FR2709418A1 - Hair dye - Google Patents

Abstract

The invention relates to a temporary hair dye which can be obtained by stably dispersing an iron oxide pigment evincing safety for man and capable of preventing the sedimentation or precipitation of a resin used even during long-term storage. The temporary hair dye causes neither separation nor gelation, and it may be prepared by dissolving a resin or a mixture of acrylic resin, vinyl acetate/crotonic acid copolymer resin and a shellac in ethanol, dispersing the iron oxide pigment in this mixture and then adding an aqueous solution of chelating agent.

Description

Caplllalre tincture Field of the invention 1) Field of the invention The

  The present invention relates to a temporary hair dye for temporarily dyeing the white hair present on the edge of the hair after dyeing the white hair (permanent dye) and

  white hair scattered throughout the hair.

  2) Description of the prior art

  As main solvent for dyeing

  temporary, ethanol was used because of its excel-

  slow drying characteristics after application of

  temporary hair dye, its excellent solubility

  tee in the resin used, high security for the hom-

  me, etc. Regarding the resin for a dye

  temporary capillary, one mainly used a re-

  acrylic anlonic sine or an acrylic ampholytic resin

  than. The resin is selected by considering its flexibility, its resistance to packaging, its resistance to water, etc. As a pigment for the temporary hair dye, carbon black or

  a tar-based dye due to their small dla-

  particle meter, 1ser good compatibility with the

  sine and dispersion stability.

  However, in the USA, the use of black

  carbon since it can be carcinogenic.

  On the other hand, a certain type of tar dye easily colors white hair and skin.

  and when used in temporary hair dye

  re, this dye poses problems like blushing

  or yellowing of white hair.

  As a high security black or brown pigment, iron oxide has been given as an example, but if an iron oxide pigment is dispersed in ethanol together with an acrylic resin or the like suitable for temporary hair dye, sites

  resin resins made insoluble in etha-

  zero by free iron ions so it's impossible

  to obtain the stability of the dispersion and we observe by-

  both sedimentation or gelation.

3 2709418

  The subject of the present invention is a dye

  temporary capillary with good stability of dis-

  pigment persion and greater safety which can be obtained by the use of a high security iron oxide pigment and a resin suitable for capll dyeing.

provisional area.

  (1) A first aspect of the present invention relates to a hair dye comprising, by weight, from 0.01 to 15% of water, from 54 to 98.48% of ethanol, from 0.5 to 20% of a resin , from 1 to 20% of a pigment and from 0.01 to 1.0%

  a chelating agent as essential components.

  (2) A second aspect of the present invention relates to

  a hair dye according to the preceding paragraph (1) in which the resin contains structural units of chemical formula (1): C3

VS

CH-C - H-C H - CH2-C-CH

I I 1

_ O = OC O = C

RI- R, -O H-O n

  in which R and R each represent a group hvdro-

I 2

  aliphatic carbonaceous from 1 to 18 carbon atoms, and n1 is

  the average degree of polymerization from 50 to 2000.

  (3) A third aspect of the present invention

  relates to a hair dye according to the preceding paragraph

  tooth (2) in which 50 to 100% by weight of the acrylic acid groups in the resin are neutralized with

  minus one alcohol chosen from triethanolamine, tri-

  isopropanolamine, 2-amino-2-methyl-1-propanol and 2-

  amlno-2-methyl-1,3-propane-dlol. (4) A fourth aspect of the invention relates to a hair dye according to the preceding paragraph '1 in which the resin contains structural units of chemical formula 2:

O - 'C-

L

-C = .-- C = -C'4 -C CH

O = C C = O

1 0 ôf- = 00- R r.

  in which R is an aliphatic hvdrucarbuné group this

  1 to 18 carbon atoms and n2 is the average degree of pu '-

merisatLlun from 50 to 3000.

