JPH01275519A - Hair-dye composition - Google Patents

Abstract

PURPOSE:To provide a hair-dye composition containing a cation-modified protein, giving excellently finished hair without damaging the hair and having excellent dyeing power and color-fastness. CONSTITUTION:The objective composition can be produced by compounding a two-pack type or a powdery one-pack type hair-dye with 0.01-10wt.%, preferably 0.05-5wt.% of a cation-modified protein (preferably having a quaternary nitrogen content of >=0.5wt.%) produced e.g. by reacting a hydrolyzed protein with a glycidyl trialkylammonium salt or a 3-halogeno-2-hydroxypropyl trialkylammonium salt. The hair-dye exhibits the effect to prevent the hair- damage and the effect to improve the color-fastness (fastness against shampoo and light) at the same time.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hair dye composition, and in detail:
This invention relates to a hair dye that has excellent dyeing properties and fastness, and causes extremely little damage to the hair.

[Prior Art and its Problems] Conventionally, two-part type hair dyes are known, for example, consisting of a first part containing an oxidizing dye and a second part containing an oxidizing agent. In the case of this hair dye, colorless, low-molecular-weight oxidative hair dye is penetrated into the hair and undergoes oxidative polymerization in the hair, producing pigments and dyeing, allowing various tones to be obtained. It is widely used because it can be used to dye hair and has excellent hair dyeing power.

However, although conventional oxidative hair dyes have excellent hair dyeing power, they can damage the hair and cause the hair to lose moisture and shine, resulting in an unnatural color that makes it easy for third parties to see that the hair has been dyed. Also, there was a drawback that the combability was poor. Furthermore, since the color gradually fades due to sunlight exposure, there was a desire for something with even better fastness.

[Problems to be Solved by the Invention] In view of the above circumstances, the inventor of the present invention sought to obtain a hair dye that has even better dyeing properties and fastness, causes extremely little damage to the hair, and dyes the hair in a natural color. As a result of various studies aimed at this purpose, it was discovered that the object of the present invention could be achieved by incorporating a cationic denatured protein into a hair dye, and the present invention was completed.

[Means for Solving the Problems] The present invention for solving the above problems resides in a hair dye composition characterized by containing a cationically denatured protein.

The present invention will be explained in detail below.

The hair dye that is the object of the present invention is not particularly limited, and various types can be used. Usually, it is a two-part type consisting of a combination of an oxidation dye and an oxidizing agent, or a one-part powder. Examples include molds.

As the oxidation dye intermediate of the first agent of the oxidation hair dye used in the present invention, conventionally known ones can be used, such as phenylenediamines, aminephenols, tolylenediamines, aminonitrophenols, diphenylamine. diaminophenylamines, N-phenylphenylenediamines, diaminopyridines, and salts thereof. The content thereof is usually about 0.01 to 10% by weight based on the total ml of the first agent.

In addition, as a coupler, resorcinol, pyrogallo),
Catechol, meta-aminophenol, meta-phenylene diamine, salts thereof, etc. can be blended.

Furthermore, the first agent contains, for example, surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylamine fatty acid amide; humectants such as glycerin and propylene glycol; and oily components such as lanolin, squalane, and liquid paraffin. ; Stabilizers such as sulfites and ascorbic acid; Thickeners such as carboxymethyl cellulose; Alkali agents such as aqueous ammonia and alkanolamines; Known compounding agents such as higher alcohols and fragrances may be appropriately blended as necessary. can.

On the other hand, the oxidizing agent for the second agent usually includes hydrogen peroxide, urea peroxide, and the like. Also in the second agent, known compounding agents such as stabilizers such as zenacetin and EDTA, oils and fats such as paraffin, higher alcohols, surfactants, acids, l) H regulators, and fragrances may be added as necessary. They can be blended as appropriate. The first agent and the second agent as described above are usually mixed immediately before use.

In the case of a one-powder type hair dye, the above-mentioned dye is usually blended in a range of 0.1 to 40.degree. In addition, ammonium salts such as ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium chloride, primary ammonium phosphate, primary ammonium phosphate, thickeners, surfactants, l) H regulators, fragrances, conditioning ingredients, etc. are also required. It is mixed accordingly. The oxidizing agent in this case is
Common examples include perflllll[l sodium, sodium percarbonate, urea peroxide, sodium sulfate-hydrogen peroxide adduct, sodium pyrophosphate-hydrogen peroxide adduct, dibasic sodium phosphate-hydrogen peroxide adduct, and the like.

When using this hair dye, add 8 to 2
It is used by dissolving it to make a paste at a concentration of 5% by weight.

In the present invention, it is an essential requirement that a cationically denatured protein be blended into the hair dye as described above. In short, by incorporating the most heavily cationic denatured proteins into hair dyes, it not only prevents hair damage during hair dyeing, but also improves the dyeability of the hair dyes, resulting in particularly good shampoo resistance and light resistance. This improves the robustness of the material.

