JP3229307B2 - Modification method of artificial cellulosic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying an artificial cellulosic fiber using a reactive resin processing agent. More specifically, it imparts a high degree of thread resistance to the artificial cellulosic fiber without impairing the dyeing properties, and has excellent water retention and water absorption and a soft feel with almost no strength reduction.
Further, the present invention relates to a modification processing method having excellent crimp standing when applied to a twisted yarn fabric.

[0002]

2. Description of the Related Art Conventionally, it has been known to process a cloth containing cellulosic fibers with a glyoxal resin in order to improve shrinkage resistance and wrinkle resistance. However, the cellulose fiber obtained by such a processing method has a problem that the water swelling rate is remarkably reduced, and the water retention / water absorption performance, which is an inherent feature of the cellulose fiber, is reduced. In addition, there were also problems that the feel became harder due to resin-like properties and the strength was reduced.

On the other hand, Japanese Patent Application Laid-Open No. 6-146168 discloses a process for suppressing fibrillation of cellulosic fibers. For example, Japanese Patent Application Laid-Open No. 6-146168 discloses the use of N-methylol such as N, N'-dimethylol-dihydroxyethylene urea. A processing method of treating with a fluorinated amine compound is disclosed. However, the cellulosic fiber obtained by such a processing method has a problem that, in addition to the above-described reduction in water retention / water absorption performance and hand hardening, a decrease in strength, when dyeing after the processing, the dyeability is poor and the dyeing becomes light. there were. In addition, the woven fabric woven using a strong twist yarn for the warp and the weft is untwisted by rubbing in water using a washer or the like to untwist and crimp the woven fabric. There is no problem. Further, the solvent-spun cellulosic fiber also has a drawback that the hand is hard.

[0004] On the other hand, Japanese Patent Publication No. 7-122218 discloses a cellulose fiber structure pad-dried with polyethylene glycol (hereinafter referred to as PEG) containing a polyfunctional epoxy compound-containing aqueous solution, followed by wet heat treatment. A working method is disclosed. However, when this method is applied to a fabric containing artificial cellulose fibers, such as copper ammonia rayon, which is easily fibrillated, the effect of suppressing fibrillation is insufficient. There is a problem that fibrils are generated upon repeated washing and repeated washing, causing whitening and a hard feeling. Further, since this method is a two-step process of impregnating with PEG, drying once, then impregnating with a reactive resin, and heating, there is a problem that the process is long and costs increase.

[0005] In addition, natural resin which is one of cellulosic fibers is subjected to various types of resin processing such as durable press processing. Cotton is a short fiber, and the yarn surface is fluffy. The difference between the original fluff on the surface and the generated fibrils is not clear, and it is difficult to determine the effect of suppressing fibrillation. Furthermore, since the yarn surface is fluffy, there is a problem that it is difficult to obtain a clear color by dyeing as compared with the filament yarn.

As described above, in particular, in artificial cellulose fibers such as cuprammonium rayon and the like which are easy to fibrillate, modified fibers which have sufficiently satisfied practical use in thread resistance, water retention / water absorption, soft feeling and dyeability. There was no processing method. For this reason, it is difficult to carry out liquid jet dyeing, which has the advantage of soft texture and high productivity, and there is a hue change and texture hardening due to repeated washing, which leads to the development of outwear and inner clothing. Was an obstacle.
In particular, in addition to the above-mentioned problems, the above-described twisted yarn fabric uses a washer or the like, and because threading occurs when rubbing in water and rubbing, the processing conditions must be mild to avoid this, As a result, there is a problem in that the grain standing property is inferior, and it takes a long time to form the grain, and there is a restriction on the product development.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a high level of thread resistance which can be subjected to jet dyeing, repeated washing, and even crimping with a washer or the like without impairing the dyeing property, and provides good crimping property. It is an object of the present invention to provide a novel reforming method with less water retention / reduction of water absorption, feeling hardening, and lower strength.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, when a glyoxal resin is reacted at a specific weight ratio with an artificial cellulose fiber in the presence of PEG, the artificial cellulose is produced. It has been found that the decrease in the water swelling ratio of the system fiber can be made relatively small, there is almost no decrease in dyeing properties, there is little feeling hardening, and it is possible to impart high thread resistance that can withstand liquid dyeing. . Further, when a cloth containing an artificial cellulose-based fiber obtained by reacting a glyoxal-based resin in the presence of PEG is rubbed with a liquid jet dyeing machine or the like, the resin and unreacted resin adhered to the fiber entanglement point fall off, and the fiber It has been found that the degree of freedom is increased, the flexibility is further increased, and the strength is hardly reduced.

