JP2012233081A - Dye composition, dyeing method using the same, and dyed thing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye composition including a natural dye of a plant origin that can obtain a dyed thing excellent in a dyeing property and solidity by a simple process, a dyeing method that can obtain a dyed thing excellent in a dyeing property and solidity by a simple process, and dyed thing that has high solidity and an excellent hue obtained by the dyeing method.SOLUTION: The dye composition includes: (A) a plant origin natural dye; (B) a natural dye adsorption auxiliary selected from a group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt; (C) a chemical dye selected from a group consisting of a reactive dye, an acid dye, a vat dye, and a disperse dye. In addition, the dye composition desirably includes (D) a solution or a dispersion of a water soluble powder that has a chemical structure same or similar with a fiber that is a thing to be dyed.

Description

  The present invention relates to a dye composition excellent in dyeability, including a natural dye derived from plants, a dyeing method for dyeing fibers using the dye composition, and a dyed product obtained by the dyeing method.

In recent years, natural dyes have been attracting attention in the growing nature-oriented, and dyeing using natural dyes such as plant dyeing has been actively performed. When dyeing fiber materials that are to be dyed with plant-derived pigments, it is difficult to obtain the desired color due to insufficient dyeability and adsorptivity between fibers and dyes. There are problems such as lack, and improvements are desired.
In the case of using a natural dye, it has been proposed to use a metal ion or a chemical cation agent together as a dyeing assistant, and it is still used (for example, see Patent Documents 1 to 4).
However, it is difficult to obtain a good hue with any of the conventional methods, and the practically sufficient fastness cannot be achieved.
For this reason, a technique for improving fastness has been proposed by using a combination of a natural dye and a chemical dye, and providing a step of adsorbing a positive ionized substance on the fiber to be dyed in the dyeing step. (For example, refer to Patent Document 5). Although this method improves dyeability and hue, it requires at least three steps: a dyeing step with a natural dye, a dyeing step with a chemical dye, and a step of adsorbing a positive ionized substance. There has been a demand for a dyeing method having fastness and hue that can withstand rust.

Japanese Patent Application Laid-Open No. Sho 62-238885 JP-A-62-250287 Japanese Unexamined Patent Publication No. 63-12783 JP-A-4-257377 JP 2005-36335 A

As described above, even when natural dyes are used, dyed materials that are suitably used for cellulose fibers such as cotton, polyester fibers, and the like, have high fastness, and achieve a preferable hue can be obtained by a simple method. The fact is that the dye composition and the dyeing method have not yet been realized.
An object of the present invention made in consideration of the above prior art is to provide a dye composition containing a plant-derived natural dye capable of obtaining a dyed product excellent in dyeability and fastness by a simple process. It is in.
A further object of the present invention is to provide a dyeing method using the dye composition of the present invention to obtain a dyed product excellent in dyeability and fastness in a simple process, and a fastness obtained by the dyeing method. The object of the present invention is to provide a dyed product having high properties and a good hue.

The above problem is solved by the following means. That is,
The invention according to claim 1
(A) a plant-derived natural dye, (B) a natural dye adsorption aid selected from the group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt, and (C) a reactive dye, an acid dye, and vat dye And a chemical dye selected from the group consisting of a dye and a disperse dye.
The invention according to claim 2
The dye composition according to claim 1, further comprising (D) a solution or dispersion of a water-soluble powder having the same or similar chemical structure as the fiber to be dyed.

The invention according to claim 3
(A) a solution or dispersion of a plant-derived natural dye, (B) a solution or dispersion of a natural dye adsorption aid selected from the group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt, and (C A solution or dispersion preparation step for preparing a solution or dispersion of a chemical dye selected from the group consisting of a reactive dye, an acid dye, a vat dye, a direct dye and a disperse dye,
Mixing each obtained solution or dispersion to obtain a dye composition;
And a step of applying the obtained dye composition to fibers in this order.
The invention according to claim 4
4. The dye composition according to claim 3, wherein the dye composition is a composition obtained by further mixing (D) a solution or dispersion of a water-soluble powder having the same or similar chemical structure as the fiber to be dyed. It is a staining method.

The invention according to claim 5
The dyeing method according to claim 3 or 4, wherein the step of applying the dye composition to the fiber is a step of immersing the fiber to be dyed in the dye composition.
The invention according to claim 6
5. The dyeing method according to claim 3 or 4, wherein the step of applying the dye composition to fibers is a step of applying the dye composition to a sheet made of fibers that are to be dyed.
The invention according to claim 7 provides:
It is the dyed material dye | stained by the dyeing | staining method of any one of Claims 3-6.

According to the present invention, a plant-derived natural dye that can be suitably used for cellulose fibers such as cotton, polyester fibers, and the like, and can obtain a dyed product with excellent dyeability and fastness of dyed matter in a simple process. A dye composition is provided.
Further, according to the present invention, there is provided a dyeing method capable of obtaining a dyed product excellent in dyeability and fastness by a simple process, and a dyed product having a good hue obtained by the dyeing method and fastness. Is done.

It is a schematic diagram which shows an example of the dye aggregate in the dye composition of this invention. It is a schematic diagram which shows the state which the aggregate of adsorption adjuvant, the natural dye, and the chemical dye adsorb | sucked to the fiber.

Hereinafter, the present invention will be described in detail.
[Dye composition]
The dye composition of the present invention comprises (A) a plant-derived natural dye, (B) a natural dye adsorption aid selected from the group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt, and (C) a reaction. A chemical dye selected from the group consisting of a reactive dye, an acid dye (C) reactive dye, an acid dye, a vat dye and a disperse dye, and a chemical dye selected from the group consisting of a disperse dye From the viewpoint of improving the adsorptivity and permeability to fibers, (D) a solution or dispersion of a water-soluble powder having the same or similar chemical structure as that of the fibers to be dyed Is preferred.
Hereinafter, each component contained in the dye composition of the present invention will be described sequentially.

