JP2008266855A - Method for dyeing deeply cellulosic fiber structure and cellulosic fiber structure dyed by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for dyeing deeply a cellulosic fiber structure at a low cost and with a good quality capable of obtaining the cellulosic fiber structure extremely deeply dyed and with excellent color fastness in comparison with a conventional method. <P>SOLUTION: The method for dyeing deeply the cellulosic fiber structure applies a deep color dying processing with a reactive dye to a fiber structure containing mainly a cellulosic fiber. In the method for dyeing deeply the cellulosic fiber structure, the cellulosic fiber structure is immersed in advance in a mixed liquid of lithium chloride/a fatty acid or a lithium chloride water solution with a lithium chloride concentration of 1-55 mass%, and then, it is washed and dried. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dark dyeing method for cellulosic fiber structures and a cellulosic fiber structure dyed by the method, and more particularly, prior to performing a deep color dyeing treatment with a reactive dye, a cellulosic fiber structure in advance. The present invention relates to a method for thickening a cellulosic fiber structure in which the fiber structure is immersed in an aqueous lithium chloride solution, and a cellulosic fiber structure dyed by the method.

Cellulosic fibers have advantages such as excellent hygroscopicity and water absorption, resistance to static electricity, and easy removal of dirt. There is a drawback that it is impossible to dye at a high density. As a method for improving this defect, a mercerization process (or mercerization process) using a caustic soda aqueous solution or the like or a process using liquid ammonia is widely known. For example, when a caustic soda aqueous solution treatment (mercerizing or mercerizing) is applied to cellulosic fibers, the dyeability is greatly improved and the dimensional stability is also improved.
However, in recent years, there has been an increasing demand for products that have not been subjected to mercerization processing on cellulosic fibers and have appealed for the soft texture inherent to cellulosic fibers.

Therefore, conventionally, when a cellulosic fiber that has not been subjected to mercerization is dyed in a deep color, a large amount of dye has been used due to poor dyeing properties. For this reason, there has been a problem in that the dye cost is greatly increased and unfixed dye adheres to the fiber surface, resulting in a decrease in dyeing fastness.
On the other hand, liquid ammonia treatment (liquid ammonia processing treatment) improves dimensional stability, but dyeability is inferior to caustic soda treatment, especially when reactive dyes used in most cotton dyeings are applied. There was a problem.

In order to solve such problems, various methods have been proposed for improving the dyeing property of a cellulosic fiber structure and performing deep color dyeing with excellent fastness (for example, patents). Reference 1 to 3).
For example, in Patent Document 1, after applying a medium temperature type reactive dye to a cellulosic fiber structure that has not been mercerized, the reactive dye is fixed before being treated with an alkaline solution and then impregnated with the alkaline solution. Cellulose fiber structure not subjected to mercerization processing, characterized in that the applied cellulose fiber structure is subjected to dry heat fixing treatment and impregnated with an alkaline solution, and then the fiber structure is subjected to steam heat fixing treatment. A method for darkening a product is disclosed. Moreover, in patent document 2, after giving a medium temperature type reactive dye and an alkali agent to the cellulosic fiber structure subjected to liquid ammonia treatment, before being fixed with the alkali solution, before the impregnation treatment with the alkali solution, The cellulosic fiber structure to which the reactive dye is applied is subjected to a dry heat fixing treatment, and after impregnating with an alkaline solution, the fiber structure is subjected to a steam heat fixing treatment. A method for thickening a cellulosic fiber structure is disclosed. In the inventions described in the above Patent Documents 1 and 2, in both cases, after the reactive dye is applied to the cellulosic fiber structure, the fiber structure is impregnated with an alkali solution before being fixed with the alkali solution. It is characterized by subjecting the product to steam heat fixing treatment.
Furthermore, in Patent Document 3, the cellulosic fiber product is treated for a predetermined time in a water vapor atmosphere at an absolute pressure of 4 kgf / cm ² or higher and a temperature of 140 ° C. or higher, and then the cellulosic fiber product is maintained in the state where the water vapor atmosphere is maintained. There is disclosed a method for dyeing a cellulosic fiber product, characterized in that water is applied to the fiber and then dyed.
However, in the above method, when the cellulosic fiber is dyed in a deep color, the dyeing property of the dye is still poor, and problems such as a decrease in dyeing fastness occur. There is a strong demand for solutions.
JP-A-6-57658 JP-A-6-128880 JP-A-11-323724

  Therefore, an object of the present invention is to obtain a cellulosic fiber structure excellent in fastness, which is dyed at a much higher concentration than the conventional method, and has a good quality at a low cost. It is to provide a deep color dyeing method.

