CN110366411A - Hair colouring compositions - Google Patents
Hair colouring compositions Download PDFInfo
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- CN110366411A CN110366411A CN201880014623.0A CN201880014623A CN110366411A CN 110366411 A CN110366411 A CN 110366411A CN 201880014623 A CN201880014623 A CN 201880014623A CN 110366411 A CN110366411 A CN 110366411A
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- Prior art keywords
- hair
- gardenia
- pigment
- crocetin
- colouring compositions
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/362—Polycarboxylic acids
-
- 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
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
- A61K8/9783—Angiosperms [Magnoliophyta]
- A61K8/9789—Magnoliopsida [dicotyledons]
-
- 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
- A61Q5/10—Preparations for permanently dyeing the hair
Abstract
The object of the present invention is to provide a kind of solid color of gardenin to hair to improve, the hair colouring compositions with excellent hair dyeing effect.By logical liquid in the case where the metha crylic weak-acid cation-exchange resin of sodium-ion type, it is not adsorbed in the resin and the rate of recovery of pigment composition that flows out becomes the specific gardenin such as 85% gardenia blue pigment below uses as direct dyes, thus, even if not using dyeing assistant, the solid color of hair is also improved, available excellent hair dyeing effect.
Description
Technical field
The present invention relates to a kind of hair colouring compositions for having used gardenin.More specifically, it is related to a kind of cape jasmine
Pigment is to the solid color raising of hair, the hair colouring compositions with excellent hair dyeing effect.
Background technique
In the dyeing of hair, although the dyeing articles for having used synthetic dyestuffs are mainstream, from the injury to hair, mistake
The worries such as quick reaction consider, in recent years, using there is the hair colouring compositions of highly-safe natural pigment to be concerned.
Gardenin is by rubiaceous cape jasmine (Gardenia augusta Merrill or Gardenia
Jasminoides Ellis) the natural pigment that is obtained as raw material of fruit, according to the difference of its manufacturing method, exist it is blue,
Three red and yellow colors.Gardenin is widely used as colouring matters such as food, but is had the following disadvantages: and be difficult to admittedly to hair
Color is also unable to get sufficient hair dyeing effect even if using in hair dyeing cosmetic.
Therefore, currently, it is various to that can improve gardenin and carried out to the hair colouring compositions of the solid color of hair
Research.Such as report has in patent document 1: the hair dye containing gardenia blue pigment, reducing agent with mercapto and alkaline agent
The dyeing of hair can be made to thicken.In patent document 2 report have: comprising the gardenia blue pigment liquid containing Geniposide and sun from
It is high to dye maroon~dun hair dyeing property for the sub- high molecular hair coloring preparation composition of property.Report has in patent document 3: packet
Hair dye combination containing the gardenia blue pigment liquid containing Geniposide, nitrous base system direct dyes and cationic surfactant
It is high to dye maroon~dun hair dyeing property for object.
But in the existing hair dyeing cosmetic for having used gardenin, have the following disadvantages: to improve gardenin
For solid color to hair to obtain excellent hair dyeing effect, dyeing assistant (reducing agent, alkaline agent, impregnation-accelerator etc.) is not
It can lack, or there are the restrictions of the compositions such as the cooperation of cationic system substance.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-133320 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2000-53544 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2000-95654 bulletin
Summary of the invention
The technical problems to be solved by the invention
The object of the present invention is to provide a kind of solid color of gardenin to hair to improve, with excellent hair dyeing effect
The hair colouring compositions of fruit.
Technical teaching for solving the problem was
The inventors of the present invention have made intensive studies to solve the technical problem, as a result, it has been found that: it is specific by that will have
The gardenin of feature used as direct dyes, even if not using dyeing assistant, also the solid color of hair is improved, can
Obtain excellent hair dyeing effect.Specifically, discovery: solid color of the gardenin shown in (i) below~(iii) to hair
It improves, even if not using dyeing assistant, excellent hair dyeing effect: (i) gardenia blue pigment also can be obtained, lead to liquid in sodium ion
In the case where the metha crylic weak-acid cation-exchange resin of type, it is not adsorbed in the resin and the pigment composition that flows out
The rate of recovery becomes 85% or less；(ii) gardenia red pigment leads to liquid in the metha crylic Subacidity cation of sodium-ion type
In the case where exchanger resin, the rate of recovery of pigment composition for not being adsorbed in the resin and flowing out becomes 60% or less；And (iii) Cape jasmine
Sub- uranidin contains or not contain alltrans crocetin containing the cis- crocetin of 13-, the case where containing alltrans crocetin
Under, when the peak area of alltrans crocetin when being analyzed using HPLC is set as 1, the peak value face of the cis- crocetin of 13-
Product is 1 or more.The present invention is completed and research is further repeated based on these opinions.
That is, the present invention provides the invention of the mode of following middle announcements.
A kind of 1. hair colouring compositions, containing following (i)~(iii) shown at least one kind of gardenin:
(i) gardenia blue pigment leads to liquid in the case where the metha crylic weak-acid cation-exchange resin of sodium-ion type,
The rate of recovery of pigment composition for not being adsorbed in the resin and flowing out becomes 85% or less.
(ii) gardenia red pigment leads to liquid in the metha crylic weak-acid cation-exchange resin of sodium-ion type the case where
Under, the rate of recovery of pigment composition for not being adsorbed in the resin and flowing out becomes 60% or less.
(iii) Gardenia Yellow contains or not contain alltrans crocetin containing the cis- crocetin of 13-, hides containing alltrans
In the case where spending acid, when the peak area of alltrans crocetin when being analyzed using HPLC is set as 1, the cis- safron of 13-
The peak area of acid is 1 or more.
2. hair colouring compositions according to item 1 of item contain gardenia blue pigment shown in (i), cape jasmine blue
The rate of recovery in element is 65% or less.
3. hair colouring compositions according to item 1 of item, contain gardenia red pigment shown in (ii), and the cape jasmine is red
The rate of recovery in element is 40% or less.
4. hair colouring compositions according to item 1 of item, contain Gardenia Yellow shown in (iii), the Gardenia Yellow
Pigment contains alltrans crocetin, when the peak area of alltrans crocetin when being analyzed using HPLC is set as 1,13-
The peak area of cis- crocetin is 1~10000.
5. hair colouring compositions according to any one of item 1~4 of item, are used in the hair dyeing of white hair.
A kind of 6. hair colouring methods of item, are dyed hair using hair colouring compositions described in any one of item 1~5.
Invention effect
Hair colouring compositions according to the present invention improve the solid color of hair by using specific gardenin,
Excellent hair dyeing effect can be obtained, therefore, the usage amount of the dyeing assistant used at present can be made to reduce, or be set as not
Therefore cooperation can inhibit the injury to hair or scalp, or inhibit the dyeing in hair dyeing to skin etc..
In the prior art, insufficient with natural pigment hair dyeing effect is originated from, it has to using there are worry in safety
Synthetic dyestuffs, but hair colouring compositions according to the present invention may be implemented to be originated from what natural pigment i.e. gardenin generated
Excellent hair dyeing effect can provide safety higher product.
In addition, hair colouring compositions of the invention due to its own using the high gardenin of the solid color to hair as
Direct dyes uses, and therefore, there is also the few advantages of the restriction on composition, can provide the dye of various compositions or form
Hair products.
It should be noted that, although the undesirable explanation limited, but it is excellent using hair colouring compositions realization of the invention
The mechanism of action of different hair dyeing effect is believed that as follows.In hair colouring compositions of the invention, more containing use
The gardenin rate of recovery of pigment composition that is not adsorbed in cation exchange resin and flows out be given value or less, there is positive electricity
The pigment composition of lotus.It is believed that pigment composition and general alkaline hair dye with this positive charge have same property
It is adsorbed in the hair of hair by matter with same principle, generates excellent dyeing effect.That is, it is considered that used in the present invention
Gardenin, the pigment composition with positive charge contained more by with the carboxyl that constitutes in Hairdresser maos of keratan into
Row electric attraction and be easy fixation, realize excellent hair dyeing effect.
