JP6968358B2 - Chemical fiber dyeing method and dyed non-denatured polyolefin fiber - Google Patents

Description

The present invention relates to a method for dyeing chemical fibers and dyed non-modified polyolefin fibers.

For example, polypropylene (PP), which is a typical polyolefin, is an excellent resin having the lowest specific gravity among general-purpose resins and exhibiting high hydrophobicity. In addition, PP has high heat resistance, strength, and heat retention, has low hygroscopicity, and has excellent chemical resistance including acids and alkalis, and is therefore expected as a dream fiber.

However, PP has a problem that it is difficult to use for highly fashionable clothing because it has almost no dyeing site to which dye molecules can be bonded due to its simple molecular structure and has poor dyeability.

In fact, PP is widely used in various fields other than textile applications, such as home appliances, stationery, automobiles, sporting goods, buckets, trash cans, food tappers, building materials, and medical equipment. On the other hand, the main uses for textiles are underwear, carpets, ropes, business socks, bedding, nets, industrial materials, etc., and the current situation is that they are rarely used especially in the apparel field.

To solve this problem, for example, a method of mixing dyeable members (dyeable resin, special filler) to spin fibers (see, for example, Patent Document 1), and a method of mixing pigments during the production of PP resin (undidding). ), A method of introducing a functional group that can be dyed into PP molecules, a method of infiltrating the dye into the inside of the fiber using a supercritical fluid, a method of modifying the surface of the fiber with an electron beam, etc. It is being tried. Further, a dyeing method using a vat dye as a dye is also disclosed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2015-148027 Special Table No. 10-503558 Gazette

However, the methods described in Patent Document 1 and other methods have problems such as lack of vividness and type of color, loss or reduction of good properties of PP due to changes in physical properties, and increase in manufacturing and dyeing costs. ..

Further, in the case described in Patent Document 2, although PP can be dyed, there are problems that the vat dye is difficult to disperse in water, the vivid color is low, and the dyeing fastness to washing and rubbing is low. .. In fact, in the examples described in Patent Document 2, only an example using a brown vat dye is given. Although there is a description that the dyeing result is dyed to a bright color tone, the examination of color variation and vividness, the evaluation of the physical properties of the dyed PP, etc. are not specifically disclosed.

Therefore, the present invention provides a dyeing method for chemical fibers and dyed non-modified polyolefin fibers that enable dyeing with vivid colors and a wide variety of colors while maintaining various excellent physical properties of chemical fibers, particularly polyolefin fibers. The purpose is.

In order to achieve the above object, in the present invention, the reduced product of the cationic dye is dyed on the chemical fiber by reducing the cationic dye with a reducing agent under basic conditions. Then, the reduced body of the cationic dye is oxidized by treating the chemical fiber dyed with the reduced body of the cationic dye with an oxidizing agent, and the cationic dye is fixed to the chemical fiber to produce the dyed chemical fiber. bottom.

That is, the chemical fiber dyeing method disclosed herein is a dyeing step in which a cationic dye is reduced in the presence of a reducing agent and an alkaline agent, and a reduced product of the cationic dye is dyed on the chemical fiber having no acidic group. After the dyeing step, the chemical fiber dyed with the reducing agent of the cationic dye is treated with an oxidizing agent to oxidize the reducing agent of the cationic dye to obtain a dyed chemical fiber. It is characterized by having a process.
Further, the chemical fiber dyeing method disclosed herein includes a dyeing step of reducing a cationic dye in the presence of a reducing agent and an alkaline agent to dye the chemical fiber with a reduced product of the cationic dye, and the dyeing. After the step, the chemical fiber dyed with the reduced product of the cationic dye is treated with an oxidizing agent to oxidize the reduced product of the cationic dye to obtain a dyed chemical fiber. The chemical fiber is characterized by being at least one selected from the group of polyolefin fibers, polyester fibers and nylon fibers.

