JP4895401B2 - Cellulose / gelatin composite viscose rayon filament, method for producing the same, and fiber product including the same - Google Patents

Description

  The present invention relates to a cellulose / gelatin composite viscose rayon filament capable of non-uniform dyeing, a method for producing the same, and a fiber product including the same.

  Non-uniform dyeings such as gradations, gradations, patterns, and marbling are conventionally treated as high-grade dyeings for special purposes. These general non-uniform dyeings are produced by blending with different fiber raw materials using the difference in dyeing of fiber products. Typical examples are spun yarns that blend a variety of fibers, including synthetic fibers such as polyester, nylon, acrylic, wool, silk, cotton, hemp, rayon, acetate, triacetate, and vinylon, natural fibers, semi-synthetic fibers, and regenerated fibers. Each of these fibers has a different dye that can be dyed, and even in the same dye, the dyeing properties are different due to the difference in the structure of the polymer constituting the fiber. In addition, as a process for changing the dyeability, cellulose fiber mercerization and mercerization, and a blend of post-processed products subjected to cationization treatment introducing quaternary ammonium are generally carried out. In the same manner as described above, the filament material is also produced by twisting and arranging various types of materials and post-processed fibers. Mixed yarns obtained by entanglement of various types of filaments are also in these categories. For some synthetic fibers, a special spinning process is used to change the crystal structure and to change the dyeing properties by changing the shape such as thickness as thick and thin, or a conjugate that simultaneously spins polymers of the same amount. There is also a gate yarn. As other means, a method in which fibers or fabrics are irradiated with a low-pressure mercury lamp in advance (Patent Document 1), a method in which a specific compound is reacted with fibers (Patent Document 2), and the like have been proposed.

  However, many of these are dominated by blending technology and spinning technology, and even if a random number table is used for mixing polymer components, it is patterned and becomes a uniform fashion product. In many cases, different materials are mixed, and the texture and physical properties of the product are mixed and different from those of the same material.

  On the other hand, there are also fashion products that make full use of dyeing techniques such as blur prints, bigo prints, pigment dyeing and decoloring, denim slen dyes and indigo surface dyeing. These are also patterned in industrial production and become a uniform product as a whole. Manufacture by hand is necessary to obtain fashion-like specialities in product units.

  Now that unique design is required, custom-made production lots will become infinitely small even if these conventional technologies are fully utilized, and it will not be possible to handle them sufficiently. .

On the other hand, the present applicant has proposed an invention (Patent Document 3) relating to a spinning dope for cellulose / protein composite fiber and a cellulose / protein composite fiber and Patent Document 4 as a method for producing a filament. However, unsatisfactory dyed fibers such as tone, tone, pattern, and marbling tone have not yet been obtained.
Japanese Patent Laid-Open No. 6-200487 JP-A-11-81131 JP 2004-149953 A JP 2007-39836 A

  In order to solve the above-mentioned conventional problems, the present invention provides a cellulose / gelatin composite viscose rayon filament capable of post-dyeing and non-uniform dyeing with the same dye, a method for producing the same, and a fiber product including the same.

  The cellulose / gelatin composite viscose rayon filament of the present invention is a cellulose / gelatin composite viscose rayon filament obtained by mixing a viscose spinning solution and a gelatin crosslinking solution immediately before the spinning nozzle, wherein the viscose spinning solution and gelatin are mixed. The filaments differ in dyeability by being heterogeneously mixed or reacted with the cross-linking solution, and are characterized by post-dyeing and non-uniform dyeing with the same dye.

  The method for producing a cellulose / gelatin composite viscose rayon filament of the present invention is a method for producing a cellulose / gelatin composite viscose rayon filament obtained by mixing a viscose spinning solution and a gelatin crosslinking solution immediately before the spinning nozzle, By maintaining the temperature at the time of mixing the viscose spinning solution and the gelatin cross-linking solution at a temperature of 38 to 45 ° C., by performing non-uniform mixing or non-uniform reaction, the dyeability differs in the length direction, and post-dyeing and the same dye are used. It is characterized in that a filament capable of non-uniform dyeing is obtained.

