JP2843517B2 - Rayon cake yarn with no difference in inner and outer layer dyeing with disperse dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rayon cake yarn capable of being dyed with a disperse dye and produced by a pot centrifugal take-up spinning machine. The present invention relates to a widely used rayon cake yarn.

[0002]

2. Description of the Related Art Rayon production has a long history, and recently spinning and scouring. Drying. Although a so-called continuous spinning yarn-making technique for continuously performing winding up has also been adopted, an old pot centrifugal winding cake-like rayon yarn is still in use. However, in the case of the centrifugal winding cake yarn, there is a problem of irrationality of using the inner and outer layers of the cake by layer due to the difference in physical properties of the inner and outer layers of the cake and the difference in dyeing. Although the taking tension and spinning speed are changed to reduce the inner and outer layer differences, they have not yet been completely solved.

That is, when the difference in dyeing between the inner and outer layers of the cake, which is the subject of the study, is represented by an index called dyeing density and the difference (R), the index value of a general cake yarn is 50 to 70;
When the guide adjustment for reducing the difference between the inner and outer layers is not performed, the difference in dye density (R) between the inner and outer layers is 3 to 6, and even when the guide adjustment is performed, (R) is at most 2-3. I'll do my best. If the inner and outer yarns of such a cake dye adjacent fabrics and knits, the difference in dyeing will appear clearly visually. One of the major drawbacks is that the conventional rayon yarn has poor light fastness to dyeing, in addition to the difference between the inner and outer layers described above.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors
After examining the characteristics of rayon yarn from all angles,
Rather than modifying the cellulose itself constituting the rayon yarn to enable dyeing into a disperse dye, the organic polymer fine particles that are dyeable to the disperse dye and preferably have good light fastness are added to viscose and mixed to form a yarn. Thereby, a rayon cake yarn in which the fine particles are uniformly dispersed in the yarn length direction is obtained,
When this is dyed with a disperse dye, the water swelling properties of rayon are utilized, and the disperse dye molecules are interposed between the cellulose molecules and dyed into organic polymer fine particles. It has been found that the inner and outer layers can be uniformly dyed irrespective of the general nonuniformity, and that the desired color can be dyed. As a result, not only can yarns be used in every field without any layer, but also, for example, a mixed fiber with a synthetic fiber mainly composed of polyester fiber can be made the same color once in the same bath. An epoch-making cake yarn capable of dyeing any of different colors can be obtained.

That is, according to the present invention, there are provided polymer fine particles having an average particle size of 0.05 to 5 μm which can be dyed with a disperse dye.
A rayon cake yarn containing about 30% by weight and having a dyeing density difference (R) of 2.0 or less between the outer, inner and inner layers of the cake yarn by a disperse dye.

In the present invention, the content of fine particles and the dyeing concentration are determined by the following methods. The outer and inner layers of the cake yarn are defined as 11 weights of the cake yarn (about 600 g) in the length direction of the yarn. Evenly divide, when the outermost layer is called “0 layer” and the innermost layer is called “10 layer”, 0 layer is outer layer, 5 layer is middle layer,
The outer layer, the middle layer, and the inner layer are defined with 10 layers as the inner layer. Then, the cake is handled as being in the same layer within the range of the layer corresponding to 1/11 weight of the whole cake.

<Content of Fine Particles> Approximately 0.1 g of rayon yarn was precisely weighed, dissolved in a copper ammonia solution, and the solution was filtered through a Teflon membrane filter to separate polymer fine particles. After drying, the weight is determined, and the content per fiber weight is determined. The content of each layer means the material n =
It means the average of three measurements.

<Dye density> Color. Using a computer (Suga. S & MCC), a standard white plate (X; 7) was used.
8.73, Y; 81.56, Z; 98.38), the color difference (ΔE) by the Hunter method (L. ab measurement) was measured for each dyed knitted fabric, The difference between the maximum value and the minimum value is defined as (R).

In the present invention, the following four items can be cited as points for uniformly dyeing with a disperse dye without any difference in inner and outer layers and providing a wide range of use. 1) Selection of organic polymer fine particles having good disperse dyeing properties and light fastness 2) Size of organic fine particles affecting dyeing properties 3) Viscose composition for minimizing the amount of added fine particles and physical property deterioration 4) Viscose And stable and uniform dispersion and kneading of fine particles into the yarn production. These important items will be described in detail below.

