JPH0768106B2 - Solid hair dye - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid hair dye. More specifically, the active hydrogen compound is added to an alkylene oxide [hereinafter referred to as AO]. Ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and the like] (a), derivatives thereof (b), and a divalent to hexavalent alcohol having a molecular weight of 100 to 200 (c).
The present invention relates to a water-soluble solid hair dye having a rinse effect, which is obtained by solidifying one or more compounds (A) selected from the group consisting of (A) as a base material.

[0002]

[Prior art] As a solid hair dye, water, lower alcohol
Ru, lower alkylene carbonate, N-alkylpyrroli
Oil-soluble gelation in liquid mixture consisting of dong, acid dye, etc.
Add agents (dibenzylidene-D-sorbitol, etc.)
And gelled (JP-A-60-109515)
News) etc. have been proposed.

[0003]

However, this is a solid material having low strength, which is fragile and difficult to mold. In addition, it is difficult to dissolve in water, as a result it is difficult to apply to the hair, the dyeing speed is too fast, it contaminates the hands, scalp, forehead, etc., and it is easy to cause spot dyeing on the hair and also has a rinse effect. Since it is not present, there are problems such as a bad touch after dyeing hair, and hairs clinging to each other.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to improve the above problems. That is, in the present invention, an alkylene oxide [hereinafter referred to as AO] is added to the active hydrogen compound. Ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO)
Etc.] (1), one or more compounds selected from the group consisting of these derivatives (b), dihydric alcohols (c) having a molecular weight of 100 to 200 (a),
In a solid hair dye comprising an acid dye (B) and a water-soluble acidic substance (C), (A) is solid at room temperature, and the proportion of (A) is 30 to 30 based on the weight of the solid hair dye. It is a water-soluble solid hair dye characterized by being 99% by weight.

[0005]

[0006] Alkylene oxide for active hydrogen compounds
As the added one (a), for example, the following (a1) to
(A5) can be mentioned.  (A1): polyhydric alcohol AO adduct; polyethylene
Recall, polypropylene glycol, polypropylene
Glycol polyethylene glycol random polymer,
Glycerin E, an EO adduct of polypropylene glycol
O adduct, sorbitol EO adduct, etc.  (A2): polyphenol AO adduct; bisphenol
A EO adduct, Bisphenol F EO / PO adduct
Etc. (a3): polyamine compound AO adduct; ethylenedia
Min EO adduct, etc.  (A4): Monohydric phenol compound AO adduct; phenol
Le EO adduct, nonylphenol EO adduct, etc. (a5): Alkylamido compound AO adduct; Steari
EO adduct of acid amide, etc.

These additional AOs are usually EO and / or PO. AO other than these [butylene oxide, tetrahydrofuran, styrene oxide and α
-Olefin oxide (dodecylene oxide, tetradecylene oxide, etc.)] may be added in an amount of 10% by weight or less (random, block, etc.) of the total AO to be added.

[0008] As the derivative (b) of (a), for example,
The following (a6) to (a8) are listed.  (A6): a compound obtained by alkylating ether (a);
Lialkylene glycol dimethyl ether, etc.  (A7): a compound obtained by alkylating (i);
Lialkylene glycol dilaurate, Polya
Rutile glycol monostearate, etc.  (A8): a compound obtained by reacting (a) with an isocyanate;
Polyethylene glycol / isophorone diisocyanate
Water-soluble polyurethane compound consisting of

The molecular weights of (a) and (b) are usually 1,
000-100,000, preferably 1,500-5
It is 10,000. When it is less than 1,000, it does not easily become solid and is not suitable as the solid hair dye of the present invention. Also, 1
When it exceeds 0,000, the viscosity on the hair is increased during use (rubbing against wet hair), the usability is deteriorated, and at the same time, the slow dyeing property becomes large, which is not preferable.

The dihydric alcohol (c) having a molecular weight of 100 to 200 includes, for example, dihydric alcohols (1,
6-hexanediol, neopentyl glycol, etc.), trihydric alcohol (trimethylolpropane, trimethylolethane, etc.), tetravalent alcohol (erythritol, pentaerythritol, arabite, etc.),
Hexahydric alcohols (sorbitol, xylitol, mannitol, etc.) can be mentioned.