  Another method for producing a cellulose / gelatin composite viscose rayon filament of the present invention is a cellulose / protein composite viscose rayon filament obtained by mixing a viscose spinning solution and a protein cross-linking solution immediately before a spinning nozzle. A method for producing a cellulose / protein composite viscose rayon filament having a plurality of nozzles and using a plurality of spinning spindles, wherein the temperature during mixing of the viscose spinning solution and the gelatin crosslinking solution is maintained at a temperature of 38 to 45 ° C. The method is characterized in that by performing non-uniform mixing or non-uniform reaction, a dyeing property is different between spinning spindles, and a filament capable of post-dyeing and non-uniform dyeing with the same dye is obtained.

  The fiber product of the present invention is a fiber product containing the cellulose / gelatin composite viscose rayon filament.

  According to the present invention, the viscose spinning solution and the gelatin cross-linking solution are mixed non-uniformly or reacted non-uniformly, whereby the filaments have different dyeability and can be dyed after dyeing and non-uniform dyeing with the same dye. / Gelatin composite viscose rayon filament can be provided. According to the production method of the present invention, when the viscose spinning solution and the gelatin crosslinking solution are mixed immediately before the spinning nozzle, the viscose spinning solution and the gelatin crosslinking solution are kept at a temperature of 38 to 45 ° C. By mixing or non-uniform reaction, it is possible to obtain a filament having different dyeability in the length direction and capable of post-dyeing and non-uniform dyeing with the same dye. According to the production method of the present invention, when a plurality of spinning nozzles are provided and a plurality of spinning spindles are obtained, the temperature at the time of mixing the viscose spinning solution and the gelatin crosslinking solution is maintained at a temperature of 38 to 45 ° C. By performing non-uniform mixing or non-uniform reaction, it is possible to obtain a filament that has different dyeability between the spinning spindles and can be post-dyed and non-uniformly dyed with the same dye. Moreover, the filament of the present invention can be made into a non-uniform dyeing such as tone, tone, pattern, marbling tone, etc. while being a yarn in the same lot.

  In the present invention, by means of chemically and physically promoting a mild reaction between cellulose and gelatin, the spinning conditions are intensively studied, and the knowledge that filaments with significantly different dyeing properties can be produced in the same line (spinning machine) is obtained. I found it. With regard to the production of filament fibre, it is a common sense to uniformly spin, and these studies have hardly been made. This is because spinnability is the most important factor for continuously produced filaments, and even if there is a concept, it is considered indispensable to set up a line with large spinning equipment, and so far there has been no realism. . The mechanism of the present invention is presumed to contribute to the difference between the weights developed in the regenerated fiber, but surprisingly the dyeing difference is so severe that the level deviates and cannot be predicted without the characteristics of the weights. As for the viscose spinning solution, gelatin, cross-linking agent and gelatin cross-linking solution used in the present invention, ie, a solution obtained by adding a cross-linking agent to an aqueous gelatin solution, those described in JP-A-2007-39836 may be used. .

  More than 100 years have passed since the viscose-processed cellulose regenerated fiber filament has been put on the market, and many of its production mechanisms have been elucidated. Manufactured by allowing alkali to act on raw pulp, aging, making xanthogen with carbon disulfide, dissolving alkali xanthate in caustic soda, spinning in sulfuric acid aqueous solution, coagulating, replacing and regenerating. Although it is called a cake method, a half cake method, a semi-spinning method, and a continuous spinning method by a spinning machine, the above-described processes are not changed, and manufacturing conditions are defined by a huge experience value for each company and each method. In general, dope production from a spinning raw material is manufactured and managed in one whole factory and supplied to several dozen to several hundred spinning machines by piping to produce filaments. In general, when a single spinning machine is used as a cake method, it is common to obtain a plurality of spinning spindles of several tens to 100 spindles. The coagulation liquid is also adjusted at the factory level, and the same one is supplied to each spinning machine. Therefore, when differentiating recycled fibers, it is not possible to change the above-mentioned conditions partially within the factory, and it is necessary to perform spinning under exactly the same control, or to establish spinning conditions for all hundreds of units (the entire factory). Instead, it involves major changes. Together with the use of large amounts of alkali and strong acid during the process, these have become a major obstacle to differentiation.