Cationic dyes are usually used as dyes that are dyed by ionic bonding with acidic groups of acrylic fibers, and chemical fibers that do not have acidic groups, especially polyolefin fibers, are usually dyed with cationic dyes. Dyeing is difficult. However, since the number of commercially available dyes is large and the selection range of colors is large, cationic dyes are extremely useful if they can be used for dyeing chemical fibers regardless of the presence or absence of acidic groups.

According to this configuration, various chemical fibers can be dyed using a cationic dye having a large number of dyes regardless of the presence or absence of an acidic group. Then, the chemical fibers can be dyed deeply and colorfully using the existing dyeing equipment. In addition, since the cationic dye is immediately ionized in water, it has high dispersibility in water and can give a uniform dyeing without spots. As a result, uniform, dark, vivid and color-variable dyeing of chemical fibers becomes possible.

The chemical fiber is preferably a polyolefin fiber, more preferably a non-modified polyolefin fiber, and particularly preferably a non-modified polypropylene fiber.

According to this configuration, even a polyolefin fiber that is difficult to dye, particularly a non-modified polypropylene fiber, can be dyed in a deep, vivid color and rich in color variation. As a result, the polyolefin fiber can be used for highly fashionable clothing and the like.

Further, it is preferable that the dyeing fastness to the friction of the dyed polyolefin fiber is 4th grade or higher in drying. Further, the dyeing fastness of the dyed polyolefin fiber for washing is preferably 4th grade or higher for discoloration and fading, and preferably 4th grade or higher for contamination.

According to this configuration, by using a cationic dye as a dye, dyeing can be performed under mild conditions, so that vivid dyeing can be performed without impairing excellent physical properties such as durability of polyolefin fibers. ..

Further, in a preferred embodiment, the C ^* value of the dyed polyolefin fiber is 10 or more.

According to this configuration, even polyolefin fibers that were difficult to dye with conventional dyes and dyeing methods can be dyed in vivid colors.

The non-modified polyolefin fiber disclosed herein is dyed with a cationic dye and has a C ^* value of 16 or more.

According to this configuration, it is possible to obtain a non-modified polyolefin fiber dyed vividly with respect to a non-modified polyolefin fiber that has been difficult to dye with a conventional dye or dyeing method. Then, it can be used for clothes with high fashionability.

As described above, according to the present invention, various chemical fibers can be dyed using a cationic dye having a large number of dyes regardless of the presence or absence of an acidic group. Then, the chemical fibers can be dyed deeply and colorfully using the existing dyeing equipment. In addition, since the cationic dye is immediately ionized in water, it has high dispersibility in water and can give a uniform dyeing without spots. As a result, uniform, dark, vivid and color-variable dyeing of chemical fibers becomes possible.

It is a flowchart which shows the process of the dyeing method of the chemical fiber which concerns on one Embodiment. It is a figure for demonstrating the process of the dyeing method of FIG. It is a graph which shows the relationship between ^{the L *} value and the C ^* value of an Example and a comparative example. It is a graph which shows the relationship between ^{the L *} value and the C ^* value of an Example and a comparative example.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The following description of preferred embodiments is merely exemplary and is not intended to limit the invention, its applications or its uses.

<Dyeing method for chemical fibers>
As shown in FIG. 1, the method for dyeing chemical fibers according to the present embodiment includes a dyeing step S1, an oxidation step S2, and a soaping step S3.

-Dyeing process-
The dyeing step S1 is a step of dyeing the chemical fiber with the cationic dye, and more specifically, a step of infiltrating the molecule derived from the cationic dye into the inside of the chemical fiber, that is, between the molecules constituting the chemical fiber.

(Chemical fiber)
The chemical fiber F is an organic polymer-based synthetic fiber, which is a polyolefin fiber such as polypropylene (PP), polyethylene (PE), polybutene-1, polymethylpentene, a polyester fiber such as polyethylene terephthalate (PET), and a nylon fiber. Examples thereof include halogen-containing fibers such as acrylic fibers, vinylon fibers, polyurethane fibers and polyvinylidene fluoride.

In particular, the method for dyeing chemical fibers according to the present embodiment is suitable as a method for dyeing polyolefin fibers that are difficult to dye with other dyes or dyeing methods, more preferably non-modified polyolefin fibers, and particularly preferably non-modified polypropylene fibers.