  As a result of intensive studies in order to overcome the problems of the prior art, the present inventors, as a pretreatment for a normal dark dyeing process, in advance for cellulosic fiber structures and cellulosic fabrics, It was found that a deep-colored dyeing product having a high quality dyed at a high concentration can be obtained by immersing in a specific concentration of lithium chloride aqueous solution, followed by washing and drying. The present invention has been completed based on this finding.

That is, according to the first invention of the present invention, there is provided a method for darkening a cellulosic fiber structure in which a fiber structure containing cellulosic fibers as a main component is subjected to a deep color dyeing treatment with a reactive dye. The cellulosic fiber structure is preliminarily immersed in a mixed solution of lithium chloride and a fatty acid, and then subjected to washing and drying treatment. Is done.
According to a second invention of the present invention, in the first invention, the mixed solution is characterized in that lithium chloride is 0.1 to 24.7 parts by mass with respect to 100 parts by mass of the fatty acid. A method for thickening a cellulosic fiber structure is provided.

According to a third aspect of the present invention, there is provided a method for darkening a cellulosic fiber structure in which a fiber structure containing cellulosic fibers as a main component is subjected to a deep color dyeing treatment with a reactive dye, The cellulosic fiber structure is pre-immersed in a lithium chloride aqueous solution having a lithium chloride concentration of 1 to 55% by mass, and then subjected to washing and drying treatment. A method is provided.
According to a fourth aspect of the present invention, there is provided the method for concentration dyeing a cellulosic fiber structure according to the third aspect, wherein the aqueous lithium chloride solution contains a fatty acid.
Furthermore, according to the fifth invention of the present invention, there is provided a method for thickening a cellulosic fiber structure according to the first, second or fourth invention, wherein the fatty acid is formic acid, acetic acid or propionic acid. Provided.

According to a sixth aspect of the present invention, there is provided the method for darkening a cellulose fiber structure according to any one of the first to fifth aspects, wherein the dipping treatment is a pad / dry method. The
According to the seventh invention of the present invention, in any one of the first to sixth inventions, after the washing / drying treatment, the cellulose-based fiber is further subjected to mercerization processing or liquid ammonia processing treatment. A method of deepening a structure is provided.
Furthermore, according to the eighth invention of the present invention, the cellulose excellent in the deep color dyeing property obtained by the method for darkening a cellulose fiber structure according to any one of the first to seventh inventions. A fiber structure is provided.

  According to the method for darkening a cellulosic fiber structure of the present invention, a dark-colored product of a cellulosic fiber structure dyed at a high concentration can be obtained at a lower cost than the conventional method. Moreover, since the dyeing rate is improved, the dye used can be used efficiently. Furthermore, according to the method for darkening a cellulosic fiber structure of the present invention, there is an effect that it is possible to prevent the fabric from being glossy.

Hereinafter, the thickening method of the cellulose fiber structure of the present invention will be described in detail for each item.
The method for darkening a cellulose fiber structure according to the present invention is a method for darkening a cellulosic fiber structure in which a fiber structure containing a cellulose fiber as a main component is subjected to a dark dyeing treatment with a reactive dye. The cellulosic fiber structure is preliminarily immersed in a lithium chloride aqueous solution having a lithium chloride concentration of 1 to 55% by mass or in a mixed solution of lithium chloride and a fatty acid, and then washed and dried. It is characterized by being applied.

