JP2018145578A - Fiber dyeing method using natural material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair dyeing method safer for human bodies, and to dye a fiber at low temperature and in a short time for energy saving.SOLUTION: A dyeing method has a reaction to oxidize a natural material having a catechol structure with periodic acid or periodate, incorporated into a dyeing process. The method makes it possible to dye natural fiber, cellulose, polyamide, acryl fiber or the like at a treatment temperature from around a room temperature to 50°C, within several hours.SELECTED DRAWING: None

Description

  The present invention relates to dyeing fibers such as yarn, fabric, paper, and wood using natural substances, and more particularly, to a dyeing method using natural substances having a catechol structure.

  In recent years, waste liquids of chemically synthesized dyes have become a social problem. Under such circumstances, dyeing using natural substances, which has been performed since ancient times, has been reviewed.

  In dyeing with chemically synthesized dyes, there are many kinds of dyes and dyeing assistants, and some have bad effects on the human body.

  In dyeing fibers using natural substances, a metal mordanting method combined with metal ions has been the mainstream since ancient times (Non-patent Document 1). From the viewpoint of energy saving, it is ideal if dyeing that becomes dark under conditions near room temperature in a short time (within several hours) is ideal, but it is difficult at present. In particular, cellulose, polyamide and acrylic fibers have low affinity with natural substances and are difficult to dye in dark colors.

  In dyeing hair, which is a kind of keratin fiber, an oxidative hair dye such as an oxidative dye is usually used. The oxidative hair dye comprises a first agent containing an oxidative dye precursor that is oxidized inside the hair to produce an oxidative dye, and a second agent containing an oxidant that oxidizes the oxidative dye precursor. Mix one agent and second agent to dye hair. It is said that a plurality of oxidative dye precursors are bonded together to increase the molecular weight of the oxidative dye produced inside the hair, and it is difficult to desorb from the inside of the hair, and high dyeing fastness can be obtained (Non-patent Document 2).

  However, there is a problem that hair is damaged by hydrogen peroxide used as an oxidizing agent, and a substance harmful to the human body is contained in the oxidation dye precursor and the dye production intermediate.

  Therefore, there is a demand for a staining method with higher safety for the human body. On the other hand, Patent Document 1 discloses a method of dyeing hair using an oxidant obtained by electrooxidizing catechin, which is a natural substance having a flavonoid skeleton, as a dye for hair. Yes. Patent Document 2 discloses a method for synthesizing the oxidant by supplying oxygen gas as an oxidizing agent to a mixed solution of water and alcohol containing catechin under a basic condition. The oxidant can dye white hair that has been chemically decolored to a dark color.

  Non-Patent Document 3 proposes a dyeing method for dyeing hair in a darker color by applying a synthetic method of an oxidant that supplies oxygen gas under basicity to a dyeing process. The method includes two stages of treatment, in which the first treatment is immersed in an aqueous catechin solution, the second treatment is immersed in a basic aqueous solution, and oxygen gas is supplied to the solution. This method shows that hair is dyed in a darker color than dyed hair using the dye disclosed in Patent Document 2. However, since a system for supplying oxygen gas as an oxidant from the outside is necessary, it lacks practicality. In addition, since it is necessary to use a basic aqueous solution, there is a problem of causing hair damage.

Japanese Patent No. 498858 Japanese Patent No. 5750664

Mitsuo Kimura and Yasuko Michiaki, “Fundamentals and Applications of Plant Dyes that Dye Nature”, Kitamasha, April 2007 Yasuhiro Arai, “Latest Hair Color Technology”, Fragrance Journal, August 2004, p. 102 Takanori Matsubara, Kenta Saegusa, Hiroto Hirayama, Yuya Matsushita, Makoto Miyata, Nami Seki, Hidekazu Yasunaga, "The 53rd dyeing chemistry discussion meeting", Textile Society dyeing research committee, September 2016 , P. 6-10

  Accordingly, the present invention has been made to solve the above-mentioned problems in the prior art in dyeing hair using a natural substance having a flavonoid skeleton, and to apply the dyeing method to various fibers.

  In order to solve the above problems, in the staining method of the present invention, the first treatment is immersed in an aqueous solution containing a natural substance, and the second treatment is immersed in an aqueous solution of periodic acid or periodate in an oxidizing agent, It is characterized by dyeing fibers.

  Natural substances that can be used are substances having a catechol structure and represented by the following general structural formulas (1), (2), and (3) and rosmarinic acid.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₆ each independently represent a hydrogen atom, a hydroxyl group, or a methyl group, and either one or both of R ₆ and R ₇ are a hydroxyl group, R ₅ represents a hydrogen atom, a hydroxyl group, a galloyl group or a sugar, and X represents> CH 2,> C═O or> CHOH.