[0009] Furthermore, it has been found that uniform and good crimps can be developed in a short time when a strong twisted yarn fabric containing an artificial cellulosic fiber obtained by reacting a glyoxal resin in the presence of PEG is rubbed in a liquid stream. I came to. That is, the present invention provides a method for modifying an artificial cellulosic fiber, in which a glyoxal resin, an acidic catalyst or a latent acidic catalyst, and polyethylene glycol are applied to the artificial cellulosic fiber, heat treatment is performed, and then liquid jetting is performed. Wherein the weight ratio of polyethylene glycol to the glyoxal resin is 1.5 to 6.0.

Hereinafter, the present invention will be described in detail. In the present invention, the artificial cellulose fiber refers to a regenerated cellulose fiber and a solvent-spun cellulose fiber.As the regenerated cellulose fiber, wood pulp is used as a raw material to obtain alkali cellulose, which is dissolved using carbon disulfide. Then, a viscose rayon, a polynosic, and a cotton ammonia linter obtained by dissolving a cotton linter in a copper ammonia solution by a so-called wet spinning method and spinning in an aqueous acid solution to prepare a viscose stock solution and coagulating the solution are exemplified. .
The present invention is particularly effective for cuprammonium rayon, which is likely to cause threading. When the present invention is applied to copper ammonia rayon, a good effect can be obtained also in terms of hand.

The artificial cellulosic fiber used in the present invention may be either a non-twisted yarn or a twisted yarn. In the case of a strongly twisted woven fabric, the number of twists is 1000 to 3000 T / m, especially 2000 to 2000 T / m.
800 T / m strong twist yarn is preferred. Twist number 1000T / m
In the above-mentioned ones, the relationship between the untwisting force generated when the fiber expands in water and the dimensional change in the yarn length direction and the cross-sectional direction of the yarn is greatly different from that of the lesser ones.
Those having a value of 00 T / m or more affect the size and uniformity of the graininess due to the above relationship. If the number of twists is less than 1000 T / m, the untwisting force is small, so that uniform crimps are not exhibited even in a short time. In addition, mixed fibers of these artificial cellulosic fibers and synthetic fibers, cross-knitted and cross-woven fibers are also included. In this case, the mixing ratio of the artificial cellulose fiber is preferably 30% or more, and more preferably 35% to 100%. Preferred total denier of the artificial cellulose fiber used is 30 d to 150 d, and single denier is 0.95 d.
~ 2.2d.

The modification method of the present invention may be applied to any of coagulated and artificial fibers before drying, dried fibers and woven or knitted fabrics. Alternatively, it is preferably applied to a twisted yarn fabric before embossing and dyeing. In the present invention, the term “thread” refers to a state in which the bonding force between the cellulose molecular chains in the artificial cellulosic fiber is reduced when wet in a graining process, a dyeing process, washing, or the like. By applying physical force to the fiber by friction with other things such as
This is a phenomenon in which the fibers are split, and fibrils refer to the split fibers.

The glyoxal resin according to the present invention includes, for example, N, N'-dimethyl- resins disclosed in European Patent No. 0036076, JP-A-64-75471 and JP-A-2-112478. Non-formalin-based resin processing agent using dihydroxyethylene urea,
Low-formalin-based resin processing agents using N, N'-dimethylol-dihydroxyethyleneurea, resin processing agents using these derivatives, and mixtures thereof. In particular, N, N'-dimethyl-dihydroxyethylene urea, a non-formalin-based resin processing agent, has a smaller decrease in the water swelling ratio of the fiber, a smaller decrease in the dyeability, and a high graininess when used in a strongly twisted fabric in a short time. It is preferably used because it stands uniformly.

Examples of the acidic catalyst used in the present invention include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids, oxyacids such as lactic acid, tartaric acid, citric acid and glycolic acid, and amine hydrochloride. Examples thereof include inorganic metal salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, zinc chloride, zinc nitrate, zinc borofluoride, magnesium chloride, and magnesium borofluoride. As these acidic catalysts and latent acidic catalysts, those suitable for the glyoxal resin used can be used alone or in combination of two or more. In particular, magnesium borofluoride alone or a mixed catalyst obtained by combining magnesium borofluoride with magnesium borofluoride is preferable because high reactivity can be obtained and strength reduction is small.