Detailed description of the invention
Fig. 1 be indicate in test example 1, with the dyeing liquor (pH7.0) containing various gardenia blue pigments by natural white hair into
Gone dyeing result figure.
Fig. 2 is to indicate to carry out natural white hair in test example 1, with the dyeing liquor (pH3.0) containing various gardenia blue pigments
The figure of the result of dyeing.
Fig. 3 be indicate in test example 1, with the dyeing liquor (pH7.0) containing gardenia blue pigment under the conditions of various temperature by day
The figure for the result that right white hair is dyed.
Fig. 4 is to indicate to carry out natural white hair in test example 2, with the dyeing liquor (pH7.0) containing various gardenia red pigments
The figure of the result of dyeing.
Fig. 5 be indicate in test example 2, with the dyeing liquor (pH3.0) of the gardenia red pigment containing embodiment 2-1 by natural white hair
The figure of the result dyed.
Fig. 6 is to indicate to carry out natural white hair in test example 3, with the dyeing liquor (pH7.0) containing various Gardenia Yellows
The figure of the result of dyeing.
Specific embodiment
1. definition
In the present invention, " color value E10% 1cm" it is the unit for indicating the concentration of color of pigment, referring to will have with absorbance meter
There is the absorbance of maximum absorption wavelength when being measured in the concentration range of reliability using the element of optical length 1cm to be scaled
The value of value in 10 weight % solution.
The maximum absorption wavelength of gardenia blue pigment is present near 600nm, therefore, the color value E of gardenia blue pigment10% 1cmIt can
It by very big absorbing wavelength specific near 600nm, measures its absorbance and finds out, but no maximum absorption wavelength the case where
Under, measure the absorbance of 600nm.Pigment solution in the measurement of the color value of gardenia blue pigment, as absorbance measurement
Retarder thinner, can be used citrate buffer solution (pH7.0) (food additives official compendium the 8th edition record lemon acid buffering
Liquid).
The maximum absorption wavelength of gardenia red pigment is present near 535nm, therefore, the color value E of gardenia red pigment10% 1cmIt can
It by very big absorbing wavelength specific near 535nm, measures its absorbance and finds out, but no maximum absorption wavelength the case where
Under, measure the absorbance of 535nm.Pigment solution in the measurement of the color value of gardenia red pigment, as absorbance measurement
Retarder thinner, acetate buffer solution (pH4.0) acetate buffer solution of record (food additives official compendium the 8th edition) can be used.
The maximum absorption wavelength of Gardenia Yellow (crocetin type) is present near 420nm, therefore, Gardenia Yellow in invention
The color value E of pigment10% 1cmIt can measure its absorbance by very big absorbing wavelength specific near 420nm and find out, but not have
In the case where maximum absorption wavelength, the absorbance of 420nm is measured.In the measurement of the color value of Gardenia Yellow, as suction
0.5% (w/v) trisodium phosphate aqueous solution can be used in the retarder thinner of the pigment solution of photometering.
2. hair colouring compositions of the invention
Hair colouring compositions of the invention are characterized in that, containing following (i)~(iii) shown at least one kind of gardenin.
Hereinafter, being described in detail to hair colouring compositions of the invention.
(i) gardenia blue pigment leads to liquid in the case where the metha crylic weak-acid cation-exchange resin of sodium-ion type,
The rate of recovery of pigment composition for not being adsorbed in the resin and flowing out becomes 85% or less (hereinafter, being denoted as " gardenia blue pigment sometimes
(i)”)。
(ii) gardenia red pigment leads to liquid in the metha crylic weak-acid cation-exchange resin of sodium-ion type the case where
Under, it is not adsorbed in the resin and the rate of recovery of pigment composition that flows out becomes 60% or less that (" cape jasmine is red hereinafter, being denoted as sometimes
Plain (ii) ").
(iii) Gardenia Yellow contains or not contain alltrans crocetin containing the cis- crocetin of 13-, hides containing alltrans
In the case where spending acid, when the peak area of alltrans crocetin when being analyzed using HPLC is set as 1, the cis- safron of 13-
The peak area of acid is 1 or more (hereinafter, being denoted as " Gardenia Yellow (iii) " sometimes).
2-1. gardenin
Hair colouring compositions of the invention are as the dyestuff (direct dyes) for dyeing hair, containing selected from by gardenia blue
It is at least one kind of in the group that pigment (i), gardenia red pigment (ii) and Gardenia Yellow (iii) are constituted.In this way, by will be specific
Gardenin is used as direct dyes, and the solid color to hair can be improved, and obtains excellent hair dyeing effect.Hereinafter, to each
The characteristic etc. of gardenin is illustrated.
2-1-1. gardenia blue pigment (i)
The characteristic of 2-1-1-1. gardenia blue pigment (i)
Gardenia blue pigment (i) used in the present invention is the gardenia blue pigment with following characteristic: leading to liquid in sodium-ion type
In the case where metha crylic weak-acid cation-exchange resin, it is not adsorbed in the resin and the recycling of pigment composition flowed out
Rate becomes 85% or less.As gardenia blue pigment (i) used in the present invention, from the further solid color improved to hair
From the perspective of, can enumerate the rate of recovery as preferably 65% or less, more preferable 45% or less, further preferred 25% with
Under, particularly preferred 15% substance below.The lower limit of the rate of recovery about gardenia blue pigment (i) used in the present invention
Value, is not particularly limited, for example, 0% or more, 0.001% or more, 0.01% or more, 0.5% or more or 1% or more.
As the rate of recovery of gardenia blue pigment (i) used in the present invention, 0~85% can be specifically enumerated, preferably
0.001~65%, more preferable 0.01~45%, further preferred 0.1~25%, particularly preferred 1~15%.
In the present invention, " lead to liquid in the case where the metha crylic weak-acid cation-exchange resin of sodium-ion type,
The rate of recovery of pigment composition for not being adsorbed in the resin and flowing out " specifically can be by shown in (1) below~(4)
Under the conditions of tested and found out.
(1) preparation of sample solution
The gardenia blue pigment for becoming measure object is diluted to ethanol water (ethyl alcohol: the capacity ratio of water is 20:80), prepares sample
Product liquid.The absorbance when concentration of gardenia blue pigment in sample liquid is to dilute 10 times with ion exchange water for the sample liquid at
It is adjusted for 1.0 mode.It should be noted that pH is adjusted to 7.0 by sample liquid.In the case where improving pH, use
0.1mol/L sodium hydrate aqueous solution in the case where reduction, uses 0.1mol/L hydrochloric acid.
(2) weak-acid cation-exchange resin
Use the metha crylic weak-acid cation-exchange resin of sodium-ion type (Na shape).The metha crylic of the Na shape
Weak-acid cation-exchange resin can be used the metha crylic weak-acid cation-exchange resin of hydrogen ion type (H-shaped)
(alkali adsorption capacity 2.5mep/ml-R or more, 1,180 μm of size distribution or more 5% or less, lower than 300 μm be 1% or less, have
Effect diameter 0.40mm or more, true specific gravity 1.13 and effective pH range 5~14) it is transformed to the metha crylic faintly acid of Na shape
Cation exchange resin.As the metha crylic weak-acid cation-exchange resin of the H-shaped, specifically, can be used
Trade name " DIAIONTMWK10 (H-shaped) " (Mitsubishi chemical Co., Ltd's system).It should be noted that by H-shaped (hydrogen ion type)
As long as metha crylic weak-acid cation-exchange resin is transformed to usually used in the method for the Na shape technical field
Method, after the metha crylic weak-acid cation-exchange resin of H-shaped is filled in column, by 10 weights
Amount %NaOH carries out logical liquid with 2 times of resin capacity amounts, SV=2, thereafter by ion exchange water with 20 times of resin capacity measure into
Method row logical liquid and fully clean alkali.