<(A) Plant-derived natural dye>
The dye composition of the present invention contains (A) a plant-derived natural dye. There is no restriction | limiting in particular in the natural dye which can be used for this invention, According to the hue which the dyeing | staining obtained is intended, it selects suitably. Only 1 type may be used for a natural dye, and 2 or more types may be mixed and used for it.
Specifically, for example, plant leaves, stems, bark, roots, flowers, fruits, and the like, powders of plants extracted from these powders, and plant dyes are representative. More specifically, examples of plant dyes include indole derivatives, carotenoids, diketones, isohinohan derivatives, anthocyans, chlorophylls, chalcone derivatives, flavonoids, tannins, naphthoquinone derivatives, dihydropyran derivatives, anthraquinone derivatives, and the like. However, the present invention is not limited to these.
Since these natural dyes have a partial structure capable of forming a hydrogen bonding interaction such as a hydroxyl group and an oxygen atom in the molecule, they are excellent in affinity with (B) natural dye adsorption aid described later.
The basic hue of the above dye is shown below.

For example, indole derivative (blue), carotenoid (carotenoid) (orange), diketone (yellow), isohinoline derivative (yellow), anthocyanin or anthocyan (red), chlorophyll (chlorophyll) (green), chalcone derivative (yellow), flavonoid (Yellow), tannin (brown), naphthoquinone (purple), dihydropyran (black), anthraquinone derivative (red), and the like. Hue may change depending on compound modification and pH conditions.
When preparing a dye composition using these natural dyes, a solution or dispersion in which natural dyes are dissolved or dispersed in advance is prepared and then blended. In addition, when using plant origin extracts, such as indigo, since the extract itself is a solution, you may use this as it is.

Since natural dyes have specific physical properties, the preparation of a solution or dispersion is adjusted by a method according to each property. In the following, representative examples of natural dyes suitable for the present invention, examples of compounds belonging to natural dyes, natural products (raw materials) as raw materials for natural dyes are listed, but natural dyes that can be used in the present invention are limited to these. Any one can be used as long as it has an affinity for (B) adsorption aid and (C) chemical dye described later.
(A-1) Since indole derivatives are excellent in alkali solubility, it is preferable to prepare them with a slightly higher pH. Specifically, when the pH exceeds 9, the possibility of gelation is reduced, which is preferable. In addition, fastness improves by combining with a vat dye as a chemical dye from a viewpoint of interaction with the chemical dye mentioned later.
Examples of indole derivatives include indigo, indoxyl, indigo isomers, indirubin and the like. These dyes are extracted from indigo grass, kiai, shellfish purple and the like.
(A-2) The carotenoids are preferably prepared as neutral to weakly acidic (pH 4.5 to 5.5) solutions or dispersions. In the alkaline region, there is a risk of decomposition, and it is difficult to obtain a preferable hue. Carotenoids are preferably used in combination with acidic dyes, reactive dyes, and disperse dyes as chemical dyes described below. When used in combination with a direct dye, it can be used stably up to about pH 8.0.
Examples of carotenoids include ζ-carotene. For example, carotenoids can be obtained from plants such as carrots, gardenia, saffron, annatto, orange and tomato.

(A-3) Diketones have an —OH group in the molecule but have good interaction with the nitrogen atom, and form a good interaction with any chemical dye. They can be used in combination, and various selections are possible according to the target hue.
There is a tendency that redness becomes strong in an alkaline atmosphere, and yellowing becomes strong when acidified. Diketones are extracted from turmeric, gadgets, shoga and the like.
(A-4) Isohinoline derivatives easily react with oxygen atoms having an —NH structure. From such a viewpoint, a good interaction is formed with any chemical dye, and the combination is arbitrary.
Examples of isohinoline derivatives include berberine, violacein, prodigiosin and the like. Isohinoline derivatives are obtained from yellowfin, yellow lotus, large yellow, black-tailed grass, and the like.

(A-5) Anthocyans retain a red color in the acidic region. It is easy to form a supply bond with nitrogen and oxygen atoms and easily adsorb with chemical dyes and dyeing assistants.
Examples of the anthocyanins include 3,5,7-trihydroxy-2-phenylbenzobililium, anthocyanin, anthocyanidin, pelargonidin, cyanidin, peonidin, delphinidin, petunidin, malvidin and the like. Anthocyanins can be obtained from, for example, apples, cherries, grapes, oyster grasshoppers, peony, roses, buzzards, carnations and the like.
(A-6) Chlorophyll exhibits a beige hue in combination with a cationic compound described below. Since it binds and stabilizes with magnesium, it is preferably used in combination with a chemical dye containing magnesium in the molecule.
Examples of chlorophyll include chlorophyll c and chlorophyll d. Usually extracted from green leaves and the like, for example, Kumazasa, mulberry, aloe, and various herbs.

Since the (A-7) chalcone derivative has a large number of hydroxyl groups in the molecule, it is preferable to prepare a solution or dispersion in the neutral range. Moreover, since redness will become strong if pH is raised, what is necessary is just to select and prepare pH and a combined use component according to the target hue.
Examples of the chalcone derivative include chalcone, chalcone glycoside, querchycene, cyanidin and the like, which are obtained from safflower, cedar, pine, hinoki and the like.
(A-8) Flavonoids have a large number of hydroxyl groups in the molecule, but because they are easily decomposed by nitrogen in the air due to their structure, it is necessary to stabilize them by forming an interaction with a chemical dye. Therefore, it is preferable to use a chemical dye capable of forming an interaction in combination.
Flavonoids include, for example, apigenin, apiin, gencanin, luteolin, baicalein, baicalin, ougonine, plantaginine, vitexin, orientin, swellticin, and other flavones; kaempferol, astragalin, aphzelin, quercetin, quercitrin, isoquercitrin, Flavonols such as rutin, myricetin, morin and icariin; flavanones such as liquiritigenin, liquiritin, naringenin, naringin, sakuranetin, sakuranin, hesperetin, hesperidin, neohesperidin; daidzein, daidzin, puerarin, formonetin, genistin, genistin, etc. Isoflavones; flavan-3-ol, kaempferol, myricetin, quertisene and the like, Riyasu, bayberry, Sophora, Garcinia, goby, is extracted from the like Scutellaria.

(A-9) Tannins can have various chemical structures. Since light fastness alone has a problem, it is necessary to stabilize by forming an interaction with a chemical dye, and it is preferable to use a chemical dye that can form an interaction in combination.
Examples of tannins include hydrolyzable tannins such as catechin, epicatechin, epigallocatechin, ganvir tannin, gallic acid, ellagic acid, quinic acid, shikimic acid, geraniin; cinnamtannin A ₁ , cinnamtannin B ₁ Condensed tannins such as, chestnuts, kepracho, Yasha Fushiko, milobaran, catechu, pomegranate, coffee, walnut, ume, etc. Among them, industrial tannins and tannic acid are often used for dyeing as industrial tannins.

