JP2010001287A - Hair-dressing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair-dressing method, by which hair can be dressed up to give a puffy style retained for a long time. <P>SOLUTION: Provided is a hair-dressing method comprising (A) increasing the intersections of hair to enlarge the volume of the hair and (B) applying an aerosol type hair cosmetic having a coating film strength of ≥800 gf/cm<SP>2</SP>measured by a coating film strength evaluation method. It is preferable that the aerosol type hair cosmetic used in the process (B) contains a coating film-forming polymer. It is also preferable that the coating film-forming polymer is a copolymer of (meth)acrylamide-based monomer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hair styling method in which a soft style lasts for a long time.

Conventionally, aerosol hair cosmetics used for hair styling generally fix hair using the fixing force of a film-forming polymer. Such hair cosmetics have hairstyling ability, but have problems such as that the finished hair is sticky, stiff, and hard. Also, the soft finish cannot last for a long time.
Patent Document 1 describes a composition for treating a keratin substance containing an anionic polymer and a cationic polymer. This composition can be applied to hair, and when used as a hair styling agent, hair styling power can be obtained, but there is a problem that the wash-off property by shampoo is poor.

JP-A-53-139734

  An object of the present invention is to provide a hair styling method in which a soft style lasts for a long time.

  The present inventors have found that a style with a soft feeling can be maintained for a long time by increasing the volume of hair by increasing hair crossing and applying a specific aerosol hair cosmetic.

The present invention provides (A) an increase in hair volume by increasing hair crossing, and (B) an aerosol-type hair cosmetic having a coating strength measured by a coating strength evaluation method of 800 gf / cm ² or more. Applying,
A hair styling method including the above is provided.

  According to the present invention, it is possible to maintain a style with excellent hair styling power and a soft feeling for a long time.

It is a figure which shows the space volume which hair surrounds. It is a figure which shows the state of the hair in which the direction of a long axis is uniform. It is a figure which shows the state of the hair in which the direction of a long axis is orthogonal.

As an effective method for creating a beautiful hairstyle, in the present invention, (A) it is necessary to increase the volume of the hair by increasing the hair crossing.
Here, in the present specification, “increasing the volume of hair” means increasing the volume of space surrounded by hairs, and in a two-dimensional manner, it means the area of the shaded portion shown in FIG.
As the state of hair, when the direction of the long axis of each hair is aligned (FIG. 2) and the case where it is orthogonal (FIG. 3) are considered to be the most extreme state, the actual hair is the state between these It is in. In the present invention, the increase in crossing means changing the state of the hair from FIG. 2 to FIG. 3, and if there is even a slight change from FIG. 2 to FIG. 3, it is included in increasing the crossing of the hair. It is a concept that includes things that change to an intermediate state between the two.

By doing in this way, the volume of hair can be increased effectively and the beautiful hairstyle with a soft feeling can be made.
And, by applying the aerosol hair cosmetics whose film strength measured by (B) film strength evaluation method is 800 gf / cm ² or more to the hairstyle made in this way, beautiful hairstyle can be kept for a long time. Can enjoy.

<Method to increase hair volume by increasing hair crossing>
In the present invention, the target head hair may be straight hair or comb hair, or may be hair that has straight hair combed by perm (curly hair, wave hair), or the comb hair is straightened by straight perm. May be. Further, the hair may be wet or dry, but a dry state is more preferable. It may be a hair care agent or a treatment that has been previously attached or not. It may or may not be dyed. Also, the length of the hair is not limited, from short hair where the hair does not reach the ears, eyebrows, and neck when not tied, to long hair where the hair ends below the chest and waist I do not care.

Next, a specific example of increasing hair volume by increasing hair crossing will be given.
(1) From the hair tip side to the root side, comb the hair with a comb, brush or finger, or squeeze (generally called “raise upside-down hair”) to change the direction of the long axis of the hair. Change to indiscriminate orientation.

(2) Bundle the hair as close to the root of the hair as possible (preferably at a position higher than the ears), and fasten it with a hairpin or with a rubber strap so that the bundled hair does not dissipate. Next, the direction of the hair's long axis direction is varied (so-called “scattering”) with the fingers, combs or brushes with respect to the hair on the tip side from the bundle. Or it is good to make reverse hair with respect to the hair of the hair tip side rather than the bundled part. The bundling position in this case is not particularly limited, and may be any of the top of the head, the back of the head, and the temporal region. Further, any number of bundles may be used.

(3) Use curling irons and hair curlers to curl and wave the hair. The curl and wave are loosened with fingers, and the direction of the long axis of the hair becomes more varied. It is also possible to perform reverse hair raising before the curl is loosened with a finger. Here, the curled portion may be a portion closer to the hair tip than a portion where the hair is bundled and bundled, or may be a portion in a state where it is lowered without being bundled or tied. Also, any of the top of the head, the back of the head, the temporal region, the ear, and the ear may be used.

These methods (1) to (3) may be used alone or in combination, or may be used in combination with other hair styling methods.
By using the method of increasing the hair crossing in this way and (B) applying an aerosol hair cosmetic with a coating strength of 800 gf / cm ² or more measured by the coating strength evaluation method, a beautiful hairstyle is lengthened. Hold and enjoy.