  In general, the viscose dope supplied to the spinning machine is maintained at a level of around 20 ° C. (± 2 ° C.) annually, and the spinning room is controlled at 20 ° C. to 26 ° C. Introduced in. That is, the reaction between the protein and the viscose via the crosslinking agent is presumed to be governed by the alkali of the viscose dope, and no other control is performed.

  In the present invention, the study was started from the viewpoint of promoting the reaction between viscose and protein. In general, the reaction of the crosslinking agent depends on the alkali and temperature in the system. However, as described above, the change in the viscose dope, the coagulating liquid and the spinning conditions is large and lacks reality. The pH of the protein stock solution cannot be increased greatly at the maximum due to temporal stability. Therefore, it was considered that the components and temperature in the system could not be changed at all, and changes at the time of protein introduction were considered.

  Possible means include (1) change in protein concentration of the protein stock solution, (2) strength and ON / OFF of stock solution injection, and (3) heating during injection. (1) and (2) are possible in principle. However, for example, in a 54 spindle cake type spinning machine, the length of viscose pipe with a diameter of 20φ is about 16m from 1 spindle to 54 spindles, and even if the protein concentration change and ON / OFF are finely performed, the length is quite long It becomes a change and I can't expect an impact dyeing difference. Further, the protein solution OFF state is a regular rayon with respect to the portion, which is a composite of different fibers and is different from the present invention, but its fashionability is not denied. In (3), considering the stability over time, it is difficult to warm the whole stock solution, and a small amount of warming is possible immediately before the introduction of viscose. However, problems still remain when considering continuous replenishment of stock solutions.

  As a result of this intensive study, it was found that if the rotational speed of the rotor of the in-line mixer is increased, the rotor chamber generates heat due to mechanical factors.

  As a result, if the temperature at the time of mixing the viscose spinning solution and the gelatin cross-linking solution is kept in the range of 38 to 45 ° C., the two are mixed non-uniformly or react non-uniformly, and the dyeing properties of the filaments are different. It was found that a filament that can be dyed and dyed unevenly with the same dye can be obtained. In particular, although a substantially stable staining property is exhibited in one weight, those having different staining properties can be obtained among a plurality of weights. This seems to be a chemically non-uniform dope in the length direction in a long pipe led to the spinning spindle. The means for controlling the temperature in the range of 38 to 45 ° C. may heat the mixing region from the outside, but it is convenient and preferable to generate heat of mixing by increasing the rotational speed of the line mixer.

  It is presumed that the reaction through the cross-linking agent is partly instantaneously progressed by being instantaneously heated simultaneously with the introduction of the protein into the viscose. In fact, the surface temperature of the rotor chamber is 29 ° C. at 1000 rpm for the in-line mixer, 36 ° C. at 2000 rpm / 38 ° C. at 2250 rpm / min, 40 ° C. at 2500 rpm / min, 43 ° C. at 2800 rpm / min, It was 45 ° C. at 3000 rpm and 49 ° C. at 3500 rpm. As for the spinnability, actual production was possible up to 3000 revolutions / min. However, when it exceeded 3100 revolutions / min, the yarn breakage slightly increased, and spinning became difficult at 3500 revolutions / min. Heating exceeding the limit in this way is considered to result in the aging of the viscose dope and disappearing of the appropriateness under the set spinning conditions, and spinning becomes difficult due to yarn breakage.

  Therefore, if the filament fineness of spinning with the rotor chamber capacity of the in-line mixer is in the range of 83.3 dtex (75d) to 133.3 dtex (120 d), the surface temperature of the rotor chamber is 38 to 45 ° C. or less, and the rotor rotational speed is 2250 to It was found that about 3000 revolutions / min is preferable.

  Heat generated by the rotation of the rotor in the in-line mixer can be easily achieved by controlling the inverter of the motor to be connected. The heat generated by the dope varies depending on the capacity of the rotor chamber, the spinning speed, and the denier, depending on the residence time in the rotor chamber. However, the surface temperature of the rotor portion can be controlled within ± 2 ° C. depending on the number of revolutions within the range of 55.6 dtex (50d) to 333.3 dtex (300 d) used for fashion clothing.