(A-10) The naphthoquinone derivative contains a large amount of oxygen in the molecule and is easily adsorbed with a cationic compound, and the dye can be stabilized by adsorption. Chemical dyes may be arbitrarily selected and used according to the target hue.
Examples of the naphthoquinone derivative include 1,2-naphthaquinone, 1,4-naphthaquinone, 2,6-naphthaquinone, and the like, and can be obtained from purple citrus, rosewood, shiso, campo, mahogany, and the like.
(A-11) The dihydropyran derivative has a hydroxyl group at the terminal and is easily adsorbed with a cationic compound. In order to obtain a black hue, the pH may be in the alkaline region. However, since the color tone is likely to change depending on the pH, it is preferable to stabilize the color tone in combination with a chemical dye.
Examples of the dihydropyran derivative include dihydrochalcone, dihydroneopterin, 7,8-dihydroneopterin triphosphate, and the like, and can be obtained from Sou, logwood and the like.

The (A-12) anthraquinone derivative is useful as a red dye and easily adsorbs with a cationic compound due to an oxygen atom, a hydroxyl group and the like in the molecule. When used in combination with a chemical dye, a brighter color is obtained.
Examples of the anthraquinone derivative include 9,10-anthraquinone, alizarin, anthraquinone-2-sulfonic acid, 2,3-dibromoanthraquinone and the like, and are obtained from Akane, Cochineal, Lac, Kermes and the like.

Although typical plant-derived natural dyes are listed here, the present invention is not limited to these.
Natural dyes may be used alone or in combination of two or more. As described above, these are contained in the dye composition in the form of a solution or a dispersion. The solvent or dispersion medium is appropriately selected according to the physical properties of the natural dye. When a plant is extracted with water, warm water, an organic solvent or the like to obtain a natural dye, the extract itself may be blended.
As the extraction of natural dyes, for example, a method is generally used in which a plant is heated as it is or a dried plant is heated and extracted with 10 to 30 times the amount of water at a temperature of 80 ° C. or more and a heating time of 30 minutes or more. . Depending on the plant, acid (eg, diketone, naphthoquinone, anthraquinone, anthocyan, etc.), alkali (eg, tannin, indole), metal compound (eg, chlorophyll, etc.), etc., should be used as combination components for color development and hue fixation. There is.

Moreover, you may use the water containing 5 mass%-50 mass% of moisturizing components, such as a dimethylaldehyde and propylene glycol, as an extract, and when using a moisturizing component together, heating temperature is 80 to 120 degreeC, high When it is desired to extract a large amount by concentration, the temperature may be 120 ° C to 250 ° C.
Further, instead of the moisturizing component, an extract obtained by adding water-soluble alcohol such as ethanol to 15% by mass to 30% by mass in water may be used. Extraction with alcohol is useful for diketones, isohinolines, anthocyanins, chlorophylls and the like.
As another extraction method, it is possible to take a method of extracting a powder obtained by freeze-drying a plant under a condition of −10 ° C. or less while adjusting pH.
The content of the natural dye (A) in the dye composition of the present invention is preferably in the range of 5% by mass to 99% by mass in terms of solid content, and more preferably in the range of 30% by mass to 99% by mass in terms of solid content. It is a range. In addition, in this specification, solid content refers to the component remove | excluding the solvent and the dispersion medium from the composition.

<(B) A natural dye adsorption aid selected from the group consisting of cationic compounds and alkali metal salts>
The dye composition of the present invention contains (B) a cationic compound and a natural dye adsorption aid selected from the group consisting of an alkali metal salt (hereinafter referred to as (B) adsorption aid as appropriate). As described above, (A) natural dyes are not sufficiently stable and fast due to their structure, and (B) by using an adsorbent aid in combination with (A) natural dyes are improved, And the adsorptivity to a fiber can also be improved.
(B) Adsorption aids include cationic compounds that may have an acid group such as a carboxy group or a sulfone group, an amino group, etc. in the molecule, such as basic amino acids, ammonium salt compounds, and more. Specifically, basic amine compounds such as polyvinylamine and polyallylamine; ammonium salt compounds such as quaternary ammonium salts and tertiary ammonium salts; basic amino acids such as arginine, and sodium isocyanurate, trifluoroacetic acid Examples thereof include alkali metal salts such as sodium, sodium iodide and lithium iodide.
Cationic compounds such as typical quaternary ammonium salts form a peptide bond between nitrogen and fiber in the molecule due to alkali, and the quaternary ammonium salt interacts with the hydroxyl group of the plant-derived natural dye. It is considered that the natural dye is stably fixed by forming and adsorbing.
These compounds are also included in the dye composition as a solution or dispersion. The solvent or dispersion medium is appropriately selected according to the physical properties of (B) the adsorption aid.
Representative quaternary ammonium salts used in the present invention are shown below.

  The content of the (B) adsorption aid in the dye composition of the present invention is preferably in the range of 1% by mass to 10% by mass in terms of solid content, more preferably in the range of 3% by mass to 5% by mass in terms of solid content. Range. Moreover, it is preferable to use it in the ratio of 3 mass parts-5 mass parts with respect to 100 mass parts of above-mentioned (A) natural dyes.