On the other hand, (B) aerosol hair cosmetic composition is at film strength, as measured by the following evaluation method is 800 gf / cm ² or higher, preferably 1000 gf / cm ² or more, more preferably 1500gf / cm ² or more, especially 2000 gf / cm ² or more, more preferably at 2300gf / cm ² or more. If the film strength is within this range, a soft hairstyle can be maintained for a longer time. On the other hand, film strength, as measured according to the following evaluation method 8000gf / cm ² or less, particularly 6000gf / cm ² or less, more 5000gf / cm ² or less, and more preferably 4000gf / cm ² or less. If the film strength is within this range, the feel of the applied hair will be good.

The film strength is measured by the following evaluation method.
<Create sample>
(1) Spray aerosol-type hair cosmetic into a container and stir with a stirrer for 2 hours to collect the stock solution after removing the propellant (if the stock solution can be obtained directly, this part of the operation is omitted) . 15 g of the collected stock solution is placed in a petri dish having a diameter of 7.5 cm (for example, a material having a film that is easily peeled off, such as Teflon (registered trademark)), and is evaporated to dryness at 25 ° C. and 65% Rh for 3 days.
(2) Place the whole petri dish for 30 minutes in a constant temperature box set at 25 ° C. and 98% Rh.
(3) Remove the softened film from the petri dish with a spatula or the like.
(4) If not peeled off, repeat (2) and (3).
(5) The film is cut into a size of 3.0 mm × 30.0 mm.
(6) For example, Teflon (registered trademark) such as Teflon (registered trademark) is difficult to adhere to the sheet of material, cut out the film so that it does not overlap, and further layered with a sheet of material difficult to adhere the film, plastic sheet, Place a weight from above so that the film does not warp.
(7) One day later, the thickness of the central part of the film is measured with a thickness gauge (manufactured by Teclock, SMD-565) (N = 5).

<Measurement of breaking strength of sample>
(1) The cut film is left in a constant temperature box set at 20 ° C. and 98% Rh for 2 hours.
(2) Remove the film from the thermostatic box and immediately measure the film breaking strength with a tensile and compression tester (TMD-200N, manufactured by Minebea Co., Ltd.) (Distance between chucks: 2 cm, length between chucks: 0.5 cm, pulling speed) : 200 mm / min).
(3) The cross-sectional area of the film is calculated from the thickness of the film measured previously.
(4) Divide the film breaking strength by the cross-sectional area to calculate the breaking stress (N = 5), which is the film strength.

Such a hair cosmetic contains a film-forming polymer.
The film-forming polymer may be any of a synthetic polymer, a natural polymer, and a modified natural polymer, and may have any anionic, amphoteric, cationic, or nonionic electrostatic properties. You may use them individually or in mixture of multiple. The case with film-forming polymer, breaking strength by the evaluation method shown below 100 gf / cm ² or more, further 200 gf / cm ² or more, in particular refers to a 300 gf / cm ² or more polymers.
Evaluation method:
15 g of a specific polymer to be evaluated dissolved in ethanol at a concentration such that the thickness of the coating is 200 to 400 μm is easily peeled off from a petri dish having a diameter of 7.5 cm (for example, Teflon (registered trademark)) It is evaluated in the same manner as the above-mentioned film strength evaluation method except that it is put into a material) and is evaporated to dryness at 25 ° C. and 65% Rh for 3 days.
Examples of film-forming polymers are given below.

<Anionic film-forming polymer>
An anionic film-forming polymer containing any one of crotonic acid, maleic acid, maleic acid monoester, and itaconic acid as a structural unit:
Although it will not specifically limit if any of crotonic acid, maleic acid, maleic acid monoester, and itaconic acid is included as a structural unit, It is copolymerized with 1 or more types of vinyl ethers, vinyl esters, and vinyl alcohols Methyl vinyl ether / alkyl maleate copolymer (Gantrez ES-225, ES-425, SP-215, etc. manufactured by ISP), vinyl acetate / crotonic acid copolymer (resin 28-1310, manufactured by National Starch), etc. ), Vinyl acetate / crotonic acid / neodecanoic acid vinyl copolymer (resin 28-2930, manufactured by National Starch Co., Ltd.), vinyl acetate / crotonic acid / vinyl propionate copolymer (rubiset CAP, manufactured by BASF), vinyl alcohol / itacon Acid copolymers (KM-118 manufactured by Kuraray Co., Ltd.) are more preferable, and methyl vinyl ether / ma Ynoic acid alkyl copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, vinyl acetate / crotonic acid / vinyl propionate copolymer further preferred.

An anionic film-forming polymer containing (meth) acrylic acid as a structural unit:
Although it will not specifically limit if it is a vinyl polymer containing (meth) acrylic acid as a structural unit, The copolymer of (meth) acrylic-acid alkylester or N-alkyl (meth) acrylamide and 1 or more types is preferable.
More preferably, an acrylic acid / ethyl acrylate / Nt-butylacrylamide copolymer (BASF Ultrahold 8, Ultrahold Strong, etc.), an octylacrylamide / acrylic acid copolymer (National Starch Anformer V-42) ), Acrylate / methacrylate / acrylic acid / methacrylic acid copolymer (Amahold DR25 manufactured by Union Carbide Co., Ltd.), acrylates / diacetone acrylamide copolymer (plus size L9540B manufactured by Kyoyo Chemical Co., Ltd. (2-amino-2 of the polymer) -Methyl-1-propyl alcohol neutralized product), etc.), acrylates / C1-18 alkyl acrylates / C1-8 alkyl acrylamide copolymer (plus size L9909B manufactured by Kyoyo Chemical Co., Ltd.) Acrylate / methacrylate / acrylic acid / methacrylic acid copolymers, acrylates / diacetone acrylamide copolymers, acrylates / C1-18 alkyl acrylates / C1-8 alkyl acrylamide copolymers, and the like. More preferred.

