and polyoxyethylene / polyoxypropylene alkyl ether are particularly 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 preferred, and fatty acid amidopropyl betaine is particularly preferred.
- the fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and particularly amide propyl betaine laurate, palm kernel fatty acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine and the like. preferable.
- 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 And alkanolamines having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).
- 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
- alkanolamines having 1 to 3 for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.
- Examples of the counter ion of the cationic residue include halide ions such as chloride ion, bromide ion and iodide ion,
- cationic surfactants and nonionic surfactants are preferred from the viewpoint of feel.
- Surfactants can be used alone or in combination of two or more. From the viewpoint of the stability of the system including solubilization of the solvent and emulsification of the oil, the content thereof is 0.01 to 10 in the hair cosmetic composition. % By mass, particularly 0.05 to 5% by mass is preferred.
- 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 ethylene glycol, glycerin, sorbitol and the like, and glycerin is particularly preferable.
- Polyhydric alcohols can be used singly or in combination of two or more, and the content thereof is preferably 0.1 to 10% by mass, particularly 0.5 to 5% by mass in the hair cosmetic.
- the hair cosmetic used in the present invention can be appropriately blended with components used in normal hair cosmetics depending on 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 hydroxyethylcellulose, methylcellulose, polyethylene glycol, clay minerals; pH of organic acids, sodium hydroxide, potassium hydroxide, etc. Conditioning agents; plant extracts; pearlizing agents; fragrances; dyes; UV absorbers; antioxidants; and others described in ENCYCLOPEDIA OF SH
- 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 to 50% by mass, and particularly preferably 5 to 20% by mass in the hair cosmetic composition of the present invention.
- 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 No. 62-042785, Japanese Utility Model Publication No. 62-042786, Japanese Utility Model Publication No. 62-042787, and those equivalent thereto. Examples described in Kaihei 7-315463, Japanese Patent Application Laid-Open No. 08-230961, and the like, 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 or two mesh bodies of 100 to 300 mesh are preferably attached.
- 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. .
- pump spray, pump foam, and aerosol foam are preferable.
- Synthesis Example 3 Organopolysiloxane C Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 75.7 g (0.763 mol) of 2-ethyl-2-oxazoline in 166 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2000.
- Synthesis Example 4 Organopolysiloxane D Dissolve 3.08 g (0.02 mol) of diethyl sulfate and 96.9 g (0.978 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 5000.
- Synthesis Example 6 Organopolysiloxane F Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 102.2 g (1.031 mol) of 2-ethyl-2-oxazoline in 220 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2700.
- Synthesis Example 7 Organopolysiloxane G Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 86.1 g (0.869 mol) of 2-ethyl-2-oxazoline in 187 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2300.
- Synthesis Example 8 Organopolysiloxane H Dissolve 12.78 g (0.0829 mol) of diethyl sulfate and 246.6 g (2.488 mol) of 2-ethyl-2-oxazoline in 519 g of dehydrated ethyl acetate, and heat to reflux for 15 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 3100.
- the reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (158 g, yield 95%).
- the final product had an organopolysiloxane segment content of 60% by mass and a weight average molecular weight of 50000.
- the reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow rubbery semi-solid (152 g, yield 97%).
- the final product had an organopolysiloxane segment content of 64 mass% and a weight average molecular weight of 50000.
- Synthesis Example 12 Organopolysiloxane L Dissolve 0.77 g (0.005 mol) of diethyl sulfate and 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline in 28 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2700.
- Hair treatment condition 1 treatment for evaluation of habitability using an iron
- a hair bundle of virgin hair Japanese female hair not subjected to chemical treatment such as hair coloring and bleaching
- chemical treatment such as hair coloring and bleaching
- the hair bundle After being removed, the hair bundle is placed in a room temperature environment, so that the temperature of the hair bundle soon reaches room temperature. After this series of treatments was completed, sensory evaluation and comprehensive evaluation were performed according to the following criteria. Each evaluation showed the average value of five expert panelists' evaluation.
- the degree of wrinkling on the hair bundle after removing the iron was visually evaluated according to the same criteria.