In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₆ each independently represent a hydrogen atom, a hydroxyl group, or a methyl group, and either one or both of R ₆ and R ₇ are a hydroxyl group, R ₁₅ represents a hydrogen atom, a hydroxyl group, a galloyl group or a sugar.

In the formula, R ₂₁ represents a hydrogen atom or a hydroxyl group.

  The dyeable fibers are natural fibers, cellulose, polyamide and acrylic fibers, blended fibers containing these fibers, or fabrics containing these fibers.

  According to the dyeing method of the present invention, hair can be dyed in a dark color as in the prior art using oxygen gas, and the treatment method is simple and practical. Dyeing is possible as a weakly acidic to neutral treatment pH, and it is possible to reduce damage to hair and the effect on the scalp.

  Further, the dyeing method can be applied to other than hair, natural fibers, cellulose, polyamide and acrylic fibers, mixed fibers containing these fibers, or fabrics containing these fibers at a low temperature around room temperature. Dyeing is possible under short conditions within several hours.

It is an example of the graph which shows the relationship between the frequency | count of hair washing, and color difference (DELTA ⁾ E ^* of the white hair which has not received the chemical decoloring process dye | stained in Example 5 of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. The natural substance having a catechol structure used in the staining method of the present invention is a compound represented by the following general structural formulas (1), (2), and (3) and rosmarinic acid.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₆ each independently represent a hydrogen atom, a hydroxyl group, or a methyl group, and either one or both of R ₆ and R ₇ are a hydroxyl group, R ₅ represents a hydrogen atom, a hydroxyl group, a galloyl group or a sugar, and X represents> CH 2,> C═O or> CHOH.

In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₆ each independently represent a hydrogen atom, a hydroxyl group, or a methyl group, and either one or both of R ₆ and R ₇ are a hydroxyl group, R ₁₅ represents a hydrogen atom, a hydroxyl group, a galloyl group or a sugar.

In the formula, R ₂₁ represents a hydrogen atom or a hydroxyl group.

Specific examples include the following. pyro represents pyrogallol.
(1) (+)-catechin or (−)-catechin or (+)-epicatechin or (−)-epicatechin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ , R ₅ : OH, X:> CH ₂
(2) (+)-Gallocatechin or (−)-Gallocatechin or (−)-Epigallocatechin R ₁ , R ₃ : H, R ₂ , R ₄ , R ₅ , R ₆ : OH, X:> CH ₂
(3) (−)-catechin gallate or (+)-epicatechin gallate R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ : OH, R ₅ : O—C═O-pyro, X:> CH ₂
(4) (−)-gallocatechin gallate or (+)-epigallocatechin gallate R ₁ , R ₃ : H, R ₂ , R ₄ , R ₆ : OH, R ₅ : O—C = 0-pyro, X :> CH ₂
(5) Taxifolin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ , R ₅ : OH, X:> C═O
(6) fustin _{R 1, R 3, R 4} , R 6: H, R 2, R 5: OH, X:> C = O
(7) Luteolin _{R 1, R 3, R 5} , R 6: H, R 2, R 4: OH, X:> C = with O, flavone structure (8) 6-hydroxyl Theo phosphorus _{R 1, R} 5, R ₆ : H, R ₂ , R ₃ , R ₄ : OH, X:> C═O, flavone structure (9) 6-methoxyltheolin R ₁ , R ₅ , R ₆ : H, R ₂ , R ₄ : OH , R ₃ : OCH ₃ , X:> C═O, flavone structure (10) quercetin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ , R ₅ : OH, X:> C═O Flavone structure (11) quercetagetin R ₁ , R ₆ : H, R ₂ , R ₃ , R ₄ , R ₅ : OH, X:> C = O, flavone structure (12) gosipepetin R ₃ , R ₆ : H , R ₁ , R ₂ , R ₄ , R ₅ : OH, X:> C═O, and a flavone structure (13) tricetin R ₁ , R ₃ , R ₅ : H, R ₂ , R ₄ , R ₆ : OH, X:> C═O, flavone structure (14) myricetin R ₁ , R ₃ : H, R ₂ , R ₄ , R ₅ , R ₆ : OH, X:> C═O, flavone structure (15) fisetin R ₁ , R ₃ , R ₄ , R ₆ : H, R ₂ , R ₅ : OH, X:> C═O, flavone Structure (16) Pinocercetin R ₁ , R ₆ : H, R ₂ , R ₄ , R ₅ : OH, R ₃ : CH ₃ , X:> C═O, flavone structure (17) pinomycetin R ₁ : H, R ₂ , R ₄ , R ₅ , R ₆ : OH, R ₃ : CH ₃ , X:> C═O, flavone structure (18) rutin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ : OH, R ₅ : OR ′ (R ′ is β-lutinose), X:> C═O, flavone structure (19) quercitrin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ : OH, R ₅ : OR ′ (R ′ is α-L-rhamnose), X:> C═O, flavone structure (20) isoquercitrin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ : OH, R ₅ : OR ′ (R ′ is β-D-glucose), X:> C═O, flavone structure (21) hyperin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ : OH, R ₅ : OR ′ (R ′ is α-D-galactose), X:> C═O, flavone structure (24) abiclarin R ₁ , R ₃ , R ₆ : H, R ₂ , R ₄ : OH, R ₅ : OR ′ (R ′ is α-L-arabinose), X:> C═O, flavone structure (25) cyanidin R ₁₁ , R ₁₃ , R ₁₆ : H, R ₁₂ , R ₁₄ , R ₁₅ : OH
(26) Delphinidin R ₁₁ , R ₁₃ : H, R ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ : OH
(27) Ruteorinijin _{R 11, R 13, R 15} , R 16: H, R 12, R 14: OH
(28) Tricetinidine R ₁₁ , R ₁₃ , R ₁₅ : H, R ₁₂ , R ₁₄ , R ₁₆ : OH
(29) 5-Mechirushianijin _{R 11, R 13, R 16} : H, R 12, R 15: OH, R 14: OCH 3
(30) 6-hydroxy-sheet annealing Jin _{R 11, R 16: H,} R 12, R 13, R 14, R 15: OH
(31) 6-hydroxy _{delphinidin-R 11: H, R 12,} R 13, R 14, R 15, R 16: OH
(32) Purcheridine R ₁₁ , R ₁₃ : H, R ₁₂ , R ₁₅ , R ₁₆ : OH, R ₁₄ : ○ CH ₃
(33) Bradylin R ₂₁ : H
(34) Hematoxylin R ₂₁ : OH
In addition, theaflavins such as theaflavin and theaflavin digallate, glycosides of the above substances, leucocyanidine and the like are also included.