A natural anionic film-forming polymer having either a carboxy group or a sulfate group:
Although it is not particularly limited as long as it is a natural polysaccharide having either a carboxy group or a sulfate group, carrageenan (Mitsubishi Rayon Co., Ltd. Soagina LX22, the same ML210 etc.), xanthan gum (Dainippon Pharmaceutical Co., Ltd. Echo Gum T etc.) and the like are preferable. Carrageenan is more preferred.

-Polyester having either a carboxy group or a sulfonic acid group:
Although not particularly limited, water dispersible polyesters (AQ38S, AQ55S, etc. manufactured by Eastman Kodak) are preferable.

  As the anionic film-forming polymer, methyl vinyl ether / alkyl maleate copolymer, acrylates / diacetone acrylamide copolymer, acrylates / C1-18 alkyl acrylates / C1-8 alkyl acrylamide copolymer are particularly preferable.

<Amotropic film-forming polymer>
Although not particularly limited, a synthetic polymer is preferable, and a vinyl polymer is more preferable. Here, an amphoteric polymer is a so-called betaine monomer having a copolymer containing one or more anionic monomers and one or more cationic monomers as constituent units, and both an anionic portion and a cationic portion in the monomer structure. It contains both copolymers containing one or more structural units.
Among them, dimethyldiallylammonium / acrylamide / acrylic acid copolymers (such as Marquat 3331 manufactured by Calgon), N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer (Mitsubishi Chemical) Yuka Former M-75, SM, etc.); octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer (National Starch Amphomer 28-4910, etc.) is preferred, and octylacrylamide / acrylate / butylaminoethyl is preferred. A methacrylate copolymer is particularly preferred.

<Cationic film-forming polymer>
Although not particularly limited, a vinyl polymer having one or more of a quaternary ammonium structure, a tertiary amine structure, a secondary amine structure, or a primary amine structure, a quaternary ammonium structure, a tertiary amine structure, a secondary amine structure, or 1 Natural polysaccharides having a secondary amine structure or modified natural polysaccharides are preferred.

・ Vinyl polymer:
(Meth) acrylic acid ester having a secondary amino group, tertiary amino group or quaternary ammonium group, (meth) acrylamide having a secondary amino group, tertiary amino group or quaternary ammonium group, N-substituted allylamines, Examples thereof include vinyl polymers having one or more members selected from N-substituted allyl ammoniums as constituent units. Among them, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymers (polymers described in Examples of JP-A-2-809911), alkylacrylamide / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymers ( Polymer described in Examples of JP-A-8-291206), polydimethyldiallylammonium chloride (such as Marquat 100 manufactured by Calgon), acrylamidopropyltrimethylammonium chloride / acrylate copolymer (such as Marcoat manufactured by Calgon), acrylamide / Dimethyl diallylammonium chloride copolymer (Mercoat 550, 2200, etc. from Calgon), methylvinylimidazolium chloride / vinylpyrrolidone Polymer (BASF's Ruby Coat FC370, FC550, FC905, HM552, etc.), vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymer (ISP's Guffcut HS-100, etc.), vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer Diethyl sulfate (ISP's Guffcut 734, 755N, 755, etc.), vinyl alcohol / dimethylaminopropyl methacrylamide copolymer (Kuraray C-318, etc.), vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer (ISP) Copolymer 845, 937, 958, etc.), vinyl pyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer (ISP copolymer VC-713, etc.), vinyl alcohol / vinyl amine copolymer (Air Product VA-120) -HCl and the like are preferred.

・ Natural polysaccharides or modified products of natural polysaccharides:
Hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer (National Starch: Cellcoat H-100, L-200, etc.), Hydroxyethylcellulose / 2-hydroxypropyltrimethylammonium chloride (Union Carbide Polymer JR-400, etc.), Gua Hydroxypropyltrimonium chloride (Henskel Cosmedia Gua C-261N, Rhone-Poulenc Jaguar C-17, etc.), Hydroxypropyl chitosan (Ichimaru Falcos Chitofilmer HV-10, etc.), Chitosan-dl -Pyrrolidone carboxylates (such as Kionmer PC manufactured by Union Carbide) are preferred. Hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer (Nelch Cell Coat H-100, L-200, etc.), hydroxyethyl cellulose / 2-hydroxypropyltrimethylammonium chloride (Union Carbide Polymer JR-400, etc.), Guahydroxypropyltrimonium chloride (Cosmedia Gua C-261N manufactured by Henkel, Jaguar C-17 manufactured by Rhône-Poulenc, etc.) is preferred.

  Among the cationic film-forming polymers, alkyl acrylamide / acrylate / alkyl aminoalkyl acrylamide / polyethylene glycol methacrylate copolymers and alkyl acrylamide / alkyl amino alkyl acrylamide / polyethylene glycol methacrylate copolymers are more preferable.

  Of these film-forming polymers, one or more copolymers selected from (B1) and (B2) are particularly preferable.