- Hair bundle treatment condition 2 treatment when drying naturally without using an iron
- a hair bundle of 35 cm long and 6 g weight Caucasian hair German curly hair not subjected to chemical treatment such as hair color and bleaching
- a model shampoo as shown below
- wipe off excess moisture with a towel Apply 0.5 g of each sample by hand with the hair bundle wet, and apply the applied agent evenly with your fingers.
- the hair flow was adjusted with fingers.
- this hair bundle was naturally dried at room temperature for 3 hours.
- sensory evaluation was performed according to the following criteria. The evaluation was performed by five expert panelists, and the average value of the evaluation was shown.
- Model shampoo composition (% by mass) 25% Sodium polyoxyethylene (2.5) sodium lauryl sulfate 62.00 Lauric acid diethanolamide 2.28 Edetate disodium 0.10 Sodium benzoate 0.50 Oxybenzone 0.03 Phosphoric acid (75% aqueous solution) 0.10 Dibutylhydroxytoluene 0.01 Sodium chloride 0.80 Red No. 106 0.00012 Fragrance 0.26 Purified water balance
- Example 53 No spray water.
- Example 54 No dryer drying.
- Example 55 Neither spray water nor dryer drying.
- Example 56 After heating the hair, the sample is applied at a temperature of 50 ° C. or higher, and the hair is wound around an iron.
- Example 57 Wrapped around a curler instead of an iron and heated with a drier (hair surface temperature is 80 ° C., all the same heating with a drier below). After cooling to room temperature, remove the curler.
- Example 58 Shaped with a comb while heating with a dryer instead of an iron. As soon as the shaping is completed, remove the heat from the dryer. Comparative Example 5: Dryer drying is performed, but no processing after ironing is performed. Comparative Example 6: After drying the dryer, it is once cooled to room temperature.
- Comparative Example 7 After drying the dryer, it is once cooled to room temperature. After that, shape with a comb or brush without heating, and then heat to 50 ° C or higher. Comparative Example 8: After drying the dryer, ironing is performed in the same manner, but the hair temperature is set to 40 ° C.
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Abstract
Description
1)皮膜形成性樹脂の皮膜により髪型を固定する毛髪化粧料、
2)粘着力により髪型を固定する毛髪化粧料、
3)毛髪への水の浸透・乾燥の過程で切断・再形成される水素結合により髪を形付けする毛髪化粧料
の3通りが知られている。
で表される繰り返し単位からなるポリ(N-アシルアルキレンイミン)セグメントが結合してなるオルガノポリシロキサンであって、
ポリ(N-アシルアルキレンイミン)セグメントの数平均分子量が1,200~5,500であり、
主鎖を構成するオルガノポリシロキサンセグメント(a)と、ポリ(N-アシルアルキレンイミン)セグメント(b)との質量比(a/b)が35/65~60/40であり、
隣接するポリ(N-アシルアルキレンイミン)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重量平均分子量が1,300~5,500であり、
主鎖を構成するオルガノポリシロキサンセグメントの重量平均分子量が7,000~100,000である、