Among these (A), preferred are alkylene oxide adducts of polyhydric alcohols having a molecular weight of 1,000 to 100,000 and 2 having a molecular weight of 100 to 200.
~ 6-hydric alcohols, more preferred are polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol and sorbitol.

In the present invention, examples of the acid dye (B) include azo dyes, triphenylmethane dyes, anthraquinone dyes, nitro dyes, nitroso dyes, xanthene dyes, azine dyes and quinoline dyes. These are described in, for example, the Cosmetic Science Guidebook [Japan, Cosmetics Engineers Association, Yakuji Nipposha Co., Ltd.], pages 260-281. Two or more kinds of these acid dyes may be used in combination.

[0013] In the present invention, the water-soluble acidic substance (C)
Inorganic substances such as phosphoric acid, sulfamic acid and boric acid
Acid, formic acid, acetic acid, oxalic acid, maleic acid, citric acid, co
Examples thereof include organic acids such as succinic acid and DL-malic acid. This
These may be used in combination of two or more kinds.

Of these, water-soluble acidic substances having a melting point of 30 ° C. or higher (sulfamic acid, maleic acid, succinic acid, D
It is preferable to use L-malic acid, citric acid).

In the present invention, the dyeing-promoting compound (D) is a compound which enables the dyeing of an acidic dye for hair to be dyed at a low temperature in a short time, for example, lower alkylene carbonate (ethylene carbonate, propylene carbonate, etc.), N-alkyl. Pyrrolidone (N-methylpyrrolidone, N-ethylpyrrolidone, etc.), formamide derivative (N-cyclohexylformamide, N-, N-dibutylformamide, N-propyl-N-butylformamide, etc.), phenols (resorcin, etc.), aralkyl alcohol (Benzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, etc.) and lower alcohols (methanol, ethanol, propanol, butanol, etc.) can be mentioned.

The dye-accelerating compound (D) is preferably one which does not lower the melting point of (A), and one which has a small melting point drop. When a liquid dyeing promoting compound (benzyl alcohol etc.) is used, the mixing amount should be as small as possible [the ratio of (D) is 10% by weight or less based on the weight of the solid hair dye],
It is preferably used in the form of microcapsules (hereinafter referred to as MC) or cyclodextrins (hereinafter referred to as CD) in advance. Of these, N-methylpyrrolidone is particularly preferable because it has a large effect of promoting dyeing and has a small melting point drop with respect to (A) even though it is a liquid substance.

[0017] As a method for producing the water-soluble MC, for example,
The method described in JP-A-63-252543 can be cited as an example.
Be done.

CD conversion can be carried out by a known method such as a saturated aqueous solution method (direct method, solvent method), a kneading method (slurry method, powder method, spray drying method).

Even if the solid hair dye of the present invention is in the form of a wax at room temperature, it may be melted and lose its shape in an atmosphere of a high temperature (for example, 50 ° C. or higher) exceeding the melting point of waxes. The shape retention is made possible by mixing the shape-retaining agent (E) capable of maintaining the shape retention property even at high temperature.

Examples of the shape-retaining agent (E) include monosaccharides, oligosaccharides, polysaccharides and modified products thereof.

[0021] Among the shape-retaining agents (E), as monosaccharides,
For example, diose, tetrose, pentose, hex
And glucose, fructose. Orient
Examples of gothose include sucrose, maltose and isomal.
Tose, cellobiose, gentiobiose, lactose
And sucrose, and as a polysaccharide,
For example, simple polysaccharides (such as starch, glycogen, cellulose
) And complex polysaccharides (hemicellulose, carrageenan)
Cosaminoglyca hyaluronic acid, xanthan gum, guaga
Etc.).

Examples of the modified product of the shape-retaining agent (E) include polysaccharide modified products (hydrophobized starch, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, etc.). Of these (E), preferred are polysaccharides and modified products thereof.

Further, in the present invention, a rinsing effect with good hair dyeing and touch can be obtained at the same time, and a rinsing agent treatment after hair dyeing can be omitted. Therefore, a cationic compound can be contained as a rinsing agent (F).