<(C) Chemical dye selected from the group consisting of reactive dyes, acid dyes, vat dyes and disperse dyes>
The dye composition of the present invention contains a chemical dye selected from the group consisting of reactive dyes, acid dyes, vat dyes and disperse dyes (hereinafter referred to as (C) chemical dyes as appropriate).
The (C) chemical dye used in the present invention is used for improving the adsorptivity of natural dyes to fibers and adjusting the hue. As described in (A) Natural dyes, (C) Chemical dyes are selected according to the physical properties of (A) natural dyes in order to contribute to the stabilization of (A) natural dyes. Further, when it is used to make the hue desired, it is arbitrarily selected and used as long as it does not cause an undesired reaction such as agglomeration or decomposition, particularly in relation to the physical properties of (A) natural dye.
Chemical dyes that can be used in the present invention include reactive dyes, acid dyes, vat dyes, direct dyes and disperse dyes.
These chemical dyes are appropriately selected in consideration of interaction with natural dyes and fibers used in combination, but are preferably selected in consideration of interaction with fibers. Specifically, for example, when dyeing cellulose fibers, reactive dyes, direct dyes, and vat dyes are preferable, and for protein fibers such as wool and silk, acid dyes and metal-containing acid dyes are preferable. Disperse dyes are preferably used for polyamide and polyester fibers. In addition, according to the dye composition of this invention, a polyester fiber can be dye | dyed in the wide range of pH 6.0-9.5.
In general, the usefulness of the present invention is clear considering that polyester fibers cannot achieve high fastness unless a reactive dye is used in a pH range of 9.0 to 9.5.
That is, the polyester fiber is usually dyed at 110 ° C to 130 ° C. According to the present invention, the polyester fiber can be dyed at 80 ° C to 100 ° C, although the pH is in the range of 4.0 to 7.0. If conditions are adjusted, dyeing | staining of a polyester fiber will be attained in the range of pH3.0-9.5, and it also has the advantage that the pH range which can be adapted spreads.

The chemical dye solution, the solution for preparing the dispersion, and the pH of the dispersion will be described. Each chemical dye is dissolved and dispersed stably in the following pH range, and there is no concern about gelation and the storage stability is also good. Therefore, it is preferable to prepare in the following pH range.
Acid dyes: Alkaline Reactive dyes: Neutral Disperse dyes: Acidic Direct dyes: Neutral Vat dyes: Neutral Solvents and dispersion media include water, water containing water-soluble alcohols and humectants, and water-based organic solvents. One or more may be selected and used, and water is preferred. The pH can also be adjusted by adding an acid component or an alkali agent.
One characteristic of the dye composition of the present invention is that a dyed product excellent in color development and fastness can be obtained even when dyed in a region where the pH is close to neutral using water as a solvent.

The content of the (C) chemical dye in the dye composition of the present invention is preferably in the range of 0.01% by mass to 30% by mass with respect to (A) the natural dye in terms of solid content.

The ratio of (A) natural dye and (C) chemical dye described above is, in terms of mass, (A) 30% to 97% of natural dye and (C) 70% to 3% of chemical dye. Is preferable.
Within this range, characteristics such as the hue of natural dyes are fully exhibited, and the effect of improving fastness is sufficiently exhibited. Particularly, it is preferable that (A) the natural dye is 70% or more and (C) the chemical dye is 30% or less, since the color tone of the natural dye is remarkably obtained.
In particular, for black dyeing, (A) natural dye is 30% to 70%, and (C) chemical dye is preferably 70% to 30%. (A) 70% to 90% of the natural dye, (C) 10% to 30% of the chemical dye, and (A) 90% to 99.9% of the natural dye in the light color On the other hand, it is preferable that the chemical dye (C) is 0.1% to 10%.

<(D) Solution or dispersion of water-soluble powder having the same or similar chemical structure as the fiber to be dyed>
The dye composition of the present invention preferably contains (D) a solution or dispersion of a water-soluble powder having the same or similar chemical structure as the fiber to be dyed.
As the water-soluble powder having the same or similar chemical structure as the fiber dyed by the dye composition of the present invention (hereinafter referred to as (D) homogeneous powder), for example, the fiber to be dyed is a wool fiber. In some cases, an aqueous solution or aqueous dispersion of chitin or chitosan containing a protein-based skeleton is used, an aqueous dispersion of silk fine powder is used for silk fibers, and a polyester is used for polyester fibers. An aqueous dispersion of fine powder, or a water-soluble polyester fine powder partially solubilized by modification, and a solution or dispersion of cellulose derivative, water-soluble cellulose or the like are used for cotton fibers.
(D) As homogeneous powder, cellulose and its derivatives, polyamide, polylactic acid, polyester, polyolefin, polyurethane, polyaramid, acrylic, rayon, triacetate, diacetate, hemp, cupra, polyvinyl chloride, vinylidene, polypropylene, etc. It is appropriately selected according to the fiber.
A compound having the same or similar chemical structure and chemically modified such as introduction of a functional group may be used for the purpose of improving solubility and dispersibility in a solvent. (D) By using a homogeneous powder, the permeability of the dye composition between fibers and the adsorptivity are further improved.

  The content of the (D) homogeneous powder in the dye composition of the present invention is preferably in the range of 0.5% by mass to 10% by mass in terms of solid content.

<Preparation of dye composition>
The dye composition of the present invention is obtained by preparing each of the essential components (A) to (C) and the component (D) which is a preferred combination component in advance as a solution or a dispersion, respectively, and mixing them. Can do.
Mixing is performed under a temperature condition of 10 ° C. to 70 ° C., and preferably performed in a temperature range of 25 ° C. to 60 ° C. which is normal temperature. In the temperature range, the reaction is performed for 0.01 hour to 1 hour, preferably 10 minutes to 30 minutes. By sufficiently heating and mixing as described above, the components (A) to (D) are adsorbed by interaction and bonded to each other by interaction as shown in the schematic diagram of FIG. Form. FIG. 1 is a schematic diagram showing a dye aggregate 10 in the dye composition of the present invention.
As shown in FIG. 1, in a preferred embodiment of the present invention, (D) homogeneous powder 12 adsorbs (A) natural dye 16 and (C) chemical dye 18 via (B) adsorption aid 14. The dye aggregate 10 is formed. In addition, depending on the physical properties of (A) natural dye and (C) synthetic dye, (A) natural dye and (C) synthetic dye form an interaction. This is considered to be stronger and improve the stability of natural dyes. The (D) homogeneous powder 12 having a weak cohesive force and a large particle size is removed by heat treatment, steam treatment, or water washing treatment after dyeing, and (B) adsorption aid as shown in FIG. 14, (A) natural dye 16 and (C) chemical dye 18 are considered to be adsorbed to fiber 20 as the object to be dyed in a state of being aggregated by interaction. FIG. 2 is a schematic diagram showing a state in which an aggregate of (B) adsorption aid 14, (A) natural dye 16, and (C) chemical dye 18 is adsorbed on fiber 20.