(3) to the logical liquid of weak-acid cation-exchange resin
The filling weak-acid cation-exchange resin 20ml in column (internal diameter 2cm, height 30cm), with ethanol water (second
Alcohol: the capacity ratio of water is 20:80) fully clean.Then, the sample solution 15ml is become 5 with space velocity (SV)
Mode carries out logical liquid.Thereafter, ethanol water (ethyl alcohol: the capacity ratio of water is 20: 80) is subjected to logical liquid, by Subacidity cation
Exchanger resin is cleaned.Efflux when efflux when by the logical liquid of the sample solution and cleaning recycles, until at
To add up to 200ml, it is set to recovered liquid.
(4) calculating of the rate of recovery of pigment composition
Measure the absorbance of maximum absorption wavelength of the obtained recovered liquid near 600nm.At this point, there is no maximum absorption wavelength
In the case where, measure the absorbance of 600nm.The rate of recovery of pigment composition is calculated according to following formula.
[number 1]
The rate of recovery (%) of pigment=[(absorbance × 200 of the maximum absorption wavelength near the 600nm of recovered liquid)/by sample
Solution dilutes the absorbance (=1.0) × 150 of 10 times of aqueous solution)] × 100
The manufacturing method of 2-1-1-2. gardenia blue pigment (i)
About the manufacturing method of gardenia blue pigment (i), can obtain the having gardenia blue pigment of the characteristic as limit, without spy
It does not limit.It can be mentioned, for example from the amino-containing compound such as amino acid, protein hydrolysate, protein, Cape jasmine will can be generated
The specific compound of sub- cyanine (i) alone or in combination, make its with from rubiaceous cape jasmine (Gardenia augusta
Merrill or Gardenia jasminoides Ellis) fruit obtained in iridoid glycocide coexist and make β-Portugal
The method of glucoside enzyme effect.In the manufacture of common gardenia blue pigment, protein hydrolysate can be used, but commercially available product is used only
Manufacture etc. in usually used protein hydrolysate, be unable to get gardenia blue pigment (i).
One scheme of the manufacturing method as gardenia blue pigment (i) can be enumerated by arginine and from rubiaceous cape jasmine
Fruit obtained in iridoid glycocide mixed and the method for given enzyme reaction.Hereinafter, to smart ammonia is used
Acid and the method for iridoid glycocide manufacture gardenia blue pigment (i) are illustrated.
<arginine>
Arginine is gardenia blue pigment (i) and the amino-containing compound appropriate that is used in order to obtain.Arginine can be
The arginine that is obtained by the hydrolysis of protein, the arginine obtained by microbial fermentation etc. are any.
< iridoid glycocide >
As iridoid glycocide, as long as the iridoid that the manufacture raw material that can be used as common gardenia blue pigment uses
Glycocide.
To the method for iridoid glycocide is obtained from the fruit of rubiaceous cape jasmine, it is not also specifically limited, can arrange
The fruit of Rubiaceae cape jasmine is such as obtained the method for iridoid glycocide for extraction process by citing.Hereinafter, to by mentioning
The method for taking processing and obtaining iridoid glycocide from the fruit of Rubiaceae cape jasmine is illustrated.
It can according to need as the fruit for extracting the Rubiaceae cape jasmine that raw material is used and be dried, fritter, crushing.
As the Extraction solvent used in extraction process, can dissolve iridoid glycocide as limit, without special
Limitation, it can be mentioned, for example water, alcohol (preferred alcohol) or their mixed liquors.
Temperature and time when about extraction process is suitably set according to the type etc. of the Extraction solvent used, can
Enumerating for example under 20~100 DEG C or so is 0.5~24 hour.
After extracting processing in this way, include the extraction containing iridoid glycocide by removing solid component
Liquid.In the extracting solution, in addition to iridoid glycocide, also therefore the extracting solution is further supplied containing uranidin ingredient
It is handled in the removing of uranidin ingredient.The removing processing of uranidin ingredient can be by using the well known method of absorption resin
It carries out.
The other raw material > of <
When making β-glucosidase effect, smart ammonia can be made as needed together with the arginine and iridoid glycocide
Other ingredients such as amino acid, protein hydrolysate other than acid further coexist.
As the amino acid other than arginine, it can be mentioned, for example: alanine, asparagine, aspartic acid, cysteine,
Glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, dried meat ammonia
Acid, serine, threonine, tryptophan, tyrosine, valine etc..These amino acid can be used alone, can also be by 2 kinds
Combination of the above and use.
As protein hydrolysate, it can be mentioned, for example: the hydrolysis of the vegetable proteins such as soybean protein, aleuronat
Object；The hydrolysate of the animal proteins such as gelatin, casein, lactoprotein；Protein from yeast etc. is originated from microorganism
Protein etc..These protein hydrolysates can be used alone, two or more combination can also be used.
Make the amino acid and/or protein hydrolysate other than arginine together with the arginine and iridoid glycocide
It in the case where coexisting, about the usage amount of amino acid and/or protein hydrolysate other than arginine, is not particularly limited, only
It to be suitably set in the range of can obtain the gardenia blue pigment (i) with given physical property.
< β-glucosidase >
As β-glucosidase, as long as β-glucosidase used in the manufacture of common gardenia blue pigment, can arrange
Lift the β-for example originating from Aspergillus niger, Trichoderma reesei, Trichoderma viride, almond etc.
Glucosidase.β-glucosidase, also can be used Sumizyme used in manufacture as gardenia blue pigment (i)
C6000, Sumizyme AC, Sumizyme C, Sumizyme X, Sumizyme BGT, Sumizyme BGA (trade name；New day
This chemical industry corporation system), CELLULOSIN AC40, CELLULOSIN T3, CELLULOSIN AL (trade name；エイチビイ
ア イ society system) Onozuka 3S, Y-NC (trade name；Yakult pharmaceutical industries society system), Cellulase A " AMANO " 3,
4 (trade name of Cellulase T " AMANO "；Amano enzyme society system) etc. commercially available products.
< utilizes β-glucosidase processing >
As long as being handled using β-glucosidase can be generated cape jasmine under the coexisting of arginine and the iridoid glycocide
It is carried out under conditions of cyanine, as long as such as in the solution for being mixed into arginine and the iridoid glycocide and water
Middle addition β-glucosidase is simultaneously hatched under the conditions of aerobic.
As long as specifically making 1~50 mass % of arginine, the iridoid with sugar using the processing of β-glucosidase
1~50 mass % of body and become relative to every iridoid glycocide 1g 1~300U or so concentration β-glucosidase
It is coexisted under the conditions of aerobic.Here, refer to will be to nitroso phenyl β glucopyranoside (pNPG) by β-glucosidase 1U
The enzyme amount that 1 μ moles of matrix is hydrolyzed as matrix, in 50 DEG C, 1 minute.
About temperature condition when acting on β-glucosidase, as long as appropriate within the scope of β-glucosidase operative temperature
Setting, it can be mentioned, for example 20~70 DEG C or so, preferably 40~60 DEG C or so.
About pH condition when acting on β-glucosidase, as long as being suitably set within the scope of β-glucosidase action pH
, it can be mentioned, for example pH4~5 or so, preferably pH4.2~4.8 or so.
About β-glucosidase effect time is made, according to the β-glucosidase or the iridoid glycocide used
Amount, temperature condition etc. are suitably set, and it can be mentioned, for example 5~100 hours or so, preferably 10~50 hours or so.
In addition, being not particularly limited, can enumerating as the method for being set as aerobic condition when β-glucosidase effect is made
Such as the mechanical method such as stirring, oscillation；The oxygen containing gas such as air is blown into the method in system；The combination of these methods
Deng.
Make β-glucosidase effect in this way and generates gardenia blue pigment (i).After making β-glucosidase effect, lead to
It crosses for solid-liquid separation treatments such as centrifuge separation, filter filterings and removes solid component, can obtain containing gardenia blue pigment (i)
Aqueous solution.Aqueous solution containing obtained gardenia blue pigment (i) can directly make in hair colouring compositions of the invention
With, but can also be concentrated and be used with the state of concentrate as needed, alternatively, it is also possible to be formed for drying process
Powdered use.
In addition, obtained gardenia blue pigment (i) can according to need for refinement treatment, remove other than gardenia blue pigment
Ingredient.