1. Cellulose-based fiber structure In the present invention, the “cellulosic fiber structure” comprises natural or regenerated cellulose fibers such as cotton, hemp, rayon, polynosic, cupra, and high-strength regenerated cellulose fibers (for example, trade name Tencel). Yarns, woven and knitted fabrics, non-woven fabrics, etc., and the fiber structure is a fiber structure containing cellulosic fibers as a main component, and contains other natural, semi-synthetic or synthetic fibers such as polyester and polyamide. Also good.
In addition, when a composite fiber in which synthetic fibers such as polyester and polyamide are mixed with these natural or regenerated cellulose fibers, the composite fiber preferably has a high content of cellulosic fibers, and the cellulosic fibers in the composite fibers In general, it is desirable that the ratio occupied by is 50% by mass or more.
Further, the cellulosic fiber structure may be in the form of threads such as sewing thread, embroidery thread, string, etc., and the form of fabric such as woven fabric, knitted fabric, knit, non-woven fabric, felt, or coat, sweater, other outer garment, Products for clothing such as underwear, pantyhose, socks, lining, interlining, sports clothing, curtains, carpets, chairs, bags, furnitures, wall materials, various belts and sling products, canvas, nets, Various types of textile products are also included, such as products for industrial materials such as ropes and heavy cloth, and artificial leather products.

2. In the present invention, an intermediate temperature type reactive dye is preferably used for dyeing the cellulosic fiber structure. Here, the “medium temperature type reactive dye” is a dye having a moderate reactivity with respect to cellulosic fibers, such as a monofluorotriazine, a sulfatoethylsulfone (vinylsulfone), and a sulfatoethylsulfone. And a dye group such as a polyfunctional type containing a (vinylsulfone) group.

  The addition of the dye to the cellulosic fiber structure can be performed using an aqueous solution (dyeing solution) containing the above-mentioned intermediate temperature type reactive dye and an alkali agent. The dyeing solution further includes, for example, a migration inhibitor, a reducing agent. An inhibitor, a hydrotrope, a penetrating / wetting agent and the like can be blended as necessary.

  As an alkaline agent mix | blended with a dyeing | staining liquid, inorganic alkalis, such as sodium bicarbonate, sodium carbonate, caustic soda, and a tertiary sodium phosphate, are mentioned, Preferably sodium bicarbonate and sodium carbonate are mentioned, for example. These alkali agents can be used in an amount generally in the range of 0.2 to 2.0 mass%, preferably 0.5 to 1.5 mass%.

As the migration inhibitor, for example, Duck Algin NSPM (manufactured by Kibun Co., Ltd.), Diaserver MG-N (manufactured by Mitsubishi Chemical Corporation), Tamanori SA-25 (manufactured by Arakawa Chemical Industries KK) and the like can be used.
Moreover, what is normally used in the said field | area can be used similarly as a reducing inhibitor, a hydrotrope agent, and a penetrating / wetting agent.

Examples of the method for applying the dyeing liquid to the cellulose fiber structure include a pad method, a spray method, and a coating method. For example, in the case of the pad method, the drawing ratio is generally 40 to 100%, preferably 60 to 80%. It is appropriate to perform within the range.
Usually, dyeing is performed by immersing the fiber material in a dye solution in which the dye is dissolved and dispersed to absorb the dye, fixing it by heating or chemical treatment, removing excess dye attached to the fiber surface by washing, Further, post-processing is performed to increase the fastness and the process is completed. The dyeing methods are roughly classified into a discontinuous method (batch dyeing method and exhaust method) and a continuous method (padding method), and either method may be used in the present invention.

The cellulosic fiber structure thus provided with the dyeing solution is usually subjected to dry heat fixing treatment after intermediate drying.
The intermediate drying can be carried out usually by holding in a dryer at 100 to 150 ° C. for about 1 to about 5 minutes, and the dry heat fixing treatment after the intermediate drying is usually 120 to 200 ° C., Preferably, it is carried out by holding in a thermo unit of 150 to 170 ° C., for example, a roller type thermosol dyeing machine or a pin tenter type heat setter for about 1 to about 6 minutes, preferably about 2 to about 3 minutes. it can.