The formation of the dye aggregate does not necessarily require (D) the homogeneous powder 12, and is ionic between the (B) adsorption aid that expresses a cationic property, (A) the natural dye, and (C) the chemical dye, Alternatively, covalent interactions are formed and stable dye aggregates are formed. This dye aggregate also quickly adsorbs on the surface of the fiber 20 due to the influence of the surface potential or the like.
That is, normally, the yarn of the fibers constituting the woven fabric is composed of a collection of fine yarns, but the dye composition is difficult to penetrate into the portion having the fiber density according to Van der Waals theory. For this reason, the temperature of the dye composition is increased and the fibers are immersed, but even if the temperature of the water is increased, the portion where the fibers are present at high density is not affected by the increase in temperature or convection of the liquid. (D) By containing the homogeneous powder, it is considered that fine dye aggregates easily enter the gaps of the fibers by the action of van der Waals forces and are easily adsorbed to the fibers. Therefore, as in a preferred embodiment of the present invention, by forming an aggregate containing (D) homogeneous powder 12, the dyed fiber 20 and (D) homogeneous powder 12 have the same or similar chemical structure. Both are excellent in affinity, and even when dyeing by dipping or when applying a dye composition on a fiber sheet such as textile printing, woven fabric, nonwoven fabric, etc. Will also be excellent.
As described above, the interaction between the dyed fiber 20 and the dye agglomerate 10 is firmly formed even through the adsorption aid 14 (B), but considering the permeability of fine fibers into the gaps. For example, (D) using the homogeneous powder 12 is preferable because uniform dyeing is possible in a shorter time.

[Dyeing method]
The dyeing method of the present invention comprises (A) a solution or dispersion of a plant-derived natural dye, (B) a solution of a natural dye adsorption aid selected from the group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt, or A solution or dispersion preparation step (solution preparation step) for preparing a dispersion and (C) a solution or dispersion of a chemical dye selected from the group consisting of a reactive dye, an acid dye, a vat dye and a dispersion dye, respectively And a step of obtaining a dye composition by mixing each obtained solution or dispersion (dye composition preparation step), and a step of applying the obtained dye composition to a fiber (dyeing step). At least in this order. That is, the dyeing method of the present invention is characterized by using the dye composition of the present invention. As described above, the dye composition of the present invention includes a dye aggregate that is excellent in stability of the contained dye and adsorptivity with the fiber. Thus, a dyed product having excellent fastness can be easily obtained.

<Solution preparation process>
In the solution preparation step, a solution or a dispersion containing (A) a natural dye, (B) an adsorption aid, and (C) a chemical dye contained in the dye composition of the present invention is prepared. As described above, (A) plant-derived natural dyes in the solid state such as powder may be dissolved in an appropriate solvent or dispersion medium, but those in the form of an extract as a plant extract dissolve natural dyes. Since it is a dispersion, the extract may be used as it is.
Further, (C) the chemical dye is preferably prepared as a solution or a dispersion in a preferable pH range as described above.
In addition, when (D) homogeneous powder is used in the dye composition, a solution or dispersion of (D) homogeneous powder may be prepared in advance and then added.
The concentrations of the components (A) to (D), the respective solutions, and the dispersion liquid may be adjusted so that the solid content concentration excluding the solvent and the dispersion medium is in the range of 0.01% by mass to 15% by mass. preferable.

<Dye composition preparation process>
In this step, the solution (A) to the component (C) obtained in the above step, and optionally a solution or dispersion of the component (D) are further mixed. Mixing is performed with heating and stirring.
Heating is performed in a temperature range of 10 ° C to 70 ° C, preferably 25 ° C to 60 ° C. If the temperature is too low, it is difficult to form the target dye aggregate, and if it is too high, there is a concern that the natural dye (A) may be deteriorated or faded.
Stirring is preferably performed for 0.01 hour to 0.5 hour, and it is estimated that the target dye aggregate can be obtained by stirring for about 10 minutes. As the stirring means, known means may be used, and examples thereof include a method using a known stirrer such as a paddle stirrer, or a method in which the stirring is carried out manually with a spatula or the like. When a high shearing force is applied during stirring, it is difficult to form a stable dye aggregate, and thus stirring is preferably performed under mild conditions.
In the dye composition thus prepared, there is a dye composition having good adsorptivity to fibers and stability of each dye, and the effect of the present invention is exhibited by this dye aggregate.

<Dyeing process>
In this step, dyeing is performed by applying the dye composition of the present invention obtained above to the fiber to be dyed. There is no restriction | limiting in particular in the application method to the fiber of a dye composition, All the well-known dyeing methods are applicable.
For example, fibers (threads); fiber sheets such as woven fabrics and non-woven fabrics; products made of fibers such as clothes and bags already formed such as T-shirts; The dye composition may be applied to fiber sheets such as woven and non-woven fabrics and already formed clothing such as T-shirts, and dyeing may be performed in the same manner as in the production of ordinary printed products.
When taking the latter method, it may be adjusted to a desired viscosity by adding a paste to the dye composition so as to be suitable for printing and transfer, and even if such adjustment is performed, the effect of the present invention is achieved. Will not be damaged.
In the case of dyeing by printing, a known post-treatment may be performed. Examples of the post-treatment include a heat treatment with steam at around 100 ° C., and a water-washing treatment that is performed after that to remove excess glue or undyed dye composition.

  In this way, the staining method of the present invention can be performed. According to the dyeing method of the present invention using the above-described dye composition of the present invention, the adsorptivity of the dye to the article to be dyed is good, and the defect is improved while taking advantage of the hue and texture of the natural dye. A dyed product having a hue of 2 and having sufficient practical fastness can be obtained by a simple process.

<Dyed article>
The dyeing method of the present invention is applied to any known fiber. For example, any of the following fibers may be applied. The fiber may be a synthetic fiber or a natural fiber.
Examples of fibers used in the present invention include cellulose fibers such as cotton and linen and derivatives thereof, regenerated fibers such as rayon, polyamide, polylactic acid, polyester, polyolefin, polyurethane, polyaramid, acrylic, triacetate, diacetate, cupra, and poly. Examples include, but are not limited to, synthetic fibers such as vinyl chloride, vinylidene, and polypropylene.
Among these fibers to be dyed, the effects of the present invention are remarkable when cotton or polyester fibers, which are usually difficult to dye with natural dyes, are used as dyed materials.