2-1-2. gardenia red pigment (ii)
The characteristic of 2-1-2-1. gardenia red pigment (ii)
Gardenia red pigment used in the present invention (ii) be in logical liquid in the metha crylic faintly acid of sodium-ion type
In the case where cation exchange resin, the rate of recovery of pigment composition that is not adsorbed in the resin and flows out become 60% spy below
The gardenia red pigment of property.As gardenia red pigment used in the present invention (ii), from the further fixation improved to hair
Property from the perspective of, can enumerate the rate of recovery as preferably 40% or less, it is more preferable 30%, further preferred 20%, especially
It is preferred that 5% gardenia red pigment.The lower limit value of the rate of recovery about gardenia red pigment used in the present invention (ii), does not have
There is special limitation, as long as such as being 0% or more, 0.001% or more, 0.01% or more, 0.5% or more or 1% or more.
As the rate of recovery of gardenia red pigment used in the present invention (ii), 0~60% can be specifically enumerated, preferably
0.001~40%, more preferable 0.01~30%, further preferred 0.1~20%, particularly preferred 1~5%.
In the present invention, " the case where logical liquid is in the metha crylic weak-acid cation-exchange resin of sodium-ion type
Under, the rate of recovery of pigment composition that is not adsorbed in the resin and flows out " specifically, in addition to gardenia blue pigment is replaced with cape jasmine
Except haematochrome, with gardenia blue pigment the case where, same method was found out.
The manufacturing method of 2-1-2-2. gardenia red pigment (ii)
Do not have about the manufacturing method of gardenia red pigment (ii) can obtain the having gardenia red pigment of the characteristic as limit
Especially limitation.It can be mentioned, for example from the amino-containing compound such as amino acid, protein hydrolysate, protein, will can be generated
The specific compound of gardenia red pigment (ii) alone or in combination, make its with from Rubiaceae cape jasmine (Gardenia augusta
Merrill or Gardenia jasminoides Ellis) fruit obtained in iridoid glycocide ester hydrolysis object it is total
It deposits, make β-glucosidase effect method.
In the manufacture of common gardenia red pigment, protein hydrolysate can be used, but lead in manufacture that commercially available product is used only etc.
The protein hydrolysate being often used is unable to get gardenia red pigment (ii).
A kind of scheme of manufacturing method as gardenia red pigment (ii) can be enumerated by arginine and from rubiaceous cape jasmine
Fruit obtained in the ester hydrolysis object of iridoid glycocide mixed and the method for given enzyme reaction.Hereinafter,
The method for using arginine and iridoid glycocide to manufacture gardenia blue pigment (i) is illustrated.
< arginine >
Arginine is gardenia red pigment (ii) and the amino-containing compound appropriate that is used in order to obtain.Arginine can be
The arginine that is obtained using the hydrolysis of protein, the arginine obtained by microbial fermentation etc. are any.
The ester hydrolysis object > of < iridoid glycocide
The ester hydrolysis object of iridoid glycocide is 4 groups of the iridoid skeleton being bonded in iridoid glycocide
For the compound of carboxyl.As the ester hydrolysis object of iridoid glycocide, as long as can be used as common gardenia red pigment
The ester hydrolysis object for the iridoid glycocide that manufacture raw material uses.
It about the method for the ester hydrolysis object for obtaining iridoid glycocide, is not particularly limited, it can be mentioned, for example by madder
The fruit of the cape jasmine of section obtains iridoid glycocide, the iridoid bone by the iridoid glycocide for extraction process
Ester bond on 4 of frame is hydrolyzed and the method that is transformed to carboxyl.
The method of iridoid glycocide is obtained for extraction process about by the fruit of rubiaceous cape jasmine, it is such as above-mentioned
As being recorded in the column of " gardenia blue pigment (i) ".
About the method that the ester bond on 4 of the iridoid skeleton of the iridoid glycocide is hydrolyzed, do not have
There is special limitation, the used method in the manufacture of common gardenia red pigment can be used, specifically, buck can be enumerated
Solution, utilizes hydrolysis of enzyme etc. at sour water solution.
It about the type of alkali used in basic hydrolysis, is not particularly limited, it can be mentioned, for example sodium hydroxides, hydroxide
Potassium, sodium carbonate, potassium carbonate etc..These alkali can be used alone, and in addition can also use two or more combination.
The type of the acid used in sour water solution, is not particularly limited, and it can be mentioned, for example hydrochloric acid, sulfuric acid, phosphoric acid etc.
Inorganic acid；The organic acids such as citric acid, formic acid, acetic acid, oxalic acid, ascorbic acid, tartaric acid, fumaric acid.These acid can individually make
With a kind, in addition two or more combination can also be used.
About the type using enzyme used in the hydrolysis of enzyme, as long as can be by the iridoid of iridoid glycocide
4 ester bonds of skeleton are hydrolyzed, and are just not particularly limited, it can be mentioned, for example esterases etc..
In these method for hydrolysis, basic hydrolysis is preferably listed.About the condition of basic hydrolysis, as long as red in common cape jasmine
Used condition when the manufacture of element, it can be mentioned, for example make iridoid glycocide and excessive alkali total in aqueous solution
It deposits, at 10~80 DEG C or so, preferably 30~60 DEG C or so, 1~48 hour or so, preferably 5~24 hours or so.After basic hydrolysis,
It is preferred that addition is sour and pH is adjusted to neutrality or less.
The other raw material > of <
When making β-glucosidase effect, can together with the ester hydrolysis object of arginine and the iridoid glycocide, according to
Need to make other ingredients such as the amino acid other than arginine, protein hydrolysate further to coexist.
As the amino acid other than arginine, it can be mentioned, for example: alanine, asparagine, aspartic acid, cysteine,
Glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, dried meat ammonia
Acid, serine, threonine, tryptophan, tyrosine, valine etc..These amino acid can be used alone, can also be by 2 kinds
Combination of the above and use.
As protein hydrolysate, it can be mentioned, for example: the hydrolysis of the vegetable proteins such as soybean protein, aleuronat
Object；The hydrolysate of the animal proteins such as gelatin, casein, lactoprotein；Protein from yeast etc. is originated from microorganism
Protein etc..These protein hydrolysates can be used alone, two or more combination can also be used.
Make the amino acid and/or egg other than arginine together with the ester hydrolysis object of the arginine and iridoid glycocide
In the case that white matter hydrolysate coexists, about the usage amount of amino acid and/or protein hydrolysate other than arginine, without spy
It does not limit, as long as being suitably set in the range of can obtain gardenia red pigment (ii) with given physical property.
< β-glucosidase >
As β-glucosidase, as long as β-glucosidase used in the manufacture of common gardenia red pigment, about
Its concrete example etc., as above-mentioned " gardenia blue pigment (i) " column in it is recorded.
< utilizes β-glucosidase processing >
It can under the coexisting of arginine and the ester hydrolysis object of the iridoid glycocide as long as being handled using β-glucosidase
To generate progress under conditions of gardenia blue pigment, about its specific condition etc., in addition to iridoid glycocide is replaced
It is recorded in such as column of above-mentioned " gardenia blue pigment (i) " except the ester hydrolysis object of iridoid glycocide.
Make β-glucosidase effect in this way and generates gardenia red pigment (ii).After making β-glucosidase effect,
Solid component is removed and for solid-liquid separation treatments such as centrifuge separation, filter filterings, can be obtained containing gardenia red pigment
(ii) aqueous solution.Aqueous solution containing obtained gardenia red pigment (ii) can be directly in the combination of coloring hairs of the invention
It is used in object, but also can according to need and be concentrated and used with the state of concentrate, alternatively, it is also possible to for being dried
And form powdered use.
In addition, obtained gardenia red pigment (ii) can according to need for refinement treatment, remove other than gardenia red pigment
Ingredient.