The rayon cake yarn of the present invention contains 5 to 30% by weight of polymer fine particles which can be dyed with a disperse dye.
It is important that they are included. Examples of the polymer that can be dyed with a disperse dye (hereinafter, sometimes abbreviated simply as a raw material) include polyamides such as nylon 6, nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polymethyl methacrylate, methyl Methacrylate / methacrylic acid copolymer,
Methyl methacrylate / methacrylic acid / styrene copolymers, acrylic acid / styrene polymers, acrylonitrile / styrene polymers, polymethylsilsesquioxanes, silicone polymers such as methyl silicone rubber, urethane polymers, etc. Polyester polymer from the viewpoint of dyeability and color fastness to the original disperse dye,
A thermoplastic polymer such as an acrylic polymer is preferably used.

Recently, blended yarns of polyester fiber and rayon have been widely used for outer applications, and the rayon cake yarn of the present invention is combined with a synthetic fiber such as polyester fiber to have excellent color matching. In order to obtain a final product, it is preferable that the dyeing characteristics of the polyester fiber and the dyeing material (original material) dispersed in rayon are close to each other. It is preferably used. However, depending on the type of the fine particles of the polyester polymer, there is a case where decomposition by viscose is rapid, and the fine particles may be decomposed or dissolved in the viscose. Confirm the solubility in the course in advance, and if the solubility is high, shorten the residence time until spinning after addition to the viscose or handle the added viscose at a low temperature to delay the alkaline decomposition of the polyester It is preferable to take such measures.

As described above, as the organic polymer fine particles,
Basically, it is preferable to use one having good dyeing properties and fastness, but in the present invention, it is presumed that these polymer fine particles are dispersed in rayon while being embedded in cellulose, Even if the fastness is not so good, the rayon often shows better fastness than the original body.

The average particle size of the polymer fine particles used in the present invention must be in the range of 0.05 to 5 μm.
If the thickness is less than 0.05 μm, the dyeing property and fastness with a dye may be reduced, or the dryness may decrease. Since a problem such as easy dissolution in an organic solvent or an alkaline solution such as cleaning may occur, a preferable lower limit is 0.1 μm, particularly 0.2 μm.
μm. On the other hand, if it exceeds 5 μm, stable spinning cannot be performed, such as clogging of a spinning nozzle and generation of fluff. In addition, the obtained fiber has low strength and elongation, and the toughness may be significantly reduced. When the physical properties of the fiber such as toughness are particularly emphasized, the upper limit of the average particle diameter of the fine particles is preferably 3.5 μm, more preferably 2.5 μm, and especially 1 μm.
Is preferred.

[0014] Such polymer fine particles can be obtained by, for example, a physical fine-graining method in which a polymer chip or powder is freeze-pulverized into a fine powder by using a known pulverizer, or a polymerization process of a polymerizable monomer. Fine particles can be produced by a polymerization technique such as a method for forming particles from a polymer solution formed into fine droplets from a polymer solution formed into fine droplets. Depending on the average particle size order of the particles used, the means of grain refinement may be selected, but in fact, depending on the type of polymer, pulverization from micron to submicron order may be extremely difficult, or even polymerization method Some cannot be manufactured. For example, in order to obtain fine particles having a particle size of about 0.05 to 1 μm, an emulsion polymerization method, a soap-free emulsion polymerization method, and a seed emulsion polymerization method are preferably employed.
In the case of ５5 μm, a seed emulsion polymerization method, a two-stage swelling method, a dispersion polymerization method and the like are suitable. Further, these polymers may be solid fine particles or hollow fine particles, and when hollow fine particles are used, high concealing properties and reduction in weight of fibers can be realized at the same time.

The rayon cake yarn of the present invention needs to contain 5 to 30% by weight of such polymer fine particles. If the amount is less than 5% by weight, the dyeing amount may not be sufficiently secured. On the other hand, if it exceeds 30% by weight, fluff is likely to be generated at the time of spinning, and the physical properties of the fiber are likely to deteriorate. From the balance between the physical properties of the fiber and the amount of dyeing that can guarantee not only light dyeing but also deep dyeing, the lower limit of the content is 5% by weight and the upper limit is 30% by weight.
% By weight. Also, if the content is within the range,
The kind of the polymer fine particles is not limited to one, and fine particles composed of two or more different polymers may be mixed. Alternatively, the same kind of polymer fine particles having different particle size distributions may be used in combination.