The PEG used in the present invention has a molecular weight of 200
It is preferable to use those in the range of
In particular, those having a range of 300 to 600 are preferable. When the molecular weight is less than 300, the cross-linking length of the cross-linked structure obtained in the cross-linking with the glyoxal-based resin is too short, so that the effect of improving the dyeability and the effect of producing grain are insufficient, and the molecular weight is 60.
If it is 0 or more, the cross-linking length is long and the thread resistance effect is insufficient, and the shrinkage of the woven fabric occurs rapidly during crimping of the strongly twisted fabric, the untwisting force is reduced, and the uniform and good crimping effect can be sufficiently exhibited. Can not.

In the method for modifying artificial cellulose fiber according to the present invention, a solution using the compound is applied and heat-treated. First, the artificial cellulose fiber is immersed in the compound solution. The wet pickup ratio of the compound solution is preferably 40% owf or more, more preferably 40 to 150%.
It is adjusted by squeezing with a mangle so that it becomes owf. Next, drying is performed at 50 to 150 ° C. for 20 seconds to 2 minutes,
Heat treatment is performed at 30 to 200 ° C. for 30 seconds to 5 minutes.

It is to be noted that the drying may be omitted and only heat treatment may be performed. However, drying is preferred because the migration of the compound can be suppressed and the compound is uniformly attached. Examples of a method of applying a solution to a fiber or a cloth include a Dip / Nip method, single-side application using a kiss roll, a spray method, and the like, and any method may be used. As a heating device, a pin tenter, a short loop, a shrink surfer or the like is used.
In addition, as a method of applying the compound to the artificial cellulose-based fiber, it is preferable to prepare a mixed solution of a glyoxal-based resin and an acidic catalyst or a latent acidic catalyst and three kinds of PEG, and apply the mixed solution to the fiber. After applying PEG, a glyoxal resin and an acidic catalyst or a latent acidic catalyst may be applied. Further, another agent such as a softener or a water repellent may be mixed. The solution is not particularly limited as long as it dissolves them, but an aqueous solution is particularly suitable.

The concentration of the glyoxal resin and catalyst used is such that the glyoxal resin is 1 to 20% by weight.
%, Especially 2 to 15% by weight, and the catalyst amount is preferably 6 to 25% based on the concentration of the glyoxal resin used. When the amount of the glyoxal resin is less than 2% by weight, the thread resistance effect is insufficient. When the amount is more than 15% by weight, the texture is impaired, and at the same time, the strength and the grain development are reduced. Similarly, if the amount of the catalyst is less than 6% of the concentration of the glyoxal-based resin, the crosslinking of the glyoxal-based resin becomes insufficient, and the thread resistance decreases. If the amount of the catalyst exceeds 25%, the cross-linking can be performed sufficiently. The damage to the surface increases, and the expression of the grain decreases. The concentration used in the present invention is expressed as a 100% concentration of the active ingredient of the drug.

Further, PEG is determined in accordance with the use concentration of the glyoxal resin, since the dyeability is improved in proportion to the use concentration, and is determined in the range of 3 to 50% by weight, particularly 3 to 30% by weight. It is preferable to use in the range of. 3
When the amount is less than 30% by weight, the effect of improving the dyeability and the effect of improving the graininess are insufficient, and when the amount is more than 30% by weight, the effect of improving the dyeability is sufficient, but the thread resistance is reduced, and good grain is developed. It becomes difficult to do. Further, the use concentration ratio (weight concentration ratio) of PEG to the glyoxal resin is 1.5-6.
0, particularly 1.5 to 4.0, the dyeability,
All the performances such as the threading resistance and the graining property are the best.

The mechanism for improving the dyeability and water absorption in the present invention is estimated as follows. When the glyoxal resin and PEG are applied to the artificial cellulose fiber, the resin and PEG permeate and diffuse into the fiber. Moisture evaporates due to the heat treatment, and the resin and PEG remain inside the fiber, and the PEG swells due to the PEG. Furthermore, the glyoxal-based resin reacts not only with hydroxyl groups on the fiber molecules but also with PEG by high-temperature heat treatment,
Is cross-linked to the fiber via the glyoxal resin, and a cross-linked structure having a relatively long cross-linking length seems to be formed. Therefore, compared to the conventional processing of glyoxal resin alone, the cross-linking length is longer and the hydrophilic group of the cross-linked PEG increases the permeability of water molecules, and the decrease in the water swelling ratio is reduced compared to the conventional processing of glyoxal resin alone. It seems to do.