  The filaments obtained by the present invention have extremely different dyeing properties for each spindle even in a single spinning machine. This variation in the dyeing difference does not vary greatly within one spindle, and continues with relatively small fluctuations until the nozzle replacement and filter replacement of the spinning machine that are regularly performed in two to three weeks. After this regular maintenance, the fluctuations between the weights are reorganized in a new disorder, and a small fluctuation passes again until the next maintenance.

  As a mechanism for developing the heterogeneous staining property, firstly, the protein reaction is promoted via cellulose via a crosslinking agent. In the reaction system, the reaction proceeds in a spot-like manner only by a temperature rise of only 10 ° C. to 20 ° C. However, it is not possible to explain all of the above phenomena. Protein amino groups, carboxyl groups, reaction between protein and hydroxyl groups of cellulose, cross-linking between protein main chains, cross-linking between cellulose molecules and between molecules, and mere coagulation are extremely complicated and cannot be specified, and naturally there are interactions. . Probably, aging of viscose and hydrolysis of protein proceed simultaneously with the acceleration of the reaction, and it is considered that there is discontinuous and non-uniform retention of components in the piping and filter part before spinning. However, even if the fiber shapes of the portions where the dyeing difference is large are compared, neither change is felt, and there is no problem such as deposition of the dope as compared with the regular rayon when replacing the filter, and the spinning is good.

  The degree of non-uniform staining in the present invention is standardized by the CIE (International Lighting Commission) in 1976 and standardized by JIS Z 8729. In the L * a * b * color system measurement, the L value is measured in the same lot. It is preferable that (lightness) is different by 2 or more. More preferably, the L value (brightness) is different within a range of 3 to 15 within the same lot. It is very difficult in production technology to obtain a difference exceeding the L value of 15 in the same lot.

  For dyeing, a reactive dye for dyeing cellulose, a direct dye, an acid dye for dyeing silk or wool, a chromium dye, and the like are appropriately selected, and there is no problem with a conventional method. Of course, it is not limited to dyeing forms such as cheese dyeing or anti-dying, and any other fiber can be mixed and is not limited. For example, by using only the filament according to the present invention as a warp of a woven fabric, it is possible to produce a vertical streak-patterned or tone-like woven fabric with a subtle pattern with an at random shade by anti-dyeing. As an example, as shown in FIG. 1, in a circular knitted jersey, an infinite number of shaded horizontal border patterns can be created by post-dying. When a blended yarn is produced from the product of the present invention, for example, as shown in FIG. 2, the marbling tone, which is also a characteristic of the spun yarn, can be expressed by a filament by post-dying. Thus, the heterogeneous filament of the present invention has a wide range of applications.

  The filament of the present invention can be applied to various products such as woven fabrics, knitted fabrics and braids. As the woven fabric, plain weave, oblique weave, satin weave, altered plain weave, altered oblique weave, altered satin weave, alter weave, crest weave, single layer weave, double structure, multiple structure, warp pile weft, weft pile weave, entanglement There are weaving etc. Examples of the knitted fabric include round knitting, weft knitting, warp knitting, pile knitting, etc., flat knitting, tengu knitting, rib knitting, smooth knitting (double-sided knitting), rubber knitting, pearl knitting, denby knitting, cord knitting, atlas knitting, There are chain tissue, insertion tissue, etc. Examples of the textile product of the present invention include the following. Clothing and daily necessities: Clothing (including outerwear, underwear, sweaters, vests, trousers, etc.), gloves, socks, mufflers, hats, bedding, pillows, cushions, stuffed animals, etc. Interior materials: chair upholstery, curtains, wallpaper, carpets, etc. It is particularly suitable for products that make use of dyeability and are fashionable.

  The present invention will be specifically described below with reference to examples. In addition, this invention is not limited to the following Example.

Example 1
Extracted with beef bone as a raw material by conventional methods (immersion treatment in 4% by mass hydrochloric acid for 2 days, water washing, immersion in pH 12.5 lime water for 20 days, water washing, hot water injection, batch method extraction). Furthermore, it was purified by a conventional method (extracted gelatin was filtered through a cotton-like filter and impurities such as metal ions were removed with an ion exchange resin).