  (5) A fifth aspect of the present invention

  concerns a hair dye according to paragraph p - ^ - e-

  tooth (4) in which 50 to 100% in puids of the acrylic acid O groups in the resin are neutralized with

  minus one alcohol selected from triethanulamine, trl-

  lsuprupanolamine, 2-aminu-2-methyl-l-prupanul and 2-

  amlno-2-methyl-1,3-propanedlol. (6) A sixth aspect of the invention relates to a hair dye according to the preceding paragraph 1, in which the resin is a vinyl acetate cupuolymer, crutunic acid having a molecular weight of

10,000 to l,000,000.

  (7) A seventh aspect of this lnventlun

  about a hair dye according to the pre-

  cendent (6) in which from 50 to 100% eri puids of cruLtunic acid groups in the resin are neutralized with at muins unr alcuul chuisl parml triélthanulamine, trl- lsuprupanulamine, 2-amirinu2-methyl-l-propanrul and

  2-amlnu-2-methyl-1,3-p) rupanedlul.

  (8) An eighth aspect of the present invention

  about a hair band according to the pre-

  cendent (1) in which the resin is a shellac.

  (9) A ninth aspect of this lnventioun

  about a hair dye according to the pre-

  cendent (1) in which the pigment is chuoisl parmil au muoins one of the black iron oxide, iron oxide rough and

yellow iron oxide.

  (10) A tenth aspect of the present invention relates to a hair dye according to paragraph (1) in which the chelating agent is chuoisl per ml ethylene-diamine-tetra-acetic acid and sudlum salt, hydruxy acid. ethyl-ethylenamine-LtriacéLtque and sun sodlum salt, diethylenetriaminepenrLa-acéLtique acid and

  sunri sodium salt and triethyletrietramirine-hexa-

acetyl and sour sodium salt.

  Detailed description of preferred embodiments

  The Applicant has carried out intensive studies

  to develop a hair dye that can prevent pigment sedimentation and gelation

  thanks to the use of a high-quality iron oxide pigment

  curity as a pigment for hair dye, and so she found that we can prevent separation and

  gelling by adding an aqueous chelating agent.

  The present invention has therefore been developed on the basis of

this finding.

  A hair dye according to the invention comprises water, ethanol, a resin, a pigment and

  a chelating agent as essential components.

  Examples of this resin are in particular a resin containing a structural unit of chemical formula (1), a resin containing a structural unit of formula

  chemical (2), a vinyl acetate / croto-acid copolymer

  pic with an average molecular weight of 10,000 to

  1,000,000 and shellac and can be used lso-

element or in combination.

  The hair dye according to the invention includes

  water, ethanol, resin, pigment and chelate

  aforementioned may still be combined with a component

  optional such as antioxidant, silicon and poly-

  peptide as hair protecting agents.

  The iron oxide pigment can usually be prepared by heating ferrous (II) sulfate FeSO 4.7H20 to about C to obtain a monohydrate product, placing it in a clay container and then baking it to

a temperature of 650 to 700 C.

  Since the cooking temperature is low, a yellow color appears predominantly (yellow iron oxide) and at an appropriate temperature, the color is very close to red and thus red iron oxide is obtained. S1 the temperature is too high, FeO304 is formed so that the color is black (black iron oxide).

  Since the chelating agent is not available

  under in ethanol alone, it is added as a so-

  aqueous solution. Preferably, the chelating agent is available.

  under in an aqueous ethanol solution and then added after the pigment and the like have

been scattered.

  A hair dye can be prepared

  visor by dissolving the resin in water and ethanul, adding the pigment, dispersing it by using a dispersing device such as a homomixer, a ball mill or a sand mill, adding the chelating agent dissolved in water, stirring the solution and

  then adding the necessary additives.

  In the hair dye according to the invention, the free iron ions generated from the iron oxide pigment undergo chelation with the added aqueous solution of chelating agent so that the

  consistency and precipitation of the resin, so

  maintain good dispersion stability of the pigment.

  Accordingly, the present invention can provide a temporary hair dye comprising a combination

  a high-security iron oxide pigment and a

  sine suitable for temporary hair dyes.