Further, the ether bond in the PEG molecule enhances the nucleophilicity of the unreacted hydroxyl group on the fiber molecule, increases the efficiency of binding of the dye molecule to the hydroxyl group on the fiber molecule, and improves the dyeability of the conventional glyoxal. It seems to be improved as compared with the processing of the base resin alone. The mechanism by which the crimping property of the strongly twisted fabric is improved is not clear, but the crimping property contributes to the increase in hydrophilicity due to the PEG component fixed to the fibers, the coefficient of static friction between fibers, the untwisting force, and the like. It is considered that these parameters change.

In the present invention, the liquid-rubbing means rubbing with a liquid stream, for example, a liquid-flow dyeing machine, a win dyeing machine,
This refers to treating a fabric with a paddle dyeing machine, a drum dyeing machine, a washer, or the like. A water stream is preferred as the liquid stream. By this liquid flow rubbing treatment, resin, unreacted substances, and the like adhering to the fibers and at the fiber entanglement point fall off, the degree of freedom of the fibers increases, and the effect of softening the texture and preventing the strength from decreasing is exhibited. This liquid jetting treatment is achieved by dyeing with a liquid jet dyeing machine or the like,
Dyeing after removing the adhered resin and unreacted substances by performing soaping or washing with a liquid jet dyeing machine or the like in advance is preferable because it can prevent staining spots and color blurring. In addition, this liquid flow rubbing treatment can be performed also as the untwisting / texturing step of the twisted yarn fabric. That is, it is possible to perform the main reforming process on the greige before the crimping of the twisted yarn fabric, and to crimp with water using a washer or the like, and simultaneously remove the adhered resin and unreacted substances.

The soaping agent used for soaping is an agent which makes it easier for the above-mentioned attached resin and unreacted resin to be desorbed from the fiber, such as an alkali agent such as sodium hydroxide and sodium carbonate, and a nonionic polyoxyethylene alkyl ether. And surfactants such as alkylthioethers and alkylphenol ethers. The concentration of the soaping agent used (the definition of the concentration used is as described above) and the processing conditions are 0.2 to 3 g / L and the pH of the processing bath is 9 to 1 in consideration of the damage to the fiber.
An appropriate amount of an alkali is used in combination at 1 to 40 to 80 ° C.
For 10 to 40 minutes.

In the present invention, when a treatment with a crosslinking agent reactive with the artificial cellulosic fiber is carried out after the grain raising step, not only the dry and wet wrinkle resistance is improved, but also
It is preferable because the shrinkage rate is remarkably reduced and the shrink resistance is improved to a level at which washing at home is possible. Crosslinking agents reactive with cellulose include aldehyde compounds, acetal compounds,
Examples include epoxy compounds and polycarboxylic acids, and specific examples include formaldehyde, urea / formaldehyde initial condensate, various methylol compounds, various glyoxal compounds, and the like. In the present invention, glyoxal-based resins such as N, N'-dimethyl-dihydroxyethylene urea, N, N'-dimethylol-dihydroxyethylene urea, and derivatives thereof have excellent shrink-proof / wrinkle-proof properties and a small amount of generated formalin. It is preferable from both aspects of safety.
As the catalyst used for this resin, the above-mentioned catalyst is preferable.

The method of treating the cross-linking agent is preferably the same except that PEG is removed in place of the above-mentioned mixed solution of the glyoxal resin, the catalyst and PEG. Various finishing agents such as a softener and a water repellent may be mixed with the two kinds of mixed solutions.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. The measurement items shown in the examples were measured by the following methods. (1) Dyeing property: using a Macbeth spectrophotometer MS-2020, a CIE Lab color system according to JIS-Z-8730, and a dyed fabric (resin untreated fabric) that has not been subjected to a modification process of resin process. ) Eab is measured for △
Eab is represented by the following equation. From △ Eab = {(△ L) 2 + (△ a) 2 + (△ b) 2} 1/2 The △ Eab, was determined dyeability according to the following criteria. 0 ≦ ΔEab <1: （(good) 1 ≦ ΔEab <5: Δ (somewhat good) 5 ≦ ΔEab: × (insufficient)

(2) Laundry test method The modified and unmodified products were subjected to JIS.
Washing and drying were performed 10 times according to -L-0217.