In addition, in this specification, "non-denaturing" means that it has not been physically or chemically modified. Specifically, by mixing dyeable members (dyeable resin, special filler) before spinning, mixing pigments during resin production, introducing dyeable functional groups to molecules of chemical fibers, and using electron beams on the fiber surface. It means that it has not been physically or chemically treated such as reforming and has not been reformed.

That is, the non-modified polyolefin is a polymer compound having a skeleton represented by the following chemical formula.

Here, m is the degree of polymerization, and R is independently hydrogen or an alkyl group of C1 to C4. Examples of such non-modified polyolefins include polyethylene (including high density and low density polyethylene and linear low density polyethylene), polypropylene and the like.

The polypropylene is not limited to the homopolymer of polypropylene, but also includes random polypropylene which is an ethylene-propylene copolymer and block polypropylene which is a blend of a propylene homopolymer and an ethylene-propylene copolymer.

Further, the chemical fiber to which the dyeing method according to the present embodiment is applied may be one of the above-mentioned synthetic fibers or a combination of a plurality of types.

(Cation dye)
The cationic dye is an ionic dye, and as described above, it is usually known as a dye that is dyed by ionic bonding with an acidic group such as acrylic fiber. Specifically, the cationic dye is, for example, a phenothiazine-based blue dye such as methylene blue, a benzothiazole azo-based blue dye, a phenoxazine-based blue dye, an acridin-based yellow dye, a red dye such as safranin, or a xanthene-based purple dye. And so on. As described above, the number of commercially available dyes for cationic dyes is large, and the selection range of colors is widened.

In the dyeing step S1 in the present embodiment, as shown in FIG. 2A, a predetermined concentration of a cationic dye ( ^{indicated by “day +} ” in FIG. 2), a reducing agent, and an alkaline agent are contained in an aqueous solution. The chemical fiber F is immersed and maintained at a predetermined treatment temperature and treatment time. Then, as shown in FIG. 2 (b), the cationic dye dye ⁺ in the aqueous solution is reduced by the reducing agent under basic conditions, and is combined with the reduced product of the cationic dye (indicated by "L-die" in FIG. 2). Then, it is introduced between the molecules of the chemical fiber F and dyed on the chemical fiber F.

Hereinafter, methylene blue will be specifically described as an example of the cationic dye dye ^+.

Methylene blue is a cation and is water soluble. When this methylene blue is treated with a reducing agent under basic conditions, it is reduced to leucomethylene blue as a reducing agent L-die shown below.

Leucomethylene blue is a neutral organic molecule, and its water solubility is lower than that of methylene blue, making it hydrophobic. Then, leucomethylene blue has an increased affinity for the molecules of the chemical fiber made of the organic polymer compound, and may be in a state of being incorporated between the molecules of the chemical fiber in the aqueous solution. Then, the cationic dye can permeate into the chemical fiber F. Since the cationic dye is immediately ionized in water, it has high dispersibility in water and can contribute to uniform dyeing without spots.

The concentration of the cationic dye can be appropriately changed depending on the type of the chemical fiber to be dyed, but from the viewpoint of improving the dyeability, for example, it is set to 1% by mass or more and 10% by mass or less with respect to the amount of the chemical fiber to be dyed. be able to.

(Reducing agent)
The reducing agent is for reducing a cationic dye, and is not particularly limited, and various general reducing agents can be used. Further, it can be appropriately changed depending on the type of the chemical fiber to be dyed. Specific examples of the reducing agent include glucose, longalit, sodium hydrosulfite, lactose, ascorbic acid, glutathione and the like. The concentration of the reducing agent can be appropriately changed depending on the type and concentration of the cationic dye, the type of the chemical fiber to be dyed, etc., but from the viewpoint of sufficiently advancing the reduction reaction of the molecule of the cationic dye, for example, 0.5 g. It can be about / L to 10 g / L.