  In other words, as a result of the addition of the aqueous chelating agent solution, the iron oxide pigment which is absolutely safe for humans can be steadily dispersed for a long time and the resin does not undergo coherence or precipitation during storage. Thus, the combination of a safe pigment and a resin suitable for temporary hair dyes allows

  the production of an excellent pruvl- hair dye

sister.

Examples

  The following examples in which the parties

  and the percentages are by weight unless stipulated countrai-

  re, serve to illustrate the invention without in any way

mimic the scope.

Example 1

  (a) 10% black iron oxide (registered trademark Talox BL-100 by Titan Kogyo Kabushiki Kaisha) (b) 20% O acrylic resin (registered trademark Plas-size L-53D by Go-oh Kagaku Kabushiki Kaisha); 50% solution in ethanol, average degree of polymerization = 500; substantially 100% of an acid group

  acrylic in resin neutralized with 2-amino-2-methvl-

  1,3-propanediol. (c) 64.5% ethanol. Dissolve (b) in (c) and a nozzle (a), then disperse (a) for 3 days using a ball mill. (d) Disodium salt of ethylene-dlamine-tetra-acetic acid 0.5,% (registered trademark Zonon D, manufactured by Dalich Kagaku Yakuhin Kabushlkl Kalsha) (e) purified water 5.0%, Dissolve (d) in (e) and the mixture is added to the dispersion of materials (a) to (c), then it is stirred and

  mixture to obtain a temporary hair dye.

Example 2

  (a) 5.0% black iron oxide (the same as in Example 1) (b) 1.0% red iron oxide (N 217 manufactured by Daito Kasel Kabushiki Kaisha) (c) Methyl vinyl ether / malleic acid 10.0% (registered trademark BEM-42S, from Osaka Yuki Kagaku Kogyo Kabushlki Kaisha; 50% solution in ethanol)

  (d) trisodium salt of hydroxyethyl acid

  ethylenediamine-triacetic 0.3%, (registered trademark Zonon OH by Dalich Kagaku Yakuhin Kabushiki Kaîsha) (e) diethylenetriaminepentaacetic acid 0.05% (Zonon DTPA by Dalîch Kagaku Yakuhin Kabushlkl Kaisha) (f) ethanol 79, 65% '(g) ) purified water 4.0% 1

  We dissolve (c) in (f) and add the pig-

  elements (a) and (b), then they are dispersed in the same way

  as in example 1. Then we add a pre-

  trimmed by dissolving (d) and (e) in (g), then shaking and mixing to obtain a pro-pure hair dye.

Example 3

  (a) Black iron oxide 8% (b) yellow iron oxide 2% (Yellow ocher n 601 manufactured by Daito Kasei Kabushlki Kalsha) (c) Vinyl acetate / crotonic acid 7% copolymer (registered trademark Resin 281310 of Kanebo NSC Kabushlki Kaîsha) (d) 2-amino-2-methyl-l-propanol 0.65% (90% neutralization equivalent added)

  (e) Disodium salt of ethylenediamine acid-

0.2% tetra-acetyl 5

(f) triethylene acid-tetramine-

  hexa-acetic 0.3% (Zono TTHA, from Dailch Kagaku Yakuhin KK) (g) Ethanol 74.85% '(h) purified water 7.0% "The alcohol (d) is dissolved in ethanol (g ) and

  we add (c) to effect the neutralization and the dis-

  solution. Then add the pigments (a) and (b) and

  disperses them in the solution as in Example 1.

  ll Add a solution prepared by dissolving the chelators (e) and (f) in water (h), then stir and

  mixed to obtain a temporary hair dye.

Example 4

  (a) Black iron oxide 5% (b) shellac 3.5%

  (registered trademark Purified Shellac GSN for medical use fabrl-

  quée Gifu Shellac K.K) (c) Disodium salt of ethylene dlamine trlacetlque 0.1%

  (d) Trisodium salt of hydroxyethyl acid

  ethylenediamlnetrlacétlque O, 07% O (e) Ethanol 89,33% (f) Purified water 2,0% O The shellac (b) is dissolved in ethanol (e) and the pigment (a) is added which disperses as in example (1). Then add a solution prepared by dissolving the chelators (c) and (d) in water (f), stir and mix to obtain a temporary hair dye. Comparative example 1 We proceed as in example 1, except that we replace the chelator (d) of example (1) by

  purified water and a pro hair dye is obtained

  visory. COMPARATIVE EXAMPLE 2 The procedure is as in Example 1, except that the aqueous solution of the chelating agents (d) and (e) of Example 1 is replaced by ethanol.

  holds a temporary hair dye.