2-1-3. Gardenia Yellow (iii)
The characteristic of 2-1-3-1. Gardenia Yellow (iii)
Gardenia Yellow used in the present invention (iii) is the Gardenia Yellow with following characteristic: containing the cis- safron of 13-
Acid contains or not contain alltrans crocetin, containing alltrans crocetin in the case where, will be full when being analyzed using HPLC
When the peak area of crocetin is set as 1, the peak area of the cis- crocetin of 13- is 1 or more.Hereinafter, will using HPLC into
When the peak area of alltrans crocetin when row analysis is set as 1, the peak area of the cis- crocetin of 13- is also abbreviated as sometimes
" peak area ratio (13-cis/All-trans) ".By using this Gardenia Yellow (iii), hair can be dyed does not have
Uneven yellow.
In the present invention, " alltrans crocetin " refers to that the double bond for being present in crocetin is complete trans-, following structures
Compound.
[chemical formula 1]
In addition, " the cis- crocetin of 13- " refers to that the double bond of 13 and 14 being present in crocetin are cis-, Xia Shujie
The compound of structure.
[chemical formula 2]
In the present invention, peak area ratio (13-cis/All-trans) is found out by the following method: can will be all-trans
HPLC analysis is carried out under conditions of formula crocetin and the cis- crocetin separation of 13-, finds out the peak area of the two, calculating will be all-trans
The peak area of the cis- crocetin of 13- when the peak area of formula crocetin is set as 1.Specifically, using Inertsil ODS-
35 μm of 4.6 × 250mm (GL science society system) are used as column, use A liquid (1% (v/v) acetic acid) and B liquid (acetonitrile) as solvent,
It was timed with flow velocity 1ml/ minutes and washes journey, so that the ratio of B liquid when 0 minute at 40 DEG C of column temperature becomes 20%, 20 point
The ratio of B liquid when clock become 80%, 30 minute when B liquid ratio become 80%, 30.01 minute when B liquid ratio at
The ratio of B liquid when being 20%, 40 minute become 20%, calculating will using use light diode array (PDA) as detector into
The 13- when peak area of alltrans crocetin made by the absorbance of 417.0nm when row measurement in chromatography is set as 1 is suitable
The peak area of formula crocetin.The peak area ratio (13-cis/All-trans) passes through the peak value face with the cis- crocetin of 13-
Product is found out divided by the peak area of alltrans crocetin.The amount of alltrans crocetin is fewer, and the value is bigger.
As Gardenia Yellow used in the present invention (iii), from the further sight improved to the solid color of hair
Point sets out, can enumerate peak area ratio (13-cis/All-trans) be preferably 1~10000, it is more preferable 1~5000, further
It is preferred that 1.5~3000, still more preferably 1.5~2000, it is further preferred 1.5~1000, still more preferably 1.5~500,
Particularly preferred 1.8~100, most preferably 1.8~15.
It should be noted that the molar absorption coefficient of the cis- crocetin of 13- is unclear present.But it is if it is considered that suitable
The molar absorption coefficient of formula crocin: the molar absorption coefficient of trans- crocin is about 63350: about 89000=about 0.7:1
When (J.Agric.Food Chem, 2008,56,1627-1637), it is believed that the molar absorption coefficient of the cis- crocetin of 13- also compares
The molar absorption coefficient of alltrans crocetin is much smaller.Therefore, it estimates: even if the peak area and 13- of alltrans crocetin are suitable
The peak area of formula crocetin is 1:1, and amount ratio is also not 1:1, and the cis- crocetin of 13- is quite a lot of.
The manufacturing method of 2-1-3-2. Gardenia Yellow (iii)
Do not have about the manufacturing method of Gardenia Yellow (iii) can obtain the having Gardenia Yellow of the characteristic as limit
Especially limitation, as preferred example, can enumerate the method included the following process: will obtain from the fruit of rubiaceous cape jasmine
The extracting solution containing crocin in crocin be hydrolyzed and obtain the mixed solution containing crocetin and (contain in the mixed solution
Have both the cis- crocetin of 13- and alltrans crocetin) process；By being removed from the obtained mixed solution containing crocetin
The process removed alltrans crocetin and obtain Gardenia Yellow (iii).The manufacturing method of this Gardenia Yellow (iii) it is specific
Condition etc., be disclosed in Japanese Unexamined Patent Publication 2011-168649 bulletin etc., according to the well known content setting.
Usage mode, the content of 2-1-4. gardenin
Hair colouring compositions of the invention can be from gardenia blue pigment (i), gardenia red pigment (ii) and Gardenia Yellow
(iii) a kind is used alone in, in addition can also combine these gardenins and use.About using in these gardenins
Which, suitably set according to the color that should assign hair.
About gardenia blue pigment (i), gardenia red pigment (ii), and/or the cape jasmine in hair colouring compositions of the invention
The content of uranidin (iii) according to the type of the gardenin used, the product form of the composition of coloring hairs, should be assigned
The concentration etc. for giving the color of hair is suitably set, specifically, range below can be illustrated.
The case where using gardenia blue pigment (i): the color value E of hair colouring compositions10%1cmAs 0.01 or more, preferably 0.01~
40, more preferable 0.5~30, further preferred 1.0~20 amount.
The case where using gardenia red pigment (ii): the color value E of hair colouring compositions10%1cmAs 0.1 or more, preferably 0.1~
40, more preferable 0.5~30, further preferred 1.0~20 amount.
The case where using Gardenia Yellow (iii): the color value E of hair colouring compositions10%1cmAs 0.1 or more, preferably 0.1~
40, more preferable 0.5~30, further preferred 1.0~20 amount.
In addition, as in hair colouring compositions of the invention gardenia blue pigment (i), gardenia red pigment (ii), and/or
The content of Gardenia Yellow (iii), can illustrate range below.
The case where using gardenia blue pigment (i): the content of gardenia blue pigment (i) is 0.01 mass % or more, preferably 0.01~30
Quality %, more preferable 0.1~20 mass %, particularly preferred 1.0~10 mass %.
The case where using gardenia red pigment (ii): gardenia red pigment (ii) content is 0.1 mass % or more, preferably 0.1~40 matter
Measure %, more preferable 0.1~30 mass %, particularly preferred 1.0~20 mass %.
The case where using Gardenia Yellow (iii): Gardenia Yellow (iii) content is 0.1 mass % or more, preferably 0.1~40
Quality %, more preferable 0.1~30 mass %, particularly preferred 1.0~20 mass %.
2-2. impregnation-accelerator (dyeing assistant)
Gardenia blue pigment (i) used in the present invention, gardenia red pigment (ii), and/or Gardenia Yellow (iii) are to hair
Solid color is high, even if not using impregnation-accelerator, it may have excellent hair dyeing effect, therefore, in coloring hairs group of the invention
Impregnation-accelerator can not contained by closing in object.But in order to by further promoting further to improve being impregnated with for hair
To the solid color of the pigment of hair, impregnation-accelerator can be contained.
As impregnation-accelerator, as long as direct dyes can be promoted to be impregnated with the impregnation-accelerator inside hair,
It can be mentioned, for example: benzylalcohol, 2- phenylethanol, cinnamyl alcohol, phenyl propanol, α-methylbenzylalcohol, dimethyl benzyl carbitol, benzyloxy
Ethyl alcohol, phenoxetol, to aromatic alcohols such as anise alcohols；The low-grade monobasic alcohols such as ethyl alcohol, isopropanol；Ethylene glycol, propylene glycol, 1,3-
The polyalcohols such as butanediol；Alkylene carbonates such as ethylene carbonate, propene carbonate etc..These impregnation-accelerators can individually make
With a kind, two or more combination can also be used.
It about the content of the impregnation-accelerator in hair colouring compositions of the invention, is not particularly limited, example can be enumerated
Such as 0~10 mass %, preferably 0~5.0 mass %, further preferred 0~0.4 mass %.Using the existing of direct dyes
Hair colouring compositions in, in the case where cooperating impregnation-accelerator, content is typically set at 0.5 mass % or more, but
In hair colouring compositions of the invention, gardenia blue pigment (i), gardenia red pigment (ii), and/or Gardenia Yellow (iii) are right
The solid color of hair is high, therefore the content of impregnation-accelerator can be set as to 0 mass % or a small amount of, can eliminate or reduce leaching
The worry of safety caused by the cooperation of saturating promotor.