(Alkaline agent)
The alkaline agent is for accelerating the reduction reaction of the cationic dye, and is not particularly limited, and various general alkaline agents can be used. Specific examples of the alkaline agent include sodium hydroxide, potassium hydroxide, calcium hydroxide, water-soluble ethanolamines and the like. The alkaline agent may be used alone or in combination of two or more. The concentration of the alkaline agent can be appropriately changed depending on the type and concentration of the cationic dye, the type of the chemical fiber to be dyed, etc., but from the viewpoint of promoting the reduction of the cationic dye, for example, 0.5 g / L to 20 g / It can be about L.

(Treatment temperature and treatment time)
The treatment temperature and treatment time in the dyeing step S1 can be appropriately changed depending on the type and concentration of the cationic dye, the type of the chemical fiber to be dyed, and the like, and the reduction of the cationic dye between the molecules of the chemical fiber F. From the viewpoint of promoting sufficient permeation of the body L-dye, for example, the treatment temperature may be 75 ° C. or higher and 120 ° C. or lower, and the treatment time may be 15 minutes or longer and 100 minutes or lower.

-Oxidation process-
In the oxidation step S2 in the present embodiment, as shown in FIG. 2C, the cationic dye reducer L-daye permeated between the molecules of the chemical fiber in the above-mentioned dyeing step S1 is oxidized to form the cationic dye dye. ^This is the process of returning to +.

Specifically, the chemical fiber F to which the reduced product L-die of the cationic dye obtained in the dyeing step S1 is fixed is immersed in an aqueous solution containing an oxidizing agent and maintained at a predetermined treatment temperature and treatment time. ..

As a result, it is possible to obtain a chemical fiber in which the cationic dye is fixed between the molecules of the chemical fiber, that is, the chemical fiber dyed with the cationic dye.

(Oxidant)
The oxidizing agent is for oxidizing the reduced form L-die of the cationic dye ^{to return to the cationic dye day +} , and various general oxidizing agents can be used without particular limitation. Specific examples of the oxidizing agent include acetic acid, potassium dichromate, hydrochloric acid, sulfuric acid, hydrogen peroxide, sodium percarbonate and the like. The oxidizing agent may be used alone or in combination of two or more. The concentration of the oxidizing agent can be appropriately changed depending on the type and concentration of the cationic dye, the type of the chemical fiber to be dyed, etc. From the viewpoint of promoting oxidative oxidation, it can be, for example, about 1 g / L to 10 g / L.

(Treatment temperature and treatment time)
The treatment temperature and treatment time in the oxidation step S2 can be appropriately changed depending on the type and concentration of the cationic dye, the type of the chemical fiber to be dyed, and the like, but the reduction of the cationic dye permeated between the molecules of the chemical fiber F. From the viewpoint of promoting sufficient oxidation of the body L-dye, for example, the treatment temperature may be 40 ° C. or higher and 80 ° C. or lower, and the treatment time may be 15 minutes or longer and 90 minutes or lower.

-Soaping process-
The soaping step S3 is a step for washing off the cationic dye that could not be completely fixed to the chemical fibers after the oxidation step S2. The soaping step S3 is performed by immersing the chemical fiber obtained in the oxidation step S2 in an aqueous solution containing a soaping agent and maintaining a predetermined treatment temperature and treatment time. Although the soaping step S3 is an arbitrary step, it is preferable to perform the soaping step S3 from the viewpoint of maintaining the vividness and durability of the color of the dyed chemical fiber.

The soaping agent is not particularly limited, and various general soaping agents can be used. Specific examples of the soaping agent include sodium carbonate, soap, and a surfactant. The concentration of the soaping agent can be appropriately changed depending on the type and concentration of the cationic dye, the type of the chemical fiber to be dyed, and the like.

The treatment temperature and treatment time can be, for example, a treatment temperature of 60 ° C. or higher and 90 ° C. or lower and a treatment time of 10 minutes or longer and 40 minutes or lower from the viewpoint of obtaining chemical fibers in a good dyed state while sufficiently washing away the residual dye.