  Comparative Example 3 The procedure is as in Example 1, except that the chelating agent (d) of Example 1 is not dissolved in water (e) and ethanol is used in place of l 'water

  (e) and the chelators (d) and (e) are added to a disper-

  to obtain a temporary hair dye.

  Comparative Examples 4, 5, 6 The procedure is as in Example 2, except that in Comparative Example 4, the chelating agent is replaced by purified water; in Comparative Example 5, the aqueous solution of chelating agent is replaced by ethanol and

  in Comparative Example 6, the expensive agent is not dissolved

  lator in water and add a corresponding amount

  ethanol to obtain provlsol hair dyes

res.

  Comparative Examples 7, 8, 9 The procedure is as in Example 3, except that in Comparative Example 7, a chelating agent is replaced by

  purified water; in Comparative Example 8, we replace

  ce an aqueous solution of chelating agent with ethanol; and in comparative example 9, the agent is not dissolved

  chelator in water and one adds a corresponding amount

  dante of ethanol to obtain pro hair dyes

  visolres. Comparative Examples 10, 11, 12 The procedure is as in Example 4, except that in Comparative Example 10, the chelators (c) and (d) are replaced by purified water; in Comparative Example (11), an aqueous solution of chelating agents (f), (c) and (d) is replaced by a corresponding amount of ethanol; and

  in Comparative Example 12, the chelates are not dissolved

  (c) and (d) in water and adding a corresponding amount

  ethanol correspondent to obtain a temporary hair dye. Comparative Example 13 The procedure is as in Example 1, except that the amount of (a) is changed to 0.005% and the complement is replaced with purified water, the other materials.

  being the same as in Example 1, to obtain a tint-

temporary hair care.

  Comparative Example 14 The procedure is as in Example 1, except that 53.9% ethanol, 15% purified water and 1.1% are used,

  of the material (d) to obtain a ptu- hair dye

  visoire, but a sediment of the material c is formed Comparative example 15 The procedure is as in example 1, except that 0.9% of a pigment, 1.8% of a resin and 0 are used. 1% of a material (d) and that the complement is replaced by ethanol, the other materials being the same as in Example 1, to obtain a temporary hair dye,

but with mediocre coloring power.

  Comparative Example 16 The procedure is as in Example 1, except that 21.0% of a pigment, 40% of a resin and 33.5% of ethanol are used, the other materials being the same as in

  Example 1, to obtain a providential hair dye

  evening, but this product has too high a viscosity

  to be able to remove it from a ball mill.

  Comparative Example 17 The procedure is as in Example 1, except that 20% of a pigment, 41% of a resin and 33.5% of ethanol are used, the other materials being the same as in 1 '

  example 1, to obtain a temporary hair dye.

  Comparative Example 18 The procedure is as in Example 1, except that 1% of a pigment and 0.9% of a resin are used, the other materials being the same as in Example 1 and

  obtains a temporary hair dye.

  Regarding these examples and these examples

  comparative, the following estimates are made lm-

  lumpiness after preparation and after storage of these products at 50 C for 1 month: (1) viscosity measurement (2) visual observation of sedimentation (3) Utility estimate Each product is applied to hair

  white with a brush and a senso-

  riel total by examining suitability for application,

  packaging properties and gloss.

  The results appear in Table 1.

  A good utility means a fa-

  eyelash, no packaging and excellent shine.