The fiber structure subjected to the dry heat fixing treatment is then subjected to an impregnation treatment with an alkaline solution. The alkali solution used for this treatment can be prepared by dissolving an alkali agent in water together with inorganic salts such as sodium sulfate and salt as required. Examples of the alkali agent that can be used here include inorganic alkalis such as sodium bicarbonate, sodium carbonate, caustic soda, sodium silicate, and potassium hydroxide, with caustic soda and sodium silicate being preferred. These alkali agents can generally be used at a concentration in the range of 0.2 to 30.0 mass%, preferably 0.5 to 10.0 mass%.
The fixing treatment with the alkali solution can be usually performed by immersing the fiber structure in the alkali solution and squeezing it within a range of 50 to 110%, preferably 80 to 100%.

  The fiber structure impregnated with the alkali solution in this way is more preferably subjected to steaming fixing treatment (steaming). This steam heat fixing treatment can be generally performed by exposing the fiber structure to heated steam, for example, by treating with atmospheric saturated steam at a temperature of about 100 to about 110 ° C. for about 20 to 10 seconds. Can be done.

  The fiber structure thus subjected to the steam heat fixing treatment can be subjected to post-treatment steps such as washing, washing and drying according to a conventional method, and thereby dyed at a much higher concentration than the conventional method. A cellulosic fiber structure excellent in fastness can be obtained.

3. Pretreatment of dark dyeing treatment In the method for darkening a cellulose fiber structure according to the present invention, before performing the dark dyeing treatment with the reactive dye, the cellulose fiber structure is preliminarily treated with lithium chloride. The greatest feature is that it is immersed in a mixed solution of fatty acid and fatty acid, or in a lithium chloride aqueous solution having a lithium chloride concentration of 1 to 55% by mass, and then subjected to washing and drying.

  The mixed solution of lithium chloride and fatty acid is desirably mixed at a ratio of 0.1 to 24.6 parts by mass of lithium chloride with respect to 100 parts by mass of fatty acid. The content of lithium chloride and fatty acid in the mixed solution is not particularly limited, but if the mixed amount of lithium chloride is less than 0.1 parts by mass, the effect of improving the thickening due to this pretreatment does not appear, If it exceeds 24.6 parts by mass, lithium chloride will not dissolve.

  The lithium chloride aqueous solution has a lithium chloride concentration of 1 to 55 mass%, preferably 5 to 20 mass%. If the lithium chloride concentration is less than 1% by mass, the effect of improving the darkening due to this pretreatment will not be exhibited. On the other hand, if it exceeds 55% by mass, the aqueous solution will be saturated and unused lithium chloride will increase. It will be disadvantageous.

  Furthermore, the lithium chloride aqueous solution can preferably contain a fatty acid such as formic acid, acetic acid or propionic acid. By including the fatty acid, the deepening effect is further exhibited. The fatty acid is not particularly limited, but is preferably formic acid, acetic acid or propionic acid, and particularly preferably formic acid.

  In addition, when mixing lithium chloride and a fatty acid, although it restrict | limits to said ratio, when adding a fatty acid to lithium chloride aqueous solution, a fatty acid can add desired amount. Moreover, also when adding water to the liquid mixture of lithium chloride and a fatty acid, water can add a desired quantity.

  Moreover, although the conditions of the said immersion process are not specifically limited, Preferably, temperature is 30-50 degreeC and immersion time is about 1 to 10 minutes. Also, a pad / dry method may be used. The pad / dry method is a method of performing a pad (padder) for applying a chemical or a processing agent to fibers, that is, a step of immersing a cloth in the chemical and uniformly squeezing the fabric, and a step of performing a subsequent drying. Generally, it can carry out using the processing machine provided with these processes. The drawing ratio is preferably 50 to 150%, and the drying conditions are preferably 100 to 140 ° C. and 30 seconds to 3 minutes.

In the present invention, it is desirable to perform the above-mentioned immersion treatment, and then to perform cleaning / drying treatment.
The washing treatment may be hot water washing or water washing, and a normal known washing treatment can be adopted. However, as a preferred embodiment, washing with hot water and further washing with water are performed.
Moreover, the usual well-known drying process is employable also as a drying process.

  In the present invention, after the washing / drying process, a mercerizing process (a mercerizing process) or a liquid ammonia process can be further performed as desired. By applying mercerization processing or liquid ammonia processing, a deep dyeing effect is further exhibited.