<Dyed chemical fiber>
-Color system-
The dyed state of the chemical fiber can be evaluated, for example, by measuring the numerical value ^{of the L *} a ^* b ^{* color system with a colorimeter.} The L ^* a ^* b ^* color system is a general color expression method based on JIS Z8781-4: 2013.

The L ^* value represents the lightness of the color, where 0 is black and 100 is white. The L ^* value depends on the type of color, but generally decreases as the amount of staining increases. In the case of yellow dyeing, it may be, for example, about 75 or more and 90 or less, and in the case of dyeing of other colors, it may be about 80 or less.

Further, the a ^* value and the b ^* value represent the chromaticity indicating the hue and saturation of the color, and are usually represented by a value from -100 to +100. The + direction of the a ^* value indicates the red direction, the-direction indicates the green direction, ^{the + direction of the b *} value indicates the yellow direction, and the-direction indicates the blue direction.

Further, ^{the saturation C *} value can be obtained ^{from the a *} value and the b ^* value by the following equation (1).

The higher the saturation C ^* value, that is, the higher ^{the absolute value of the a *} value and / or the b ^* value, the more vividly the color is dyed.

^{The L *} value of the chemical fiber dyed using the dyeing method according to the present embodiment is, for example, 75 or more and 90 or less in the case of yellow dyeing in which the ^{a *} value is -20 or more and +20 or less and the b ^{* value is +30 or more.} It can be preferably 77 or more and 85 or less.

^{In the case of other than the above yellow dyeing, the L *} value of the chemical fiber dyed by the dyeing method according to the present embodiment may be preferably 70 or less, more preferably 60 or less, and particularly preferably 55 or less. Specifically, for example, in the case of blue staining in which the ^{a *} value is -15 or more and +15 or less and the b ^{* value is -10 or less, the L *} value can be, for example, 10 or more and 50 or less, preferably about 20 or more and 40 or less. .. Further, for example, in ^{the case of red staining in which the a *} value is +10 or more and the b ^* value is -15 or more and +15 or less, the L ^* value can be, for example, 10 or more and 70 or less, preferably about 20 or more and 60 or less.

In cases other than the above yellow dyeing, when non-modified polypropylene fiber is used as the chemical fiber, the L ^* value of the chemical fiber dyed by the dyeing method according to the present embodiment is preferably 70 or less. It can be more preferably 60 or less, and particularly preferably 55 or less.

^{The C *} value of the chemical fiber dyed by the dyeing method according to the present embodiment is preferably 10 or more, more preferably 16 or more and 100 or less, and particularly preferably 20 or more and 90 or less. Specifically, for example, in the case of the above-mentioned blue staining or red staining, the C ^* value can be preferably 10 or more and 100 or less, more preferably 12 or more and 60 or less, and particularly preferably 14 or more and 50 or less.

Further, in particular, when a non-modified polypropylene fiber is used as the chemical fiber, the C ^* value is preferably 16 or more, more preferably 20 or more and 100 or less, and particularly preferably 25 or more and 90 or less in any color dyeing. be.

-Stiffness-
Further, the chemical fiber dyed by the dyeing method according to the present embodiment retains the physical characteristics of the chemical fiber before dyeing, and is excellent in durability and the like.

The durability of the chemical fiber can be evaluated by a dyeing fastness test or the like.

Specifically, according to the case of the drying test of the dyeing fastness test method for JIS L 0849 friction, the dyeing fastness test for friction can be performed using a Gakushin type friction tester. The dyeing fastness to the friction of the dyed chemical fiber of the present embodiment is preferably a dry grade 4 or higher.

In addition, the dyeing fastness test for washing can be performed in accordance with the test type A-1 method (washing method with soap) of the dyeing fastness test method for JIS L 0844 washing. The dyeing fastness of the dyed chemical fiber of the present embodiment to washing is preferably a discoloration / fading grade 4 or higher, and preferably a contamination grade 4 or higher.

Next, a specific embodiment will be described.

<Dyeing experiment on polypropylene (PP) circular knitted cloth>
A dyeing experiment was carried out using a PP circular knitted fabric (stretched yarn 300D / 72F) as a non-modified polypropylene fiber.