2-3. reducing agent (dyeing assistant)
In hair colouring compositions of the invention, reducing agent can not contained.But in order to further improve to hair
The solid color of pigment can contain reducing agent.
It about the type of reducing agent, is not particularly limited, the sulphite such as sodium sulfite, sodium hydrogensulfite, L- can be enumerated
Sodium ascorbate, compound with mercapto etc..These reducing agents can be used alone, and can also combine two or more
And it uses.
About the content of the reducing agent in hair colouring compositions of the invention, it is not particularly limited, it can be mentioned, for example 0~
1 mass %, preferably 0~0.8 mass %, further preferred 0~0.2 mass %.In the existing hair for having used direct dyes
In colouring compositions, in the case where cooperating reducing agent, content is typically set at 0.3 mass % or more, but in hair of the invention
It sends out in colouring compositions, gardenia blue pigment (i), gardenia red pigment (ii), and/or Gardenia Yellow (iii) consolidate hair
Color is high, therefore the content of impregnation-accelerator can be set as to 0 mass % or a small amount of, can eliminate or reduce matching for reducing agent
The worry of safety caused by closing.
2-4. alkaline agent (dyeing assistant)
In hair colouring compositions of the invention, alkaline agent can not contained.But in order to further by opening epidermis
The solid color to the pigment of hair is improved, alkaline agent can be contained.
About the type of alkaline agent, it is not particularly limited, it can be mentioned, for example: the alkali metal hydrogen-oxygen such as sodium hydroxide, potassium hydroxide
Compound；Monoethanolamine, diethanol amine, triethanolamine, single Propanolamine, isopropanolamine, dipropanolamine, tripropanol amine, 2- amino -2-
The alkanolamines such as methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, 2- amino -2- hydroxymethyl -1,3- propylene glycol and
Its salt；Ammonia and its salt；The alkane diamines such as 1,3- propane diamine and its salt；Guanidine carbonate, bicarbonate guanidine, sodium carbonate, sodium bicarbonate, carbonic acid
Carbonate such as potassium, saleratus, lithium carbonate etc..These alkaline agents can be used alone, two or more combination can also be made
With.
It about the content of the alkaline agent in hair colouring compositions of the invention, is not particularly limited, as long as can satisfy
The mode of aftermentioned pH range is suitably set, it can be mentioned, for example: 0~1.5 mass %, preferably 0~1.0 mass %, into one
Walk preferably 0~0.4 mass %.In the case where cooperating alkaline agent in the existing hair colouring compositions for having used direct dyes,
Its content is typically set at 0.5 mass % or more, in hair colouring compositions of the invention, gardenia blue pigment (i), gardenia red
Pigment (ii), and/or Gardenia Yellow (iii) are high to the solid color of hair, therefore the content of alkaline agent can be set as 0 matter
% or a small amount of is measured, the worry of safety caused by the cooperation of alkaline agent can be eliminated or reduce.
The other ingredients of 2-5.
In hair colouring compositions of the invention, gardenia blue pigment (i), gardenia red pigment (ii), and/or Gardenia Yellow are removed
(iii) it except, can according to need containing direct dyess such as acid dyes, natural dye, nitroso-dyes, disperse dyes；Oxygen
Change reaction type dye such as dyestuff etc..About the presence or absence of the cooperation of such other dyestuffs, according to the tone etc. that should assign hair
Determination.
In addition, hair colouring compositions of the invention are in addition to the foregoing components, it can be containing in hair colouring compositions
The other ingredients being typically used in agent.As this ingredient, for example, can suitably cooperate higher alcohols, organic silicon, hydro carbons,
Wax class, animal and plant fat, higher aliphatic acids, organic solvent, tackifier, organic acid, cationic surfactant, both sexes table
Face activating agent, nonionic surfactant, anionic surfactant, cation property copolymer, anionic polymer,
Amphoteric polymer, protein, protein hydrolysate, amino acids, preservative, chelating agent, stabilizer, antioxidant, antibacterial agent,
Moisturizer, pH adjusting agent, animal extracts, plant extracts, yeast extract, vitamins, pigment, fragrance, ultraviolet light are inhaled
Receive agent, educate Mao Chengfen, wool ingredient, anti-dandruff ingredient etc..The content of these ingredients can according to the type of the ingredient used,
Product form of hair colouring compositions etc. is suitably set.
2-6.pH
It about the pH of hair colouring compositions of the invention, is not particularly limited, as long as such as in the range of pH3.0~11.0
It suitably sets.From the viewpoint of inhibiting to the injury of hair and further to improve pigment to the solid color of hair,
As the pH of hair colouring compositions of the invention, it can enumerate preferably 3.0~8.5, is further preferred 4.0~7.5, particularly preferably
6.0~7.0.
2-7. applicable object product form etc.
Hair colouring compositions of the invention are used to be dyed hair.Hair colouring compositions of the invention can
To be suitable for any hairs such as white hair, dark hair, tea hair, golden hair, but white hair is easy to appear hair colouring compositions of the invention
The hair dyeing effect of generation is preferred applicable object.
In addition, hair colouring compositions of the invention can be any products such as permanent hair dye, semipermanent hair dye
Form, but semipermanent hair dye is preferably listed.
Permanent hair dye is that the hair dye of the reaction type dye such as oxidation dye has been used (in Japan, to be classified as medical portion
Outer product).In the case where hair colouring compositions of the invention to be made to the product form of permanent hair dye, as dyestuff, remove
Except gardenia blue pigment (i), gardenia red pigment (ii), and/or Gardenia Yellow (iii), the response types dye such as cooperation oxidation dye
Expect and carries out formulation.
Semipermanent hair dye is the hair dye (in Japan, being classified as cosmetic preparation) for having used direct dyes, is sent out by this
In the case that the product form of semipermanent hair dye is made in bright hair colouring compositions, as direct dyes, gardenia blue is used
Pigment (i), gardenia red pigment (ii), and/or Gardenia Yellow (iii), can also be added other direct dyess as needed, into
Row is formulation.
In order to use hair colouring compositions of the invention to have hair dyed, with the product form phase with hair colouring compositions
The method answered carries out, for example, being with flushings such as water being coated on the hair that have hair dyed after placing given time
It can.In addition, about temperature condition when using the hair colouring compositions of the invention to be had hair dyed, as long as room temperature, but
It is that temperature when having the tendency that hair dyeing is higher, hair dyeing effect more improves, therefore, according to the composition of hair colouring compositions or should
The concentration etc. for assigning the color of hair is suitably set.
Embodiment
In the following, illustrating the present invention in further detail according to embodiment, but the present invention is not by these any restrictions.
Test example 1: the hair dyeing of gardenia blue pigment has been used to test
1. the manufacture of gardenia blue pigment
Firstly, 60% (v/v) ethanol water 25000g is added in the drying cape jasmine fruit 2500g of crushing, stirred at 60 DEG C
It mixes 1 hour and extracts.It adds appropriate 50% (v/v) ethanol water again in residue and carries out second extraction, merge
As the extracting solution containing crocin.The obtained extracting solution containing crocin is concentrated under reduced pressure, color value E is obtained10% 1cmIt is 500
The concentrated extracting solution containing crocin.The concentrated extracting solution containing crocin is synthesized in styrene-divinylbenzene system and is adsorbed
Agent (" DIAIONTMHP20 ": Mitsubishi chemical Co., Ltd's system) in logical liquid, adsorpting pigment ingredient carried out with SV=2.Then, will
20% (v/v) ethyl alcohol carries out logical liquid with SV=2, takes outflow component.By the way that the outflow component be concentrated under reduced pressure removing
Uranidin obtains the gardenia fruit extract (liquid) containing geniposide.The capital of the gardenia fruit extract (liquid)
The flat glycosides content of Buddhist nun is 45.0% (w/w).
