JP6326459B2 - Deep-colored cloth and clothing - Google Patents

Description

  The present invention relates to a deep color treated cloth and clothes. More specifically, the present invention relates to a deep-colored cloth and a garment in which a dyed cloth is deepened by coating with a deep-colored resin.

  Traditionally, there has been a demand to process deep colors while maintaining the color of dyed fabrics. In normal dyeing, as the dye concentration increases, the saturation and density of the resulting dyed fabric increases. However, when the dye concentration reaches a predetermined concentration, even if the dye concentration is increased further, the saturation and density of the dyed fabric will not increase, and the dyeing effect will be saturated. In the case of a chromatic color, as the dyeing effect is further increased, the dyed fabric color gradually becomes dull as the dye concentration is further increased. Therefore, it is known that there is a limit in obtaining a deep color feeling only by dyeing.

  In order to solve this problem, a processing method called deepening is known as a method for obtaining a deep color feeling while maintaining color. Various methods are included in the deep color treatment. Among them, a method of suppressing surface reflection by attaching a resin having an optically low refractive index to the fiber surface is known. As a technique related to such a deep color processing, a technique disclosed in the following Patent Documents 1-3 is known. In addition, about the technique which ozone-treats animal hair fiber, the technique disclosed by the following patent documents 4-5 is known.

Japanese Patent Laid-Open No. 11-267971 JP 2006-200098 A JP 2004-360137 A JP 2001-164460 A JP 2003-293258 A

Patent Document 1 discloses a deep color treatment method using a predetermined deep color resin, which can be used for wool fibers. Patent Document 2 discloses a method that is optimized by controlling the pH of a treatment liquid containing a deep colorant when using a deep color resin, and can be used for wool fibers. . However, these Patent Documents 1 and 2 do not mention any pretreatment of the cloth to be treated.
Moreover, in the said patent document 3, after pre-processing using a cationic polymer resin, it dyes | stains and performs deep color processing after that, compared with the case where the said pre-processing is not performed, it is a deep color characteristic. Is disclosed. However, the method of Patent Document 3 is to coat a deep color resin after coating a cationic polymer resin as a pretreatment for the fibers. In such a method, since multiple layers of resin coating are required, a fabric using animal hair fibers may significantly reduce significant characteristics inherent in animal hair fibers.

  Further, Patent Document 4 discloses that anti-pilling property (hair-balling) is achieved by spraying a treatment liquid containing ultrafine bubbles of ozone onto animal hair fibers to chemically modify the epidermal tissue of the animal hair fibers. A method for improving difficult properties is disclosed. Moreover, the said patent document 5 is disclosing the processing apparatus for performing an ozone treatment in order to improve the shrink-proof property and anti-pilling property of animal hair fiber. However, Patent Document 4 and Patent Document 5 show that ozone treatment contributes to anti-pilling properties, but no investigation has been made on the effect of deep coloration.

  The present invention has been made in view of the above circumstances, and is a fabric that is dyed after being subjected to ozone treatment and then deepened, and has a deep color property superior to that of the prior art. It is an object of the present invention to provide a deep color treated cloth and a garment using the deep color treated cloth.

The present invention is as follows.
The deep color-treated cloth of claim 1 is a deep-colored cloth in which the surface of animal hair fibers constituting the dyed cloth is coated with a deep-colored resin,
The gist of the animal hair fiber is that it has vertical corrugated surface irregularities and does not have scale pieces arranged in a Matsukasa shape constituting the scale .
A deep color treated cloth according to claim 2 is characterized in that the deep color treated cloth according to claim 1 is dyed black, red or purple.
The deep-colored treated cloth according to claim 3 is the deep-colored treated cloth according to claim 1 or 2, wherein the dyeing is reactive dyeing or acid mordant dyeing.
The garment of claim 4 is characterized by using the deep color treated cloth according to any one of claims 1 to 3.
The garment of claim 5 is the garment of claim 4 , wherein the garment is a formal garment.

The deep color treated cloth of the present invention is a deep color treated cloth obtained by deeply treating a dyed dyed cloth after contacting the cloth with a treatment liquid in which ozone is bubbled. In such a deep-colored cloth, a deep color property superior to the conventional product can be obtained. That is, a particularly small lightness L * value can be obtained.
In the above deep color-treated cloth, when the cloth is a knitted fabric and the mass ratio of the animal hair fibers contained in the woven fabric is 50% by mass or more, a deepening effect by the deep color treatment can be obtained more sufficiently. Can do.

The manufacturing method of the deep-colored treatment cloth includes an ozone treatment process in which a cloth containing animal hair fibers is brought into contact with a treatment liquid in which ozone is bubbled,
A dyeing process of dyeing an ozone-treated cloth into a dyed cloth;
A deepening step of coating the surface of the animal hair fiber constituting the dyed cloth with a deepening resin.
In this method, by providing the above steps in a predetermined order, it is possible to manufacture a deep color treated cloth having deep color properties superior to those of conventional products. That is, it is possible to manufacture a deep color treated cloth having a particularly small lightness L * value.
In this method, in the case where a pre-oxidation step in which the cloth is brought into contact with the oxidizing agent aqueous solution is provided before the ozone treatment step, it is possible to obtain further excellent deep color properties as compared with the case where the pre-oxidation step is not provided. .
In this method, when the fabric is a knitted fabric and the mass ratio of the animal hair fibers contained in the woven fabric is 50% by mass or more, a deep color effect by the deep color treatment can be more sufficiently obtained.
According to the clothes of this invention, it can be set as the clothes which had the deep color property excellent compared with the conventional product. That is, it is possible to obtain a garment using a fabric having a lightness L * value that is smaller than that of a conventional product.

