JPH0345138B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to highly colored fibers, that is, a method for imparting deep colors to fibers. Although much research has been conducted on the dyeing of fibers, no fibers that produce the original colors of dyes have yet been developed. In particular, synthetic fibers are said to have poor color development and lack depth of color. Various techniques have been proposed for its improvement.
For example, there is a method of treating the fiber surface with a low refractive index resin such as a silicone resin. It is well known that when fibers are treated with silicone resin, a silicone resin coating is formed on the fiber surface and the color development of the fibers is improved, but the improvement effect of this method is not so remarkable. For example, considering our objective of imparting coloring properties to synthetic fibers such as polyester that are comparable to those of natural fibers, this degree can be said to be extremely low. As another method, a method has been proposed in which the fiber surface is plasma etched to create fine irregularities on the fiber surface to improve color development (e.g.,
99400). However, in this method, although the fine irregularities on the fiber surface absorb light and significantly improve color development, the color loses its luster, and the fine irregularities are extremely easily crushed by abrasion, which is a fatal drawback for practical use. ing. In researching how to increase the color development of fibers, the present inventors discovered that by treating fibers with resin and then subjecting the treated fibers to electrical discharge treatment, fibers with a significantly deeper color than natural fibers could be obtained. This led to the present invention. The present invention provides fibers in a dyeing process (A), a resin coating process, and
(B), discharge step (C), and the order of the three steps is (A)/(B)/(C), (B)/(C)/
This is a method for producing a highly colored fiber characterized by containing either (A) or (B)/(A)/(C). The fibers used in the present invention include polyester fibers such as polyethylene terephthalate, polyamide fibers such as nylon, acrylic fibers such as polyacrylonitrile, synthetic fibers such as polyvinyl alcohol fibers such as vinylon, and natural fibers such as cotton, silk, hemp, and wool. , semi-synthetic fibers such as acetate, and recycled fibers such as rayon. Among these fibers, polyester fibers having poor color development properties and fabrics in which polyester fibers and other fibers are mixed by a well-known method are particularly preferred because the effects of the present invention are large. In addition, as polyester fibers, fibers with irregularities on the surface of the fibers, such as those manufactured by Japanese Patent Application No. 15468/1980, Japanese Patent Application No. 28747/1982, and Japanese Patent Application Laid-Open No. 52-99400, etc., may be used. It is preferable to use a fiber having irregularities on the order of the wavelength of light, since the effects of the present invention can be obtained synergistically compared to the case of using ordinary polyester fiber. The fiber in the present invention is not particularly limited in shape, and may be in any shape such as a thread, a sheet, a woven fabric, or a nonwoven fabric. The resin coating process in the present invention refers to forming a thin layer on the surface of the fibers, and the methods include immersion in a resin solution, pad method, pad steam method, resin solution spray coating method, or resin solution coating method. Although not particularly limited, a dipping method or a pad method is preferred from the viewpoint of controlling the amount of adhesion to the fibers. In addition, if a part or the entire surface of the fiber is subjected to an electric discharge treatment such as corona discharge or glow discharge before the resin coating process, the resin can be uniformly coated on the fiber surface.
In particular, it is more preferable to carry out such pretreatment since the effect of improving color development is remarkable. For coating resin, the resin solid content is calculated based on the fiber weight.
It is desirable to deposit 0.1 to 10% by weight, preferably 0.2 to 5% by weight. If the adhesion amount is less than 0.1% by weight, the surface of the single fibers will not be completely covered and a sufficient effect will not be obtained. Furthermore, if the adhesion amount is 10% by weight or more, adhesion between single fibers becomes noticeable and the texture becomes rough and hard, making it undesirable for use in clothing. The resin used as the coating resin has a refractive index of