オルガノポリシロキサン。
で表される繰り返し単位からなるポリ(N-アシルアルキレンイミン)セグメントが結合してなるオルガノポリシロキサンであって、
ポリ(N-アシルアルキレンイミン)セグメントの数平均分子量が1600~3500であり、
主鎖を構成するオルガノポリシロキサンセグメント(a)と、ポリ(N-アシルアルキレンイミン)セグメント(b)との質量比(a/b)が42/58~58/42であり、
隣接するポリ(N-アシルアルキレンイミン)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重量平均分子量が1600~3500であり、
主鎖を構成するオルガノポリシロキサンセグメントの重量平均分子量が7,000~100,000である、
オルガノポリシロキサンを含有する毛髪化粧料を提供するものである。
本発明の整髪方法は、まず成分(A)を含有する毛髪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、形付けした髪型を固定することによるものである。
成分(A)を含有する毛髪化粧料の毛髪への適用(塗布)手段は、剤型の種類によって一様ではないが、通常、スプレー等の噴射、手による塗布及びその両者の組合せ等によればよい。
毛髪温度を50℃以上に加熱するには、ヘアアイロン、ドライヤー、ヒーター、コテ、カーラー、ホットカーラー等を使用することができる。温度としては、50~220℃、更には60~200℃、更には80~180℃が好ましい。
・カーラーで形付けを先に行い、ドライヤーで加熱する。
・ドライヤーで加熱しながらくしで形付ける。
・ドライヤーで加熱した後、(温度が下がらないうちに)くしで形付ける。
・アイロンで加熱と形付けをほぼ同時に行う。
・ホットカーラーで加熱しながら形付ける。
のいずれの態様であってもよい。要は、形付けが毛髪温度50℃以上の状態で行われれば足りる。
・成分(A)を含む毛髪化粧料を適用した後、カーラー等で形付けを行い、(カーラー等を解放する前に)その後加熱する。
・カーラー等で形付けを行った後(カーラー等を解放する前に)、加熱した後、毛髪温度が50℃以上の状態で成分(A)を含む毛髪化粧料を適用する。
・カーラー等で形付けを行った後(カーラー等を解放する前に)、成分(A)を含む毛髪化粧料を適用し、50℃以上に加熱する。
のいずれであってもよい。しかし、整髪の行いやすさ、成分(A)を含む毛髪化粧料の髪への広げやすさの観点から、成分(A)を含む毛髪化粧料を適用した後に、形付けと加熱を行うことが好ましい。
本発明において、「冷却」とは、意識して温度を下げる(例えば冷風をかける)ことのみならず、周囲の温度により自然に温度を下げることも含む概念である。
・形付けを行う力を解放することなく、50℃未満に冷却し、その後、形付けを行う力を解放する(カーラーによる処理など)。
・形付けを行う力を解放するのと同時に、50℃未満に冷却すること(例えば50℃に設定したアイロンでの巻き付けを解放すると、力の解放と50℃未満への冷却がほぼ同時に行われる)。
・形付けを行う力を解放した後、50℃未満に冷却すること(この場合には、解放後の時間経過が長すぎると、折角付与した形付けが崩れるおそれがあるので、解放後直ちに冷却することが好ましい。なお、例えばアイロンの設定温度が50℃よりも高温であればあるほど、また巻き付けた髪の束が太いほど、髪の巻き付けを解放してから50℃未満に冷却されるまでの時間は長くなるが、これらは形付けが崩れない限り、構わない。あるいは、形付けを行う力を解放した後も、わずかな時間、50℃以上に温度が保たれても構わない。)。
などのいずれの態様であってもよい。ここで「直ちに」とは、好ましくは30秒以内、より好ましくは15秒以内、より好ましくは5秒以内、より好ましくは3秒以内をいうものとする。
本発明の整髪方法に用いる成分(A)のオルガノポリシロキサンは、50℃以上に加熱すると柔らかくなり、冷却すればすぐに弾力性を取り戻すという特徴的な熱可塑性を有するため、一旦整髪した後であっても、簡単に何度でも再整髪することができる。このため、一度作った髪形が仮に失敗しても容易に修正することができ、慣れない人であっても簡単に満足できる髪型を得ることができる。この場合の再整髪は、本発明の整髪方法によって整髪した毛髪を、再度毛髪温度50℃以上において毛髪を形付けした後、毛髪の温度を50℃未満に冷却して形付けすればよい。具体的な方法としては、前述の方法と同じである。この際、成分(A)を含む毛髪化粧料を毛髪に追加適用してもよいが、最初の整髪の際に、既に成分(A)を含む毛髪化粧料が適用されているため、追加適用しなくても再整髪することができる。
本発明の整髪方法に用いる成分(A)のオルガノポリシロキサンは、前記一般式(1)で表される繰り返し単位からなるポリ(N-アシルアルキレンイミン)セグメントが、主鎖を構成するオルガノポリシロキサンセグメントのケイ素原子の少なくとも2つに、ヘテロ原子を含むアルキレン基を介して結合したものであり、50~220℃といった毛髪でも耐えられる温度領域に加熱すると柔らかくなり、加熱をやめて室温に戻る過程で直ぐに弾力性を取り戻すという特徴的な熱可塑性を有する。
溶離液:1mMトリエチルアミン/THF
流量 :0.35mL/min
カラム温度:40℃
検出器:UV
サンプル:50μL
本発明のオルガノポリシロキサンは、例えば、下記一般式(3)
で表される変性オルガノポリシロキサンと、下記一般式(4)
で表される環状イミノエーテル(以下「環状イミノエーテル(4)」とする)を開環重合して得られる末端反応性ポリ(N-アシルアルキレンイミン)とを反応させることにより製造される。
2)カルボキシ基と水酸基との縮合によるエステルの形成反応
3)カルボキシ基とアミノ基との縮合によるアミドの形成反応
4)ハロゲン化アルキル基と、1級、2級又は3級アミノ基との2級、3級又は4級アンモニウムの形成反応
5)Si-H基を有するオルガノポリシロキサンへのビニル基の付加反応
6)エポキシ基とアミノ基とのβ-ヒドロキシアミン形成反応