(3) Abrasion Resistance A 3 cm square sample was taken from a total of 9 points, three points at the left and right ends, three points at the center, and three points at random in the length direction after dyeing and washing, and then using an optical microscope. Observed in, further sampled in 1 cm square around the place where the thread condition was the largest, took a scanning electron microscope (SEM) photograph at a magnification that included 20 or more confounding units, and quantified the thread condition by the following. And the thread ratio were calculated.

The term "entanglement unit" as used herein refers to a portion where the warp yarns of the fabric are entangled and appear on the surface. For example, in the case of a warp yarn, the warp yarns are separated by the entanglement with the adjacent weft yarns on both sides. When the cloth is plain weave, the texture points are alternately entangled units. The thread condition is visually observed, and one or two single fibers are fibrillated: 0.5 Three or more single fibers are fibrillated, or one fibrillated is 100 μm or more: scored as 1 The thread ratio was calculated by the following equation. Thread rate (%) = total fibrillation score / total number of confounding units x 100

(4) Feeling (softness): The texture was judged to be tactile for the modified and untreated ones by 10 subjects, and the texture hardening was evaluated as 0 points and the texture softness as 1 point. Each person was evaluated, and the texture (softness) was determined from the total score according to the following criteria. 8 to 10 points: ○ (good) 4 to 7 points: △ (somewhat good) 0 to 3 points: (insufficient)

(5) Water swelling ratio (water retention): 20 ° C. × 60
% Rh was immersed for 30 minutes in a deionized water, and the centrifugally dehydrated at 3500 rpm for 5 minutes, and the absolute dry weight was W2 (g). (G), and the water swelling ratio was calculated by the following equation. The higher the water swelling ratio, the higher the water retention. Water swelling ratio (%) = (W1−W2) ÷ W2 × 100

(6) Resin sticking rate: JIS-L-1041
The amount (%) of resin fixed to the fiber is determined in accordance with the above.

(7) Cracking: The surface shape of the twisted fabric is measured using an electron beam three-dimensional roughness measuring device (ERA-5000 manufactured by Elionix Inc.), and the Yanagi method is one of the surface analysis methods. (Yanagi et al., Journal of the Japan Society for Precision Engineering, Vol. 61, No. 1, P
65 (1995); No. 2, P243 (199
5)) was analyzed to extract surface shape parameters. From the correlation of the results of the surface roughness parameters and the surface roughness parameters of the sensory evaluation by the multiple regression analysis, the following prediction formula of the surface roughness can be obtained, and the surface roughness can be quantified. Formula for estimating graininess: 16.98 + 0.0551 × (average wavelength) −3.77
2 × (plane inclination angle Krut) −0.0473 × (average mountain interval variance) −14.37 (distribution index) The larger the value calculated from this prediction formula, the better the graining property and the difference in numerical value If there is more than 1, there is a significant difference.
This prediction formula can also evaluate the uniform state of the grain and the height of the grain.

(8) Tear strength: In the case of woven fabric, JIS-L
According to the pendulum method, in the case of a knitted fabric, JI
SL-1018 Performed according to the single tongue method.

(9) Shrinkage of washing: JIS-
The knitting is performed according to the JIS-L-1018-G method (home electric washing machine method) in accordance with the L-1042-G method (home electric washing machine method).

[0036]

Example 1 A Bemberg Georgette greige machine having a warp density of 71 yarns / inch and a weft density of 77 yarns / inch, composed of copper ammonia rayon yarn (75 d / 45 f, twist number SZ 2500 T / m) for both the warp and the weft, was used. '-Dimethyl-dihydroxyethylene urea: 3.6% by weight, magnesium borofluoride catalyst: 0.5% by weight, and the use concentration of PEG-400 was 5.5% by weight, 8.0% by weight, and 12.0% by weight, respectively. After immersion in the mixed processing agent solution, the mangle (5 kg /
cm ² ), squeeze to 60% wet pick-up, 50 ° C
, Dried at 170 ° C for 45 seconds,
Then, after embossing for 2 hours with a washer, it was scoured and dried in a usual manner. Then, using a liquid flow dyeing machine, Sumifi
x Black B (manufactured by Sumitomo Chemical Co., Ltd.) with 5% owf, anhydrous sodium sulfate 50 g / L and sodium carbonate 20 as auxiliary agents
The dyeing bath containing g / L was dyed at a bath ratio of 1:20, subjected to a sufficient soaping treatment after dyeing, dehydrated, and dried using a shrink surfer manufactured by Hirano Techseed to obtain Examples 1-. . These were uniform and good embossed products in appearance. The SEM photograph of thread resistance was 75 times. Table 1 shows the evaluation results.