(Comparative Example 1)
The original cloth of PP circular knitted cloth before the dyeing experiment was used as Comparative Example 1.

(Examples 1 and 2)
A dyeing experiment was conducted on PP circular knitted fabric using a cationic dye. The procedure is shown below.

Water and 5% by mass of cationic dye (Acryl Blue 5GT manufactured by Ssangyong Co., Ltd. or Basic Red 2 manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the first container and heated to 60 ° C. Then, glucose was added to 2 g / L and sodium hydroxide was added to 1 g / L, and after 5 minutes, PP round knitted cloth was added. Then, the first container was heated to 100 ° C. and kept at 100 ° C. for 30 minutes.

Next, the PP circular knitted cloth was taken out from the first container and put into the second container containing an acetic acid aqueous solution having a water temperature of 50 ° C. and a concentration of 3 g / L. Then, after holding at a water temperature of 50 ° C. for 30 minutes, the PP circular knitted cloth was taken out and washed well with water.

Finally, the PP circular knitted cloth treated as described above was put into a third container containing an aqueous solution at 80 ° C. containing a 3 g / L soaping agent, and soaping was performed at a water temperature of 80 ° C. for 20 minutes. Then, the PP circular knitted cloth was taken out from the third container, washed well with water, and dried. Then, a dyed PP circular knitted cloth was obtained.

(Comparative Example 2)
A dyeing experiment was conducted on PP circular knitted fabric using a bat dye. The procedure is shown below.

Water and 5% by mass of bat dye (Indigo manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the first container and heated to 60 ° C. Glucose was added to 2 g / L and sodium hydroxide was added to 1 g / L, and after 5 minutes, PP round knitted cloth was added. Then, the first container was heated to 100 ° C. and kept at 100 ° C. for 30 minutes.

Next, the PP circular knitted cloth was taken out from the first container and put into the second container containing an acetic acid aqueous solution having a water temperature of 50 ° C. and a concentration of 3 g / L. After holding at a water temperature of 50 ° C. for 30 minutes, the PP circular knitted cloth was taken out from the second container and washed well with water.

Finally, the PP circular knitted cloth subjected to the above treatment was put into a third container containing an aqueous solution at 80 ° C. containing a 3 g / L soaping agent, and soaping was continued at a water temperature of 80 ° C. for 20 minutes. Then, the PP round knitted cloth was taken out from the third container, washed well with water, and dried to obtain a lightly colored PP round knitted cloth.

(Comparative Example 3)
A dyeing experiment was carried out on the PP circular knitted fabric using a vat dye under different conditions from Comparative Example 2. The procedure is shown below.

Water and 5% by mass of bat dye (Indigo manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the first container and heated to 60 ° C. Then, 1 g / L of hydrosulfite sodium, 1 g / L of longalit, and 9 g / L of sodium hydroxide were added, and after 5 minutes, a PP round knitted cloth was added. Then, the first container was heated to 100 ° C. and kept at 100 ° C. for 30 minutes.

Next, the PP circular knitted cloth was taken out from the first container and put into the second container containing an acetic acid aqueous solution having a water temperature of 50 ° C. and a concentration of 3 g / L. After holding at a water temperature of 50 ° C. for 30 minutes, the PP circular knitted cloth was taken out from the second container and washed well with water.

Finally, the PP circular knitted cloth treated as described above was put into a third container containing an aqueous solution at 80 ° C. containing a 3 g / L soaping agent, and soaping was continued at a water temperature of 80 ° C. for 20 minutes. Then, the PP round knitted cloth was taken out from the third container, washed well with water, and dried to obtain a slightly colored PP round knitted cloth.

<Color measurement test for PP circular knitted cloth>
For the PP circular knitted fabrics of Comparative Examples 1 to 3 and Examples 1 and 2, the lightness L ^* value and the chromaticity a ^* b ^{* were used using a commercially available colorimeter (SPECTOR PHOTO METER CM-3600d manufactured by KONICA MINOLTA).} Values were measured under D65 light source. Further, from the obtained a ^* b ^{* values, the saturation C *} value was calculated using the above equation (1).