本発明で用いる毛髪化粧料は、上記した成分(A)のオルガノポリシロキサンを含有する。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。
(b2) 窒素原子に炭素数1~18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2~4のアルキレンカーボネート
(b4) 数平均分子量100~1,000のポリプロピレングリコール
(b5) 一般式(6)、(7)又は(8)で表されるラクトン又は環状ケトン
〔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。〕
ポリビニルピロリドン
市販品として、ルビスコールK12、K30(以上BASF社製)、PVP K15、K30(以上GAF社製)等が挙げられる。
市販品として、ルビスコールVA28、VA73(以上BASF社製)、PVP/VA E-735,S-630(以上GAF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、937、958(以上GAF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(GAF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、ES-425、SP-215(以上GAF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(ナショナル・スターチ社製)、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(ナショナル・スターチ社製)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(株)製)、ダイヤホールド(三菱油化(株)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)、アンフォマーV-42(ナショナル・スターチ社製)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、SM(以上三菱油化(株)製)等が挙げられる。
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(ナショナル・スターチ社製)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、L-200(ナショナル・スターチ社製)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(一丸ファルコス社製)等が挙げられる。
市販品として、カイトマーPC(ピロリドンカルボン酸塩)、カイトマーL(乳酸塩)(以上、ユニオンカーバイド社製)等が挙げられる。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン93.8g(0.947モル)を脱水した酢酸エチル203gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、2500であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(190g、収率95%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は50質量%、重量平均分子量は60000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン106.6g(1.075モル)を脱水した酢酸エチル229gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、2800であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(200g、収率94%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は47質量%、重量平均分子量は64000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン75.7g(0.763モル)を脱水した酢酸エチル166gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、2000であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(169g、収率93%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は55質量%、重量平均分子量は55000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル3.08g(0.02モル)と2-エチル-2-オキサゾリン96.9g(0.978モル)を脱水した酢酸エチル203gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、5000であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量40000、アミン当量3800)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(188g、収率94%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は50質量%、重量平均分子量は80000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約24モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン116.1g(1.171モル)を脱水した酢酸エチル248gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