Specific examples of the target fiber in the dyeing method of the present invention include the following.
(1) Human gray hair (2) Chemically bleached human black hair (3) White yak hair (4) Wool fiber and fabric (5) Silk fiber and fabric (6) Cotton fiber and cotton fabric (7) Hemp fiber And linen fabric (8) rayon fiber and rayon fabric (9) nylon fiber and nylon fabric (10) acrylic fiber and acrylic fabric (11) paper (12) wood In addition, blended fibers and fabrics containing the above fibers are also included.

  Examples of the oxidizing agent that can be used in the staining method of the present invention include periodic acid, sodium orthoperiodate, sodium metaperiodate, potassium orthoperiodate, and potassium metaperiodate.

The staining method of the present invention is a method including an oxidation reaction of a natural substance having a catechol structure in a staining process. Specifically, there are the following two methods.
(1) A dyeing method (dyeing method A) in which a solution containing a natural substance and a solution containing an oxidizing agent are mixed, and immediately after that, fibers are introduced and immersed.
(2) A dyeing method (dyeing method B) in which fibers are immersed in a solution containing a natural substance, and then the treated fibers are transferred to a solution containing an oxidizing agent.

  In the above staining method, the staining method B is more preferable.

  In the dyeing method B for human hair, the treatment temperature using a solution containing a natural substance is preferably 30 to 50 ° C, more preferably 50 ° C. Above 50 ° C, human hair damage occurs.

  In the dyeing method B intended for other than human hair, the treatment temperature using a solution containing a natural substance is preferably 30 to 50 ° C, more preferably 30 ° C.

  In the dyeing method B, the treatment pH using a solution containing a natural substance is preferably pH 4-8.

  In the dyeing method B, the treatment pH using a solution containing a natural substance is preferably pH 4-8, more preferably pH 5-7.

  In the dyeing method of the present invention, a viscosity adjuster, a surfactant, a pH adjuster, a fragrance, a stabilizer, and the like can be blended in the treatment solution as needed within a range that does not impair the effects of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to a following example.