It is preferable that the refractive index is 1.50 or less and 0.03 or more lower than the refractive index of the base fiber. If the refractive index of the resin is 0.03 or more lower than the refractive index of the base fiber but exceeds 1.50, or if a resin with a refractive index of 1.50 or less and less than 0.03 lower than the refractive index of the base fiber is used, color development will occur. The improvement effect is not sufficient. When the refractive index of the resin is 1.50 or less and 0.03 or more lower than the refractive index of the base fiber, the effect of improving color development becomes clear, and this tendency becomes more pronounced as the refractive index of the resin becomes lower than the refractive index of the base fiber. become. When the refractive index of the resin is lower than the refractive index of the base fiber by 0.1 or more, coloring properties superior to those of natural fibers can be obtained.For this reason, a more preferable coating resin is one that has a refractive index of 1.50 or less, and A resin having a refractive index that is 0.1 or more lower than the refractive index of the base fiber is desirable. These preferred coating resins include silicon-containing resins, acrylic resins such as polyacrylic acid (methacrylic acid) esters containing long-chain alkyl groups, polyacrylic acid (methacrylic acid) esters containing polyalkylene oxide groups, and fluorine-containing resins. , vinyl ether resin, cellulose resin, urethane resin,
vinyl alcohol resin, acetate resin, etc., such as tetrafluoroethylene-hexafluoropropylene copolymer, polypentadecafluorooctyl acrylate, polytetrafluoroethylene, polyundecafluorohexyl acrylate, polynonafluoropentyl acrylate,
Fluorine-containing resins such as polytrifluorovinyl acetate, polypentafluoropropyl acrylate, polytrifluoroethyl acrylate, polytrifluoroisopropyl methacrylate, polyvinylethyl ether, polyvinyl isobutyl ether, polyvinyl butyl ether, polyvinyl hexyl ether, polyvinyl methyl ether, Vinyl ether resins such as ethyl cellulose, cellulose resins such as methyl cellulose, acetate resins such as polyvinyl acetate, polyvinyl alcohol, polybutyl acrylate, polyisopropyl methacrylate, polytetradecyl acrylate, polymethyl acrylate, polyisobutyl acrylate, poly-n-butyl methacrylate Acrylic acid (methacrylic acid) ester resins, polyurethane resins such as water-soluble polyurethane, polydimethylsiloxane, carbinol-modified silicones, epoxy-modified silicones,
Examples of preferred coating resins include amino-modified silicone, polytrimethylvinylsiloxane, and polyvinyltrichlorosilane. Note that silicone resins having dimethylsiloxane as a skeleton are particularly preferred resins because, although the reason is not clear, coloring properties are greatly improved by plasma treatment. Furthermore, copolymer resins of these monomers and other monomers, mixed resins of these resins and other resins or low-molecular substances, etc. may be mentioned, but as long as the above conditions are satisfied, the resins are limited to the above-mentioned resins. It's not something you can do. Furthermore, friction durability can be increased by adding other silicones having a lubricating effect or low polymerization degree resins having long chain alkyl to the above resin, and polyethylene glycol,
Preferably, antistatic properties can be improved by adding a quaternary ammonium salt, a compound containing sodium sulfonate, or the like. Furthermore, water repellency can be imparted by adding a fluorine-containing compound, silicone, or the like that has water repellency. However, among the above-mentioned resins, when a resin whose main component is a silicone resin, a fluorine acrylate resin, a fluorine acrylate-containing copolymer resin, or a mixed resin thereof is used, the coloring properties are remarkable, and these resins are particularly preferred. The discharge step in the present invention is a step in which the fibers are exposed to a discharge that starts and continues by applying a high voltage, thereby crosslinking the fibers and the coating resin. There are various forms of discharge such as corona discharge and glow discharge, but there are no particular limitations as long as the form of discharge does not cause thermal damage to the fibers, but it is possible to improve the depth of color due to the uniformity of discharge. Glow discharge can be said to be a more preferable discharge form because it has a remarkable effect of improving uniformity and color depth. Corona discharge is a discharge that starts and lasts when high voltage is applied under atmospheric pressure, and glow discharge is
This is a discharge that begins and continues when a high voltage is applied to a gas atmosphere under low pressure. Processing conditions such as discharge power vary depending on the type of resin and processing equipment, and excessive processing can cause the thin layer of resin to be etched away and the coloring properties developed by the discharge process to be lost. For these reasons, it is necessary to select the most preferable conditions for the discharge treatment depending on the resin-treated fiber. Note that if the discharge treatment is extremely strong, extremely fine irregularities, such as uniform irregularities with a depth of 500 Å or more, will be formed on a part of the resin or fiber surface, improving color development, but in this case, the color will not be glossy. This cannot be said to be a desirable selection of conditions. Therefore, it is necessary to select weak processing conditions that will not form such unevenness. Gases used for discharge treatment include Ar, N ₂ , He, CO ₂ , CO,