Examples of the rinsing agent (F) include quaternary ammonium salts [quaternary ammonium salts from aliphatic amines {mono (di) higher alkyltri (di) lower alkylammonium salt, mono (di) higher alkyldi (mono) ) Lower alkylbenzyl ammonium salts, etc.}, quaternary ammonium salts from cyclic amines (alkylooxymethylpyridinium salts, alkylpyridinium salts, etc.), amine salts {mono (di) higher alkyldi (mono) lower alkylamine salts, mono ( Di) higher alkyl mono (di) lower alkylbenzylamine salt, etc.}, amino-modified silicone oil [both terminal methyl / side chain primary amine: SF8417 (Toray Dow), both ends OH / side chain primary amine: BY16-
892 (manufactured by Toray Dow), aminopolyether: BY1
6-837 (manufactured by Toray Dow)].

Of these rinse agents (F), preferred are quaternary ammonium salts derived from aliphatic amines and amino-modified silicone oils, and two or more of these may be used in combination.

If desired, the solid hair dye of the present invention may contain other components which are generally added. Examples of the other components include moisturizers, inorganic salts, chelating agents, antioxidants, ultraviolet absorbers, hair restorers, fragrances and preservatives. The weight ratio of these other components in the solid hair dye of the present invention is usually 10% by weight or less in total. Further, water (ion-exchanged water or the like) may be contained in an amount of 10% by weight or less.

Constituting the solid hair dye of the present invention (A)
The ratio of the component (F) to the total of (A) to (F) is as follows. Normal Preferred especially preferred Ingredients Ratio (wt%) Ratio (wt%) Ratio (wt%) (A) Thirty ~ 99 40 ~ 99 50-99 (B) 0.01-5 0.05-4 0.07-3 (C) 0.01 ~ 5 0.05-4 0.05-3.5 (D) 0 ~ 50 0 to 45 0-40 (E) 0 ~ 30 0-25 0 ~ 20 (F) 0-10 0-8 0 to 5 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (A) to (F) 100 100 100 Of

If the content of (A) is less than 30% by weight, the product tends to be soft or paste-like and the desired product may not be obtained, which is unsuitable as the hair dye of the present invention, and the dye of the present invention is not suitable. The leveling dyeing and the effect of preventing skin contamination, which are the characteristics of hair agents, are insufficient. If it exceeds 99% by weight, the slow dyeing effect is too strong and the dyeing property of the acid dye on the hair is deteriorated.

When the content of (B) is less than 0.01% by weight, the dyeing concentration is too light to serve the purpose of the solid hair dye of the present invention. Even if it is used in excess of 5% by weight, no further effect is obtained and it is uneconomical. When (C) is less than 0.01% by weight, the effect of dyeing the hair with the acid dye becomes poor.
Even if used in excess of 5% by weight, no further dyeing effect can be obtained, which may cause irritation to the skin such as the scalp.
Not preferable. When (D) is used in an amount of more than 50% by weight, no further dyeing promoting effect can be obtained. (E) is 3
When it is used in excess of 0% by weight, the solid hair dye is poorly dissolved in hair. Even if (F) is used in an amount exceeding 10% by weight, no further rinse effect is obtained. Further, the dyeing property of the acid dye is suppressed, and the dyeing density becomes light.

Exemplifying the method for producing the solid hair dye of the present invention,
(A), acidic dye (B), water-soluble acidic substance (C) and dyeing promoting compound (D) are put into a mixing tank, and 60 to 7
Heat to 0 ° C. and mix uniformly while dissolving. Next, the melt is put into a dedicated molding machine, cooled and solidified to obtain the solid hair dye of the present invention.

The solid hair dye of the present invention is conveniently stored in a container of push-up type, rotary extrusion type (lipstick type) or the like and partially exposed at the time of use.

[0032] The solid hair dye of the present invention is suitable for shampooing.
It is convenient to use. Ie shampoo hair
-When foaming (before washing with water) on the entire hair
On the other hand, the solid hair dye of the present invention is rubbed evenly. This state
Hold for 10 to 20 minutes (wash) and wash in hot water. Undyed
The dye is washed off.

[0033] The aim of dyeing when shampooing is the head
Dye with shampoo foam on hair, neck and forehead
Then, even if the dye liquor directly contacts each part, it will be dyed
This is because that is alleviated. Therefore, even if a little contaminated
If you don't mind, leave the bubbles when you shampoo and dye
It doesn't matter if you don't take the method. My hair is water
Dyeing is possible as long as it is wet.

[0034]

【Example】 Hereinafter, the present invention will be described in more detail with reference to Examples.
Is not limited to this. In the following,% is heavy
Amount% is shown. The test method in the test example is as follows.
is there.