The reason why such excellent effects of the present invention are obtained is not clear, but cationically denatured proteins have more than twice as much positive charge as conventional hydrolyzed proteins, and they have a positive charge that is more than twice that of conventional hydrolyzed proteins. It has a structure that allows it to easily adsorb to the hair surface by binding or interacting with keratin proteins, so when dye enters the swollen hair during hair dyeing, cationically denatured proteins adsorb into the gaps in the hair epidermis. When combined with keratin protein, a thin polymeric film is formed on the hair surface, and the dye that has entered the hair is well fixed and is retained for a long period of time.

The cationically modified protein used in the present invention can be obtained, for example, by reacting a hydrolyzed protein with a glycidyltrialkylammonium salt or a 3-halogen-2-bitroxypropyltrialkylammonium salt.

The above-mentioned hydrolyzed protein is produced by hydrolyzing natural proteins such as collagen, keratin, fibroin, elastin, and casein using enzymes, acids, alkalis, etc.
It is a polypeptide with a molecule ff of 12,000 to 50°OOO. This is a commercially available product (product name: Clotin Q
J) can be purified and used as necessary.

Examples of glycidyltrialkylammonium salts to be reacted with this hydrolyzed protein include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyldimethylethylammonium chloride, glycidylmethyldiethylammonium chloride, glycidyltripropylammonium chloride, and glycidylmethylethylpropylammonium chloride. and corresponding promid, yoshito, etc. can be used. Further, as the 3-halogen-2-hydroxypropyltrialkylammonium salt, for example, 3-
Chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro-2-hydroxypropyldimethylethylammonium chloride, 3
-Chloro-2-hydroxypropylmethyldiethylammonium chloride, 3-chloro-2-hydroxypropyltriprobylammonium chloride, 3-chloro-2
-Hydroxypropylmethylethylpropylammonium chloride and the corresponding bromides, iosites, and the like.

The reaction of a hydrolyzed protein with a glycidyl trialkylammonium salt or a 3-halogen-2-hydroxypropyl trialkylammonium salt is carried out by adding a solution or suspension of the hydrolyzed protein in the presence of an alkaline catalyst such as sodium hydroxide. This is carried out by adding a solution of glycidyl trialkylammonium salt or 3-halogen-2-hydroxypropyl trialkylammonium salt, heating the reaction, and then neutralizing the reaction mixture with an acid such as hydrochloric acid. When a hydrophilic solvent such as acetone is added to the reaction mixture thus obtained, the cationically denatured protein precipitates as a white solid, which is collected and dried.

In this case, it is preferable to carry out the reaction under conditions such that the quaternary nitrogen content of the cationically modified protein is 0.5% by weight or more. If the quaternary nitrogen content is less than 0.5% isolated, the affinity for hair and skin will be insufficient.

The amount of this cation-denatured protein added to the hair dye is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the hair dye. If the amount is too small, the effects unique to the present invention as described above cannot be obtained, and on the other hand, if the amount is too large, the effect remains the same and is not economical.

Furthermore, the cationic denatured protein may be incorporated into the two-component hair dye either in the first or second component, or in some cases both, but it is usually best to incorporate it in the first component.

[Effect of the invention 1] The hair dye composition of the present invention not only has good hair dyeing properties, but also has no damage to the hair, has a good finish, and has good shampoo resistance and light fastness. It is excellent. As described above, in the present invention, by incorporating a cationically modified protein, the properties as a hair dye are significantly improved unexpectedly. It is known that cationic denatured proteins are incorporated into hair cosmetics, but when incorporated into hair dyes, they stably exist during oxidation and polymerization of oxidation dye intermediates, prevent hair damage and improve fastness. It is surprising that two effects of improvement can be exerted at the same time.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 The following four types of hair dye compositions [A] to [D] were prepared.

[Composition A] (Product of the present invention) 1st agent P-phenylenediamine 1.0% (limb %
, hereinafter the same) Propylene glycol 10.0 EDTA
-Na 3.0 Sodium sulfite 0.5 Cation modified collagen polypetite 0.1 Ammonia PH10.0
Make it 100% with water.

2nd agent Hydrogen peroxide 6.0% Make it 100% with water.

[Composition B] (Product of the present invention) 1st agent P-phenylenediamine 1.0% propylene glycol 10.0 EDTA-Na
3.0 Sodium sulfite
0.5 Cation modified keratin polypebutite 0.05 Ammonia 100% with water that has a pH of 10.0
Make it.

2nd agent Hydrogen peroxide 6.0% Make it 100% with water.

[Composition C1 (product of the present invention) 1st agent P-phenylenecyamine 1.0% propylene glycol 10.0 EDTA-Na
o, 3 Sodium sulfite
0.5 Cation modified fibroin polypeptide 0.2 Ammonia 100% with water that has a pH of 10.0
Make it.

2nd agent Hydrogen peroxide 6.0% Make it 100% with water.