(B1) (a) General formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or an alkyl group having 4 to 12 carbon atoms, but both R ² and R ³ are hydrogen atoms. Never)
30 to 80% by mass of a (meth) acrylamide monomer represented by
(b) General formula (2)

(In the formula, R ¹ represents the same as above, and R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)
2 to 50% by mass of a (meth) acrylamide monomer represented by
(c) General formula (3)

(Wherein R ¹ represents the same as described above, R ⁶ represents an alkylene group having 2 or 3 carbon atoms, R ⁷ and R ⁸ are the same or different and represent a methyl group or an ethyl group. A represents 0 or 1) Indicates the number of
(Meth) acrylic acid ester monomer or (meth) acrylamide monomer represented by 0-30% by mass, and
(d) General formula (4)

(Wherein R ¹ represents the same as above, R ⁹ and R ¹⁰ are the same or different and represent an alkylene group having 2 to 4 carbon atoms, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or phenyl. And b and c each represent a number from 0 to 50, but b and c are not 0 at the same time)
(Meth) acrylic acid ester monomer represented by 0-40% by mass
A copolymer of
(B2) (a) General formula (5)

(Wherein R ¹² represents a hydrogen atom or a methyl group, and R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or an alkyl group having 4 to 12 carbon atoms, or R ¹³ and R ¹⁴ are adjacent to each other. To form a ring with the nitrogen atom)
30 to 80% by mass of a (meth) acrylamide monomer represented by
(b) General formula (6)

(Wherein R ¹² represents the same as described above, and R ¹⁵ represents an alkyl group having 1 to 4 carbon atoms)
(Meth) acrylic acid ester monomer represented by 5 to 45% by mass,
(c) General formula (7)

(Wherein R ¹² represents the same as described above, R ¹⁶ represents an alkylene group having 2 or 3 carbon atoms, R ¹⁷ and R ¹⁸ are the same or different and represent a methyl group or an ethyl group. A represents 0 or 1) Indicates the number of
(Meth) acrylic acid ester monomer or (meth) acrylamide monomer represented by 2-30% by mass, and
(d) General formula (8)

(Wherein R ¹² represents the same as described above, R ¹⁹ and R ²⁰ are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, R ²¹ represents a hydrogen atom or a methyl group. Shows a number from 0 to 50, but b and c are not 0 at the same time)
(Meth) acrylic acid ester monomer represented by 0-30% by mass
Copolymer.

Among these, the (a) (meth) acrylamide monomer represented by the general formula (1) in (B1) is, for example, Nn-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N -Octyl (meth) acrylamide, N-lauryl (meth) acrylamide, N-1-methylundecyl (meth) acrylamide, N-2-ethylhexyl (meth) acrylamide, N-tert-octyl (meth) acrylamide is mentioned. Among these, N-branched alkyl (meth) acrylamides such as N-tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, and N-2-ethylhexyl (meth) acrylamide are particularly preferable.
These are used alone or in combination of two or more, and are used in an amount of 30 to 80% by mass, preferably 40 to 70% by mass, based on the whole monomer.

(b) Examples of the (meth) acrylamide monomer represented by the general formula (2) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide may be mentioned. Among these, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are particularly preferable.
These are used alone or in combination of two or more, and are used in an amount of 2 to 50% by mass, preferably 10 to 35% by mass, based on the whole monomer.

(c) Examples of (meth) acrylic acid ester and (meth) acrylamide monomers represented by the general formula (3) include N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth). Examples include acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide.
These may be used alone or in combination of two or more, and may be used in an amount of 0 to 30% by mass, preferably 0 to 10% by mass, and more preferably 0.5 to 5% by mass based on the entire monomer.

Further, (d) the monomer represented by the general formula (4) is a (meth) acrylic acid ester having a polyoxyalkylene chain. In the formula, R ¹¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Examples of the (meth) acrylic acid ester monomer (4) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and methoxypolyethylene glycol mono (Meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, butoxypolyethyleneglycol mono (meth) acrylate, and phenoxypolyethyleneglycol mono (meth) acrylate. The polyoxyalkylene chain is a homopolymer or copolymer of C2-4 alkylene oxide, and in the case of a copolymer, it may be a block copolymer such as ethylene oxide or propylene oxide, or a random copolymer. The degree of polymerization of the alkylene oxide can be analyzed by gas chromatography, and an average value of 1 to 50 is preferable.
These are used alone or in combination of two or more, and are used in an amount of 0 to 40% by mass, preferably 5 to 30% by mass, and more preferably 10 to 25% by mass, based on the whole monomer.

As the copolymer of (B1),
N-tert-butyl (meth) acrylamide / N, N-dimethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethyl (meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate,
N-tert-butyl (meth) acrylamide / N-methyl (meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate,
N-tert-butyl (meth) acrylamide / N-methyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide,
N-tert-octyl (meth) acrylamide / N, N-diethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate,
N-tert-octyl (meth) acrylamide / N, N-dimethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / 2-hydroxyethyl (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-diethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate is preferred,
N-tert-butyl (meth) acrylamide / N, N-dimethyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate is particularly preferred.

Examples of the (meth) acrylamide monomer represented by (a) general formula (5) in (B2) include (meth) acrylamide, Nn-butyl (meth) acrylamide, and N-tert-butyl (meth). Examples include acrylamide, N-octyl (meth) acrylamide, N-lauryl (meth) acrylamide, and (meth) acryloylmorpholine, among which N-butyl (meth) acrylamide, N-octyl (meth) acrylamide, and N-lauryl (meth). Acrylamide is particularly preferred.
These are used alone or in combination of two or more, and are used in an amount of 30 to 80% by mass, preferably 40 to 70% by mass, based on the whole monomer.