The rayon cake yarn of the present invention in which such fine particles are blended has a dyeing behavior for disperse dyes similar to that of ordinary polyester fibers, shows good dye exhaustion, and is dyed in a deep color. Depending on the dyeing conditions, such as whether to make a light-color dyeing, the exhaustion amount of the dye can be appropriately set,
It has the ability to dye 0.1 g or more, more preferably 1 mg or more, particularly preferably 4 mg or more of disperse dye per 1 g of fiber weight. This dyeing amount is 0.1mg
If it is less than / g, even if it is a light color, sufficient coloring property cannot be obtained, so it is better not to adopt it. The upper limit of the amount of dyeing does not have a critical special meaning since it largely depends on the dye used, but it is preferably 200 mg / g or less from the viewpoint of the amount of the dye used in deep color dyeing. In addition, the measuring method of the dyeing amount is different between that after dyeing and that before dyeing. For example, for a product dyed with a single dye, 57% A Soxhlet extraction was carried out with an aqueous pyridine solution, and if necessary, the extract was diluted with a 57% aqueous pyridine solution at the same dilution for both fibers, and the adjusted liquid was subjected to the following spectrophotometer [Hitachi 307 color: An analyzer (manufactured by Hitachi, Ltd.)] measures the absorbance at the maximum absorption wavelength, and the amount of dyeing can be determined from another calibration curve. For unstained dyes, the dyeing amount can be determined by a method described below.

Even if the polymer fine particles themselves are dyeable with a disperse dye, in the fiber of the present invention, the fine particles are surrounded by cellulose molecules immiscible with the disperse dye, so that the disperse dye molecules cannot directly contact the fine particles. Although the reason why the disperse dye is dyed on the fine particles in spite of the fiber structure is not clear, rayon swells with moisture in the dyeing process, and the molecular movement of cellulose becomes active, and the arrangement becomes loose. It is presumed that the dispersed dye molecules penetrate into the places where they are, and as a result, the dye molecules dye the fine particles.
This phenomenon is surprising, since no attempt was made to dye rayon cake yarn with a disperse dye. In addition, the cake yarn dyed with a disperse dye was further washed (washed with water) to re-swell the fibers. It is also unexpected that, even when the dye is placed in an environment where the dye is easily detached from the fiber, the dye is still strongly dyed and exhibits an excellent color fastness of washing fastness of class 3 or higher.

Although the rayon cake yarn of the present invention can be dyed with a disperse dye, it is not only that the yarn is dyed with a disperse dye but also that the fastness to washing after dyeing is 3 or higher. It is a rayon cake yarn that can be dyed with disperse dyes. The rayon cake yarn of the present invention is preferably 40% or more, particularly preferably 60% or more when subjected to a dyeing treatment under the following conditions (hereinafter, may be simply referred to as standard dyeing conditions). It is desirable that the cake yarn has a dye dyeing rate of 3 or more, more preferably a fastness to dry cleaning of 3 or more, a sublimation fastness of 3 or more, and a light fastness to carbon arc lamp of 3 or more. It has the above-mentioned color fastness.

<Dyeing Conditions>Dye; Sumikaron Brill Red SE-2BF (Sumitomo Chemical) 3% owf auxiliary agent; Disper TL 1 g / l Ultra MT level 1 g / l Bath ratio; 1:50 Dyeing temperature / time; 120 ° C. × 40 minutes (heated from 40 ° C to 120 ° C in 30 minutes and kept at 120 ° C for 40 minutes) Reduction washing; NaOH 1 g / l, Na ₂ S ₂ O ₄ 1 g / l, amilazine (Daiichi Kogyo Seiyaku) 1 g / l, 80 ° C. × 20 minutes, washing with water; 30 minutes, drying; 60 ° C. × 10 minutes