、3000であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(204g、収率92%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は45質量%、重量平均分子量は67000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン102.2g(1.031モル)を脱水した酢酸エチル220gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、2700であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(194g、収率93%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は48質量%、重量平均分子量は63000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン86.1g(0.869モル)を脱水した酢酸エチル187gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、2300であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(179g、収率93%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は52質量%、重量平均分子量は58000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル12.78g(0.0829モル)と2-エチル-2-オキサゾリン246.6g(2.488モル)を脱水した酢酸エチル519gに溶解し、窒素雰囲気下15時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、3100であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2010)166.7gの33%酢酸エチル溶液を一括して加え、12時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(422g、収率99%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は39.4質量%、重量平均分子量は108000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、アミノ基は残存していないことがわかった。
硫酸ジエチル5.92g(0.038モル)と2-エチル-2-オキサゾリン60.7g(0.613モル)を脱水した酢酸エチル135gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、1700であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量1980)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色固体(158g、収率95%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は60質量%、重量平均分子量は50000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約24モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン50.1g(0.505モル)を脱水した酢酸エチル114gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、1400であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量32000、アミン当量1900)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色ゴム状半固体(152g、収率97%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は64質量%、重量平均分子量は50000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約24モル%のアミノ基が残存していることがわかった。
硫酸ジエチル6.17g(0.04モル)と2-エチル-2-オキサゾリン34.7g(0.35モル)を脱水した酢酸エチル83gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、1000であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量30000、アミン当量2000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を淡黄色ゴム状半固体(141g、収率97%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は71質量%、重量平均分子量は42000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果、約20モル%のアミノ基が残存していることがわかった。
硫酸ジエチル0.77g(0.005モル)と2-エチル-2-オキサゾリン12.9g(0.13モル)を脱水した酢酸エチル28gに溶解し、窒素雰囲気下8時間加熱還流し、末端反応性ポリ(N-プロピオニルエチレンイミン)を合成した。数平均分子量をGPCにより測定したところ、2700であった。ここに、側鎖一級アミノプロピル変性ポリジメチルシロキサン(重量平均分子量100000、アミン当量20000)100gの33%酢酸エチル溶液を一括して加え、10時間加熱還流した。反応混合物を減圧濃縮し、N-プロピオニルエチレンイミン・ジメチルシロキサン共重合体を無色固体(108g、収率95%)として得た。最終生成物のオルガノポリシロキサンセグメントの含有率は88質量%、重量平均分子量は114000であった。溶媒としてメタノールを使用した塩酸による中和滴定の結果アミノ基は残存していないことがわかった。