By various amino acid or protein shown in the gardenia fruit extract obtained in this way (liquid) 18.3g and table 1
The specified rate of hydrolysate is dissolved in after water, and pH is adjusted to 7.0 using sodium hydroxide, so that total amount is reached 100mL with water.It connects
, β-glucosidase (1500U/g, " Sumizyme C ", new Nippon Chemical Ind's system) 2.0g is added, at 50 DEG C
At a temperature of after air agitation 42 hours, carried out at 90 DEG C 1 hour heat.Then, solid-liquid point is implemented by filtering
From processing, gardenia blue pigment solution is obtained.
2. the analysis of gardenia blue pigment
Make each gardenia blue pigment solution obtained above with color value E10% 1cmMode as 1 is dissolved in 20% (v/v) ethanol water
Solution prepares sample solution.The metha crylic Subacidity cation that sodium-ion type is filled in the glass column of internal diameter 2cm is handed over
Change resin (" DIAIONTMWK10 (H-shaped) " (Mitsubishi chemical Co., Ltd's system；Alkali adsorption capacity 2.5mep/ml-R or more, moisture
53~59%, 1,180 μm of size distribution or more 5% or less, lower than 300 μm be 1% or less, effective diameter 0.40mm or more,
True specific gravity 1.13, effective pH range 5~14 and 150 DEG C of durable temperature or less) 20ml points, by the ion exchange resin with usual
Method be transformed to after Na shape, be adjusted with usual way.Here, be added sample solution 15ml, with flow velocity SV=5 into
The logical liquid of row.Thereafter, ion exchange resin is cleaned with 20% (v/v) ethanol water.By the sample solution lead to liquid when efflux,
And efflux when cleaning is recycled, until becoming total 200ml, as recovered liquid.Obtained recovered liquid is measured to exist
The absorbance of maximum absorption wavelength near 600nm.It should be noted that in the case where without maximum absorption wavelength, measurement
The absorbance of 600nm.Value by obtained absorbance calculates the rate of recovery (%) of pigment composition according to formula above-mentioned.In addition, right
The gardenia blue pigment (" Network チ Na ブ ル ー カ ラ ー 1250P ", Glico nutraceutical Co. Ltd. system) of commercially available product, also carries out
Same analysis.The rate of recovery (%) of the pigment composition of each cape jasmine blue is as shown in table 1.
[table 1]
3. hair dyeing test (1)
The a part for extracting gardenia blue pigment solution obtained above out, is diluted with water, to become color value E10% 1cm
=8.0, thereafter, pH is adjusted to 7.0 using 0.1mol/L sodium hydrate aqueous solution, using the liquid as dyeing liquor.
By the natural white hair sufficiently cleaned with water (be not the hair to be decolourized and naturally as people's hair of white hair
Hair) it is used as hair sample.It is a branch of (about 1g) that it is put into hair sample in dyeing liquor 40mL obtained above, vibrates 30 at 30 DEG C
Minute.Thereafter, hair sample is taken out, washes with water, is dried with drier, using resulting hair as dyeing hair.In addition,
In order to compare, gardenia blue pigment (" the Network チ Na ブ ル ー カ ラ ー 1250P ", Glico nutraceutical strain formula meeting of commercially available product are used
The dyeing liquor of society；Comparative example 1-15), also it is subjected to the same test.
The appearance of observation dyeing hair and the dye-free hair not handled with dyeing liquor, further uses color difference
Meter, measurement L value, a value and b value, hue difference ah E value when finding out using dye-free hair as benchmark.
The obtained results are shown in Fig. 1 and tables 2.It, can hardly in the case where having used the gardenia blue pigment of commercially available product
Hair is had hair dyed into (comparative example 1-15).In addition, even if in the rate of recovery for having used pigment composition being more than 85% gardenia blue pigment
In the case where, also absolutely not see hair dyeing effect or insufficient.It in contrast, is 85% in the rate of recovery using pigment composition
In the case where gardenia blue pigment below, Δ E value becomes significantly high value, further also confirmed excellent hair dyeing effect in appearance
Fruit (embodiment 1-1~1-4).
[table 2]
4. hair dyeing test (2)
Using gardenia blue pigment solution obtained in embodiment 1-1, comparative example 1-1,1-2 and 1-6, it is diluted with water, so that
It becomes color value E10% 1cm=8.0, thereafter, pH is adjusted to 3.0 with hydrochloric acid and obtains dyeing liquor.Using obtained dyeing liquor,
Hair dyeing test is carried out under the conditions of with above-mentioned " 3. hair dyeing test (1) ".
The obtained results are shown in table 3 and Fig. 2.This as a result, in the dyeing liquor for being adjusted to pH3.0, using pigment at
Point the rate of recovery be 85% gardenia blue pigment (comparative example 1-1,1-2 and 1-6) below in the case where, with pH be 7.0 the case where
It compares, hair dyeing effect increases, but cannot still say sufficiently.On the other hand, using pigment composition the rate of recovery be 85% with
Under gardenia blue pigment (embodiment 1-1) in the case where, in the case where pH3.0, with pH be 7.0 compared with, although hair dyeing effect
It reduces, still, it can be seen that sufficient hair dyeing effect.
[table 3]
4. hair dyeing test (3)
It using gardenia blue pigment solution obtained in embodiment 1-1, is diluted with water, to become color value E10% 1cm=
8.0, thereafter, pH is adjusted to 7.0 with sodium hydroxide and obtains dyeing liquor.
By the natural white hair sufficiently cleaned with water (be not the hair to be decolourized and naturally as people's hair of white hair
Hair) it is used as hair sample.It is a branch of (about 1g) that hair sample is put into dyeing liquor 100mL obtained above, 30 DEG C, 50 DEG C,
Or it is vibrated 40 minutes at 70 DEG C.Thereafter, hair sample is taken out, washes with water, is dried with drier, resulting hair is made
To dye hair.
The obtained results are shown in table 4 and Fig. 2.Confirmed by the result: temperature when hair dyeing is higher, and the degree of dyeing more mentions
It is high.
[table 4]
Test example 2: the hair dyeing of gardenia red pigment has been used to test
1. the manufacture of gardenia red pigment
Uranidin is removed from dry cape jasmine fruit under the conditions of shown in the test example 1, obtains the Cape jasmine containing geniposide
Sub- fruit extract (liquid).After obtained gardenia fruit extract (liquid) 50g is dissolved in water, hydroxide is used
PH is adjusted to 13.0 by potassium, so that total amount is reached 60mL with water, is reacted 24 hours at 40 DEG C, and the ester of iridoid glycocide is generated
Hydrolysate.Then, pH is adjusted to 4.5 using pH adjusting agents such as citric acids in obtained reaction solution, β-glucosidase is added
(1500U/g, " Sumizyme C ", new Nippon Chemical Ind's system) 10.0g is further added various shown in table 4
The specified rate of amino acid, 50 DEG C at a temperature of air agitation 24 hours after, carried out at 90 DEG C 1 hour heat.It connects
, liquid separating treatment is implemented by filtering and obtains gardenia red pigment solution.
2. the analysis of gardenia red pigment
The measurement wavelength of absorbance is set as the maximum absorption wavelength near 535nm, in addition to this, with above-mentioned test example 1
" analyses of 2. gardenia blue pigments " it is same under the conditions of find out each cape jasmine red pigment composition the rate of recovery (%).Each cape jasmine
The rate of recovery (%) of the pigment composition of blue is as shown in table 5.In addition, to the gardenia red pigment (" ガ ー デ ニ ア Application レ of commercially available product
ッ De G " (TAISHO TECHNOS society system), is also similarly analyzed.
[table 5]
3. hair dyeing test (1)
The a part for extracting gardenia red pigment solution obtained above out, is diluted with water, to become color value E10% 1cm=
2.7, thereafter, it will use 0.1mol/L sodium hydrate aqueous solution that pH is adjusted to 7.0, using the solution as dyeing liquor.It uses
The dyeing liquor arrived carries out hair dyeing test under the conditions of " the 3. hair dyeing test (1) " with above-mentioned test example 1 is same.