The disperse dye dyeing ratio in the present invention is defined as
Dyeing ratio (%) = [(S ₀ −S ₁ ) / S ₀ ] × 100 S ₀ : A value obtained by the following method when dyeing under the standard dyeing conditions: Acetone aqueous solution for the dye solution before dyeing (Acetone / water = 1/1 volume ratio) The dye solution diluted and adjusted to a predetermined dilution was measured at the maximum absorption wavelength measured with a spectrophotometer [Hitachi 307 type color analyzer (manufactured by Hitachi, Ltd.)]. Absorbance S ₁ : Maximum absorption measured by a spectrophotometer of a dye solution that has been adjusted to a predetermined dilution with an aqueous acetone solution (acetone / water = 1/1 volume ratio) as necessary, for the remaining dye solution after dyeing. Absorbance at Wavelength In the case of dilution, it is desirable to dilute so that the maximum value of the absorbance is about 0.6. Further, the dye solution before dyeing is diluted, and the dye remaining solution may not need to be diluted because the dye concentration is low.In this case, the dilution ratio of the solution before dyeing is determined by the absorbance of the remaining solution. It is necessary to determine the dyeing rate by the value multiplied by.

The present invention is also characterized in that it exhibits extremely good fastness to various dyeing fastness tests as described above, and such dyeing fastness is just as excellent as ordinary polyester fibers. Color fastness. As further noted, the fibers of the present invention, in addition to these color fastnesses,
It has a wet friction fastness of 2 or more, especially 3 or more.

In the present invention, the various color fastnesses are determined by the following methods. I. Robustness against washing; JIS L0844-1986 (A-2 method) (attached white cloth uses cotton and nylon) b. Fastness to dry cleaning; JIS L0860-1974 (attached white cloth uses cotton and nylon) c. Sublimation fastness: JIS L0850-1975 (B-2 method) (However, hot pressing temperature is 160 ° C and time is 6 hours)
0 second, use polyester for attached white cloth) d. B. Light fastness to carbon arc lamps; JIS L0842-1988 (exposure method employs third exposure method) Wet friction fastness; JIS L0849-1971 (Type II is used for testing machine)

Next, a method for producing the rayon cake yarn of the present invention will be described. The rayon cake yarn of the present invention is obtained by adding the polymer fine particles to viscose, uniformly dispersing and mixing the fine particles by a dispersing / mixing means such as a stirring blade, defoaming and degassing, and then regenerating a bath from a spinning nozzle. , Stretched, and wound into a pot at a predetermined speed.

The addition of the fine polymer particles to the viscose can be performed in any step until the stock spinning solution is spun from the nozzle. The fine polymer particles may be added directly to the stock spinning solution as it is. According to such a method, the fine particles are easily aggregated, so that a concentrated aqueous dispersion of the fine particles is prepared in advance, and this is added to the spinning dope line so as to have a predetermined concentration and mixed, or such an aqueous dispersion is separately prepared. Without preparing, it is preferable to prepare a spinning dope containing fine particles so as to have a predetermined concentration from the beginning.

However, in order to make the difference (R) between the inner and outer layers of the obtained cake yarn between the inner and outer layers smaller than 1.5 as in the present invention, the average value of the content of the fine particles contained in the cake yarn is required. Is n, n in the length direction of the cake yarn
It is desirable that the fine particles are dispersed and compounded in a range of ± 0.1 n. For that purpose, it is important to uniformly disperse the fine particles in the spinning dope (dope). That is the point. However, it should be noted that spinning using an undiluted solution containing air due to excessive stirring results in a decrease in spinnability.

In order to achieve uniform dispersion, the influence of the size of the fine particles cannot be ignored.
In other words, a difference in the specific gravity between the undiluted viscose and the fine particles causes a concentration gradient of the fine particles. As described above, the smaller the particle diameter, the more stable and difficult to separate. However, in any case, it is necessary to reduce the agglomeration of the fine particles and to keep the dispersed state uniform during the stirring and defoaming after the addition. For this purpose, appropriate stirring conditions and low-speed stirring during defoaming are required.