表2~6に示す毛髪化粧料を調製し、下記方法に従ってその評価を行った。この結果を各表中に併せて示す。なお、環境を明記していない部分については、室温(25℃)、相対湿度40%の環境で操作を行うものとする。
長さ30cm、重さ6gのバージン毛(ヘアカラー、ブリーチ等の化学処理を行っていない日本人女性毛)の毛束を評価に用いた。
この毛束に霧吹きの水0.6gを塗布後、各サンプルを0.2g塗布し、DELRIN社製リングコームで表裏5回くしを通した。次いで毛束をドライヤーで完全に乾燥させた後、5名の専門パネラーに、温度を150℃に設定した株式会社クロイツ製アイロン(型番:J72010M)に髪を巻きつけてもらい、10秒間保持し、その後、アイロンを外してもらった。外した後は、室温環境下に置かれるので、毛束の温度もほどなく室温となる。
この一連の処理が完了した後、以下の基準に従って官能評価及び総合評価を行った。各評価は5名の専門パネラー評価の平均値を示した。
・アイロンでのくせづけしやすさ
毛束処理条件1において、髪をアイロンに巻く際の巻きやすさについて、以下の判定基準により目視評価した。
5:とても良い
4:良い
3:ふつう
2:悪い
1:とても悪い
毛束処理条件1において、アイロンを外した後の毛束についたくせの度合いについて、同様の判定基準により目視評価した。
毛髪処理条件1において、形付けした部分を手で握ったときの感触(ごわつきのなさ)について、前述と同様の判定基準により官能評価した。
温度30℃、相対湿度80%の環境下で、毛髪処理条件1において一連の処理が完了した後の毛束を吊るして放置した。15分間放置した時、放置の前後で形付けした部分の変化の度合いを目視で評価した(毛髪の形状保持に強く関係する水素結合は、空気中の水分量が多い場合は速やかにその結合が緩和するために、温度30℃、相対湿度80%の環境における15分間放置は25℃、相対湿度40%の環境の12時間放置に相当する)。
5:変化なし
4:ほとんど変化なし
3:少し変化あり
2:変化あり
1:すごく変化あり
毛髪処理条件1において一連の処理が完了した後の毛束を、温度を150℃に設定した株式会社クロイツ製アイロン(型番:J72010M)に再び巻きつけ、10秒間保持した。処理時のくせのつけやすさについて、以下の判定基準により目視評価した。
5:とても良い
4:良い
3:ふつう
2:悪い
1:とても悪い
毛髪処理条件1における、アイロンでのくせづけしやすさ、ヘアスタイルの仕上がり、感触(ごわつきのなさ)、経時の持ち、再度くせづけしやすさの総合的評価について、以下の判定基準により評価した。
5:とても良い
4:良い
3:普通
2:悪い
1:とても悪い
毛束処理条件1においてくせづけされた毛束を、市販のくし歯間隔5mmのくし(Y. S. PARK Professional製、片細鬼歯)を用いて3回くし通しを行い、くし通し前後の毛束の形の変化について、以下の判定基準により目視評価した。
5:変化なし
4:ほとんど変化なし
3:少し変化あり
2:変化あり
1:すごく変化あり
毛束処理条件1においてくせづけされた毛束を手で握ったときの感触(ハリコシ感)について、以下の判定基準により官能評価した。
5:ハリコシを感じる
4:ややハリコシを感じる
3:どちらともいえない
2:あまりハリコシを感じない
1:ハリコシを感じない
毛束処理条件1においてくせづけされた毛束のまとまり性について、以下の判定基準により目視評価した。
5:まとまっている
4:ややまとまっている
3:どちらともいえない
2:あまりまとまっていない
1:まとまっていない
毛束処理条件1においてくせづけされた毛束の手で触ったときの感触(すべり感)について、以下の判定基準により官能評価した。
5:すべりが良い
4:ややすべりが良い
3:どちらともいえない
2:あまり滑りが良くない
1:すべりが良くない
長さ35cm、重さ6gのコーカシアンクセ毛(ヘアカラー、ブリーチ等の化学処理を行っていないドイツ人カーリー毛)の毛束を評価に用いた。
この毛束を、以下に処方を示すモデルシャンプーで洗浄した後、タオルで余分な水分を拭き取り、毛束が湿った状態で各サンプルを手で0.5g塗布し、塗布した剤を手指で均一に馴染ませると同時に手指で毛流れを整えた。次いでこの毛束を室温で3時間自然乾燥した。
この一連の処理が完了した後、以下の基準に従って官能評価を行った。評価は5名の専門パネラーにより行い、評価の平均値を示した。
(質量%)
25%ポリオキシエチレン(2.5)ラウリルエーテル硫酸ナトリウム 62.00
ラウリン酸ジエタノールアミド 2.28
エデト酸二ナトリウム 0.10
安息香酸ナトリウム 0.50
オキシベンゾン 0.03
リン酸(75%水溶液) 0.10
ジブチルヒドロキシトルエン 0.01
塩化ナトリウム 0.80
赤色106号 0.00012
香料 0.26
精製水 バランス
・自然乾燥したときのセット性
毛束処理条件2で処理された毛束のカールの位相が揃っている度合いを以下の判定基準により目視評価した。
5:揃っている
4:やや揃っている
3:どちらともいえない
2:やや乱れている
1:乱れている
毛束処理条件2で処理された毛束を、温度30℃、湿度80%の環境下で15分間放置したとき、放置の前後での毛束の形状変化の度合いを目視で評価した。
5:変化なし
4:ほとんど変化なし
3:少し変化あり
2:変化あり
1:大きな変化あり
表7に示す毛髪化粧料を調製し、毛髪処理条件1においてそれぞれ一部の処理を変更して評価を行った。評価基準は前記のとおりである。この結果を表7に併せて示す。
・実施例54:ドライヤー乾燥なし。
・実施例55:霧吹きの水、ドライヤー乾燥共になし。
・実施例56:髪を加熱後、50℃以上の状態でサンプルを塗布し、アイロンに毛髪を巻きつける。