It is an enlarged image by the electron microscope which concerns on Experimental example 5. FIG. It is an enlarged image by the electron microscope which concerns on Experimental example 1. FIG. It is an enlarged image by the electron microscope which concerns on the experiment example 30. FIG. It is an enlarged image by the electron microscope which concerns on the experiment example 31. FIG. It is an enlarged image by the electron microscope which concerns on Experimental example 6. FIG. It is an enlarged image by the electron microscope which concerns on Experimental example 7. FIG. It is an enlarged image by the electron microscope which concerns on Experimental example 8. FIG. It is an enlarged image by the electron microscope which concerns on the experiment example 9. FIG. It is an enlarged image by the electron microscope which concerns on Experimental example 10. FIG. It is an enlarged image by the electron microscope which concerns on Experimental example 11. FIG.

[1] Deep color treatment cloth The deep color treatment cloth of the present invention is a deep color treatment cloth in which the surface of animal hair fibers constituting the dyed cloth is coated with a deep coloration resin,
Animal hair fibers are characterized in that they have surface irregularities in the form of vertical hooks, and do not have scale pieces arranged in a Matsukasa shape constituting the scale .

The form of the cloth used in the present invention is not limited, and any cloth may be used. For example, it may be a knitted fabric, a non-woven fabric, or a fabric of another form. Among these, a woven fabric is preferable. Examples of the knitted fabric include woven fabric (woven fabric), knitted fabric (knitted fabric), and other knitted fabrics. Among these, a woven fabric is preferable. Furthermore, although the fabric weight of the cloth to be used is not particularly limited, a cloth of about 80 to 500 g / m ² is preferable because it is easy to handle, and further, a cloth of 100 to 400 g / m ² , particularly 150 to 300 g / m ^2. Is preferred.

The cloth used in the present invention contains at least animal hair fibers as described above. Since the ozone treatment described later acts on animal hair fibers, a deep coloration effect can be obtained with a cloth containing animal hair fibers compared to a cloth not subjected to ozone treatment.
Examples of animal hair fibers include wool, cashmere, mohair, camel, alpaca, llama, vicuna, guanaco, and angora. These may use only 1 type and may use 2 or more types together.
The animal hair fiber contained in the cloth may be contained in the cloth in any form, but is usually contained as a yarn constituting the cloth. This yarn may be an animal hair fiber yarn formed only from animal hair fibers, or may be an animal hair fiber mixed yarn containing both animal hair fibers and other fibers.
In the case of a mixed yarn, the form of the yarn is not particularly limited and includes, for example, a blended yarn and a twisted yarn. Further, a covered yarn or a decorative yarn (design twisted yarn) in which other fibers are used as the core yarn and the periphery of the core yarn is covered with animal hair fibers are included. These various yarns may use only 1 type and may use 2 or more types together.

The animal hair fiber contained in the yarn constituting the cloth is preferably as high as possible in the present invention. Specifically, the mass ratio of animal hair fibers contained in the yarn is preferably 30% by mass or more (100% by mass or less) with respect to 100% by mass of the entire yarn. In this range, it is possible to more reliably enjoy the effect of deepening colors by using a fabric that has been subjected to ozone treatment. The mass ratio of the animal hair fibers is more preferably 50% by mass or more, and further preferably 70% by mass or more.
Moreover, it is preferable that 30 mass% or more (100 mass% or less) animal hair fiber is contained with respect to 100 mass% of the whole cloth with respect to the whole cloth, 50 mass% or more is more preferable, and 70 mass%. The above is more preferable.

The yarn constituting the cloth may be composed only of the yarn containing the animal hair fiber described above, or the yarn containing the animal hair fiber and the yarn not containing the animal hair fiber may be used in combination. That is, as a knitted fabric, an interwoven fabric in which a yarn containing animal hair fibers and a yarn not containing animal hair fibers are used in combination, and a yarn containing animal hair fibers and a yarn not containing animal hair fibers are used in combination. Includes knit fabric.
Examples of fibers that do not contain animal hair fibers (including other fibers used as the above-described core yarn) include fibers derived from organisms other than animal hair fibers, synthetic fibers, semi-synthetic fibers, and regenerated fibers. .
Among the above, examples of fibers derived from other organisms include fibers collected from silk cocoons, and fibers derived from plants such as cotton, hemp, and flux. Examples of synthetic fibers include polyester fibers, nylon fibers, acrylic fibers, urethane fibers, and the like. Furthermore, acetate fiber is mentioned as a semisynthetic fiber. An example of the regenerated fiber is rayon. Only 1 type may be used for the fiber which does not contain these animal hair fibers, and 2 or more types may be used together.

In dyeing, various dyes can be used, and the kind is not particularly limited. Examples of the dye include acid dyes, mordant dyes, reactive dyes, basic dyes, metal complex dyes, direct dyes, vat dyes, sulfur dyes, and disperse dyes. These may use only 1 type and may use 2 or more types together. Among these, acidic dyes, mordant dyes, reactive dyes, basic dyes, metal complex dyes and the like are preferable from the viewpoint of dyeability and durability to animal hair fibers. Furthermore, among these, an acid mordant dye and a reactive dye having both characteristics of an acid dye and a mordant dye are more preferable.
The acidic dye is a dye having an acidic group such as a —SO ₃ ^— group and a —COO ^— group. The mordant dye is a dye that forms an insoluble complex salt with a dye using a mordant containing a metal element such as Cr, Al, Fe, and Sn. Furthermore, the acid mordant dye refers to a dye having both of these characteristics. In the present invention, the acid mordant dye is preferably an acid mordant dye using Cr mordant.
On the other hand, the reactive dye is a dye that is dyed by forming a covalent bond with animal hair fibers. That is, the reactive dye usually has a reactive group in its structure that can be bonded to groups such as —NH ₂ group, —OH group, and —SH group of animal hair fiber.

  Further, the ozone treatment will be described in detail later, but this is a treatment in which the fabric before dyeing is brought into contact with a treatment liquid in which ozone is bubbled. By performing this treatment, although the reason is not clear, deepening of the color is remarkably improved as compared with the case where the ozone treatment is not performed. This ozone treatment is used as a scale treatment method, but an excellent deep color can be obtained as compared with the case where a chlorination treatment known as a similar scale treatment method is performed.