In the case of moderate stirring, it is necessary not to add excessive foam to viscose due to excessively high speed stirring, but to perform stirring at a maximum speed so as to prevent foaming as much as possible. In addition, even during vacuum or stationary defoaming, 40 to 50 rpm.
It is necessary to stir at such a low speed that the defoaming can be carried out smoothly and the dispersion stability of the fine particles becomes good. In particular, when the specific gravity difference between the viscose stock solution and the fine particles is large or the particle size is large, if this low-speed stirring is neglected, the fine particles are likely to be separated in the concentrated dispersion tank, and in the length direction of the produced yarn, The content of fine particles is not constant, resulting in a difference in dyeing.

In order to stably disperse the fine particles in the dispersion or the stock solution for spinning, it is preferable to use a dispersing aid. For example, a nonionic dispersing aid such as polyoxyethylene alkylamino ether is added to the fine particles. 1 for
It is preferable to add about 5 to 30% by weight.

When a variety of brands having different fine particle concentrations are produced, it is more reasonable to separately prepare the aqueous dispersion and to add and mix the solution to the spinning stock solution line according to the brand.
It is necessary to carefully adjust the aqueous dispersion of the fine particles so that the fine particles do not aggregate in the dispersion. For this purpose, the aqueous dispersion is adjusted so that the fine particle concentration becomes 10 to 50% by weight, particularly 15 to 30% by weight. It is preferred to prepare the dispersion.

Next, even if it is possible to produce rayon cake yarn having no dyeing difference between the inner and outer layers, it is necessary that the yarn can be widely used. This is because the addition of a large amount of fine particles to the yarn as in the present invention is accompanied by a remarkable decrease in physical properties, and the degree of the physical property decrease is drastic with an increase in the added amount. As a method of suppressing this remarkable decrease in physical properties, the alkali concentration of the viscose composition is important. In the present invention, the alkali concentration of viscose is 6.5 to 8% by weight, particularly preferably 7 to 7.5% by weight.
The wet strength of the fiber is 0.4 g / d or more, preferably 0.45
g / d or more.

If the alkali concentration exceeds 8%, problems such as a decrease in spinning speed and insufficient refining properties tend to occur due to delay in coagulation and regeneration. On the other hand, if it is less than 6.5%, it is difficult to keep the wet strength within the range of the present invention. In addition, the maturity and the viscosity of the viscose can adopt known conditions, for example, the conditions of a maturity of 8 to 15 cc and a viscosity of 20 to 60 poise.

The bath composition of the coagulation / regeneration bath is, for example, as follows:
8-12% sulfuric acid, 13-30% sodium sulfate, 0 zinc sulfate
２2%, and the bath temperature is generally 45-65 ° C.

Although there are some overlaps with the above-mentioned contents, points to be noted in adding and dispersing fine particles in viscose in manufacturing the cake yarn of the present invention are summarized below. (1) In the case of mixing any of viscose, alkali, and aqueous dispersion of fine particles, the mixture is stirred so that bubbles are not bitten as much as possible. (2) When mixing the fine particle aqueous dispersion, about 400 rpm
It is preferable to stir at a high speed of not less than m and at the maximum number of revolutions at which air is not caught. (3) The fine particle aqueous dispersion is preferably added to an alkali solution having a concentration as low as possible. In the case of making a concentrated solution by a mixing method immediately before spinning, the aqueous dispersion is dispersed at an alkali concentration of 20% or less, particularly 15% or less. It is preferred to add the liquid slowly and slowly as possible. (4) Therefore, it is advisable to mix the alkali solution for correcting alkali concentration and viscose first, and then gradually add the aqueous fine particle dispersion. (5) Further, the concentration of the aqueous fine particle dispersion added to the viscose is preferably as low as possible.
It is particularly preferable to adjust the content to 25% or less. (6) 15% as fine particle concentration after addition to viscose
In the following, it is particularly preferable to mix so as to be 10% or less from the viewpoint of dispersion stability. (7) If a large amount of a dispersing aid for improving the dispersibility of the fine particles is contained, the defoaming property is reduced, so that the whole liquid moves during vacuum defoaming so that the foam can easily move to the upper layer part of the liquid. It is preferred to stir at low speed.

As the spinning apparatus used in the present invention, a conventionally known centrifugal spinning machine can be used.
Generally, the conditions for scouring, washing, and drying can be the same as those conventionally known.