1. Compression test  The test is performed according to JIS K6301, and the compression force [M
c: Load per cross-sectional area (kgf / cm2 )]
It was

2. Dissolution test Wet 10 g of human hair with water (water content 250%)
Rub the solid hair dye (cylindrical type) 10 times on the broken hair,
The dissolution rate of the solid hair dye was calculated.  Dissolution rate (%) = (ab) x 100 / a  a: Initial weight of test piece  b: Weight of test piece after rubbing

3. Dyeability test (level dyeing and build-up
Characteristics)  10 g of thoroughly washed human hair (15 cm in length) with water
Wet with water (water content 250%) and apply solid hair dye evenly
Attach, leave at 30 ° C for 10 minutes, rinse with running water, and dry
Then, the level dyeing property and build-up property were checked.

[0038] (Level dyeing and build-up test) Dyeing
For each whitened human hair, 5 pieces each with a multi-source spectrophotometer
Color measurement was performed (L ab measurement). The left end L. a.
b. Each color difference (ΔE) was calculated. Number of △ E
A low value indicates level dyeing. Also,
The thing with a small L value (brightness) has good build-up.
Indicates.

[0039] 4. Rinse effect test  1) Combability  20 g of thoroughly washed human hair (15 cm in length)
Wet with water (moisture content 250%) and apply solid hair dye evenly
Apply, leave at 30 ° C for 10 minutes, rinse with running water, and centrifuge.
The sample was dehydrated and wet. Furthermore, part of it is dried and dried.
Of the sample. And each hair is not caught
After brushing until complete, the combability was measured.
(B).  Thoroughly washed human hair (long hair) as a blank test
Wet 20 g (15 cm in length) with water (water content 250%),
After leaving it at 30 ° C for 10 minutes, centrifuge dehydration and wet sample
did. Further, a part was dried and used as a sample after drying. And
Brush each hair until it is not caught
After that, combability was measured (a).

[0040] (Measurement condition)  Equipment used: Instron (Shimadzu)  Comb moving speed: 200 mm / min  (Combability improvement rate)  Improvement rate (%) = (ba) / a × 100 The larger the numerical value, the better the combability.

[0041] 2) Amount of static electricity generated  The dyed human hair of 1) (dried) is
I brushed 30 times with an arbrush and it occurred at this time.
The amount of static electricity was measured. Measuring device: Current collector type potentiometer, KS-525 (Kasuga Denki
(Manufactured) Measuring conditions: 20 ° C, 65% RH

[0042] 3) The state of the hair coat (cuticle)  1) The hair scalp of the dyed human hair (dried)
The condition of hair follicles was checked by observing with an electron microscope. Electron microscope: Scanning electron microscope, S-800 (manufactured by Hitachi
Made by Seisakusho) Measurement conditions: magnification × 1000, 20 ° C  (Decision)  ◎: The best is because the small hairs are closely overlapped in a scaly shape.
Is in a state  ○: The scale of the hairy skin is slightly raised and raised.
It is in a good condition  Δ: The scale of the hairy skin is in a state of being peeled off considerably  ×: Most of the scales of the hairy skin are peeled off
Ru

[0043] 4) Sensory test  The touch of the dyed human hair (dry) of 1)
I checked.  (Decision)  ⊚: Hair after dyeing has combability (smoothness), flexibility and
The bulkiness was very good  ◯: Hair after dyeing has combability (smoothness), flexibility and
The bulkiness was good  Δ: Hair after dyeing has combability (smoothness), softness and
Bulky was not particularly good  X: The hair after dyeing has combability (smoothness), flexibility and
The bulkiness was bad

[0044] Examples 1-5  Planetary mixer according to the blending ratio shown in Table 1.
Was charged with (A), heated to 60 to 70 ° C., and melted.
Under stirring, (B), (C), (D), (E), (F) and
A mixed solution of water and water was charged and uniformly mixed. The melt blend
Made of stainless steel (50 mm x 50 mm x 30 mm)
Put it in a molding machine and cool to prepare the solid hair dye of the present invention.
It was  Comparative Example 1  Planetary mixer according to the blending ratio shown in Table 1.
Charge water, ethyl alcohol and acid dye to 60 ~
Warmed to 70 ° C. N-methylpyrrolidone in another mixing tank
And dibenzylidene-D-sorbitol were charged, and the temperature was 70 ° C.
It was heated to dissolve it. Add this solution to the previously prepared solution
Add and mix. Cooled to 30 ° C or below, comparative gel-like acid
A sex hair dye was created.