(b) Examples of (meth) acrylate monomers represented by the general formula (6) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Is mentioned.
These are used alone or in combination of two or more, and are used in an amount of 5 to 45% by mass, preferably 10 to 40% by mass, based on the entire monomer.

(c) Examples of (meth) acrylic acid ester and (meth) acrylamide monomers represented by the general formula (7) include N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth). Examples include acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide.
These are used alone or in combination of two or more, and are used in an amount of 2 to 30% by mass, preferably 5 to 20% by mass, based on the whole monomer.

Examples of (d) (meth) acrylic acid ester monomers represented by the general formula (8) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, and methoxypolypropylene glycol mono (meth) acrylate may be mentioned. The polyoxyalkylene chain is a homopolymer or copolymer of C2-4 alkylene oxide, and in the case of a copolymer, it may be a block copolymer such as ethylene oxide or propylene oxide, or a random copolymer. The degree of polymerization of the alkylene oxide can be analyzed by gas chromatography, and an average value of 1 to 50 is preferable.
These are used alone or in combination of two or more, and are used in an amount of 0 to 30% by mass, preferably 5 to 15% by mass, based on the whole monomer.

As a copolymer of (B2),
N-tert-butyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate / ethyl (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate / ethyl (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate / methyl (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-diethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate / ethyl (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / ethyl (meth) acrylate,
N-tert-octyl (meth) acrylamide / N, N-dimethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate / n-butyl (meth) acrylate,
N-tert-octyl (meth) acrylamide / N, N-diethylaminoethyl (meth) acrylate / methoxypolyethylene glycol (meth) acrylate / n-butyl (meth) acrylate,
N-tert-butyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / ethyl (meth) acrylate is preferred,
N-tert-butyl (meth) acrylamide / N, N-dimethylaminopropyl (meth) acrylamide / methoxypolyethylene glycol (meth) acrylate / ethyl (meth) acrylate is particularly preferred.

  The copolymers of (B1) and (B2) can be produced by combining the above monomers, for example, by the method described in JP-A-8-291206 or JP-A-2-180911. it can.

  The weight average molecular weight (by gel filtration chromatography (in terms of polyethylene glycol)) of the obtained copolymer can be controlled to 1,000 to 1,000,000 if the polymerization conditions are selected. In the present invention, the weight average molecular weight is Those of 10,000 to 500,000, particularly 20,000 to 200,000 are preferred.

  The copolymer thus obtained can be used by neutralizing its tertiary amino group with an inorganic acid or an organic acid in order to impart water solubility. In this case, it is preferable to neutralize 50% or more of all tertiary amino groups.

  Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid; examples of organic acids include acetic acid, glycolic acid, dimethyl glycolic acid, lactic acid, dimethylolpropionic acid, tartaric acid, citric acid, maleic acid, and malic acid. It is done.

  The amino group in the copolymer can also be quaternized using an appropriate quaternizing agent. In this case, it is preferable to quaternize 50% or more of all tertiary amino groups.

  Examples of the quaternizing agent include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl halides such as methyl chloride, propyl bromide and benzyl chloride, and aralkyl halides.

  Such a quaternized copolymer can also be obtained by a method in which the monomer (3) or (7) is quaternized with a quaternizing agent and then copolymerized.

  Examples of the film-forming polymer used for aerosol hair cosmetics include poly (N-acylalkylenimine) -modified silicone. Examples of the poly (N-acylalkylenimine) -modified silicone include a compound represented by the formula (9a) in the molecule.

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and n is 2 or 3)
A segment of poly (N-acylalkyleneimine) composed of a repeating unit represented by formula (1) and an organopolysiloxane segment, and at least one silicon atom at the terminal or side chain of the organopolysiloxane segment is a heteroatom. It is preferable that a poly (N-acylalkylenimine) segment composed of a repeating unit represented by the formula (9a) is bonded via an alkylene group containing The mass ratio of the poly (N-acylalkylenimine) segment to the organopolysiloxane segment is preferably 1/50 to 20/1, more preferably 1/40 to 20/1, and the molecular weight is preferably Is 500 to 500,000, more preferably 1,000 to 300,000. R is preferably a methyl group or an ethyl group.

  The alkylene group containing a hetero atom in at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment is an alkylene group having 2 to 20 carbon atoms containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms. In particular, an alkylene group having 2 to 5 carbon atoms containing a nitrogen atom is preferable.

  Preferred examples of such poly (N-acylalkylenimine) modified silicone include poly (N-formylethyleneimine) modified silicone, poly (N-acetylethyleneimine) modified silicone, poly (N-propionylethyleneimine) modified silicone, and the like. Is mentioned. Among them, a poly (N-propionylethyleneimine) modified silicone (INCI) having a weight average molecular weight of about 20,000 to 200,000 and a ratio of poly (N-propionylethyleneimine) segment in the molecule of about 3 to 50% by mass. Name: Polysilicone-9 (Kao Corporation)) is preferred.

  The poly (N-acylalkylenimine) -modified silicone can be produced by a known method, for example, a method described in JP-A-7-133352, and is synthesized, for example, by the following method. First, a segment of poly (N-acylalkylenimine) composed of a repeating unit represented by the formula (9a) is obtained by cationic ring-opening polymerization of a cyclic imino ether compound represented by the formula (9b).