  Mercerization is also called mercerization, and is a process of applying caustic soda to cotton fabric (or yarn) while applying tension. When cotton is subjected to a strong alkali (caustic soda in this case) at a relatively low temperature, the fibers swell, the fibers are not twisted, and the surface is smoothed. At this time, the cross-sectional shape of each originally flat fiber is deformed into a nearly circular shape at the same time as it swells. Therefore, if an appropriate tension is applied to the fabric (or yarn) at the same time, the smoothness of the fiber surface It becomes better and more glossy. The mercerize is named because it gives a silky luster in the process of treating a cotton yarn fabric under tension with a concentrated caustic soda solution (eg, 20% or more). In mercerization, merchandise is not only glossy, but also changes in the fine structure of the fiber, increasing the absorption of dyes and chemicals, improving dyeability, increasing fiber strength, and providing dimensional stability. is there.

Further, the liquid ammonia processing is a treatment with liquid ammonia, and the texture and anti-mold property having a feeling of swelling which cannot be obtained by mercerization processing are greatly improved. Since liquid ammonia has a lower viscosity and surface tension than water, it easily penetrates into the cotton fibers, and the reaction is completed within a few seconds, and the reaction is uniform. When cotton is dipped in liquid ammonia, the flat and twisted cotton instantly swells, becomes circular and does not twist. Due to the liquid ammonia processing, cotton becomes (i) hard to shrink, (ii) hard to become wrinkles, (iii) the rebound of each fiber increases, (iv) softens, (v) becomes strong, etc. When combined with resin processing, excellent shrinkage and weather resistance can be obtained.
Generally, when cotton fibers are swollen by mercerization or liquid ammonia processing, gloss, touch, strength and elongation are improved. In addition, the reaction with dyes and processing agents is improved, and the form stability is increased. Usually, it is processed in the state of cloth, but it can be performed even at the yarn or raw cotton stage.

4). Dark-dyed product of cellulosic fiber structure The dark-dyed product of cellulosic fiber structure that has been dyed at a high concentration and has excellent fastness can be obtained at a low cost by the method for darkening cellulosic fiber structure of the present invention. Can be obtained at
In addition, dark-dyed products of cellulosic fiber structures can be used for textile products of various uses because of the good quality dyed at high concentrations. For example, only for clothing applications such as shirts, blousons, and pants. In addition, apparel materials such as cups and pads, curtains, carpets, mats, wallpaper, furniture and other interior applications and vehicle parts, belts, nets, ropes, heavy cloth, bags, sewing thread industrial materials, felt, It can also be suitably used for nonwoven fabrics, filters, artificial turf and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to the following Example. In addition, the physical property in an Example is measured and evaluated by the following method.
Dyeing degree (dyeing property): The dyeing property of the dye was evaluated by the K / S value of the dyed fabric (the higher the value, the darker). For the K / S value, the reflectance of the dyed cloth was measured using the colorimeter data color 3890, and the K / S value was calculated by the following Kubelca-Munk equation.

[Example 1]
As a sample fiber (fabric), 100% cotton poplin (50 count single yarn, warp density 148 pieces / inch, weft density 80 pieces / inch) after paste removal, scouring, and bleaching was used.
First, as a pretreatment, the sample fiber was immersed in a mixed solution of lithium chloride / formic acid at a mass ratio of 30/122 at 40 ° C. for 5 minutes, then rinsed with hot water, further washed with water, and dried. went.
Next, the dried product was subjected to a dyeing process. Details of the staining process are as follows.
As a dye,
Navy PROPION NAVY H-EXL: 4.5owf%
CIBACRON GRAY GE 01: 2.5owf%
DRIMAREN RED X-2B: 1.0owf%
as well as,
Bow glass: 9.0 owf%
Soda ash: 1.9 owf%
The cotton was dyed at 90 ° C. according to a conventional method using a liquid dyeing machine at a bath ratio of 1:20.
The obtained fabric had an excellent texture for clothing and showed a bright dark dyeing degree (K / S: 412).