[0037]

Example 2 Copper-ammonia rayon yarn (75d / 45f) before coagulation regenerated by coagulation and regeneration by wet flow tension spinning
N, N'-dimethyl-dihydroxyethylene urea: 1
3% by weight, and magnesium borofluoride catalyst: weight 2.2
%, PEG-400: 30% by weight, a wet-on-wet application to a wet pickup 100% with a kiss roll, and drying at 150 ° C. for 10 seconds. Using this yarn, a greige machine similar to that of Example 1 was prepared in accordance with a conventional method, crimped with a washer for 2 hours, scoured and dried, and then dyed and dried in the same manner as in Example 1. Was obtained. This was a good embossed product having a uniform appearance in the same manner as in Example 1. Table 1 shows the evaluation results.

[0038]

Example 3 The same greige machine as in Example 1 was crimped for 2 hours under gentle conditions in which threading was not likely to occur, and a scoured and dried fabric was prepared under normal conditions, and the fabric was N, N'-dimethyl- Dihydroxyethylene urea: 3.6% by weight, magnesium borofluoride catalyst: 0.5% by weight, PEG-40
After being immersed in a mixed processing agent solution of 0: 8.0% by weight, it was squeezed with a mangle (5 kg / cm ² ) to 100% of a wet pickup, dried at 140 ° C. for 1 minute, and cured at 170 ° C. for 1 minute. Subsequently, dyeing and drying were carried out in the same manner as in Example 1 to obtain Example 3. This is compared with the first and second embodiments.
Although the appearance of the grain was slightly inferior in appearance, the grain was relatively uniform. Table 1 shows the evaluation results.

[0039]

Example 4 N, N'-dimethylol-dihydroxyethylene urea: 3.6% by weight on the same greige as in Example 1.
A mixed catalyst of magnesium chloride and magnesium borofluoride: immersed in a mixed processing agent solution of 0.3% by weight and PEG-400: 20% by weight, squeezed to 100% of wet pickup with a mangle (5 kg / cm ² ), and heated at 140 ° C. It was dried for 1 minute, cured at 170 ° C. for 1 minute, and then crimped with a washer for 2 hours, and then scoured and dried according to a usual formulation. Subsequently, dyeing and drying were performed in the same manner as in Example 1 to obtain Example 4. This product is uniform in appearance,
It was found that the glyoxal resin was inferior to the non-formalin-based resin processing agent in comparison with the non-formalin-based resin processing agent in terms of the raised surface. Table 1 shows the evaluation results.

[0040]

COMPARATIVE EXAMPLE 1 The same greige machine as in Example 1 was embossed with a washer for 3 hours, scoured and dried in a usual manner, and then dyed and dried in the same manner as in Example 1 to obtain Comparative Example 1. Comparative Example 1 was not subjected to the modification processing of the present invention, and thus was a grain-deteriorated product having a non-uniform appearance and overall poor appearance despite the fact that the surface was textured for 3 hours using a washer. A whitening phenomenon due to thread was observed on the entire surface of the surface. Table 1
Shows the evaluation results.

[0041]

Comparative Example 2 The same greige machine as in Example 1 was immersed in a mixed processing agent solution of N, N'-dimethyl-dihydroxyethylene urea: 3.6% by weight and magnesium borofluoride catalyst: 0.5% by weight. (5 kg / cm ² ), squeeze to 60% wet pickup, dry at 50 ° C. for 2 minutes,
The mixture was cured at 0 ° C. for 45 seconds, and then crimped with a washer for 2 hours, and then scoured and dried according to a usual formulation. Subsequently, dyeing and drying were performed in the same manner as in Example 1 to obtain Comparative Example 2.
In Comparative Example 2, since PEG was not contained in the processing agent as compared with Example 1, the graining property was extremely low and nonuniform. Table 1 shows the evaluation results.