The deep color resin used in the deep color treated cloth of the present invention is a resin that makes the reflectance of the dyed cloth surface after coating smaller than the reflectance of the dyed cloth surface before coating. Specifically, the deepening resin for the dyed cloth dyed black is preferably a resin that can reduce the reflectance with respect to light in the entire wavelength range of visible light (for example, wavelength 400 to 700 nm). In addition, the deepening resin for dyed cloth dyed in other chromatic colors (red, blue, green, yellow, etc.) must be a resin that can reduce the reflectance in the maximum absorption wavelength range for light in the visible light range. However, as in the case of the black color, a resin capable of reducing the reflectance with respect to light in the entire wavelength region of visible light can also be used.
As such a deep color resin, a resin having a refractive index of 1.50 or less is usually used. Specifically, a fluorine resin, a silicone resin, a urethane resin, or the like can be given.

Among the above, the fluororesin is a resin having a fluoroalkyl group. That is, it is a resin having a group having a structure in which one or two or more hydrogen atoms in an alkyl group are substituted with fluorine atoms. Examples of the fluoroalkyl group include a fluoromethyl group such as a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group, a fluoroethyl group such as a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. Can be mentioned. These fluoroalkyl groups may use only 1 type and may use 2 or more types together.
The structural unit forming the skeleton structure of the fluororesin is not particularly limited. For example, unsaturated organic acids such as acrylic acid, methacrylic acid and maleic acid, ethylene, butene, 2-methyl-1-propene, 3-methyl Examples include structural units derived from aliphatic vinyl compounds such as -1-pentene, butadiene and isoprene, and aromatic vinyl compounds such as styrene and divinylbenzene. These structural units may use only 1 type and may use 2 or more types together.

  Among the above, the silicone resin is a polysiloxane compound having a main skeleton of a siloxane bond. Specific examples include polydimethylsiloxane, methyl hydrogen polysiloxane, methylphenyl polysiloxane, and various modified products thereof. Among these, modified products include amino-modified products, epoxy-modified products, polyether-modified products, alkyl-modified products, fluoroalkyl-modified products, and carboxyl-modified products. These polysiloxane compounds may be used alone or in combination of two or more.

Among the above, the acrylic resin is a resin having a structural unit derived from acrylic acid, methacrylic acid, and ester derivatives thereof. In addition to this, acrylic resins include aliphatic vinyl compounds such as ethylene, butene, 2-methyl-1-propene, 3-methyl-1-pentene, butadiene and isoprene, and aromatic vinyl compounds such as styrene and divinylbenzene. And the like derived from structural units. These structural units may use only 1 type and may use 2 or more types together.
The urethane-based resin is a polyurethane compound having a main skeleton of urethane bonds. For example, it can be obtained as a reaction product of a polyol and a polyisocyanate. Among these, examples of the polyol include polyether polyol, polyester polyol, epoxy-modified polyol, acrylic-modified polyol, and silicone-modified polyol.

[2] Method for producing deep color treated cloth The method for producing a deep color treated cloth includes an ozone treatment step, a dyeing step, and a deep coloration step.

The “ozone treatment step” is a step of bringing a cloth containing animal hair fibers into contact with a treatment liquid in which ozone is bubbled.
The treatment liquid used in this step only needs to be bubbled with ozone, and the type of the liquid medium is not limited. For example, water, an alcohol-based liquid medium, other organic liquid medium, and the like can be used, and water is particularly preferable from the viewpoint of safety.

In this step, normally, ozone generated using an ozone generator is drawn into the processing liquid to form a state in which the processing liquid is bubbled with ozone. And the process liquid and the cloth (cloth before dyeing | staining) in which ozone was bubbled are made to contact. The contact method between the treatment liquid and the cloth is not particularly limited. For example, the treatment liquid may be sprayed on the cloth, the cloth may be immersed in the treatment liquid, and further, the cloth may be contacted by other methods. Good. Among these, the method of immersing the cloth in the treatment liquid is preferable. That is, it is preferable that the cloth is immersed in a treatment liquid in which ozone is bubbled to bring the cloth and the treatment liquid into contact with each other.
Furthermore, the cloth immersed in the treatment liquid may be left as it is, but the cloth and the treatment liquid are more positively contacted by flowing the treatment liquid or moving the cloth in the treatment liquid. More preferably, it is preferable to move at least one of the cloth and the treatment liquid to the extent that the treatment liquid can pass from one side of the cloth to the other side by liquid pressure.

  Further, when ozone is bubbled, bubbles can be broken in order to reduce the bubble diameter in the treatment liquid. That is, for example, after the treatment liquid into which ozone has been drawn is passed through the line mixer, the treatment liquid that has passed through the line mixer can be brought into contact with the cloth. By doing so, it is possible to bring the ozone into contact with the cloth, which has been broken in the line mixer and has a smaller bubble diameter. Furthermore, by drawing ozone from a plurality of systems into the processing liquid and making the drawn ozone jets flow relative to each other, the bubbles of ozone can collide with each other in the processing liquid, and the bubbles of ozone can be broken. Even in this case, the ozone can be brought into contact with the ozone, which has been broken in the same manner as described above, and has a smaller bubble diameter.

In this ozone treatment step, the contact condition between the cloth and the ozone treatment liquid is not particularly limited, but it is preferable to use a treatment liquid having a temperature of 0 to 90 ° C. The temperature of the treatment liquid is more preferably 0 to 60 ° C, and particularly preferably 10 to 40 ° C. In addition, the pH of the treatment liquid is preferably 12 or less, preferably 6 or less, and more preferably 1 or 2.
The amount of ozone gas introduced into the treatment liquid is not particularly limited, but is preferably 0.005 to 1 L / min with respect to 1 L of the treatment liquid. The introduction amount is more preferably 0.01 to 0.1 L / min, and particularly preferably 0.01 to 0.05 L / min.
Furthermore, the contact time between the ozone treatment liquid and the cloth is not particularly limited, but is preferably 0.5 to 120 minutes. The contact time is more preferably 1 to 30 minutes, and particularly preferably 1 to 5 minutes.