Table 1

  Immediately after preparation Example Viscosity Sedimentation Usefulness (cp) 1 5.8 none good

2 6.2 ""

3 3.6 ""

4 4.8 ""

comparison 1 6.5 ""

2 4.1 ""

3 4.5 ""

4 7.3 ""

5.0 ""

6 4.8 "" i

7 4.5 "" I

8 3.0 ""

9 3.5 "" i

4.8 ""

11 4.9 ""

12 4.7 ""

13 7.5 ""

  14 10.1 white sediment "2.0 nil" 16 C o I 1 e c t a g e impossible 17 15.1 nil good

18 2.0 ""

  Table 1 (continued) After storage at 50 C for i month Example Viscosity (cp) sedimentation utility 1 5.9 sediment slightly observed, but

easy to disperse by agi-

light tation

2 6.5 ""

3 3.3 ""

  4 4.2 l "" Comparative 1 required measurement - visible separation - visible use (gelling not possible)

2 ""

  3 and it "4 58.0" difficult application

no shine-

spear noted

90.0 ""

6 measure imposed- "user-

  sible (gelation) impossible

7 ""

  8 180 separation visible- difficult application,

no shine-

throw

Table 1

  Example After storage at 50 ° C for 1 month comparative Viscoslté Sedimentatlon Utlllté (cp) 9 measurement imposed - separation sible use (gelling) visible impossible

"" "

11 "" "

il If I 12 f "

13 "" "

  14 10.9 white sediment solid visible white

2.1 none concentrated

  tion too fab le 16 C o 1 1 e c t a g e i m p o s s 1 b 1 e

17 15.1 none too much re-

sine, shelled

pe age [-

  cells 18 1.5 separation noticeable user not possible

Claims (10)

  1. Hair dye which contains from 0.01 to% by weight of water, from 54 to 98.48% by weight of ethanol. from 0.5 to 20% by weight of a resin, from 1 to 20% by weight of a pigment and from 0.01 to 1.0% by weight of a chelating agent as essential components.   2. Hair dye according to claim 1.   in which the resin contains structural patterns corresponding to the chemical formula (1): C C '-C-C: ± C --C -: - " j C = I I O = C O-- O = C R2-- R-- H-- j   in which R and R each represent a hydro- I 2   aliphatic carbonaceous from 1 to 18 carbon atoms and n1 is   an average degree of polymerization between 50 and 2000.   3. hair dye according to claim 2,   in which 50 to 100% by weight of the acryll- acid groups   that in the resin are neutralized with at least one alcohol chosen per ml, triethanolamine, trilsopropanolamine,   2-amino-2-methyl-1-pLopanol and 2-amino-2-methyl-1., 3-   propanedlol. 4. Hair dye according to claim 1,   in which the resin contains structural patterns according to the chemical formula (2): F1O - C-, C- --C: - CH - CM. I i I O C CO W H O--   in which R is an aliphatic hydrocarbon group of   1 to 18 carbon atoms and n2 is the average degree of polv- merit between 50 and 3000.   5. Capllaire dye according to claim,   in which 50 to 100% in polds of the acrvli- acid groups   that in the resin are neutralized using at least one   alcuul chosen per ml triethanolamine, trilsoprupanol-   amine, 2-amino-2-methyl-1-propanol and 2-amino-2-   methyl-1,3-propane-diol. 6. Hair dye according to claim 1, in which the resin is a vinyl acetate / crotonic acid copolymer having an average molecular mass of 10,000 to 1,000,000.   7. Hair dye according to claim 6,   in which from 50 to 100% by weight of the raw acid groups   resins in the resin are neutralized with at least one al-   cool chosen from triethanolamine, triisopruopanolamine,   2-amino-2-methyl-1-propanol and 2-amino-2-methvl-1,3- prupaned ol.   8. Hair dye according to claim 1,   in which the resin is shellac.   9. Hair dye according to claim 1, in which the pigment comprises at least one of the oxides black, red and yellow iron.   10. Hair dye according to claim 1, wherein the chelating agent comprises at least one   compound chosen from ethylene-dlamine-tetra- acid   acetic acid and its sodium salt, hydroxyethyl acid   ethylene-dlamine-triacetic and its sodium salt, diethylenetriaminepenta-acetic acid and its sodium salt and triethylenetetraminehexa-acetic acid and its salt sodium.