The strength of the fiber when wet depends on the purpose of use of the fiber.
It is preferably at least 5 g / d. However, when mixed with a synthetic fiber having good strength such as a polyester fiber, if it is 0.4 g / d as described above, it can be put to practical use.

As described above, by selecting the organic fine particles, the size of the fine particles, the amount of the fine particles added, measures to reduce the physical properties due to the addition, and the control of the fine particle content, it is possible to produce rayon cake yarn having no difference in dyeing between the inner and outer layers. As mentioned above, rayon
Denier compensator and level dyeing for cake yarn production. Guide compensators have never been better to be reinforced. As described in the section of the prior art, this compensator is intended to reduce as much as possible the difference in fineness, physical property and dyeing due to the change of centrifugal force with time during centrifugal winding of rayon cake yarn. is there. Normally, the difference in fineness is reduced by gradually increasing the speed, and the difference in physical properties and dyeing is reduced by gradually increasing the guide angle. However, since the spinning speed and the tension increase in the inner layer, the fluff and breakage also increase.
It is not preferable to give a compensator unnecessarily. According to the present invention, good results can be obtained without giving any compensator at all regardless of the difference in dyeing between the inner and outer layers.

[0037]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the present invention, the average particle size, the dyeing amount of the disperse dye per 1 g of cellulose fiber, the wet strength, and the fine particle content were determined by the following methods.

(1) Average particle size: 5,000 by electron microscope
Regarding the fine particles observed in the fiber cross section magnified up to 20,000 times, the diameter is measured when the fine particle shape is a perfect circle or a substantially circular shape, and the major diameter is measured when the shape is non-circular. An average value is obtained, and this is performed in five or more sections, and the average value is obtained. In the case of the fine particle dispersion, the particle size distribution was measured using a Microtrac particle size distribution analyzer, and the maximum peak point particle size (M
V value) is defined as the average particle size.

(2) Dyeing amount: The dye concentration of the dyeing solution before dyeing is determined by the following formula as D {dye weight (mg) per gram of dyed material} in accordance with the above-described method of measuring the dyeing rate. Dyeing amount (mg / g) = (S ₀ −S ₁ ) × D / S _{0 In} addition, it is desirable to use a single dye dyeing solution at this time.

(3) Wet strength: A fiber sample is immersed in water at room temperature for 2 minutes, measured in a wet state with a serometer at a pulling speed of 20 cm / 24 seconds, and obtained by dividing the final strength value by the weight fineness. .

In the examples, the knitted fabric and the dyeing conditions used for measuring the dyeing density are as follows. Knitted fabric preparation: A knitted fabric is prepared at a needle spacing of 36 gage for 75 denier yarn and 24 gage for 120 denier yarn. Staining conditions Disperse staining conditions: Terasil Navy GRL-C 3.0% owf.
40 minutes bath ratio 1:50 Direct staining conditions; Direct Sky Blue 6B 0.2% owf.
60 minutes bath ratio 1:30

Example 1 Viscose (cellulose concentration 8.
0%, an alkali concentration of 6.0%) and a concentrated alkaline solution of 350 g / l were added thereto. After stirring at 15 rpm for 15 minutes, a 25% dispersion of styrene-acrylic polymer fine particles (OP62, manufactured by Rohm and Haas Co., Ltd., average particle diameter: 0.45 μm) was added, and the fine particle-to-cellulose addition ratio was 15
%, The alkali concentration is adjusted to 7.0, and the same as 5
Stirring was performed for 1 hour at a rotation speed of 00 rpm. Then 50
rpm. While stirring at a low speed, vacuum degassing was performed all day long. Then, the undiluted solution was poured from a spinneret of 0.07 mm × 40 holes into a coagulation regeneration bath (H ₂ SO ₄ ; 155 g / l,
ZnSO ₄ ; 22 g / l, Na ₂ SO ₄ ; 250 g /
1,50 ° C) discharge rate 10.45cc / min (light weight rate is 5
At 95% of the normal discharge rate), and wound up at a spinning speed of 100 m / min with a conventional centrifugal take-up type spinning device at an immersion length of 150 mm and a draw ratio of 18%, followed by scouring and drying Was done. In addition, during this spinning,
A speed increase rate of 7.5% was applied to adjust the denier of the inner and outer layers, but the guide adjustment was constant at 12 ° for leveling. The life of the nozzle plate showing the spinning condition and the clogging of the filter occurred was about 10 days.