Prior to the ozone treatment step, a pre-oxidation step for pre-oxidizing animal hair fibers contained in the cloth can be provided before the ozone treatment step. That is, in this method, a pre-oxidation process and an ozone treatment process can be provided in this order.
By providing the preliminary oxidation step, it is possible to prompt the ozone to act on the animal hair fibers in the subsequent ozone treatment step. That is, impurities that consume an oxidizing agent other than animal hair fibers are attached to the cloth. Therefore, by performing a preliminary oxidation process, these impurities can be oxidized beforehand, and it can suppress that an impurity consumes ozone in an ozone treatment process. Therefore, the treatment result in the ozone treatment process can be stabilized by providing the preliminary oxidation process.

In addition, by performing the preliminary oxidation step, the unevenness formed by the scale on the surface of the animal hair fiber can be effectively reduced in the subsequent ozone treatment step. The scale is a plurality of scale pieces (see FIG. 7) arranged in a Matsukasa shape on the surface of the animal hair fiber. The scale is arranged on the hair root side of the animal hair fiber so as to overlap with the other scale, while the edge is open (exposed) to the surface of the animal hair fiber on the hair tip side. Therefore, the untreated animal hair fiber surface has regular unevenness due to the edge of the hair end side of the scale. That is, this unevenness is an unevenness formed by the scale described above. In this method , it is difficult to sufficiently reduce the unevenness due to the scale only by the ozone treatment step, but the unevenness formed by the scale can be effectively reduced by performing preliminary oxidation. And the value of the brightness (L *) obtained can be suppressed small by making the unevenness | corrugation by a scale small. That is, more excellent deep color can be obtained.

In this method , Examples described later (Experimental Examples 1 and 7, Experimental Examples 9 and 10, Experimental Examples 12 and 14, Experimental Examples 15 and 16, Experimental Examples 17 and 18, Experimental Examples 20 and 21, Experimental Examples 23 and 24) As shown in each comparison of Experimental Examples 26 and 27), for example, as a scale treatment method, oxidation treatment is performed using a conventionally known chlorination treatment, and then the cloth subjected to oxidation treatment is dyed. It is also possible to obtain a deep-colored cloth by performing a deep color treatment. However, the deep color-treated cloth obtained by using the cloth that has been subjected to the ozone treatment is more excellent in deep color than the deep color-treated cloth thus obtained. Even if the oxidation treatment is the same, it is not clear why the deep color property is improved by the ozone treatment compared to the chlorination treatment.

However, as shown in Examples described later, when ozone treatment is performed (Experimental Example 5 (FIG. 1), Experimental Example 1 (FIG. 2)), when chlorination treatment is performed (Experimental Example 7 (FIG. 1)). Compared with 6)), a phenomenon in which the unevenness due to the scale becomes smaller is observed.
Further, when ozone treatment is performed after performing the preliminary oxidation step (Experimental Example 1 (FIG. 2), Experimental Example 30 (FIG. 3), Experimental Example 31 (FIG. 4)), only ozone treatment is performed. Compared with (Experimental example 5 (FIG. 1)), a phenomenon in which the unevenness due to the scale is further reduced is observed.
In the experimental example in which the unevenness due to the scale is small, a phenomenon in which the deep color property is improved is recognized as compared with the experimental example in which the unevenness is large.
That is, the experimental example 5 (L * = 9.35) and the experimental example 1 (L * = 9.24) treated with ozone compared to the experimental example 7 (L * = 11.09) treated with chlorination. The unevenness due to the scale is small, and the L * value is also small. Similarly, Experimental Example 1 (L * = 9.24) and Experimental Example 29 (L * = L) where the preliminary oxidation process was performed compared to Experimental Example 5 (L * = 9.35) where the preliminary oxidation process was not performed. 9.28) In Experimental Example 30 (L * = 9.06), the unevenness due to the scale is small, and the L * value is also small. From these results, it is considered that deep color properties can be effectively improved by selecting a method capable of making the unevenness due to the scale smaller in the oxidation treatment.

However, as shown in Examples described later, when the ozone treatment is performed after excessive preliminary oxidation, the unevenness of the scale can be almost eliminated (Experimental Example 31 (FIG. 4)). However, when the oxidation proceeds to such an extent that the scale irregularities are removed, the surface of the animal hair fiber becomes a smooth surface comparable to the synthetic fiber. When such an excessively smooth surface is formed, the deep color of the resulting deep color-treated cloth is obtained when moderately pre-oxidized (Experimental Example 1 (FIG. 2), Experimental Example 5 (FIG. 1). ) And Experimental Example 30 (FIG. 3)). For this reason, it is preferable to perform the preliminary oxidation rather than not to perform it, and it is preferable to keep it at a moderate level of oxidation rather than excessively.
Whether or not the oxidation is appropriate varies depending on the type and form of the animal hair fiber, but it is preferable that the surface irregularities of the animal hair fiber not caused by the scale remain. That is, it is preferable that the large unevenness caused by the scale is made as small as possible while the small unevenness caused by the scale is left. This control can be adjusted by the concentration of the oxidizer aqueous solution in the preliminary oxidation step.

In the pre-oxidation step, an aqueous oxidant solution in which a water-soluble oxidant is dissolved is brought into contact with the cloth to pre-oxidize the animal hair fibers constituting the cloth. Ozone used in the aforementioned ozone treatment process generally has a stronger oxidizing action than water-soluble oxidants. However, since it is hardly dissolved in water, it is considered that strong oxidation occurs on the surface of the animal hair fiber in the ozone treatment process. On the other hand, since the pre-oxidation step uses an oxidant dissolved in water, the oxidant can easily penetrate into the fiber. And compared with ozone treatment, although oxidation by a water-soluble oxidant proceeds slowly, it is considered that oxidation can be applied to the inside of animal hair fibers. That is, both the ozone treatment process and the pre-oxidation process can be regarded as oxidation processes, but the actions and effects of these processes on animal hair fibers are different.
In the pre-oxidation step, pre-oxidation of animal hair fibers can be promoted by exposure to an oxygen-containing environment (such as the atmosphere) or heating after contact with the oxidant aqueous solution.