[0042]

Comparative Example 3 N, N'-dimethylol-dihydroxyethylene urea: 6% by weight of a mixed catalyst of magnesium chloride and borofluoride: immersed in a 0.3% by weight mixed processing agent solution, and then wet picked up with a mangle (5 kg / cm ² ).
%, Dried at 50 ° C. for 2 minutes, cured at 170 ° C. for 45 seconds, and then crimped with a washer for 2 hours, and then scoured and dried according to a normal formulation.

Next, dyeing and drying were carried out in the same manner as in Example 1 to obtain Comparative Example 3. In Comparative Example 3, since PEG was not contained in the processing agent and N, N'-dimethylol-dihydroxyethylene urea was used, the graininess was lower and unevenness was lower than that of Comparative Example 2, and the dyeing was further lightened. The staining spot was remarkable. Table 1 shows the evaluation results.

[0044]

COMPARATIVE EXAMPLE 4 The same greige machine as in the first embodiment was used in the same manner as in the third embodiment.
After erecting, the fabric scoured and dried in the usual formula is PEG-4
After immersion in a 00: 30% by weight solution, mangles (5 kg /
cm ^Two ) And squeeze to 100% wet pickup
Dry at 20 ° C. for 3 minutes. Further, the fabric obtained by the above method
To N, N'-dimethylol-dihydroxyethylene urine
Element: After immersion in 7.0% by weight of a processing agent solution, mangle (5
kg / cm^Two ) To 90% wet pickup
And dry at 140 ° C for 1 minute and cure at 170 ° C for 1 minute.
Ringed. Then, dyeing and drying were performed in the same manner as in Example 1.
Thus, Comparative Example 4 was obtained. Comparative Example 4 had low graining property and
It is uniform, and the entire surface of the fabric is
Whitening phenomenon was observed. Table 1 shows the evaluation results.

[0045]

[Table 1]

[0046]

Embodiment 5 The warp yarn is a copper ammonia rayon yarn (75 d /
45f), the weft is copper ammonia rayon yarn (100 d
/ 70f, twist density 2700T / m)
Book / inch, weft density 74 pieces / inch
A cloth that has been crimped under gentle conditions that is unlikely to cause threading, scoured and dried is prepared, and the cloth is N, N'-dimethylol-
Dihydroxyethylene urea: 7% by weight, mixed catalyst of magnesium chloride and magnesium borofluoride: 0.7% by weight
%, PEG 400 (polyethylene glycol having an average molecular weight of 400): immersed in a mixed processing agent solution of 30% by weight, and then wet picked up with a mangle (5 kg / cm ² ).
It was squeezed to 0%, dried at 100 ° C. for 1 minute, and cured at 160 ° C. for 3 minutes. Then, dyeing was performed in the same manner as in Example 1,
Drying was performed to obtain Example 5. Here, the resin fixation rate of the modified example 5 of Example 5 was 10.7%. Table 2 shows the evaluation results.

[0047]

Example 6 In the same manner as in Example 5, the cloth which had been crimped, scoured and dried was used to obtain N, N'-dimethyl-dihydroxyethylene urea: 7% by weight, magnesium borofluoride: 1.0% by weight, and PEG 400: 15% by weight. After being immersed in a mixed processing agent solution, the wet pickup was squeezed with a mangle (5 kg / cm 2) to 100%, dried at 100 ° C. for 1 minute,
Cured at 3 ° C. for 3 minutes. Subsequently, dyeing and drying were performed in the same manner as in Example 1 to obtain Example 6. Table 2 shows the evaluation results.

[0048]

Example 7 N, N'-dimethylol-dihydroxyethylene urea was added to a copper ammonia rayon yarn (75d / 45f) before coagulation and regenerated by a wet flow tension spinning method.
7% by weight, mixed catalyst of magnesium chloride and magnesium borofluoride: 1.0% by weight, PEG400: 30% by weight
To 150% of wet pickup with a kiss roll in Wet on Wet
Dried at 10 ° C. for 10 seconds.

Similarly, copper ammonia rayon yarn (100
d / 70f) was also subjected to the above resin processing. Using these yarns, a greige machine described in Example 5 was prepared, embossed, scoured, and dried according to a conventional method, and then dyed in the same manner as in Example 1.
After drying, Example 7 was obtained. Table 2 shows the evaluation results.