[Example 2]
In Example 1, instead of using a mixed solution of lithium chloride / formic acid at a mass ratio of 30/122, a lithium chloride aqueous solution containing 1.6% by mass of lithium chloride, 13.4% by mass of formic acid, and 85% by mass of water was used. Were all carried out in the same manner as in Example 1.
The obtained fabric had an excellent texture for clothing, and exhibited a dark color dyeing degree (K / S: 348) better than that of Comparative Example 1.

[Comparative Example 1]
All were performed in the same manner as in Example 1 except that no pretreatment was performed. The resulting fabric had a dark dyeing degree of K / S: 315.

[Example 3]
In Example 1, an aqueous solution of 10% by mass of lithium chloride and 0.5% by mass of formic acid was used in place of the lithium chloride / formic acid (mass ratio 30/122) mixed solution, and the pad / dry method (120 The process was performed in the same manner as in Example 1 except that mercerization was performed after washing and drying.
The obtained fabric had an excellent texture for clothing and showed a bright dark dyeing degree (K / S: 533).

[Example 4]
In Example 3, it carried out similarly to Example 3 except having used the aqueous solution of 10 mass% of lithium chloride instead of the aqueous solution of 10 mass% of lithium chloride, and 0.5 mass% of formic acid.
The obtained fabric had an excellent texture for clothing and showed a vivid dark dyeing degree (K / S: 482).

[Comparative Example 2]
All were performed in the same manner as in Example 3 except that no pretreatment was performed. The resulting fabric had a dark dyeing degree of K / S: 324.
The evaluation results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1.

  As is clear from the evaluation results of Examples and Comparative Examples shown in Table 1, Examples 1 and 2 (method of the present invention) were darker than Comparative Example 1. Further, Examples 3 and 4 (the method of the present invention) were darker than Comparative Example 2. Further, from the comparison between Example 3 and Example 4, the effect of formic acid addition to the lithium chloride aqueous solution is also apparent.

  According to the method for darkening a cellulose fiber structure of the present invention, a dark-dyed product of a cellulose fiber structure excellent in fastness dyed at a high concentration can be obtained at low cost. Cellulosic fiber structure thickening method can be used for textile products of various uses, for example, not only for clothing such as shirts, blousons and pants, but also for clothing materials such as cups and pads, curtains and carpets. , Mats, wallpaper, furniture and other interior uses and vehicle component uses, belts, nets, ropes, heavy cloth, bags, sewing thread industrial material uses, felts, non-woven fabrics, filters, artificial turf, etc. .

Claims (8)

A method for darkening a cellulose fiber structure in which a fiber structure containing a cellulose fiber as a main component is subjected to a deep color dyeing treatment with a reactive dye,
The cellulosic fiber structure is preliminarily immersed in a mixed solution of lithium chloride and a fatty acid, and then subjected to washing and drying treatment.   The said mixed liquid is 0.1-24.7 mass parts of lithium chloride with respect to 100 mass parts of fatty acids, The method of deep-dyeing the cellulose fiber structure of Claim 1 characterized by the above-mentioned. A method for darkening a cellulose fiber structure in which a fiber structure containing a cellulose fiber as a main component is subjected to a deep color dyeing treatment with a reactive dye,
The cellulosic fiber structure is preliminarily immersed in a lithium chloride aqueous solution having a lithium chloride concentration of 1 to 55% by mass, and then subjected to washing and drying treatment. Dyeing method.   The method for concentration dyeing a cellulose fiber structure according to claim 3, wherein the lithium chloride aqueous solution contains a fatty acid.   5. The method for thickening a cellulose fiber structure according to claim 1, wherein the fatty acid is formic acid, acetic acid or propionic acid.   6. The method for darkening a cellulose fiber structure according to any one of claims 1 to 5, wherein the dipping treatment is a pad / dry method.   After the washing / drying treatment, a mercerization processing treatment or a liquid ammonia processing treatment is further performed, and the method for deepening a cellulose fiber structure according to any one of claims 1 to 6.   A cellulosic fiber structure excellent in deep color dyeability, obtained by the method for darkening a cellulosic fiber structure according to any one of claims 1 to 7.