Common gases such as air can be used, and are not particularly limited and should be preferably selected depending on the type of resin. The dyeing process in the present invention may be any well-known process for dyeing fibers, and is not particularly limited. Further, this step may be performed either before or after the resin treatment or before or after the discharge treatment, and may be appropriately selected depending on the type of resin, manufacturing process, etc. For example, for single-colored fibers, a resin treatment and discharge treatment process may be adopted after the dyeing process, and for printed cloth, a dyeing process is adopted after the resin treatment and discharge treatment processes. It is only necessary to make a preferable selection. Also, the dyeing method is
Conventional dyeing methods such as dip dyeing methods such as the pad roll method, pad dry method, and pad steam method, or textile printing methods may be employed, and may be appropriately selected depending on the type of fiber, purpose, etc. Note that the dye may be selected from among various well-known dyes. The present invention provides the above-mentioned dyeing process (A) and resin coating process.
(B) and discharge step (C) are essential process elements, and at least these three steps are taken, and the order of these steps is (A)/(B)/(C), (B)/(C). )/(A), (B)/(A)/(C), the depth of color is significantly improved synergistically. For example, if the dyeing process or discharge process is used alone, there will be almost no improvement in color development, and if the fiber is subjected to intensive treatment, extremely fine irregularities will be formed on the fiber surface and color development will improve, but the luster will be lost and other desirable effects will occur. cannot be obtained. In addition, only a very slight improvement in color development was observed in the dyeing process and resin treatment process, and there was almost no noticeable change in the resin treatment process and discharge process, and no treatment was observed other than a slight yellowing of the fibers. . The fibers produced according to the present invention may be subjected to commonly used post-processing such as water-repellent finishing, hydrophilic finishing, and antistatic finishing.
At this time, care must be taken so that a large amount of post-processing resin does not adhere and impair the depth of the color. The fibers produced by the method of the present invention: (1) have a greater depth of color than natural fibers; (2) There is no change in color depth due to friction or washing. (3) Furthermore, depending on the resin, water-repellent effects and hydrophilic effects that are durable against friction, washing, etc. can be obtained. It has excellent characteristics that cannot be obtained by conventional processing methods such as Evaluation of the fibers in the present invention was performed based on the following criteria. (1) Depth of color (color development) was determined visually based on the following criteria. Grade 5: Noticeable depth compared to untreated fabric. Grade 4: It has a much deeper feel compared to untreated cloth. Grade 3 There is a difference from untreated cloth. Grade 2: There is no difference from untreated fabric. Grade 1: Less depth than untreated. (2) The abrasion fastness of color depth was measured using a Gakushin-type dyed fabric abrasion durability tester, applying a load of 200g, rubbing the cloth against each other 100 times, and then displaying it in 5 levels using a gray scale for discoloration and fading. . Note that those with a degree of discoloration and fading of grade 4 or higher are those that are practically usable in the present invention. Hereinafter, one embodiment of the present invention will be described based on Examples. Example 1 A 75-denier, 36-filament polyester fiber was twisted at 2500 T/M, and a jersey fabric consisting of strongly twisted yarns in the S and Z directions was washed and embossed in a conventional manner, and then set in dry heat at 180°C. 98
The fabric was treated by immersing it in a 5% caustic soda aqueous solution at a temperature of 0.degree. C. to reduce the weight of the fabric by 25% relative to the weight of the fabric before treatment. This fabric is Dianix Black FB−FS
(Manufactured by Mitsubishi Kasei Corporation, disperse dye) After dyeing at 130℃ for 60 minutes in a dye bath consisting of 15% OWF at a bath ratio of 1:30, the resulting black color is obtained by reduction washing, washing with water, and drying. The dyed polyethylene terephthalate dioset fabric was immersed in a solution of 2 g of dimethylpolysiloxane (Toray Silicone SH-200 Oil (100CS)) dissolved in 100 ml of tetrachlorethylene at room temperature for 5 minutes, and then dried in a hot air dryer at 120°C for 5 minutes. Dry. The cloth was then subjected to plasma treatment using an internal electrode type low temperature plasma treatment machine under the following conditions. Plasma conditions: Gas Ar Pressure 0.6 Torr Applied voltage 3 kV Processing speed 1 m/min The fibers of the present invention produced in this manner, fibers treated with resin in the same manner after dyeing (Comparative Example 2), and untreated fibers ( Comparative Example 1) was also evaluated for color depth (color development) using the visual test described above. The results are shown in Table 1.