[0050]

Example 8 N, N'-dimethylol-dihydroxyethylene urea: 7% by weight, mixed catalyst of magnesium chloride and magnesium borofluoride: 0.
7% by weight, PEG 400: 30% by weight, immersed in a mixed processing agent solution, squeezed with a mangle (5 kg / cm 2) to 100% wet pickup, dried at 100 ° C. for 1 minute,
The mixture was cured at 60 ° C. for 3 minutes, and then crimped according to a normal formulation and scoured and dried. Then dyed in the same manner as in Example 1,
After drying, Example 8 was obtained. Table 2 shows the evaluation results.

[0051]

Comparative Example 5 The crimped, refined and dried fabric of Example 5 was dyed and dried in the same manner as in Example 1 without performing the modification treatment of the present invention, to obtain Comparative Example 5. Table 2 shows the evaluation results of the woven fabric. In addition, this woven fabric was uneven and poor in appearance on the whole, and a whitening phenomenon due to thread was observed on the entire surface of the fabric.

[0052]

Embodiment 9 A stretchable elastic warp knitted fabric having a six-course satin net as a basic structure was knitted using a four reed, 28 gauge Raschel warp knitting machine. That is, cupra copper ammonia rayon yarn (75d / 45f) is used for the front reed, nylon multifilament yarn (30d / 10f) is used for the first reed,
A first stretchable elastic yarn (7
0d), the second resilient elastic yarn (40d) made of polyurethane is arranged in a full set on the rear reed, the front reed, the first reed,
The knitting structure of the middle reed, the second middle reed and the rear reed was set as follows, and a greige was obtained. Front reed: 11/1/11/11/21/11 First middle reed: 10/12/21/23/21/12 Second middle reed: 00/22/22/33/11/11 Rear reed: 00 / 22/11/33/11/22

The greige was blanched at 90 ° C. for 20 seconds.
Preset for 45 seconds at 0 ° C. The fabric was immersed in a mixed processing agent solution of N, N'-dimethyl-dihydroxyethylene urea: 4% by weight, magnesium borofluoride: 0.6% by weight, PEG 400: 8% by weight, and then mangle (5 kg / c).
m ² ), squeeze to 60% wet pickup, 160 ° C
For 45 seconds. Subsequently, dyeing was carried out in the same manner as in Examples 1 and 2, and drying and setting were carried out at 180 ° C. to obtain Example 9. The SEM photograph of thread resistance was 35 times. Table 2 shows the evaluation results.

[0054]

Comparative Example 6 A greige machine similar to that in Example 9 was blanched at 90 ° C. for 20 seconds and preliminarily set at 190 ° C. for 45 seconds. Subsequently, dyeing was carried out in the same manner as in Example 1, and a drying set was carried out at 180 ° C. to obtain Comparative Example 6. Table 2 shows the evaluation results.

[0055]

Comparative Example 7 A greige machine similar to that in Example 9 was blanched at 90 ° C. for 20 seconds and preliminarily set at 190 ° C. for 45 seconds. N, N'-dimethyl-dihydroxyethylene urea: 4% by weight, magnesium borofluoride: 0.6% by weight
Mangle (5 kg / c)
m ² ), squeeze to 60% wet pickup, 160 ° C
For 45 seconds. Then, dyed in the same manner as in Example 1,
Drying set was performed at 180 ° C. to obtain Comparative Example 7. Table 2 shows the evaluation results.

[0056]

[Table 2]

[0057]

Industrial Applicability The method for modifying artificial cellulose fiber of the present invention imparts high thread resistance to artificial cellulose fiber without impairing dyeing properties, and has excellent water retention and water absorption with almost no decrease in strength. It can have both softness and softness. Further, the obtained artificial cellulosic fiber is characterized in that it does not have a hue change or a feeling hardening due to repeated washing. Furthermore, the obtained twisted yarn fabric made of the artificial cellulosic fiber is characterized in that it has uniform and good crimping properties in a short time.

Claims (1)

(57) [Claims] Claims: 1. A method for modifying an artificial cellulosic fiber, which comprises applying a glyoxal resin, an acidic catalyst or a latent acidic catalyst, and polyethylene glycol to the artificial cellulosic fiber, heat-treating the liquid, and then rubbing the liquid. A method for modifying artificial cellulose fibers, wherein the weight ratio of polyethylene glycol to glyoxal resin is 1.5 to 6.0.