The solvent constituting the oxidizer aqueous solution contains at least water, but may contain other solvents miscible with water, such as alcohol, if necessary. The oxidizing agent aqueous solution usually contains 50% by mass or more of water with respect to 100% by mass of the whole solvent.
Examples of the water-soluble oxidant include persulfuric acid, persulfate, hydrogen peroxide, peracetic acid, peracetate, formic acid, and formate. These may use only 1 type and may use 2 or more types together.
Of these oxidizing agents, persulfates are preferred. Examples of the persulfate include potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate, and sodium persulfate. These may use only 1 type and may use 2 or more types together. Of these, potassium hydrogen persulfate is preferred.

When potassium hydrogen persulfate is used as the oxidant, the concentration of potassium hydrogen persulfate is preferably 0.1 to 20 g / L when the reaction is completed in the treatment bath, and preferably 0.5 to 10 g / L. Is more preferable, and 1-3 g / L is particularly preferable. In the case of exposure to the atmosphere after contact with the oxidizing agent aqueous solution, 5 to 200 g / L is preferable, 10 to 150 g / L is more preferable, and 30 to 100 g / L is particularly preferable.
Furthermore, the temperature of the oxidizing agent aqueous solution is preferably 0 to 80 ° C, more preferably 5 to 60 ° C, and particularly preferably 10 to 50 ° C.

Furthermore, a reduction treatment process can be provided after the ozone treatment process. That is, in this method, the preliminary oxidation step, the ozone treatment step, and the reduction treatment step can be provided in this order.
In the reduction treatment step, the cloth can be immersed in a reducing agent solution in which the reducing agent is dissolved, and the animal hair fibers constituting the cloth can be reduced.
Although the solvent which comprises a reducing agent solution is not specifically limited, Usually, water is used. Further, as the reducing agent, sulfite, bisulfite, thiosulfate, or the like can be used. These may use only 1 type and may use 2 or more types together.
Of these reducing agents, sulfites are preferred. Examples of sulfites include sodium sulfite, potassium sulfite, ammonium sulfite, and calcium sulfite. These may use only 1 type and may use 2 or more types together. Of these, sodium sulfite is preferable.
When using sodium sulfite, although the density | concentration of a reducing agent solution is not specifically limited, For example, it can be set as 1-80 g / L. This concentration is preferably 5 to 40 g / L. Moreover, 0-90 degreeC is preferable and the temperature of a reducing agent solution has more preferable 10-80 degreeC.

The “dyeing step” is a step of dyeing an ozone-treated cloth to obtain a dyed cloth. In the dyeing step, the various dyes exemplified above can be dyed under conditions suitable for each. Among them, the acid mordant dye and the reactive dye are preferable as described above. That is, it is preferable to perform acid mordant dyeing or reactive dyeing.
As a mordant for acid mordanting, a metal salt that is soluble in water (water-soluble metal salt) is preferable. Such a metal salt may be an ionic salt or a complex salt. These may be used alone or in combination.
As the base constituting the metal salt, bases derived from various inorganic acids and organic acids can be used. These may be used alone or in combination. Of these, examples of the inorganic acid include sulfuric acid, hydrochloric acid, and nitric acid, and examples of the organic acid include acetic acid and succinic acid. These may be used alone or in combination. Examples of the complex salt ligand include ethylenediaminetetraacetic acid.
Furthermore, examples of the metal element constituting the metal salt include Cr, Fe, Cu, Al, Ti, Sn, etc. Among them, Cr is preferable. These may be used alone or in combination.

  In the dyeing process, any method such as dip dyeing, printing, and other methods may be used for dyeing. Further, the contact between the cloth and the mordant and the contact between the cloth and the dye may be performed first. That is, the mordanting may be performed by pre-mordanting or post-mordanting.

The “deep coloration step” is a step of coating the surface of the animal hair fibers constituting the dyed cloth with a deep color resin. In general, a deep colorant containing a deep color resin is diluted with water as a medium so as to obtain a suitable concentration, a deep color treatment solution is prepared, and immersed in this deep color treatment solution. Do it. The soaked cloth is coated with a deep color resin.
Further, the deepening process may include a fixing process in order to fix the deepening resin coated with the animal hair fibers on the surface of the animal hair fibers. The fixing of the deep color resin is preferably an appropriate method in accordance with the characteristics of the deep color resin to be used, but can be fixed by heating, for example.
In addition to the deepening resin, various additives can be added to the deepening treatment liquid. Examples of the additive include a deep color improver, a crosslinking agent, a fastness fastness agent, an antifoaming agent, a chelating agent, a leveling agent, a stabilizer, and an inorganic salt. These may use only 1 type and may use 2 or more types together.

Furthermore, various water-soluble acids and bases can be blended for the purpose of adjusting the pH of the deep color treatment solution. Examples of the water-soluble acid include organic acids such as formic acid, acetic acid and maleic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. These may use only 1 type and may use 2 or more types together.
Examples of the base in the aqueous solution include inorganic bases such as sodium carbonate, sodium phosphate, sodium hydroxide, and ammonia, and organic bases such as alkylamine and alkanolamine. These may use only 1 type and may use 2 or more types together.

[3] Clothes using a deep color treated cloth The clothes of the present invention are characterized by using the above-described deep color treated cloth of the present invention. Specifically, clothes used in various dresses, mourning, etc. can be mentioned. In other words, dressing clothes, mourning clothes and the like are included. Among these clothes, it is particularly suitable for formal use. That is, it can be a formal garment. Formal clothes include formal clothes and mourning clothes.

Hereinafter, the present invention will be described specifically by way of examples.
[1] Manufacture of deep color-treated cloth Using the following various cloths (C1-C6), various combinations described in Table 1 to Table 3 (pre-oxidation process, ozone treatment process, reduction treatment process, chlorination) The treatment process and the dyeing process) were performed to obtain a deep color treated cloth of Experimental Example 1-31. The results are shown in Tables 1 to 3.