  Proteolytic enzyme (serine protease) was allowed to act on the extracted and purified gelatin to perform hydrolysis, and the processing time was changed while monitoring the jelly strength in accordance with JIS K6503 to prepare various hydrolyzed gelatins. Each gelatin solution was concentrated and the enzyme was inactivated with hydrogen peroxide solution. The solid content concentration of the obtained gelatin solution was measured by a weight method after evaporating water at 110 ° C. for 5 hours. The solid content concentration was 40 ± 2% by mass. Further, when analyzed by high performance liquid chromatography, the number average molecular weight of gelatin was 28000, and the gel point was 21 ° C.

  20 kg of this gelatin solution was put into 20 kg of hot water adjusted to 45 ° C. and stirred to obtain a gelatin solution. 50 mass% sodium hydroxide was added to the solution to adjust the pH to 10. After confirming that the solution was uniform, 2 kg of a water-soluble polyfunctional aliphatic epoxy compound (Denacol EX851 (manufactured by Nagase ChemteX)) was added to the solution over 30 minutes, and stirring was performed for 3 hours. Temperature control was stopped and the solution was allowed to cool slowly. A gelatin cross-linking solution of about 19% by weight gelatin was obtained. This gelatin cross-linking solution may be prepared sequentially in this amount ratio as necessary.

  Next, in a viscose spinning solution (alpha cellulose 8.3% by mass, NaOH 5.7% by mass, carbon disulfide 32% by mass) prepared by a conventional method, gelatin is 20% by mass (solid content) with respect to cellulose. The gelatin cross-linking solution was injected with a gear pump so that the amount added was equivalent to 870.4 g of the gelatin cross-linking solution per 10 kg of the viscose spinning solution, and an in-line mixer (TK pipeline homomixer; Using PRIMIX 2S type), mixing was performed immediately before spinning.

  The spinning conditions by the cake method having 54 spindles are not particularly limited, but are spun at a spinning speed of 69 m / min to 210 g / L of sodium sulfate, 115 g of sulfuric acid, 30 g / L of zinc sulfate (Müller bath), The discharge amount per spindle was 5.27 ml / min and the switching time was 18 hours, and the product was wound on a cake (pot motor rotation speed: 8200 rotations / min). Next, the cake was scoured and dried to produce a filament with a total fineness of 83.3 dtex (75d) and 24 filaments. At this time, spinning was started at a rotor speed of 2500 rpm for the inline mixer. The surface temperature of the rotor chamber was in the range of 39.6 ° C. to 40.5 ° C. throughout the measurement.

  Referring to FIG. 3, the viscose spinning solution 1 is fed to the in-line mixer 5 by the gear pump (P1) 2 and simultaneously the gelatin crosslinking solution 3 is injected to the in-line mixer 5 by the gear pump (P2) 4. In the in-line mixer 5, the viscose spinning solution 1 and the gelatin crosslinking solution 3 are mixed, fed to a spinning nozzle (die) 6, the filament 7 is extruded at a spinning speed of 69 m / min, and the spinning solution (sodium sulfate in the coagulation tank 8). It was solidified with 210 g / L, sulfuric acid 115 g / L, zinc sulfate 30 g / L (Mueller liquid)) 9, and wound around cake 13 in cake box 12. After 18 hours, the cake was taken out (switched) and scoured in a batch system to complete the coagulation regeneration, and dried to produce a filament. Reference numerals 10 and 11 are Nelson rollers.

  Spinning was carried out 5 times at a switching time of 18 hours, nozzle exchange and filter exchange were carried out, and spinning was continued from the 6th order to the 10th order. All the cakes (spinning spindles) obtained were numbered and scoured and dried by conventional methods to obtain cake yarns. A part of the yarn on each spindle from 1 spindle to 54 spindles was knitted by a sock knitting machine for about 5 cm. A knitted fabric of 1 to 54 weights was prepared, and chrome dyeing was performed in the same bath on the 1st, 3rd, 5th, 6th, 8th and 10th orders.