[Composition D] (Control amount) 1st agent P-phenylenediamine 1.0% propylene glycol 10.0 EDTA-Na
0.3 Sodium sulfite
0.5 Ammonia PH10.0
Make it 100% with water.

2nd agent Hydrogen peroxide 6.0% Make it 100% with water.

Composition E (control amount) A composition in which the cationically modified collagen polypeptide of Composition A was replaced with collagen polypeptide.

Composition F (control amount) Composition B except that the cationically modified keratin polypeptide was replaced with keratin polypeptide.

Composition G (control amount) Cationically modified fiproin polypeb of Composition C.

Tite is changed to phylloin polypeptide.

Hair dye test example> For each of the hair dye compositions AI to [G] above, the first part and the second part were mixed at a ratio of 1:1, applied to the hair at room temperature, and dyed for 20 minutes.
Leave it for a minute, then rinse thoroughly with 40'C warm water.
After drying, a hair dye test is carried out, and the color is completed.
The fastness, hair finish, hair damage and tensile strength were checked and the results shown in Table 1 were obtained.

Table 1 (Note) Evaluation method (1) Finished dyeing panel - The test was conducted on 20 people, and the results showed the most common evaluation responses.

Q: Finished dyed with a moisturized, mellow luster Δ: Finished dyed with a slightly moisturized finish, lacking a mellow luster ×: Finished dyed with a moisturized finish, lacking a mellow luster (2) Fastness <Work> Shampoo resistance Dyed hair Shampoo twice with a commercially available shampoo (Shelina Moisture Shampoo for normal hair, manufactured by Horny Co., Ltd.), then dry the hair 30 times, targeting the dyed hair that does not undergo this process, as shown below. It was evaluated as follows.

○: Excellent △: Slightly inferior ×: Inferior <II> Light resistance Dyed hair was exposed to sunlight for 60 days (cumulative amount of solar radiation 27000c
al/car> (b) Perform the treatment (t) h (b) The dyed hair was evaluated in the same manner as in (H) above.

(3) Hair finish panel - The test was conducted on 20 people, and the results showed the most common evaluation responses.

O: Flexible and good at passing through the fence △: Poor suppleness and passing through the fence × No flexibility and poor combing (4) Damage to hair The surface of the dyed oil-immersed hair is examined using an electron microscope (3000x magnification)
The degree of damage to the hair cuticle was evaluated.

○: Same as before dyeing, no damage observed △: Slight damage such as bumps, cracks, and peeling was observed on the hair epidermis.

X: Significant damage such as bumps, cracks, and peeling is observed in the hair epidermis.

(5) Tensile strength The dyeing operation was repeated 5 times, the length and thickness of the fibers were selected in a normal distribution, and the fibers were immersed in water for 24 hours.
The tensile strength (20% index and breaking strength) was measured using a tensile tester at ±2°C, 275±10% RH). Similarly, the measured value of undyed fibers was set to 10096, and the ratio of the measured value of dyed fibers to that was calculated and evaluated as follows.

0195% to 100% △: 90% to less than 95% 25.0 Liquid paraffin 5.0 Isopropyl alcohol 5.0 Glycerin
5.0 Cation modified elastin polypeptite 0.1 Ammonia 100 when covered with water to give a pH of 9.5
% and the same amount of this cream hair dye (first agent) as 6%.
Mix it with hydrogen peroxide (second agent) and apply it to gray hair, leave it at room temperature for 2 minutes.
After leaving the hair for 0 minutes, the hair was washed with shampoo, and as in Example 1, the hair was dyed to a strong dark brown color with excellent dyeing and a good finish.

Example 3 [Example of gel hair dye] (First agent) Paraphenylene diamine 2.0% orthoaminophenol 0.5 resorcinol
0.5 lauryl diethanolamide 10. O Polyoxyethylene alkyl phenyl ether 20.0 Olein@5.0 Polyethylene glycol 20.0 Sodium sulfite 0.5 Cation modified casein polypeptide 0.3 Fragrance
Suitable monoethanolamine pH9.5
This gel-like hair dye (1st part) and the 2nd part of Example 3 were mixed to 100% with water.
Mix it in step 1, apply it to gray hair, leave it at room temperature for 20 minutes,
When the hair was washed with a shampoo, the hair was dyed in a solid black color with excellent dyeing performance and a good finish, as in Examples 1 and 2.

Example 4 [Example of powder hair dye] Para-phenylene diamine 3.0% para-aminophenol 1.0 Meta-aminophenol 1.0 Sodium percarbonate 40.0 Ammonium carbonate 14.0 Cation-modified keratin polypeptide 10.0 Fragrance 1.0 Take 200% of this powdered hair dye, dissolve it in 100ml of water, apply it to gray hair, leave it at room temperature for 20 minutes, and then wash your hair with shampoo. A solid black-brown dyed hair with a good finish and a bright finish was obtained.

Claims (1)

[Claims] (1) A hair dye composition characterized by containing a cationically modified protein.