The dyeing property of the dyed fiber obtained in the present invention was evaluated according to the following method. The fibers were dyed under the conditions shown below, washed with an aqueous solution containing a cleaning agent and distilled water, dried naturally, and then measured using a spectrocolorimeter (CM-2600d manufactured by Konica Minolta). In the evaluation of the dyeability of the present invention, L ^* a ^* b ^* color system (CIE 1976) was used as the color system unless otherwise specified. ^{Here, L * a * b * L} * value in ^(Elster Esuta Bee Star) color system represents the lightness measure of the relative brightness of the color. a ^* and b ^* both represent chromaticity (hue / saturation). Hue is a measure of color perception attributes such as red, yellow, green, and blue. Saturation refers to the vividness of a color at the same brightness as the distance from an achromatic color.

Example 1 (Dyeing test of human hair)
<Dyeing method A>
0.29 g of (+)-catechin in 80 ml of 0.1 M phosphate buffer (pH = 7), 0.21 g of sodium metaperiodate in 20 ml of 0.1 M phosphate buffer (pH = 7) Each was dissolved and mixed, and immediately after that, white hair that was not chemically decolored was added and dyed at 50 ° C. for a predetermined treatment time. Subsequently, after washing | cleaning with 30 degreeC anionic surfactant aqueous solution, it wash | cleaned twice with 30 degreeC distilled water, Then, it was made to dry naturally.

<Dyeing method B>
0.29 g of (+)-catechin was dissolved in 100 ml of distilled water, and white hair that had not been chemically decolored was added and treated at 50 ° C. Thereafter, 0.21 g of sodium metaperiodate was dissolved in 100 ml of 0.1 M phosphate buffer (pH = 7), and catechin-treated hair was added thereto, followed by dyeing treatment at 30 ° C. for 40 minutes. Subsequently, after washing | cleaning with 30 degreeC anionic surfactant aqueous solution, it wash | cleaned twice with 30 degreeC distilled water, Then, it was made to dry naturally.

(result)
Table 1 shows the color measurement results. The dyed hair was dyed brown. Dyeing method B can be dyed darker than dyeing method A, and has a color tone that is practically preferred.

Example 2 (Yak white hair dyeing test)
<Dyeing method B>
0.29 g of (+)-catechin was dissolved in 100 ml of distilled water, and yak white hair that had not been chemically decolored was added and treated at 50 ° C. Thereafter, 0.21 g of sodium metaperiodate was dissolved in 100 ml of 0.1 M phosphate buffer (pH = 7), and the treated yak white hair was added thereto, and the dyeing treatment was performed at 30 ° C. for 40 minutes. did. Subsequently, after washing | cleaning with 30 degreeC anionic surfactant aqueous solution, it wash | cleaned twice with 30 degreeC distilled water, Then, it was made to dry naturally.

  Table 2 shows the color measurement results. The dyed hair was dyed brown. The higher the (+)-catechin treatment temperature, the darker the color.

Example 3 (Dyeing test of fabrics composed of various fibers)
<Dyeing method B>
Five silk fabrics, wool fabrics, cotton fabrics, rayon fabrics, nylon fabrics, acrylic fabrics, and polyester fabrics cut into 4 cm × 4 cm were each put into 100 ml of a solution in which 0.29 g of (+)-catechin was dissolved, and 30 Treated for 40 minutes at ° C. Thereafter, 0.21 g of sodium metaperiodate was dissolved in 100 ml of 0.1 M phosphate buffer (pH = 7), and catechin-treated fabrics were respectively added thereto, followed by dyeing treatment at 30 ° C. for 40 minutes. . Next, after washing with a 30 ° C. soap solution and twice with 30 ° C. distilled water, it was naturally dried.

(result)
Table 3 shows the color measurement results. All the fabrics were dyed brown. As a result, there was a difference in dyeability depending on the type of fiber, and it was relatively darkly dyed with silk fabric, wool fabric, cotton fabric, rayon fabric, and nylon fabric.

Example 4 (Dyeing test of silk fabric using various natural substances)
<Dyeing method B>
Five silk fabrics cut into 4 cm × 4 cm were cut into 0.29 g (+)-catechin, 0.30 g hematoxylin, 0.36 g rosmarinic acid, 0.30 g tea extract Sanphenon EGCg (Taiyo Kagaku) , 0.30 g of tea extract Sanphenon 90S (Taiyo Chemical Co., Ltd.), 0.30 g of Sunphenon BG-3 (Taiyo Chemical Co., Ltd.), 0.075 g of black tea extract Theaflavin TF40 (Yakisui Sanka Chemical Co., Ltd.) The solution was added to 100 ml of the solution and treated at 30 ° C. for 40 minutes. Thereafter, 0.21 g of sodium metaperiodate was dissolved in 100 ml of 0.1 M phosphate buffer (pH = 7), and the fabrics treated with natural substances were respectively added thereto and dyed at 30 ° C. for 40 minutes. Treated. Next, after washing with a 30 ° C. soap solution and twice with 30 ° C. distilled water, it was naturally dried.