<Dyeing>
The dyed product of the present invention is a fiber characterized by being dyed by the dyeing method of the present invention, and the form thereof is arbitrary. That is, it may be in a yarn state, a fiber sheet such as woven fabric or non-woven fabric, or a final product such as clothing or rope. As for the dyeing method, the whole may be dyed uniformly by dipping, or the dye composition may be applied to the article to be dyed in a pattern to dye it as a printed product.
The dyed product obtained by the dye method of the present invention has the advantage of being excellent in fastness while utilizing the hue of the natural dye.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all by these Examples.

[Example 1-1]
<Adjustment of dye composition>
A base was prepared by mixing 100 g of a quaternary ammonium salt (manufactured by Ziontec Co., Ltd .: Thior HP: 3% aqueous solution: (B) component) with 2 g of water-soluble cellulose (Metroze: (D) component). Into this, put 300 ml of plant pigment bayberry extract (80% 45 minutes extract with 80% tap water mixed with 20% propylene glycol: component (A)) and 3 g reactive dye (Shinko, Remazole: component (C)) The mixture was stirred for 20 minutes while maintaining the temperature at 60 ° C. to obtain a dye composition. Further, 30 g of an algin paste (a paste containing 69.6% sodium alginate and 0.01% metal) was added to the dye composition for adjusting the viscosity.

<Dyeing: Printing method>
The obtained dye composition after adjusting the viscosity is applied in a pattern to a broad print (fiber sheet) made of cotton No. 60 single yarn to be dyed, dried, steamed at 100 ° C. for 10 minutes, and washed with water. The paste and the excess dye composition were removed and dried to obtain a dyed product. The obtained dyed product exhibited a dark hue of yellow lake derived from the extract of bayberry peach.
<Light fastness test>
When the obtained dyed product was subjected to a light fastness test in accordance with JIS L0842 (2010) third exposure method, it was grade 4 and light resistance without practical problems was obtained.
Moreover, although the wash fastness based on JIS L0844 (2010) A-1 was performed, fade was not recognized and it became the result of the 4th-5th grade, and the washing-resistance was a level which has no problem practically. It was.

<Dyeing: Immersion method>
In a stainless steel cylinder containing 30 l of water, 30 ml of a 25% aqueous solution of caustic soda was added, and the dye composition obtained in Example 1 was added with 10 / OWF (on water fabric) and stirred well.
The T-shirt was washed with water and charged into a cylinder containing the dye composition while containing water (mass of T-shirt: 150 g). The dye composition was stirred for 30 minutes while being heated and maintained at 70 ° C., and was subjected to immersion dyeing. Thereafter, it was washed with water and dried.
The dyed product (T-shirt) obtained was dyed evenly, and the color was different from that of the chemical dye alone, and it was a yellow lake hue characterized by the hue of the bayberry extract.
When the light fastness was applied in the same manner as in the printing method, it was grade 3, and the wash fastness carried out in the same manner was 4 'to 5 grade, both of which had no practical problem.

[Example 1-2]
A dye composition of Example 1-2 was obtained in the same manner except that the water-soluble cellulose as component (C) used in Example 1 was not used. Using this, it dye | stains by the immersion method in Example 1-1, and when the obtained dyeing | staining thing was evaluated similarly to Example 1-1, light fastness is a 3rd-4th grade, and wash fastness is good. The degree was 4th grade, and they were practically no problem. In addition, by contrast with Example 1-1, it was found that Example 1-1 using the component (C) has improved light fastness.
[Comparative Example 1]
A dye composition of Comparative Example 1 was obtained in the same manner except that the quaternary ammonium salt as the component (B) used in Example 1 was not used. Using this, it dye | stained by the immersion method in Example 1-1, and when the obtained dyeing | staining thing was evaluated similarly to Example 1-1, light fastness is 1, and wash fastness is 3 The grades were inferior, and were inferior and practically problematic.

[Example 2]
<Adjustment of dye composition>
A pace was prepared by mixing 1 ml of water-soluble sericin (silk powder solution: component (D)) with 1 ml of a quaternary ammonium salt (manufactured by Ziontech: Siol HP 25% aqueous sodium hydroxide solution). , 300 ml of plant dye 10% solution (cuttlefish fruit extract, mixed with 10% propylene glycol: component (A)) and 2 g of acid dye (Tanaka Naosha, acid dye: component (C)), 60 ° C. The mixture was stirred for 20 minutes while maintaining the temperature to obtain a dye composition. Furthermore, 25% of algin paste (salt containing 69.6% sodium alginate, 0.01% metal) was added to the dye composition for viscosity adjustment.

<Dyeing: Printing method>
The obtained dye composition after adjusting the viscosity is applied in a pattern to 20 匁 silk satin (fiber sheet) which is to be dyed, dried, steamed at 110 ° C for 10 minutes, washed with water, and the paste and extra The dye composition was removed and dried to obtain a dyed product. The obtained dyed product had a deep blue hue derived from gardenia dyes.
<Light fastness test>
A light fastness test was conducted on the dyed product in the same manner as in Example 1. As a result, it was grade 4 and light fastness having no practical problem was obtained.
Moreover, although the fastness to washing was carried out in the same manner as in Example 1, no fading was observed, resulting in a third grade, and the washing resistance was at a level causing no practical problems.
According to this method, it was found that the effect of improving the light fastness of the dyed product using natural dye on the silk fiber was observed.

[Example 3]
<Adjustment of dye composition>
10 parts by mass of quaternary ammonium salt (manufactured by Ziontec: Peciol CHP: trade name, 3% protein-containing aqueous solution: component (B)) with respect to 2 parts by mass of liquid polyester (modified polyester solution: component (D)) Part is heated to 130 ° C or higher and mixed to make a pace. In this base 50 ml, plant dye Kumazasa (dye in which magnesium in chlorophyll is replaced with copper: component (A)) 200 ml, disperse dye (powder) Of blue (Sumikaron Blue: manufactured by Sumitomo Chemical Co., Ltd.) and yellow (Sumikaron Yellow: manufactured by Sumitomo Chemical Co., Ltd.) 1.5 g dispersed in 10 times the amount of water mixed to prepare a green dye: ( Component C) 2 g and 148 ml of water were mixed and mixed while stirring at 60 ° C., and 0.5 g of citric acid was mixed to obtain a dye composition.