The obtained results are shown in Fig. 4 and tables 6.In the case where the gardenia red pigment of use commercially available product, almost without inciting somebody to action
Hair has hair dyed (comparative example 2-6).In addition, even if the case where using the rate of recovery of pigment composition to be more than 60% gardenia red pigment
Under, also almost without seeing hair dyeing effect (comparative example 2-1~2-5).In contrast, it is being using the rate of recovery of pigment composition
In the case where 60% gardenia red pigment below, Δ E value becomes significantly high value, further also confirmed excellent dye in appearance
It sends out effect (embodiment 2-1~2-5).
[table 6]
4. hair dyeing test (2)
It using gardenia red pigment solution obtained in embodiment 2-1, is diluted with water, to become color value E10% 1cm=
2.7, thereafter, pH is adjusted to 3.0 with hydrochloric acid and obtains dyeing liquor.Using obtained dyeing liquor, with above-mentioned " 3. hair dyeings are tested
(1) " hair dyeing test is carried out under the conditions of.
The obtained results are shown in table 7 and Fig. 5.This is as a result, be 60% cape jasmine below using the rate of recovery of pigment composition
In the case where haematochrome (embodiment 2-1), in the dyeing liquor for being adjusted to pH3.0, compared with pH is 7.0, although hair dyeing effect
It reduces, but sufficient hair dyeing effect can be seen.
[table 7]
Test example 3: the hair dyeing of Gardenia Yellow has been used to test
1. the manufacture of Gardenia Yellow
50% (v/v) ethanol water 25000g is added in the drying cape jasmine fruit 2500g of crushing, it is small that 1 is stirred at 60 DEG C
When and extract.It adds appropriate 50% (v/v) ethanol water again in residue and carries out second extraction, merging is made
For the extracting solution containing crocin.The obtained extracting solution containing crocin is concentrated under reduced pressure, obtain color value 500 contains crocin
Concentrated extracting solution.The concentrated extracting solution 450g containing crocin of color value 500 is diluted with water 2050g and color value 90 is made
Crocin contain liquid 2500g.Contain in the crocin and add 10 mass % potassium hydroxide aqueous solutions in liquid, is adjusted to
pH12.0.It is stirred 20 hours at 35 DEG C by remaining untouched, crocin is hydrolyzed to conduct flower acidification of going forward side by side.Thereafter, add
Enriching hydrochloric acid and be adjusted to pH3.0 and stir 60 minutes, crocetin thus is precipitated.The crocetin of precipitation is made using pressure filter
For the recycling of thick crocetin cake.The thick crocetin cake is washed to sour disappearance.Water is dispersed by the crocetin cake 50g after washing
500g adds 10 weight % potassium hydroxide aqueous solutions and is adjusted to pH12.0 and stirs 30 minutes, thus dissolves crocetin cake
And obtain the alkaline mixed solution containing crocetin.Concentrated hydrochloric acid is added to the alkaline mixed solution containing crocetin, is adjusted to pH7.7, by
This obtains the alkalescent mixed liquor containing crocetin.Promptly again by the alkalescent mixed liquor containing crocetin adjusted
It is filtered with pressure filter, obtains Gardenia Yellow and contain liquid (filtrate of the cis- crocetin of Gao Hanyou 13-).The cake at the moment contains for height
There is the cake of crocetin, by the way that the cake to be dried and crush, available crocetin powder of the height containing crocetin
End.Contain in Gardenia Yellow and add hydrochloric acid in liquid (filtrate of the cis- crocetin of Gao Hanyou 13-), is adjusted to pH3.0 and makes it
It is precipitated.Obtained cake is dried using pressure filter and obtains the Gardenia Yellow powder (hiding of the cis- crocetin of Gao Hanyou 13-
Spend sour powder).
2. the analysis of Gardenia Yellow
It is analyzed, is asked using high performance liquid chromatography (HPLC) under the following conditions by the Gardenia Yellow powder that will be obtained
The ratio (peak area ratio (13-cis/All-trans)) of the peak area of alltrans crocetin and the cis- crocetin of 13- out.Its
As a result, the peak area ratio (13-cis/All-trans) of obtained Gardenia Yellow powder is 5.7.
The condition > of < HPLC
Column: 5 μm of 4.6 × 250mm of Inertsil ODS-3 (GL science society system)
Solvent: A liquid: 1% (v/v) acetic acid, B liquid: acetonitrile
Flow velocity: 1ml/ minutes
Column temperature: 40 DEG C
Detector: light diode array (PDA) (417.0nm)
Journey is washed in timing:
3. hair dyeing test
Gardenia Yellow powder obtained above is diluted with water, to become color value E10% 1cm=2.7, it thereafter, will
PH is adjusted to 7.0 using 0.1mol/L sodium hydrate aqueous solution, using the solution as dyeing liquor.Using obtained dyeing liquor,
Hair dyeing test is carried out under the conditions of " the 3. hair dyeing test (1) " with above-mentioned test example 1 is same.In addition, use is commercially available in order to compare
Gardenia Yellow (" Network チ Na カ ラ ー 400PS ", Glico nutraceutical Co. Ltd. system of the height containing crocin type；Compare
Example 3-1) and commercially available Gardenia Yellow (" Network チ Na カ ラ ー 1600P ", Glico nutraceutical of the height containing crocetin type
Co. Ltd. system；Comparative example 3-2), it is carried out similarly test.
It should be noted that the color value about the commercially available high Gardenia Yellow (comparative example 3-1) containing crocin type
E10% 1cm, found out by measuring the absorbance of maximum absorption wavelength being present near 420nm.
The obtained results are shown in Fig. 6 and tables 8.For the commercially available high Gardenia Yellow containing crocin type, Δ E
It is worth low, hair can hardly be had hair dyed (comparative example 3-1).In addition, with regard to the commercially available high Gardenia Yellow containing crocetin type
For, although Δ E value is high, it is coloured to be unsuitable for the functionization to dyeing with the orange of red unevenness.
In contrast, in the case where having used the Gardenia Yellow of embodiment 3, Δ E value is high, and can be by coloring hairs at uniform
Yellow.
[table 8]
Claims (6)
1. a kind of hair colouring compositions, containing following (i)~(iii) shown at least one kind of gardenin:
(i) gardenia blue pigment leads to liquid in the case where the metha crylic weak-acid cation-exchange resin of sodium-ion type,
The rate of recovery of pigment composition for not being adsorbed in the resin and flowing out becomes 85% or less；
(ii) gardenia red pigment leads to liquid in the metha crylic weak-acid cation-exchange resin of sodium-ion type the case where
Under, the rate of recovery of pigment composition for not being adsorbed in the resin and flowing out becomes 60% or less；
(iii) Gardenia Yellow contains or not contain alltrans crocetin containing the cis- crocetin of 13-, hides containing alltrans
In the case where spending acid, when the peak area of alltrans crocetin when being analyzed using HPLC is set as 1, the cis- safron of 13-
The peak area of acid is 1 or more.
2. hair colouring compositions according to claim 1, wherein
Containing gardenia blue pigment shown in (i), the rate of recovery in the gardenia blue pigment is 65% or less.
3. hair colouring compositions according to claim 1, wherein
Containing gardenia red pigment shown in (ii), the rate of recovery in the gardenia red pigment is 40% or less.
4. hair colouring compositions according to claim 1, wherein
Containing Gardenia Yellow shown in (iii), which contains alltrans crocetin, will be carried out using HPLC
When the peak area of alltrans crocetin when analysis is set as 1, the peak area of the cis- crocetin of 13- is 1~10000.
5. the composition of coloring hairs according to any one of claims 1 to 4, wherein
It is used in the hair dyeing of white hair.
6. a kind of hair colouring methods contaminate hair using hair colouring compositions described in any one of Claims 1 to 55
Color.
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| JP2017061589 | 2017-03-27 | ||
| JP2017-061589 | 2017-03-27 | ||
| PCT/JP2018/011743 WO2018181008A1 (en) | 2017-03-27 | 2018-03-23 | Hair coloring composition |
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| CN112022792A (en) * | 2020-09-27 | 2020-12-04 | 黑龙江省中医药科学院 | Preparation method of edible traditional Chinese medicine hair dye with homology of medicine and food |
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| JPWO2018181008A1 (en) | 2020-02-06 |
| JP7364463B2 (en) | 2023-10-18 |
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