  These cyclic imino ethers are described, for example, in Liebigs Ann. Chem. , P996 to p1009 (1974). These compounds may be used alone as a monomer for ring-opening polymerization, or may be used in combination of two or more.

  Examples of the polymerization initiator for ring-opening polymerization of the cyclic imino ether include toluenesulfonic acid alkyl ester, sulfuric acid dialkyl ester, trifluoromethanesulfonic acid alkyl ester, and alkyl halide, but are not limited thereto. These initiators can be used alone or in a mixture.

  A molecular chain of poly (N-acylalkylenimine) can be obtained by ring-opening polymerization of the cyclic imino ether compound represented by the formula (9b) using these initiators. A homopolymer chain or a copolymer chain may be used, and the copolymer chain may be a random copolymer chain or a block copolymer chain.

  The molecular weight of the molecular chain of the poly (N-acylalkylenimine) is preferably 150 to 50,000, more preferably 500 to 10,000.

  The modified silicone used in the present invention reacts a polymerization active species produced by ring-opening polymerization of the cyclic imino ether compound represented by the formula (9b) and an organopolysiloxane having a functional group capable of reacting with the polymerization active species. Can be obtained.

  Examples of the functional group capable of reacting with the above-mentioned polymerization active species include primary, secondary or tertiary amino groups, mercapto groups, hydroxyl groups, carboxylate groups, etc. Among them, amino groups are preferable. The organopolysiloxane containing an amino group in the molecule preferably has a molecular weight of 300 to 400,000, more preferably 800 to 250,000.

  The reaction between the organopolysiloxane containing an amino group and the reactive terminal of poly (N-acylalkylenimine) obtained by cationic polymerization of a cyclic imino ether can be carried out as follows.

  Initiator is a polar solvent, preferably acetonitrile, valeronitrile, dimethylformamide, dimethylacetamide, chloroform, methylene chloride, ethylene chloride, ethyl acetate, methyl acetate, etc., or a mixed solvent with other solvents as required And heated to 40 to 150 ° C, preferably 60 to 100 ° C. The cyclic imino ether represented by the general formula (9b) is charged all at once, or dropped when the reaction is intense, and polymerization is carried out. The progress of the polymerization can be traced by quantifying the residual amount of the cyclic imino ether as a monomer with an analytical instrument such as gas chromatography. Even when the cyclic imino ether is consumed and the polymerization is completed, the active species at the growing end maintain the reactivity. Without isolating the polymer, the polymer solution and the organopolysiloxane containing an amino group in the molecule are mixed and reacted at 5 to 100 ° C., preferably 20 to 60 ° C. The mixing ratio can be appropriately selected as desired, but it is preferable to react at a ratio of 0.1 to 1.3 molar equivalents of poly (N-acylalkylenimine) to 1 mole of amino group in the organopolysiloxane.

  By the reaction as described above, a block copolymer or graft polymer having poly (N-acylalkyleneimine) segments attached to polydimethylsiloxane can be obtained.

  In the aerosol hair cosmetic (B), one or more film-forming polymers can be used, preferably two or more of the above-mentioned film-forming polymers, and more preferably the above-mentioned film-forming polymer. It is preferable to select only from the functional polymers. The film-forming polymer contains 0.6 to 24% by mass, particularly 1.3 to 20% by mass, and more preferably 2.0 to 16% by mass in the hair cosmetic stock solution (hereinafter the same), and has high hair styling ability. It is preferable from the viewpoint of balance between shampoo detachment, good touch and compatibility with the propellant.

  The hair cosmetic further contains ethanol and / or water. These contents are preferably 70 to 99% by mass, more preferably 80 to 97% by mass in the stock solution, from the viewpoint of improving the solubility and spray state of the copolymer and plasticizer contained in the cosmetic. 85-95 mass% is preferable.

Some solvents and nonionic surfactants soften the film-forming polymer and lower the breaking strength (these are also generally called plasticizers). These solvents include a solvent having 3 or more carbon atoms and a hydroxyl group in the molecule, an ester solvent, N-hydroxyethylcarboxylic acid amide, and a nonionic surfactant.
Specific examples of the solvent having 3 or more carbon atoms and a hydroxyl group in the molecule include monohydric alcohols such as propanol, butanol, benzyl alcohol, ethoxyethyl alcohol, and phenoxyethanol, propylene glycol, 1,3-butylene glycol, glycerin, Examples thereof include polyhydric alcohols such as isopentylene glycol, hexylene glycol, dipropylene glycol, polypropylene glycol (degree of polymerization 9), polyethylene glycol 600 and the like.
Examples of ester oils include fatty acid triglycerides such as (capryl / capric acid) triglyceride and oleic acid triglyceride, neopentyl glycol dipalmitate, fatty acid esters of dihydric alcohols such as (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, And fatty acid esters of monohydric alcohols such as isopropyl myristate.

Examples of N-hydroxyethylcarboxylic acid amide include N-acetylethanolamide.
Specific examples of nonionic surfactants include fatty acid monoglycerides such as oleic acid monoglyceride and caprylic acid monoglyceride, fatty acid diethanolamides such as palm kernel oil fatty acid diethanolamide, sorbitan monooleate, and sorbitan monolaurate. Polyoxyalkylene sorbitan fatty acid esters such as sorbitan fatty acid ester, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, isostearyl glyceryl ether, isodecyl Alkyl glyceryl ethers such as glyceryl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene tetraoleate Fatty polyoxyethylene sorbit such Rensorubitto, polyoxyethylene (9) tridecyl ether, such as polyoxyalkylene alkyl ethers such as polyoxyethylene (9) lauryl ether.