[Table] As shown in Table 1, the products of the present invention, that is, the cloths subjected to plasma treatment after resin treatment, had significantly higher color development. Example 2 An undyed polyester fiber dioset fabric was dyed black, red, and blue using a printing method and then treated with carbinol-modified silicone (Toray Silicone Co., Ltd. SF8428).
After immersing 2 g in 100 ml of isopropyl alcohol at room temperature for 5 minutes, drying and low-temperature plasma treatment were carried out under the same conditions as in Example 1. The coloring properties of the product of the present invention produced in this way and the fiber treated with resin but not subjected to plasma treatment (Comparative Example 2) were evaluated. The results are shown in Table 2.

【table】

[Table] As shown in Table 2, the products of the present invention, that is, the printed fabrics treated with resin and then plasma treated, had remarkable color development in each color. Example 3 After treating polyester, nylon, and acrylic fibers with various resins with different refractive index, Example 1
Plasma treatment was performed in the same manner as above, and each fiber was dyed using a conventional dyeing method. The coloring properties of these fibers were investigated and the results are shown in Table 3.

[Table] As shown in Table 3, when each fiber was treated with a resin whose refractive index was 0.03 or more lower than the base fiber and then plasma-treated, the color development increased compared to untreated fibers. In particular, those treated with a resin whose refractive index was 0.1 or more lower showed a marked increase in color development. Example 3 A polyethylene terephthalate dioset cloth dyed black using a conventional dipping method was immersed for 5 minutes at room temperature in a solution in which 2 g of various resins with different refractive indexes shown in Table 3 were dissolved in 100 ml of each solvent, and then soaked at 120°C.
It was dried in a hot air dryer for 5 minutes. The cloth was then subjected to plasma treatment using the low-temperature plasma treatment machine used in Example 1 under the same conditions as Example 1, and the results are shown in Table 4. Note that the refractive index of the polyester fiber was 1.62.

[Table] As shown in Table 4, when a resin with a refractive index of 1.50 or less is used in the present invention, the coloring property is excellent, and in particular, the coloring property of silicone is significantly improved by plasma treatment. Example 5 The black-dyed polyester dioset used in Example 1 was mixed with Toray Silicone SF-8428, polyethylene glycol dimethacrylate (NK Ester 14G, Shin Nakamura Chemical Co., Ltd.), Toray Silicone BY-16-805, and the aforementioned polyethylene. Glycol dimethacrylate (NK ester 14G)
The 2 Vol% solution was immersed at room temperature for 5 minutes, dried in a heat chamber dryer at 120°C for 5 minutes, and then subjected to plasma treatment under the same conditions as in Example 1. Table 5 shows the results.

[Table] As shown in Table 5, the products of the present invention, that is, the cloths that were treated with resin and then plasma treated, had a significantly higher color development (Products 1 and 2 of the present invention). Furthermore, product 3 of the present invention, in which a silicone resin having a low friction effect was mixed into the resin, had excellent color development and friction durability. Example 6 White (undyed) Tetron dioset cloth was mixed with 1 g of Toray silicone BY-16-805 and 3.34.4.5.5.666
After immersing 1 g of nonafluorohexyl acrylate polymer in 100 ml of isopropyl alcohol at room temperature for 5 minutes, it was dried in a hot air dryer at 120°C for 5 minutes. The cloth was then subjected to plasma treatment under the same conditions as in Example 1, and then dyed under the same conditions as described above. 6th result
Shown in the table.

[Table] As shown in Table 6, the products of the present invention, that is, those that were subjected to plasma treatment after resin treatment, had significantly higher color development. Example 7 Polyester fiber dioset was treated with a resin in the same manner as in Example 2, and then printed in black, red, and blue using the same printing method as in Example 2. This product was subjected to plasma treatment under the same conditions as in Example 1 (Example 7). For comparison, a dioset (comparative example) was prepared which was subjected to resin treatment and then print dyeing, but which was not subjected to plasma treatment. The coloring properties of these were evaluated in the same manner as in Example 1 and are shown in Table 7. As shown in Table 7, it can be seen that the coloring properties of Example 7 are significantly superior to those of Comparative Examples in terms of color development for each color.

【table】

Claims (1)

[Claims] 1. The fibers are treated in at least three steps: a dyeing step (A), a resin coating step (B), and an electric discharge step (C), and the order of the three steps is (A)/(B)/(C). , (B)/(C)/(A) or (B)/(A)/(C).