<Dyeing: Printing method>
The obtained dye composition is applied in a pattern to a polyester, regular 50-denier taffeta (fiber sheet) to be dyed, dried, steamed at 110 ° C. for 10 minutes, washed with water, Excess dye composition was removed and dried to obtain a dyed product. The obtained dyed product exhibited a dark yellowish green hue derived from the Kumazasa extract.
<Light fastness test>
The obtained dyed product was subjected to a light fastness test in the same manner as in Example 1. As a result, it was grade 3 and light resistance with no practical problems was obtained.
Moreover, although the fastness to washing was carried out in the same manner as in Example 1, no fading was observed, resulting in a third grade, and the washing resistance was at a level causing no practical problems.

[Comparative Example 2]
<Adjustment of dye composition>
To 300 ml of plant dye extract (Kuchinashi Blue: component (A)), 2 g of reactive dye (Shinko Co., Ltd .: Remazol Turquoise Blue: component (C)) dissolved in 10 times the amount of water was added, The mixture was stirred and mixed while maintaining the temperature at 60 ° C. to obtain a dye composition of Comparative Example 2.

<Dyeing: Immersion method>
The obtained dye composition is put into a stainless steel pan, and 30 g of a 50 cm × 50 cm cotton cloth (cotton 100%) as a material to be dyed is put therein, heated to 80 ° C. and stirred for 30 minutes. Immersion dyeing was performed. After confirming that the fabric had a pale blue color, the fabric was lifted. After that, when washed with water, the color of the cloth almost disappeared, and the vegetable dye, garden blue, was not dyed on the cloth.

[Examples 4-1 to 4-6]
<Adjustment of dye composition>
(Prescription 4 of dye composition)
・ 20% aqueous solution of acid dye [Nippon Kayaku, kayak: (C) component] 5ml
・ Plant dye [component (A): the following dye] 200ml
・ Cationic compound (manufactured by Ziontec: Siol CHP:
(B) component) 50 ml of aqueous solution
-Sericin [[D] component] 5% aqueous solution solid content 3g
・ Soda ash 15% aqueous solution 3ml
・ Separation regulator (dextrin) 20% aqueous solution 5ml
・ 44 ml of purified water

These were blended to 300 ml and stirred at 60 ° C. for 2 hours to obtain a dye composition. The types and hues of (A) natural dyes used in the formulation are shown below.
1. Natural pigment logwood (concentration 20%: blue expression)
2. Natural pigment rose (concentration 20%: pink expression)
3. Natural pigment grape skin (concentration 20%: purple expression)
4). Natural pigment walnut (concentration 20%: beige expression)
5. Natural pigment mulberry leaves (concentration 20%: green expression)
6). Natural pigment logwood (concentration 20%: gray expression)

  In addition, (C) the acidic dye was matched with a desired designated color, the ratio of the dye was determined by a beaker test, and then mixed to obtain a dye composition. Furthermore, 25% of algin paste (69.6% sodium alginate, 0.01% metal paste) was added to the resulting dye composition for viscosity adjustment. This was left to stand for 10 days.

<Dyeing: Printing method>
Using the obtained dye composition (Examples 4-1 to 4-6) after viscosity adjustment to 20 匁 silk decyne (silk 100%), which is the object to be dyed, using a curved printing pattern, The fabric was printed at 10 m to prepare a dyed product. Each of the six printings using the six colors of Examples 4-1 to 4-6 was printed by hand printing, and a six-color printing was performed. Thereafter, steam treatment was performed at 100 ° C. for 60 minutes, followed by washing with water to remove glue and excess dye and drying.
The obtained dyed product was visually observed, and there was no print unevenness in all six colors.
When the obtained dyed product was subjected to a light fastness test in the same manner as in Example 1, the print portion of any color tone was grade 4, and light resistance with no practical problems was obtained.

[Example 5]
(Prescription 5 of dye composition)
-Reactive dye [Procion, manufactured by Ziontec Corporation, 10% aqueous solution: component (C)]
4g in solid content
・ Plant dye [component (A): gardenia extract] 20% aqueous solution 390 ml
・ Cationic compound (manufactured by Ziontec: Siol CT: (B) component)
80ml aqueous solution
Water-soluble cellulose [manufactured by Shin-Etsu Chemical, Metroles 20% aqueous solution: component [D]]
5ml
・ Soda ash 15% aqueous solution 2ml
・ Separation regulator (dextrin) 20% aqueous solution 10ml
・ Purified water 9ml
These were mixed to make 500 ml, and stirred at 60 ° C. for 2 hours to obtain a dye composition of Example 5.

<Dyeing: Immersion method>
The obtained dye composition after viscosity adjustment (Example 5) was dyed to 280 g, 30 m of 165 cm width metery jersey of 100% cotton No. 40 single yarn as the article to be dyed. The apparatus used was a liquid flow machine (Hisaka liquid flow machine). As for the bath ratio, water having a bath ratio 30 times that of the article to be dyed was added. The weight of the article to be dyed was 8.6 kg, and the dye composition was dyed by the following procedure at 5% in OWF conversion.
First, the liquid dyeing machine was filled with water, the dough was wound on a cylinder and put into the dyeing machine, and the pieces were joined together. The water in the bath ratio was satisfied, the moisture was averaged on the dough, and then soda ash was added to adjust the Ph to 10. Slowly rotate and fully penetrate, then dissolve 500 ml of dye in 4500 ml of water and begin slowly. The temperature starts to rise after the machine begins to turn the color. The temperature is raised to 80 ° C. at a temperature rising rate of 5 ° C./1 minute, maintained at 80 ° C., rotated for 30 minutes, the liquid blown, and then added with a neutralizing agent (acetic acid) and further rotated for 20 minutes. . Blow again, add water 15 times the amount to be dyed, remove excess dye, rotate and blow for 30 minutes, lightly wash again, dehydrate, and dry with a tenter to obtain a dyed product .
When the obtained dyed product was observed with the naked eye, it was dyed in the light color of gardenia and there was no uneven dyeing.
The obtained dyed product was subjected to a light fastness test in the same manner as in Example 1. As a result, it was grade 3, was wash fastness 4-5, and had practically no light and wash resistance. Got.