  From the viewpoint of improving brittleness, the above solvents and nonionic surfactants are contained in the stock solution in an amount of 0 to 5% by mass with respect to the polymer that forms a brittle film while keeping the breaking strength of the film-forming polymer high. It is preferably contained, more preferably 0 to 2% by mass, still more preferably 0 to 1% by mass, and still more preferably not contained.

  Hair cosmetics are various components used in normal hair cosmetics such as cationic surfactants, anionic surfactants, nonionic surfactants other than those mentioned above, amphoteric surfactants, pH adjusters, vitamins , Proteins, amino acids, herbal medicines, preservatives, ultraviolet absorbers, antioxidants, colorants and the like can be contained according to the purpose.

The hair cosmetic is further made into an aerosol hair cosmetic using a propellant.
The mass ratio between the components other than the propellant (hereinafter referred to as the stock solution) and the propellant is (stock solution) / (propellant) = 70/30 to 30/70, particularly 60/40 to 40/60. However, it is preferable for improving workability and obtaining hair-styling power.

  Aerosol hair cosmetics are manufactured by filling a pressure-resistant container with a stock solution and a propellant. The aerosol hair cosmetic may be any of hair foam, hair mousse (foam), or hair spray (fog), but is preferably a hair spray.

  The stock solution has a viscosity of 15 mPa · s or less, particularly 10 mPa · s or less, at 30 ° C., in order to eject the stock solution as fine droplets. The viscosity herein refers to a value measured with a Brookfield viscometer (rotor BL adapter, rotation speed 30 rpm, 60 seconds, 30 ° C.).

Examples of the propellant include liquefied natural gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas, and a mixture thereof. Alternatively, alternative CFCs such as HFC-152a can be used.
Moreover, it is preferable to adjust the pressure in a pressure-resistant container so that it may become 0.12-0.45 MPa at the temperature of 25 degreeC from a viewpoint of obtaining a favorable injection characteristic and a favorable adhesion characteristic.

  The valve used for the pressure vessel preferably has a stem hole diameter φ0.33 to 0.46 mm, a housing lower hole diameter φ0.33 to 0.65 mm × a vapor tap diameter φ0 to 0.64 mm. In the prescription system containing water, it is particularly preferable that the stem hole diameter is 0.33 to 0.42 mm, the lower hole diameter of the housing is 0.33 to 0.42 mm, and there is no vapor tap, and in the non-aqueous system, the stem hole diameter is especially 0.40 to 0.46 mm. The housing lower hole diameter φ0.42-0.65 mm × vapor tap hole diameter φ0.33-0.46 mm is preferable.

Hair cosmetics have an average particle diameter of 10 to 60 μm, more preferably 15 to 50 μm, especially 20 to 40 μm when ejected from a container. This is preferable because the time until fixing can be well balanced.
The average particle size is measured using a laser diffraction particle size distribution measuring device HELOS SYSTEM manufactured by Sympatec GmbH, system-Partikel-technik, measuring range R4 (focal length 200 mm, particle size measuring range 0.5 / 1.8 to 350 μm) Thus, it is assumed that the volume cumulative distribution is 50% when measured by directly spraying the laser beam (measurement distance: 15 cm).

  (B) The method of applying the aerosol hair cosmetic composition is not particularly limited, for example, spraying from a distance of 10 cm or more from the hair, not spraying continuously for more than 1 second in the same place (moving evenly It is preferable to improve the touch by not applying a large amount of agent to a specific place by spraying.

In the present invention, (A) after increasing the hair volume by increasing hair crossing, (B) aerosol hair cosmetic may be applied, or (B) aerosol hair cosmetic may be applied. After application, (A) the hair volume may be increased by increasing the hair crossing. In particular, (A) after increasing the volume of hair by increasing the hair crossing, (B) applying aerosol hair cosmetics can easily make reverse hair and make hairstyles quickly Moreover, it is preferable for producing a sustained effect.
By shaping the hair in this way, the hair can be bonded in a “cross shape”, and a soft style can be maintained for a long time.

Synthesis Examples In the following synthesis examples, the content of the organopolysiloxane segment is a value obtained from a proton nuclear magnetic resonance ( ¹ H-NMR) spectrum, and the weight average molecular weight of the final product is a calculated value. The molecular weight of poly (N-propionylethyleneimine) is a number average molecular weight determined by gel permeation chromatography (GPC).
Column: Two K-804L (Showa Denko, GPC column) in series Eluent: 1 mmol / L Farmin DM20 (Kao) / chloroform Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample amount: 5 mg / mL, 100 μL
Polystyrene conversion

  Dissolve 0.8 g (0.005 mol) of diethyl sulfate and 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline in 29 g of dehydrated ethyl acetate, and heat and reflux for 8 hours under a nitrogen atmosphere. Poly (N-propionylethyleneimine) was synthesized. The number average molecular weight was 2700 as measured by GPC. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery semi-solid (111 g, yield 98%). The final product had an organopolysiloxane segment content of 88% by mass and a weight average molecular weight of 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Examples 1-7 and Comparative Examples 1-2
According to a conventional method, a hair spray stock solution shown in Table 1 is prepared, and together with a propellant, filled in an aerosol container having the following valves and buttons with the stock solution / propellant (mass ratio) shown in Table 1, and aerosol hair A cosmetic was produced. The film strength of the obtained hair cosmetic was measured. Moreover, using these, hair styling was performed, and volume maintenance under high humidity was evaluated. The results are also shown in Table 1. In addition, the evaluation result in a table | surface was shown as an average value of five expert panelists.
Valve: Stem hole diameter φ0.60mm, Housing lower hole diameter φ0.65mm x Vapor tap hole diameter φ0.42mm
Button: Diameter 0.50mm (with mechanical breakup): (Mitani Valve)