The results are shown in Table 1 and FIG. In FIG. 3, Examples 1 and 2 are indicated by reference numerals E1 and E2, respectively, and Comparative Examples 1 to 3 are indicated by reference numerals C1 and C3, respectively.

As shown in Table 1 and FIG. 3, it was found that ^{the lightness L *} value was lower and the saturation C ^* value was higher in Examples 1 and 2 than in Comparative Examples 1 and 3. Further, as compared with Comparative Example 2, it was found that in ^{Examples 1 and 2, the lightness L *} value showed the same value, but the saturation C ^{* value was high.}

From the above, it was found that the dyeing method according to the present embodiment enables dyeing of non-modified polypropylene fibers with abundant color variations and deep and vivid colors.

<Dyeing fastness test against friction of dyed PP circular knitted cloth>
A PP circular knitted fabric dyed with the dye Acrylic Blue 5G-T manufactured by Ssangyong Co., Ltd. of Example 1 is subjected to a friction test of a Gakushin type according to the case of a drying test of a dyeing fastness test method for JIS L 0849 friction. A dye fastness test against friction was performed using a machine. Specifically, one 140 mm × 50 mm test piece each in the vertical and horizontal directions of the dyed PP circular knitted cloth is used with a 50 mm × 50 mm friction white cotton cloth under a load of 9 ± 0.2 N. The white cotton cloth for friction was rubbed back and forth 10 times on average for 10 seconds between 100 mm of the test piece, and the degree of coloring of the white cotton cloth for friction was compared with the gray scale for contamination specified in JIS L 0805 to determine the fastness.

As a result, it was dry 4th grade (vertical direction) and dry 4th grade (horizontal direction).

<Dyeing fastness test for washing dyed PP circular knitted cloth>
The PP circular knitted cloth dyed with the dye Acryl Blue 5G-T manufactured by Ssangyong Co., Ltd. of Example 1 was dyed with JIS L 0844. ), And the dyeing fastness test for washing was performed. Specifically, a 100 mm x 40 mm dyed PP round knitted cloth is sandwiched between two 100 mm x 40 mm attached white cloths (multi-fiber mixed woven cloth No. 1 and PP round knitted cloth before dyeing), and all four sides are covered. A composite test piece was obtained by sewing. This composite test piece was put into a 550 mL test bottle containing a 100 mL aqueous solution adjusted so that the amount of unadded soap specified in JIS K 3302 was 5 g / L and a stainless iron ball having a diameter of 6 mm. Then, the test bottle was rotated at 40 ± 2 ° C. for 30 minutes at 40 times / minute in a constant temperature bath. Then, the composite test piece was taken out from the test bottle, washed with water and dried. The degree of fading of the composite test piece and the degree of contamination of the attached white cloth were compared with the gray scale for fading specified in JIS L 0804 and the gray scale for contamination specified in JIS L 0805, respectively, to determine the fastness.

As a result, it was 4th grade of discoloration and fading, 4th grade of contamination (multi-fiber mixed woven fabric No. 1), and 4-5th grade of contamination (PP circular knitted fabric before dyeing).

<Dyeing experiment for chemical fibers>
Dyeing experiments with cationic dyes were conducted using polyethylene, polyethylene terephthalate (PET), and nylon as chemical fibers other than PP.

(Comparative Examples 4 and 5)
Polyethylene (split yarn 700D) and PET (stretched yarn 50D / 36F) before the dyeing experiment were designated as Comparative Examples 4 and 5, respectively.

(Examples 3 to 5)
Water and 5% by mass of a cationic dye (Acryl Blue 5G-T manufactured by Ssangyong Co., Ltd.) were added to the first container with respect to the object to be dyed, and the mixture was heated to 60 ° C. Then, glucose was added to 2 g / L and sodium hydroxide was added to 1 g / L, and after 5 minutes, chemical fibers (polyethylene: split yarn 700D, PET: drawn yarn 50D / 36F, nylon: monofilament yarn 500D) were added. Was put in. Then, the first container was heated to 100 ° C. and held at 100 ° C. for 30 minutes.