<1> Cloth type C1 used in Table 1 to Table 3 above: Woven fabric containing 87% by weight of wool and 13% by weight of polyester (original yarn) (a plain weave of warp 50 count single yarn, weft 50 count single yarn, 165 g / m ²
C2: Woven cloth (warp 60 count double yarn, containing 99% by weight of wool and 1% by weight of nylon (original yarn)
Twill weave with 60 weft yarns, basis weight 225g / m ² )
C3: Woven fabric containing 95% by weight of wool and 5% by weight of silk (original yarn) (warp 72nd double yarn, weft 72nd double yarn twill, basis weight 230g / m ² )
C4: Woven fabric consisting only of wool (warp 72nd weft, weft 72nd weave, weave 19
5g / m ² )
C5: Woven fabric containing 99.7% by weight of wool and 0.3% by weight of carbon fiber (warp 72nd double yarn, weft 48th single yarn twill, basis weight 235g / m ² )
C6: Woven fabric containing 77% by weight of wool and 23% by weight of polyester (original yarn) (warp 70 count single yarn, weft 70 count single yarn plain weave, basis weight 170 g / m ² )

<2> Steps used in Table 1-3 above (1) Pre-oxidation step An aqueous oxidizer solution containing potassium hydrogen persulfate and a surfactant is prepared, and the types of cloth shown in Table 1-3 are prepared with this aqueous oxidizer solution. Pre-oxidized. In Table 1-3, “◯” is shown for the experimental example in which the pre-oxidation process was performed, and “-” is shown for the experimental example in which the pre-oxidation process was not performed.
In each of the experimental examples in Tables 1 and 2, an aqueous solution containing 1.5 g / L potassium hydrogen persulfate and a 0.2 g / L surfactant was prepared as an oxidizing agent aqueous solution. Then, the amount of the oxidant aqueous solution was adjusted to 1:20 in the ratio of cloth weight: oxidant aqueous solution weight, and the cloth was immersed for 40 minutes at a liquid temperature of 50 ° C.
In Experimental Examples 29-31 in Table 3, potassium hydrogen persulfate having a concentration of 50 g / L in Experimental Example 29, a concentration of 100 g / L in Experimental Example 30, a concentration of 200 g / L in Experimental Example 31, and 2 g / L, respectively. An aqueous solution containing a surfactant having a concentration was prepared as an aqueous oxidizer solution. Then, after dipping the cloth for 2 seconds at a liquid temperature of 20 ° C., the aqueous oxidizer solution contained in the cloth was squeezed with a roll.

(2) Ozone treatment process The cloth (the cloth which performed the preliminary oxidation process, or the cloth which has not performed the preliminary oxidation process) was immersed in the aqueous solution adjusted to pH 1.6 or less using sulfuric acid. Then, ozone-treated water bubbled with ozone gas adjusted to a concentration of 100 g / m ³ was sprayed on a cloth (width 50 cm) for 3.5 minutes at a flow rate of 1.5 L / min. Subsequently, the ozone treatment liquid was sprayed on the back surface in the same manner for 3.5 minutes. Thereafter, the cloth was washed with water. In Table 1-3, “◯” is shown for the experimental example in which the ozone treatment process was performed, and “−” was shown for the experimental example in which the ozone treatment process was not performed.

(3) Reduction treatment step An aqueous solution containing 20 g / L sodium sulfite was prepared as a reducing agent solution. Further, the amount of the reducing agent solution was adjusted to be 1:20 in the ratio of cloth weight: solution weight, and the cloth was immersed in the reducing agent solution adjusted to a temperature of 50 ° C. for 20 minutes. Then, the cloth pulled up from the reducing agent solution was washed with water. Further, after washing with water, the cloth was dipped in an acetic acid solution prepared so that the concentration of 80% by mass of acetic acid was 2 g / L, neutralized, and then further washed with water. In Table 1-3, “◯” is shown for the experimental examples in which the reduction treatment process was performed, and “−” is shown for the experimental examples in which the reduction treatment process was not performed.

(4) Chlorination treatment process After passing the cloth through a chlorination treatment solution (sodium hypochlorite, sulfuric acid, penetrant and water, effective chlorine concentration 50 g / L), squeeze with a roll, and then rinse. It was. Next, the cloth was passed through an aqueous sodium hydrogen sulfite solution for dechlorination and neutralization, then washed with water and dried. In Table 1-3, “◯” is shown for the experimental examples in which the chlorination treatment step was performed, and “-” is shown for the experimental examples in which the chlorination treatment step was not performed.

(5) Dyeing process Either the following acidic metal mordant dyeing or reactive dyeing was performed. That is,
Acidic metal mordanting was performed by dip dyeing. That is, the cloth was immersed in a dyeing solution in which a dye and a dyeing assistant (pH adjusting agent and leveling agent) were dissolved so that the weight ratio of cloth weight: dyeing solution was 1:20. The dyeing solution was heated at a heating rate of 1 ° C./min and boiled for 40 minutes. Then, after cooling until the temperature of the dyeing solution reached 70 ° C., 0.2% by mass of potassium dichromate was added to the dye. Subsequently, the dyeing solution was boiled for 20 minutes to perform chroming (chromium mordanting).
Reactive dyeing was performed by dip dyeing. That is, the cloth was immersed in a dyeing solution in which a dye and a dyeing assistant (pH adjusting agent and leveling agent) were dissolved so that the weight ratio of cloth weight: dyeing solution was 1:20. Then, the dyeing solution was heated at a heating rate of 1 ° C./min and boiled for 60 minutes. Then, after cooling until the temperature of the dyeing solution reaches 80 ° C., 5% by mass of ammonium carbonate is added to the fabric weight, and the dyeing solution is treated at a temperature of 80 ° C. for 20 minutes to bind the dye to the fabric. Staining was performed.
In Table 1-3, “D1” is shown for the experimental example in which acidic metal mordanting is performed, and “D2” is shown in the experimental example in which reactive staining is performed. Furthermore, all the experimental examples in Table 1 and Table 3 were dyed black, but Table 2 shows the dyed colors.