  As dyeing conditions, a knitted fabric is made of a dye solution containing 2% OWF of chrome dye (manufactured by Yamada Chemical Co., Ltd .: chrome black PLW), 2% owf of sodium sulfate, and 1% owf of formic acid. The temperature was further raised and kept at 100 ° C. After 40 minutes, potassium dichromate 1% owf was added, and further kept at 100 ° C. for 20 minutes for staining. The temperature was adjusted, and after cooling, the solution was thoroughly washed with water and dried. The transition of the L value of each weight is shown in FIGS. 1st order, 3rd order, and 5th order tend to be similar between weights, and 6th order, 8th order, and 10th order also have similar dyeing difference although the pattern of specific weight is different from the previous term. I understand. When the gray scale (JIS L 0804: Gray scale for color change) was selected with a difference of 3.5 or higher, the dark, medium and light colors were as shown in FIG. This also shows that a similar pattern is repeated.

  Similarly, the knitted fabric of the 2nd order and the 7th order was prepared, and reactive dye SumifixSupra (manufactured by Sumitomo Chemical Co., Ltd .: SumifixSupraYellow 3RF 0.5% owf, Red 4BNF 0.5% owf, Blue BRF 0.5% owf), 20 g / L of sodium sulfate was added at a bath ratio of 1:20, and after 30 minutes at a temperature of 60 ° C., a fixing treatment was carried out for 30 minutes with 8 g / L of sodium carbonate, followed by subsequent steps such as drying. After that, a brown dyed cloth was obtained. Further, similarly, the fourth and ninth orders of knitted fabrics were prepared, and the reactive dye Sumifix HF (manufactured by Sumitomo Chemical Co., Ltd .: Sumifix HF Yellow 3R 0.62% owf, Red 3G 0.48% owf, Blue BG 0. 36% owf), 20 g / L of sodium sulfate was added after 10 minutes at a bath ratio of 1:20 and a temperature of 90 ° C., kept for another 20 minutes, and the temperature was changed to 80 ° C., and 10 g / L of sodium carbonate was added. Was added in portions and fixed for 30 minutes, followed by subsequent steps such as drying to obtain a brown dyed cloth. These dyeings were similar to those in FIG. 1, and visually, the difference in dyeing due to these reactive dyes was almost the same as the above-mentioned chromium dye.

  FIG. 7A shows a cross section of the lightly dyed portion of the filament obtained in the fifth order, and FIG. 7B shows an electron micrograph of the same side (magnification: 3000 times). Further, FIG. 8A shows a cross section of the deeply dyed portion of the filaments obtained in the fifth order, and FIG. 8B shows an electron micrograph of the same side (magnification: 3000 times). From the photographs in FIGS. 7 to 8, a clear difference in shape between the deeply dyed portion and the lightly dyed portion is not felt. Each of them has a flat cross section and smooth side surfaces, and is clearly different from the shape of viscose rayon. From this, it can be judged that the non-uniform dyeing is not due to fine spots, but due to non-uniform mixing or non-uniform reaction of the viscose spinning solution and the gelatin cross-linking solution.

(Example 2)
Using the same type of spinning machine in the same factory as in Example 1, spinning was performed in exactly the same manner except that the rotational speed of the in-line mixer was set to 3000 rpm / min (the surface temperature of the rotor chamber was 44.7 ° C.). 1 to 54 spindles were knitted. Although the thread breakage was somewhat large and there were some missing weights, the result of chrome dyeing had almost the same dyeing difference as in the examples. Next, 3500 revolutions / min (the surface temperature of the rotor chamber was 49 ° C.) was tried, but many yarn breaks occurred, spinning was interrupted, and no data was obtained.

(Example 3)
Spinning was performed in exactly the same manner as in Examples 1 and 2, except that the total fineness was 133.3 dtex (120d), the number of filaments was 44, and the spinning speed was 81 m / min, the discharge rate was 11.03 ml / min, and the switching time was 10 hours. Carried out. The results of chrome dyeing are shown in FIG. Compared with Example 1 of 83.3 dtex (75d), the L value slightly decreased and the color became darker, but the variation was similar. This slight decrease in the L value is considered to be caused by a large discharge amount and a decrease in residence time in the rotor at 120d compared to 75d.