Next, the chemical fiber was taken out from the first container and put into the second container containing an acetic acid aqueous solution having a water temperature of 50 ° C. and a concentration of 3 g / L. After holding at a water temperature of 50 ° C. for 30 minutes, the chemical fiber was taken out from the second container and washed well with water.

Finally, the treated chemical fiber was put into a third container containing an aqueous solution at 80 ° C. containing a 3 g / L soaping agent, and soaping was continued at a water temperature of 80 ° C. for 20 minutes. Then, the chemical fiber was taken out from the third container, washed well with water, and dried to obtain a dyed chemical fiber.

<Chemical fiber color measurement test>
For the chemical fibers of Examples 3 to 5 and Comparative Examples 4 and 5, the brightness L ^* value and the chromaticity a ^* b ^* values were measured under a D65 light source in the same manner as in the PP circular knitted fabric. Further, from the obtained a ^* b ^{* values, the saturation C *} value was calculated using the above equation (1). Since the nylon yarn of Example 5 was a transparent yarn, the L ^* a ^* b ^* value of the nylon raw yarn was not measured.

The results are shown in Table 2 and FIG. In FIG. 4, Examples 3 to 5 are indicated by reference numerals E3 to E5, respectively, and Comparative Examples 4 and 5 are indicated by reference numerals C4 and C5, respectively.

As shown in Table 2 and FIG. 4, it was found that ^{the lightness L *} value was lower and the saturation C ^* value was higher in Examples 3 to 5 as compared with Comparative Examples 4 and 5. As a result, it was found that the dyeing method according to the present embodiment enables deep and vivid dyeing of chemical fibers such as polyolefin fibers and nylon.

INDUSTRIAL APPLICABILITY The present invention is extremely useful because it can provide a method for dyeing chemical fibers, in particular, a method for dyeing chemical fibers, which enables dyeing with vivid colors and abundant color variations while maintaining various excellent physical properties of polyolefin fibers. ..

F Chemical fiber dye ⁺ cationic dye L-dye Reduced cation dye S1 Dyeing step S2 Oxidation step S3 Soaping step

Claims (9)

A dyeing step of reducing a cationic dye in the presence of a reducing agent and an alkaline agent and dyeing a reduced product of the cationic dye on a chemical fiber having no acidic group.
After the dyeing step, the chemical fiber dyed with the reduced product of the cationic dye is treated with an oxidizing agent to oxidize the reduced product of the cationic dye to obtain a dyed chemical fiber. A method for dyeing chemical fibers, which is characterized by being provided with. A dyeing step of reducing a cationic dye in the presence of a reducing agent and an alkaline agent and dyeing a reduced product of the cationic dye on chemical fibers.
After the dyeing step, the chemical fiber dyed with the reduced product of the cationic dye is treated with an oxidizing agent to oxidize the reduced product of the cationic dye to obtain a dyed chemical fiber. Equipped with
The chemical fiber is at least one selected from the group of polyolefin fiber, polyester fiber and nylon fiber.
A method for dyeing chemical fibers. The method for dyeing a chemical fiber according to claim 2 , wherein the chemical fiber is a polyolefin fiber. The method for dyeing a chemical fiber according to claim 3 , wherein the polyolefin fiber is a non-modified polyolefin fiber. The method for dyeing a chemical fiber according to claim 4 , wherein the non-modified polyolefin fiber is a non-modified polypropylene fiber. The method for dyeing a chemical fiber according to any one of claims 3 to 5 , wherein the dyeing fastness to friction of the dyed polyolefin fiber is 4th grade or higher in drying. The dyeing of the chemical fiber according to any one of claims 3 to 6 , wherein the dyeing fastness of the dyed polyolefin fiber to washing is 4th grade or higher for discoloration and fading, and 4th grade or higher for contamination. Method. The method for dyeing a chemical fiber according to any one of claims 3 to 7 , wherein the dyed polyolefin fiber has a C ^* value of 10 or more. A non-modified polyolefin fiber dyed with a cationic dye and having a C ^{* value of 16 or more.}

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