(result)
Table 4 shows the color measurement results. All the fabrics were dyed brown.

Example 5 (Hair-washing fastness test of dyed human hair)
0.30 g of tea extract Sanphenon 90S (Taiyo Kagaku Co.) was dissolved in 100 ml of distilled water, and white hair that had not been chemically decolored was added and treated at 50 ° C. Thereafter, 0.21 g of sodium metaperiodate was dissolved in 100 ml of 0.1 M phosphate buffer (pH = 7), and catechin-treated hair was added thereto, followed by dyeing treatment at 30 ° C. for 40 minutes. Next, after washing with an aqueous anionic surfactant solution at 30 ° C. and twice with distilled water at 30 ° C., the hair was naturally dried and the dyed hair was measured with a spectrocolorimeter. Furthermore, after washing with an aqueous anionic surfactant solution at 30 ° C., washing twice with distilled water at 30 ° C., drying, and then measuring the hair again. This operation was repeated 31 times. The color change after shampooing before and shampooing n times (color _{^{difference), ΔE * = {(a}} * n -a * 0) 2 + (b * n -b * 0) 2 + (L * n -L * 0 ² } ^(1/2) (a ^* ₀ , b ^* ₀ , L ^* ₀ : Color value of dyed hair before washing, a ^* _n , b ^* _n , L ^* _n : dyed hair after washing n times Color value). For comparison, the results of using a commercial oxidative hair dye and a commercial acid hair dye are also shown in the figure.

(result)
FIG. 1 shows the number of shampooing and changes in the color of dyed hair due to shampooing. As shown in the figure, the hair wash fastness was comparable to that of a commercially available oxidative hair dye, and it was confirmed that the hair wash fastness was higher than that of a commercially available acid hair dye.

  According to the present invention, it is possible to dye a fiber using a natural substance at a low temperature and in a short time, instead of the conventional metal mordant dyeing method.

  In dyeing human hair, it is possible to provide a dyeing method that is safer and easier to handle for the human body, instead of a commercially available oxidative hair dye.

  The present invention is applied to an ink jet printing machine, and it becomes possible to carry out dyeing of fibers using natural substances more easily.

Claims (6)

A method of dyeing fibers,
(A) a step of immersing the fiber in a solution of a natural substance having a catechol structure;
(B) a step of immersing the fiber in an oxidant solution;
A method for dyeing fibers using a natural substance characterized by comprising:   The method for dyeing fibers using a natural substance according to claim 1, wherein the fiber is immersed using a solution in which the natural substance and the oxidizing agent are mixed.   The method for dyeing fibers using a natural substance according to claim 1, further comprising a step of immersing the fiber in an oxidizing agent solution after the step of immersing the fiber in the natural substance solution. .   The oxidizing agent is periodic acid, periodate, hydrogen peroxide, inorganic or organic alkali metal peroxide, peroxide, inorganic perhydrate salt, alkyl or aryl peroxide or peroxidase, oxidase, The natural substance according to any one of claims 1 to 3, which is at least one selected from the group consisting of uricase, percarbonate, persulfate, peroxomonocarbonate, and a mixture thereof. The dyeing method of the used fiber.   The fiber is a fiber selected from the group consisting of natural fiber, cellulose, polyamide and acrylic, a mixed fiber containing these fibers, a fabric containing these fibers, or paper or wood. The dyeing | staining method of the fiber using the natural substance as described in any one of -4. The natural substance is at least one selected from the group consisting of substances represented by the following general structural formulas (1), (2), and (3) and rosmarinic acid: A method for dyeing fibers using the natural substance according to any one of the above.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₆ each independently represent a hydrogen atom, a hydroxyl group, or a methyl group, and either one or both of R ₆ and R ₇ are a hydroxyl group. , R ₅ represents a hydrogen atom, a hydroxyl group, a galloyl group or a sugar, and X represents> CH 2,> C═O or> CHOH.)

(In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₆ each independently represent a hydrogen atom, a hydroxyl group, or a methyl group, and either one or both of R ₆ and R ₇ are a hydroxyl group. R ₁₅ represents a hydrogen atom, a hydroxyl group, a galloyl group or a sugar.

(In the formula, R ₂₁ represents a hydrogen atom or a hydroxyl group.)

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