・実施例57:アイロンの代わりにカーラーに巻きつけてドライヤーで加熱する(髪の表面温度は80℃。以下ドライヤーによる加熱は全て同じ。)。室温まで冷却した後、カーラーを外す。
・実施例58:アイロンの代わりに、ドライヤーで加熱しながらくしで形づける。形づけが完了してくしを外したら、ただちにドライヤーの加熱をやめる。
・比較例5:ドライヤー乾燥は行うが、アイロン処理以降の処理なし。
・比較例6:ドライヤー乾燥の後、いったん室温に冷却する。その後加熱せずにくし・ブラシ等で形付けを行う。
・比較例7:ドライヤー乾燥の後、いったん室温に冷却する。その後加熱せずにくし・ブラシ等で形付けを行い、その後50℃以上に加熱する。
・比較例8:ドライヤー乾燥の後、同様にアイロン処理するが、髪の温度が40℃となるようにする。
Claims (17)
- 下記成分(A)を含有する毛髪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、形付けした髪型を固定する整髪方法。
成分(A):主鎖を構成するオルガノポリシロキサンセグメントのケイ素原子の少なくとも2つに、ヘテロ原子を含むアルキレン基を介して、下記一般式(1);
で表される繰り返し単位からなるポリ(N-アシルアルキレンイミン)セグメントが結合してなるオルガノポリシロキサンであって、
ポリ(N-アシルアルキレンイミン)セグメントの数平均分子量が1,200~5,500であり、
主鎖を構成するオルガノポリシロキサンセグメント(a)と、ポリ(N-アシルアルキレンイミン)セグメント(b)との質量比(a/b)が35/65~60/40であり、
隣接するポリ(N-アシルアルキレンイミン)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重量平均分子量が1,300~5,500であり、
主鎖を構成するオルガノポリシロキサンセグメントの重量平均分子量が7,000~100,000である、
オルガノポリシロキサン。 - 成分(A)におけるポリ(N-アシルアルキレンイミン)セグメントがヘテロ原子を含むアルキレン基を介して結合するケイ素原子の1以上が、主鎖を構成するオルガノポリシロキサンセグメントの両末端以外のケイ素原子である請求項1記載の整髪方法。
- 一般式(1)中のR1が、炭素数1~3のアルキル基である請求項1又は2記載の整髪方法。
- 毛髪を形付けした後における50℃未満への冷却のタイミングが、毛髪を形付けする力を「解放する前」、「解放するのと同時」及び「解放した後」のいずれかである請求項1~3のいずれかに記載の整髪方法。
- 請求項1~4のいずれかの整髪方法によって整髪した毛髪を、再度毛髪温度50℃以上において毛髪を形付けした後、毛髪の温度を50℃未満に冷却して形付けした髪型を固定する整髪方法。
- 成分(A)を含有する毛髪化粧料を毛髪に適用する前に、毛髪に水を適用する請求項1~5のいずれかに記載の整髪方法。
- 成分(A)を含有する毛髪化粧料を毛髪に適用した後、毛髪温度50℃以上において毛髪を形付けする前に、毛髪を乾燥させる請求項1~6のいずれかに記載の整髪方法。
- 下記成分(A)を含有する毛髪化粧料。
成分(A):主鎖を構成するオルガノポリシロキサンセグメントのケイ素原子の少なくとも2つに、ヘテロ原子を含むアルキレン基を介して、下記一般式(1);
で表される繰り返し単位からなるポリ(N-アシルアルキレンイミン)セグメントが結合してなるオルガノポリシロキサンであって、
ポリ(N-アシルアルキレンイミン)セグメントの数平均分子量が1600~3500であり、
主鎖を構成するオルガノポリシロキサンセグメント(a)と、ポリ(N-アシルアルキレンイミン)セグメント(b)との質量比(a/b)が42/58~58/42であり、
隣接するポリ(N-アシルアルキレンイミン)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重量平均分子量が1600~3500であり、
主鎖を構成するオルガノポリシロキサンセグメントの重量平均分子量が7,000~100,000である、
オルガノポリシロキサン。 - 更に下記成分(B)及び(C)を含有する請求項8記載の毛髪化粧料。
成分(B):次の(b1)~(b5)から選ばれる有機溶剤
(b1) 一般式(5)で表される化合物
(b2) 窒素原子に炭素数1~18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2~4のアルキレンカーボネート
(b4) 数平均分子量100~1,000のポリプロピレングリコール
(b5) 一般式(6)、(7)又は(8)で表されるラクトン又は環状ケトン
成分(C):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 - 成分(B)がベンジルアルコール又は2-ベンジルオキシエタノールである請求項9記載の毛髪化粧料。
- 成分(C)が乳酸、リンゴ酸又はこれらの塩である請求項9記載の毛髪化粧料。
- 成分(B)の含有量が0.1~40質量%、成分(C)の含有量が0.1~30質量%である請求項9~11のいずれかに記載の毛髪化粧料。
- 更に下記成分(D)を含有する請求項8~12のいずれかに記載の毛髪化粧料。
成分(D):セットポリマー - 成分(D)がアクリル系ポリマー及びビニルピロリドン系ポリマーから選ばれる請求項13記載の毛髪化粧料。
- 成分(D)の含有量が0.05~20質量%である請求項13又は14記載の毛髪化粧料。
- 成分(A)の含有量が0.01~50質量%である請求項8~15のいずれかに記載の毛髪化粧料。
- ヘアスタイリング剤又はヘアコンディショニング剤である請求項8~16のいずれかに記載の毛髪化粧料。
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JP (2) | JP5647992B2 (ja) |
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