(Comparative Example 1)
Spinning was carried out in the same manner as in Examples 1 and 2, except that the rotor of the in-line mixer was rotated at 1000 rpm / min (the surface temperature of the rotor chamber was 29 ° C.) during normal operation. The results of chromium dyeing of 1 to 54 spindles of the knitted fabric are plotted in FIG. As is clear from FIG. 10, Comparative Example 1 was a uniform fiber and lacked variability.

(Comparative Example 2)
The operation was performed in the same manner as in Comparative Example 1 except that the rotation speed of the in-line mixer was changed to 2000 rotations / min (the surface temperature of the rotor chamber was 36 ° C.), and the results are also shown in FIG. It can be seen that Comparative Example 2 also has little variation in dyeing difference compared to Example 1.

Example 4
Two yarns obtained in Example 1 and Comparative Example 2 were randomly arranged, and two sock knitted fabrics were prepared with a round net automatic test knitting machine MR-1 (manufactured by Maruzen Sangyo Co., Ltd.). Each was dyed with a chromium dye under the same conditions as in Example 1. What was obtained was a sock knitted fabric in which gray shades as shown in FIG. 1 exist clearly and discontinuously. Further, the same knitted fabric was dyed brown with a reactive dye in the same manner as in Example 1. As a result of being dyed with the above-mentioned chrome dye, a brown knitted fabric was obtained.

(Example 5)
Using the yarns obtained in Example 1 and Comparative Example 3, mixed yarns were prepared by a conventional method. After the sock knitted fabric was prepared in the same manner as in Example 4, it was dyed with a chromium dye in the same manner as in Example 1. The dyed knitted fabric had a gray frost-like color of spun yarn as shown in FIG. Unlike spun yarn, it is made of 100% filament, so there is no fluff, and it is plain and unprecedented in quality while being marbling.

(Example 6)
Filaments 75D / 24F obtained by the production method of Example 1 were randomly extracted, combined with polyester (semi-dal) 33T / 12F, twisted 1400 times / m in the S and Z directions by conventional methods, 5488 A book thread was obtained. 40 whales, 1372 whales, 4 throughs (grating width 130 cm: 1056 wings / cm 5488) SZ 2 warps alternately, and the weft yarn is the same as the warp yarn except that the filament obtained by the method of Comparative Example 1 is used. Two twisted yarns with polyester were driven alternately. A filament fabric of 72% recycled fiber (including the present invention) and 28% polyester was used. The obtained georgette fabric was dyed by a conventional method (two-bath dyeing with a disperse dye and a reactive dye). In addition, it dye | stained so that the filament of Comparative Example 1 used for a weft and polyester (semi-dall) might become the same color. As specific dyeing conditions, Sumikaron dye (manufactured by Sumitomo Chemical Co., Ltd .: disperse dye Sumikaron Yellow E-RPD 0.21% owf Red E-RPD 0.11% owf, Blue E-RPD 0.05% owf) Adjust pH to 5 with acetic acid and sodium acetate, add 0.5 g / L of Nikkasan Salt RM-340E (manufactured by Nikka Chemical Co., Ltd.) as a leveling assistant, and rise from the liquid temperature at a bath ratio of 1:20. Warmed and kept at 125 ° C. for 40 minutes. After cooling to 70 ° C. and washing with modified liquid, as a reactive dye, Kaycelon React dye (manufactured by Nippon Kayaku Co., Ltd .: Kaycelon React Golden Yellow CN-GL 0.22% owf, Red CN-3B 0.065% owf, Blue CN- MG 0.10% owf), sodium sulfate 40 g / L and kayak buffer NP-7 1 g / L were added, and the mixture was heated from the liquid temperature at a bath ratio of 1:20 and fixed at 100 ° C. for 40 minutes. Washed with water, washed with hot water, dehydrated, and dried with warm air.
Unlike the regular strife tone, the resulting fabric was an elegant brown chilemen-like fabric with discontinuous and delicate warp running.