(6) Deep color process The deep color process was performed with respect to the dyed dyeing | staining cloth in the following procedures. That is, after immersing the dyed fabric dyed in the dyeing step of (5) above in a deepening treatment solution containing a deepening agent (including a deepening resin), a stabilizer, a crosslinking agent, a penetrating agent, and water. Then, the deep color treatment solution was squeezed from the liquid by a roll. This operation was performed twice, and after the dyeing cloth was soaked with the deep color treatment solution, drying and heat treatment were performed. Drying conditions were 130 ° C. for 4 minutes, and heat treatment conditions were 170 ° C. for 1 minute.
In addition, since the deep color process was performed with respect to all the experimental examples, description of the presence or absence of the process was abbreviate | omitted in Table 1-3.

<3> Evaluation of Experimental Examples (1) Evaluation of deep color properties JIS Z8729 (color display method-L *, a *, b * color system and L *, u *, v * color system) In accordance with this, lightness L * was measured as a value representing the degree of deep color using a colorimeter (Macbeth model “Color-EYE3000”). In this case, the C light source was used as the light source, and the viewing angle was 10 degrees. The smaller the L * value, the better the deep color.

(2) Enlarged photographing with an electron microscope Images obtained by enlarging animal hair fibers in the following various states with an electron microscope were obtained. The obtained images are shown in FIGS. 1-10, respectively.
1-7 is an enlarged image of 2000 times, and FIG. 8-10 is an enlarged image of 1000 times.

  FIG. 1 shows the state of animal hair fibers contained in the fabric of Experimental Example 5, in which the pre-oxidation step is not performed, the ozone treatment step and the reduction treatment step are performed, and the state before the dyeing step is performed. It is an image which shows the state of a hair fiber. In addition, all the fibers recognized in FIG. 1 are animal hair fibers.

  FIG. 2 shows the state of animal hair fibers contained in the fabric of Experimental Example 1, and after the preliminary oxidation step, the ozone treatment step and the reduction treatment step, the state of the animal hair fibers before the dyeing step is performed. It is an image which shows a state. In addition, all the fibers recognized in FIG. 1 are animal hair fibers.

  FIG. 3 shows the state of animal hair fibers contained in the fabric of Experimental Example 30, and after the preliminary oxidation step (concentration of 10% by mass), the ozone treatment step and the reduction treatment step, before the dyeing step. It is an image which shows the state of the animal hair fiber of a state. In addition, all the fibers recognized in FIG. 3 are animal hair fibers.

  FIG. 4 shows the state of animal hair fibers contained in the fabric of Experimental Example 31, and after the preliminary oxidation step (20% by mass concentration), the ozone treatment step and the reduction treatment step, before the dyeing step. It is an image which shows the state of the animal hair fiber of a state. Of the two front fibers shown in the center of FIG. 4, the upper fiber is a polyester fiber, and the lower fiber is an animal hair fiber.

  FIG. 5 shows the state of animal hair fibers contained in the fabric of Experimental Example 6, in which a preliminary oxidation step (concentration of 10% by mass) was performed, an ozone treatment step was not carried out, a reduction treatment step was carried out, and then dyeing was performed. It is an image which shows the state of the animal hair fiber of the state before performing a process. In addition, all the fibers recognized in FIG. 5 are animal hair fibers.

  FIG. 6 is an image showing the state of animal hair fibers in the state of animal hair fibers included in the fabric of Experimental Example 7, and after the chlorination treatment step and before the dyeing step. In addition, all the fibers recognized in FIG. 6 are animal hair fibers.

  FIG. 7 shows the state of the animal hair fibers contained in the fabric of Experimental Example 8, and the state of the animal hair fibers in a state in which the preliminary oxidation process, the ozone treatment process, the reduction treatment process, and the dyeing process are not performed at all. It is the image shown. Of the two fibers in the foreground projected in the center of FIG. 7, the fiber positioned on the upper side is animal hair fiber, and the fiber positioned on the lower side is polyester fiber.

  FIG. 8 shows the state of animal hair fibers contained in the fabric of Experimental Example 9, in which all of the preliminary oxidation step, the ozone treatment step, the reduction treatment step, the dyeing step, and the deep color treatment step are performed in this order. It is an image which shows the state of animal hair fiber.

  FIG. 9 is an image showing the state of the animal hair fibers in the state of the animal hair fibers contained in the fabric of Experimental Example 10 in a state where the chlorination treatment step, the dyeing step, and the deep color treatment step are performed in this order. It is.

  FIG. 10 shows the state of the animal hair fibers contained in the fabric of Experimental Example 11, and the preliminary oxidation step, the ozone treatment step, and the reduction treatment step are not performed, and only the dyeing step and the deep color treatment step are performed in this order. It is an image which shows the state of the animal hair fiber of the state where it was.

<4> Effect of Experimental Example (1) From Experimental Example 1-4, it can be seen that a high deep color effect can be obtained if the amount of animal hair fiber is generally large.
(2) From Experimental Example 5-8, it can be seen that the deep color property is improved in the example in which any of the oxidation treatments is performed as compared with Experimental Example 8 in which any of the oxidation treatments is not performed. Moreover, it turns out that the deep color property which was excellent in the deep color processing cloth which performed ozone treatment compared with chlorination processing is acquired. Furthermore, when the preliminary oxidation treatment and the ozone treatment are compared, it can be seen that the ozone treatment contributes more to the deep color. Furthermore, it can be seen that remarkably excellent deep color can be obtained by using the preliminary oxidation treatment and the ozone treatment in combination.

(3) From Experimental Example 9-11, Experimental Example 12-14, and Experimental Example 15-16, it can be seen that the example in which any oxidation treatment is performed improves the deep color property. Moreover, it turns out that the deep color property which was excellent in the deep color processing cloth which performed ozone treatment compared with chlorination processing is acquired. Furthermore, it can be seen that in the dyeing process, an excellent deepening effect is obtained in any of the dyeing methods of acidic metal mordant dyeing (D1) and reactive dyeing (D2).
(4) From Experimental Examples 17-19, Experimental Examples 20-22, Experimental Examples 23-25, and Experimental Examples 26-28, it can be seen that a high deepening effect can be obtained not only for achromatic colors but also for chromatic colors.
(5) From Table 3, it can be seen that deep colorability is improved by performing the preliminary oxidation step. On the other hand, if the concentration of the oxidizing agent in the preliminary oxidation step is gradually increased, the deep color effect increases up to 20% by mass, but the deep color effect is saturated when it exceeds 20% by mass. .