(Evaluation methods)
Volume maintenance under high humidity:
The grated bangs are the length that reaches from the lips to the chin, and the girth and back hairs are so-called long hairs that reach 30-40 cm below the earlobe. The women who have been dyed several times and who have not gone permanent for the past two years have been evaluated as the expert panelists using the following method.
That is, according to the procedures (1) to (4), the panelist creates a hairstyle with a volume on his / her head, applies the hair spray to be evaluated, and sits quietly in a chair at room temperature and humidity for 30 minutes. I dried my hair. After that, we entered a constant humidity room at 30 ° C. and 98% RH and sat quietly for 1 hour in a chair, and evaluated the hair style holding according to the following criteria.

(1) Face down and tie the hair on the parietal side of the ear and tie it tightly with rubber. After that, the face is raised and the hair bundle is expanded so as to be pulled radially.
(2) The hair is crossed by creating reverse hair with the fingertips on the entire tied hair, and the volume is increased.
(3) Wrap the tip of the hair in a knot so as not to crush the volume, and make a soft bun hair. Fasten it with several pins.
(4) Spray the whole dumpling for 3 seconds and spray on the neck for 2 seconds. Gently press down the hair that protrudes from your hair.

(Evaluation criteria)
4: A soft volume was maintained over the entire hairstyle.
3: Although a slight volume decrease was seen at the top of the dumpling, it was hardly anxious and the soft volume was maintained as a whole hairstyle.
2: It can be seen that some volume reduction is seen at the top and the periphery of the dumpling, and the volume of the hairstyle as a whole is slightly reduced, but this is acceptable, not to the extent that the beauty of the fluffy hairstyle is impaired.
1: The volume has decreased overall, and the fluffy beauty of the first hairstyle has been lost.

Claims (4)

(A) Increasing the volume of hair by increasing the crossing of hair, and (B) applying an aerosol-type hair cosmetic having a coating strength measured by a coating strength evaluation method of 800 gf / cm ² or more,
Including hairdressing methods.   The hair styling method according to claim 1, wherein the aerosol hair cosmetic used in (B) contains a film-forming polymer. The hair styling method according to claim 1 or 2, wherein the aerosol hair cosmetic used in (B) contains at least one copolymer selected from (B1) and (B2).
(B1) (a) General formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or an alkyl group having 4 to 12 carbon atoms, but both R ² and R ³ are hydrogen atoms. Never)
30 to 80% by mass of a (meth) acrylamide monomer represented by
(b) General formula (2)

(In the formula, R ¹ represents the same as above, and R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)
2 to 50% by mass of a (meth) acrylamide monomer represented by
(c) General formula (3)

(Wherein R ¹ represents the same as described above, R ⁶ represents an alkylene group having 2 or 3 carbon atoms, R ⁷ and R ⁸ are the same or different and represent a methyl group or an ethyl group. A represents 0 or 1) Indicates the number of
(Meth) acrylic acid ester monomer or (meth) acrylamide monomer represented by 0-30% by mass, and
(d) General formula (4)

(Wherein R ¹ represents the same as above, R ⁹ and R ¹⁰ are the same or different and represent an alkylene group having 2 to 4 carbon atoms, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or phenyl. And b and c each represent a number from 0 to 50, but b and c are not 0 at the same time)
(Meth) acrylic acid ester monomer represented by 0-40% by mass
A copolymer of
(B2) (a) General formula (5)

(Wherein R ¹² represents a hydrogen atom or a methyl group, and R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or an alkyl group having 4 to 12 carbon atoms, or R ¹³ and R ¹⁴ are adjacent to each other. To form a ring with the nitrogen atom)
30 to 80% by mass of a (meth) acrylamide monomer represented by
(b) General formula (6)

(Wherein R ¹² represents the same as described above, and R ¹⁵ represents an alkyl group having 1 to 4 carbon atoms)
(Meth) acrylic acid ester monomer represented by 5 to 45% by mass,
(c) General formula (7)

(Wherein R ¹² represents the same as described above, R ¹⁶ represents an alkylene group having 2 or 3 carbon atoms, R ¹⁷ and R ¹⁸ are the same or different and represent a methyl group or an ethyl group. A represents 0 or 1) Indicates the number of
(Meth) acrylic acid ester monomer or (meth) acrylamide monomer represented by 2-30% by mass, and
(d) General formula (8)

(Wherein R ¹² represents the same as described above, R ¹⁹ and R ²⁰ are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, R ²¹ represents a hydrogen atom or a methyl group. Shows a number from 0 to 50, but b and c are not 0 at the same time)
(Meth) acrylic acid ester monomer represented by 0-30% by mass
Copolymer (A) After increasing hair volume by increasing hair crossings,
(B) A hair styling method to which an aerosol hair cosmetic material having a film strength measured by a film strength evaluation method of 800 gf / cm ² or more is applied.

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