[0045]

[Table 1]

Each symbol in Table 1 is as follows  A-1: Polyethylene glycol (number average molecular weight 600
0) A-2: Polyethylene glycol (number average molecular weight of 20,000)
/ Sorbitol (6/4 weight ratio) A-3: polyoxyethylene (300 mol) polyoxy
Propylene (55 mol) A-4: Polyoxyethylene (300 mol) Polyoxy
Styrene (30 mol) A-5: Polyethylene glycol (number average molecular weight 110
00) α-olefin oxide having 12 and 14 carbon atoms
(10% by weight) Additive A-6: Sorbitol B-1: Orange 205 / Purple 401 / Black 401
(4: 3: 4 weight ratio) B-2: Black 401 / red 206 (3: 6 weight) B-3: Red 203 / green 201 / black 401
(4: 3: 7 weight ratio) B-4: Blue No. 201 / Red No. 206 (8: 2 weight ratio) C-1: Citric acid C-2: Phosphoric acid  D-1: N-methylpyrrolidone D-2: Benzyl alcohol / N-methylpyrrolidone
(3: 7 Weight Ratio) D-3: Ethylene Carbonate E-1: Hydroxyethyl Cellulose E-2: Hydroxypropyl Cellulose E-3: Carboxymethyl Cellulose F-1: Lanolin Ethyl Sulfate Aliphatic Aminopyropyrethi
Rudimethylammonium (65%) F-2: Stearyl dimethylbenzyl ammonium chloride
(85%) EA: ethyl alcohol DBS: dibenzylidene sorbitol water :purified water

[0047] Comparative evaluation of the solid hair dye of the present invention and a comparative product
Dyeings obtained in Examples 1 to 6 and Comparative Example 1
Each test was conducted on hair agents, and the results are shown in Table 2.

[0048]

[Table 2]

[0049]

EFFECTS OF THE INVENTION The present invention provides a novel water-soluble solid hair dye in which an acid dye or the like is hardened. The solid hair dye of the present invention is (1) harder to break because it has higher strength than the conventional gelled product (easy to mold), (2) easier to dissolve in water than the conventional gelled product, and thus easy to apply to the hair ( 3) Since it has a slow dyeing ability (suppresses dyeing), it can perform level dyeing and prevent contamination of the skin of the scalp, neck, forehead, hands, etc.
(Even if the dye contaminates the skin, it is easy to wash off the dye by washing with water or soap). (4) Since it contains a rinse agent, the combability after touching the hair and the touch are good, and the hairs are entangled with each other. Absent.

Claims (7)

[Claims] 1. An alkylene oxide [hereinafter referred to as AO] as an active hydrogen compound. Ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and the like] (a), derivatives thereof (b), and a divalent to hexavalent alcohol having a molecular weight of 100 to 200 (c).
A solid hair dye comprising at least one compound selected from the group consisting of (A), an acid dye (B) and a water-soluble acidic substance (C), wherein (A) is solid at room temperature and solid hair A water-soluble solid hair dye, wherein the ratio of (A) is 30 to 99% by weight based on the weight of the agent. 2. The water-soluble solid hair dye according to claim 1, which further contains a dyeing promoting compound (D). 3. The water-soluble solid hair dye according to claim 1, wherein the dyeing promoting compound (D) is N-methylpyrrolidone. 4. (A) has a molecular weight of 1,000 to 100,0.
4. An alkylene oxide adduct (al) of polyhydric alcohol of 00, and a dihydric alcohol (c) of 2 to 6 having a molecular weight of 100 to 200, and at least one selected from the group of claims 1 to 3. Water-soluble solid hair dye. 5. The water-soluble solid hair dye according to any one of claims 1 to 4, wherein (A) is at least one selected from the group consisting of polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol and sorbitol. . 6. The water-soluble composition according to claim 1, which further comprises, as the shape-retaining agent (E), one or more selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides and modified products thereof. Solid hair dye. 7. The water-soluble solid hair dye according to claim 1, which further contains a cationic compound as a rinse agent (F).