  As described above, according to the present invention, a filament in which protein is combined with cellulose having variable variation capable of non-uniform staining is produced. Even with 100% use of the product of the present invention, a product (textile product) rich in shade design can be created. Even if it is combined with a uniform filament in which a protein is combined with cellulose as shown in the comparative example, the design property is further changed. Moreover, if different materials (such as synthetic fibers such as polyester, nylon, acrylic, etc., recycled fibers such as rayon, natural fibers such as cotton, hemp and wool) are selected and combined as appropriate, the variation will be further increased. It becomes a variety.

FIG. 1 is a plan view of a dyed product showing a horizontal border pattern of a circular knitted jersey using fibers obtained in one embodiment of the present invention. FIG. 2 is a plan view of a dyed product showing a marbling pattern. FIG. 3 is a schematic explanatory view showing a spinning process in Example 1 of the present invention. FIG. 4 is a graph showing variation in the non-uniform dyeing L value of the obtained fiber. FIG. 5 is a graph showing variation in the uneven dyeing L value of the obtained fiber. FIG. 6 is a graph showing the period of variation in uneven dyeing of the obtained fibers. FIG. 7A is a cross-sectional photograph of the light-colored part of the fiber, and FIG. 7B is a planar photograph (magnification: 3000 times). FIG. 8A is a cross-sectional photograph of the dark portion of the fiber, and FIG. 8B is a planar photograph (magnification: 3000 times). FIG. 9 is a graph showing variations in the non-uniform dyeing L value of the fiber obtained in Example 3 of the present invention. FIG. 10 is a graph showing variation in non-uniform dyeing L value of the fibers obtained in Example 1 and Comparative Example 1 of the present invention. FIG. 11 is a graph showing variations in non-uniform dyeing L values of the fibers obtained in Comparative Example 2.

Explanation of symbols

1 Viscose spinning solution 2, 4 Gear pump 3 Gelatin cross-linking solution 5 In-line mixer 6 Spinning nozzle (clasp)
7 Filament 8 Coagulation tank 8
9 Mueller liquid 10, 11 Nelson roller 12 Cake box 13 Cake

Claims (6)

A cellulose / gelatin composite viscose rayon filament obtained by mixing a viscose spinning solution and a gelatin crosslinking solution immediately before the spinning nozzle,
The cellulose is characterized in that the viscose spinning solution and the gelatin cross-linking solution are heterogeneously mixed or non-uniformly reacted so that the filaments have different dyeability and can be dyed after dyeing and with the same dye. / Gelatin composite viscose rayon filament.   In the L * a * b * color system measurement standardized by the CIE (International Lighting Commission) in 1976 and standardized by JIS Z 8729, the degree of non-uniform staining is measured in the same lot. 2) The cellulose / gelatin composite viscose rayon filament according to claim 1, wherein 3 or more are different. A method for producing a cellulose / gelatin composite viscose rayon filament obtained by mixing a viscose spinning solution and a gelatin crosslinking solution immediately before a spinning nozzle,
By maintaining the temperature at the time of mixing the viscose spinning solution and the gelatin cross-linking solution at a temperature of 38 to 45 ° C., by performing non-uniform mixing or non-homogeneous reaction, the dyeability differs in the length direction, and post-dye and the same dye A method for producing a cellulose / gelatin composite viscose rayon filament characterized in that a filament capable of non-uniform dyeing is obtained. Cellulose / protein composite viscose which is a cellulose / protein composite viscose rayon filament obtained by mixing a viscose spinning solution and a protein crosslinking solution immediately before the spinning nozzle, and has a plurality of spinning nozzles and uses a plurality of spinning spindles. A method of manufacturing a rayon filament,
By maintaining the temperature at the time of mixing the viscose spinning solution and the gelatin cross-linking solution at a temperature of 38 to 45 ° C. and performing non-uniform mixing or non-uniform reaction, the dyeing properties differ among the spinning spindles, and post-dyeing and the same dye A method for producing a cellulose / gelatin composite viscose rayon filament characterized in that a filament capable of non-uniform dyeing is obtained.   4. The method for producing a cellulose / gelatin composite viscose rayon filament according to claim 3, wherein the means for controlling the temperature in the range of 38 to 45 [deg.] C. is heat of mixing by increasing the rotational speed of a line mixer.   A fiber product comprising the cellulose / gelatin composite viscose rayon filament according to claim 1 or 2.

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