[Example 6]
(Prescription 6 of dye composition)
Disperse dye [Nippon Kayaku, B-4, 10% aqueous solution: component (C)] 5 g in solid content
・ Plant dye [component (A): rack extract] 20% aqueous solution 100 ml
・ Cationic compound (manufactured by Ziontec Co., Ltd .: Pe-Chiol CHP: trade name:
(B) component) 60ml
・ Water-soluble polyester (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose, 10% aqueous solution: component (D))
2ml
・ Citric acid 15% aqueous solution 1ml
・ Separation regulator (ethylene glycol) 2ml
・ Purified water 30ml
These were blended to make 200 ml and stirred at 60 ° C. for 2 hours to obtain a dye composition of Example 6.

<Dyeing: Immersion method>
The viscosity-adjusted dye composition (Example 6) is a polyester product (T-shirt) to be dyed, and 10 T-shirts with the same quality as a polyester smooth jersey and neck-piped (weight of one). 200 g) The total was 2 kg. The addition amount of the dye composition was 200 ml of 10% OWF.
A Hisaka liquid flow machine was used as the staining apparatus. As for the bath ratio, water having a bath ratio 30 times that of the article to be dyed was added. The weight of the article to be dyed was 8.6 kg, and the dye composition was dyed by the following procedure at 5% in OWF conversion.
First, water was added to the dyeing apparatus, a T-shirt was put, and the mixture was rotated and stirred. Citric acid was added and the pH was adjusted to 5. Next, 200 ml of the dye composition is dissolved in 2000 ml of water, and slowly put into the water. The temperature starts to rise after the machine begins to turn the color. The temperature is raised to 100 ° C. at a temperature rising rate of 5 ° C./1 minute, and the liquid is blown while maintaining the temperature at 100 ° C. and rotated for 40 minutes. Thereafter, 30 liters of water, which is 15 times the amount to be dyed, was added and rotated at 60 ° C. for 10 plates, then dehydrated and dried with a tumbler dryer to obtain a dyed product.
As a result of visual observation, the obtained dyed product was dyed light red in the rack, and there was no uneven dyeing.
The obtained dyed product was subjected to a light fastness test in the same manner as in Example 1. As a result, it was grade 3, was wash fastness 4-5, and had practically no light and wash resistance. Got.

[Example 7]
<Adjustment of dye composition>
(Prescription 7 of dye composition)
・ Reactive dye 10% aqueous solution [manufactured by Shinko, Remazole: component (C)] 3 ml
・ Plant dye [component (A): the following dye] 400ml
・ Cationic compound (manufactured by Ziontec Co., Ltd .: Siol CHP: Brand name: (B) component) 80 ml
・ Water-soluble cellulose [manufactured by Shin-Etsu Chemical Co., Ltd., Metrose: [D] component] 10% aqueous solution 3 ml
・ Separation regulator (ethylene glycol) 10% aqueous solution 10ml
・ Purified water 4ml
These were blended to 500 ml and stirred at 60 ° C. for 2 hours to obtain a dye composition. The types and hues of (A) natural dyes used in the formulation are shown below.

1. Natural pigment logwood (concentration 20%: black expression)
2. Natural pigment rack (concentration 20%: pink expression)
3. Natural pigment pomegranate (concentration 20%: gray expression)
4). Natural pigment catechu (concentration 20%: tea expression)
5. Natural pigment golden flower (concentration 20%: yellow expression)
6). Natural pigment rack (concentration 20%: red expression)
7). Natural pigment betel wax (concentration 20%: beige expression)
8). Natural pigment olive green (concentration 20%: tea expression)

<Dyeing: Printing method>
The obtained dye composition after adjustment of viscosity (Examples 7-1 to 7-8) is printed by printing a dyed article to be dyed, 100% cotton No. 60 single yarn loan, 130 cm wide meter basis weight of 55 g, 30 m. Stained.
That is, the obtained eight-color dye composition after adjusting the viscosity (Examples 7-1 to 7-8) was printed on a 60-single yarn loan fabric to be dyed using a pattern for printing. Each of the dyes was printed on eight plates using the eight colors of Examples 7-1 to 7-8 and printed in eight colors. Thereafter, steam treatment was performed at 100 ° C. for 60 minutes, and then washing with water was performed to remove glue and excess dye, followed by drying.
When the obtained dyed article was visually converted, there was no print unevenness.
When the obtained dyed product was subjected to a light fastness test in the same manner as in Example 1, all samples were grade 4 and light resistance with no practical problems was obtained.

  As described above, according to this example, the dye composition and the dyeing method of the present invention can provide a desired colored product with excellent fastness even when a natural dye is used by a simple method. I understand. Furthermore, from the results of the examples, improvement of light resistance of dyed products by combination of natural dyes and silk fibers, which has been difficult in the past, improvement of light resistance of dyed products by low-temperature treatment of 100 to 110 ° C. on polyester fibers It can be seen that is achieved.

DESCRIPTION OF SYMBOLS 10 Dye aggregate 12 (D) Homogeneous powder 14 (B) Adsorption adjuvant 16 (A) Natural dye 18 (C) Chemical dye 20 Fiber (to be dyed)

Claims (7)

  (A) a plant-derived natural dye, (B) a natural dye adsorption aid selected from the group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt, and (C) a reactive dye, an acid dye, and vat dye A dye composition comprising: a chemical dye selected from the group consisting of a dye and a disperse dye.   The dye composition according to claim 1, further comprising (D) a solution or dispersion of a water-soluble powder having the same or similar chemical structure as the fiber to be dyed. (A) a solution or dispersion of a plant-derived natural dye, (B) a solution or dispersion of a natural dye adsorption aid selected from the group consisting of a cationic compound, an ammonium salt compound, and an alkali metal salt, and (C A solution or dispersion preparation step for preparing a solution or dispersion of a chemical dye selected from the group consisting of a reactive dye, an acid dye, a vat dye, a direct dye and a disperse dye,
Mixing each obtained solution or dispersion to obtain a dye composition;
And a step of applying the obtained dye composition to a fiber, in this order.   4. The dye composition according to claim 3, wherein the dye composition is a composition obtained by further mixing (D) a solution or dispersion of a water-soluble powder having the same or similar chemical structure as the fiber to be dyed. Dyeing method.   The dyeing method according to claim 3 or 4, wherein the step of applying the dye composition to the fiber is a step of immersing the fiber to be dyed in the dye composition.   The dyeing method according to claim 3 or 4, wherein the step of applying the dye composition to fibers is a step of applying the dye composition to a sheet made of fibers that are to be dyed.   The dyed material dye | stained by the dyeing | staining method of any one of Claims 3-6.