Even if the ozone treatment is not performed, if the animal hair fibers are oxidized using only the preliminary oxidation step, it is possible to improve the deep color property of the deep color treated cloth as a result. However, the oxidizing agent used in the preliminary oxidation step has a weaker oxidizing action than ozone and has a higher solubility in water than ozone. Therefore, when the animal hair fiber surface is sufficiently oxidized, it penetrates and diffuses to the inside of the animal hair, and as a result, the inside of the animal hair fiber is oxidized and the fiber is damaged. That is, the fabric is damaged. For this reason, it is practically difficult to oxidize only in the preliminary oxidation step.
On the other hand, the ozone treatment has a high oxidation rate and the dissolution in water is negligibly small, so that the surface of the animal hair fiber can be sufficiently oxidized while suppressing the oxidation reaching the inside of the animal hair fiber. it is conceivable that.
Therefore, it can be said that it is preferable to perform dyeing and deep color treatment after oxidizing the animal hair fiber using at least an ozone treatment process. Furthermore, it turns out that these characteristics can be made to function synergistically by using together a preliminary oxidation process and an ozone treatment process.
From the data of the electron microscope, it can be seen that by performing preliminary oxidation, the unevenness of the scale covering the surface of the animal hair fiber is effectively reduced in the subsequent ozone treatment. That is, the unevenness due to the scale does not change greatly only by the ozone treatment, but the unevenness due to the scale can be reduced by performing preliminary oxidation.
When the oxidation treatment in the preliminary oxidation proceeds excessively, if the ozone treatment is performed thereafter, the surface of the animal hair fiber becomes extremely uneven like the surface of the synthetic fiber. If it becomes such a surface, the effect which disperse | distributes the reflected light resulting from the unevenness | corrugation of the animal hair fiber surface will be suppressed, and it will be thought that the brightness L * will become large as a result. For this reason, it is preferable to perform preliminary oxidation in an appropriate range. Specifically, in the range where potassium persulfate is used, the concentration is preferably suppressed to less than 20% by mass.

In addition, the animal hair fibers of Experimental Example 1 (FIG. 2) and Experimental Example 5 (FIG. 1) subjected to ozone treatment were the same as those of Experimental Example 6 (FIG. 5) not subjected to the ozone treatment process. Compared with the animal hair fiber of Experimental Example 8 (FIG. 5) which has not been applied, the outline of the scale is unclear, and it can be seen that the unevenness due to the scale is reduced.
Furthermore, the animal hair fiber of Experimental Example 30 (FIG. 3) has a more unclear outline of the scale than the animal hair fiber of Experimental Example 5 (FIG. 1) that has not been subjected to the pre-oxidation step. It can be seen that the unevenness has almost disappeared.
Moreover, since the animal hair fiber of Experimental Example 31 (FIG. 4) has a high concentration of the oxidizing agent aqueous solution in the preliminary oxidation step, the unevenness due to the scale is smaller than the animal hair fiber of Experimental Example 30 (FIG. 3) whose concentration is low. At the same time, it can be seen that other fine irregularities are also almost disappeared.
Furthermore, since the animal hair fiber of Experimental Example 6 (FIG. 5) has not been subjected to the ozone treatment step, it can be seen that the unevenness due to the scale is clear. However, since the preliminary oxidation process is performed, it can be seen that fine furrows are formed on the animal hair fibers.
Moreover, since the animal hair fiber of this experimental example 8 (FIG. 7) is an animal hair fiber which has not performed any process, it turns out that the shape of a scale and the unevenness | corrugation by a scale are clear.

Furthermore, the animal hair fiber of Experimental Example 11 (FIG. 10) is obtained by performing only the dyeing step and the deep color treatment step without performing the preliminary oxidation step, the ozone treatment step, and the reduction treatment step. Therefore, the shape of the scale is clearly raised on the surface of the animal hair fiber, and the unevenness due to the scale is also clear. And it turns out that the deep color resin is attached so that it may be caught in the front-end | tip part of this scale, but does not cover the other part of animal hair fiber.
Also. The animal hair fiber of Experimental Example 10 (FIG. 9) has been subjected to a chlorination treatment step, a dyeing step, and a deep color treatment step. It can be seen that by performing the chlorination treatment, the deep color resin is sufficiently and uniformly attached to the surface of the animal hair fiber.
Furthermore, the animal hair fiber of Experimental Example 9 (FIG. 8) is obtained by performing all of the preliminary oxidation step, the ozone treatment step, the reduction treatment step, the dyeing step, and the deep color treatment step. By performing these treatments, it can be seen that the deep color resin is sufficiently and uniformly attached to the surface of the animal hair fiber.
In Experimental Example 9 and Experimental Example 10, in any animal hair fiber, the deep color resin is sufficiently and uniformly attached, but when the lightness L * is measured, as shown in Table 1, there is a large difference. In experiment example 10, L * = 10.13, whereas in experiment example 9, L * = 9.33, which is a very small value.

  In addition, in this invention, it can restrict to what is shown to said specific Example, It can be set as the Example variously changed within the range of this invention according to the objective and the use.

Claims (5)

A deep-colored cloth in which the surface of the animal hair fibers constituting the dyed cloth is coated with a deep-colored resin;
The deep-colored cloth is characterized in that the animal hair fibers have vertical ridge-like surface irregularities and do not have scales arranged in a Matsukasa shape constituting a scale . The deep-colored cloth according to claim 1, which is dyed black, red, or purple. The deep-colored cloth according to claim 2, wherein the dyeing is reactive dyeing or acid mordant dyeing.   A garment using the deep-colored cloth according to any one of claims 1 to 3. The garment according to claim 4 , wherein the garment is a formal garment.