The resulting yarn has an average fineness of 10
9.7dr, dry strength 1.37g / d, wet strength 0.63g
/ D. The difference between the average value of the fine particle content and the content ratio between the inner and outer layers of the cake yarn was 14.6% and 1.2%, respectively.
%, The difference in dye density between the inner and outer layers due to the disperse dye (R)
Is 0.7, which is a reduction of the dyeing density difference of about 1/4 compared with the dyeing density difference (R) of direct rayon of 2.7. In addition, the fastness to washing, the fastness to dry cleaning, the fastness to sublimation of this cake yarn,
The light fastness was 3 or higher. In the direct dyeing, the innermost layer was the darkest color, whereas in the disperse dyeing, the innermost layer was not dark. Table 1 shows the fineness, physical properties, dyeing concentration, and fine particle content of each layer of cake yarn.

[0044]

[Table 1]

Comparative Example 1 A conventional semi-dal (TiO ₂ ;
1%) A cake yarn was produced in the same manner as in Example 1 except that the discharge rate was 11.00 cc / min using viscose. The resulting cake yarn has a dye concentration of 5
At 9.5, the dyeing density difference R was 2.9, which was almost the same value as R when the cake yarn obtained in Example 1 was directly dyed with a dye.

Example 2 The addition ratio of cellulose to polymer fine particles was 5%, the nozzle was 0.07 mm × 30 holes, and the discharge amount was 6.6.
Rayon cake yarn was produced in the same manner as in Example 1 except that the flow rate was changed to 7 cc / min. The life of the nozzle plate showing the spinning condition and the clogging of the filter occurred was about 15 days.

The resulting yarn has an average fineness of 69.
0 denier, dry strength 1.61 g / d, wet strength 0.83 g
/ D. The difference between the average value of the fine particle content and the content ratio between the inner and outer layers of the cake yarn is 4.3% and 0.8%, respectively.
The difference in dyeing density (R) between the inner and outer layers by the disperse dye is 0.6, which is a remarkable reduction in the difference in dyeing density compared to the dyeing density difference (R) of 5.6 by rayon direct dye. It had been. In the direct dyeing, the innermost layer was the darkest color, whereas in the disperse dyeing, the innermost layer was not dark. Also, the cake fastness of this cake yarn,
The fastness to dry cleaning, the fastness to sublimation, and the fastness to light were all three or more.

Example 3 The polymer addition ratio of cellulose to cellulose was 30%, the nozzle was 0.07 mm × 30 holes, and the discharge amount was 6.1.
A rayon cake yarn was produced in the same manner as in Example 1 except that the flow rate was changed to 2 cc / min. The life of the nozzle plate showing this spinning condition and the clogging of the filter occurred was about 8 days.

The resulting yarn had an average fineness of 65.
7 denier, dry strength 1.20 g / d, wet strength 0.48 g
/ D. The difference between the average value of the fine particle content and the content ratio between the inner and outer layers of the cake yarn was 27.8% and 1.9, respectively.
%, The difference in dye density between the inner and outer layers due to the disperse dye (R)
Was 1.5, and the dyeing density difference (R) of the direct dye of rayon was 3.1, and the dyeing density difference was reduced to about half. In the direct dyeing, the innermost layer was the darkest color, whereas in the disperse dyeing, the innermost layer was not dark. Further, the cake yarn had a fastness to washing, a fastness to dry cleaning, a fastness to sublimation, and a fastness to light.

Comparative Example 1 An alkali liquid was added to the same viscose as in Example 1 by the same method, and acrylic fine particles 2 having an average particle diameter of 4.0 μm were prepared.
A 5% dispersion was added, and the mixture was adjusted so that the addition ratio to cellulose was 20% and the alkali concentration was 6.0%. The stirring was performed at the rotation speed of 1 hour. Without subsequent stirring, vacuum defoaming was performed all day and night. Then, this undiluted solution,
A discharge rate of 6.33 cc / min from a spinneret of 0.07 mm × 30 holes into the same bath (light weight rate 8%, discharge rate is a normal 92
%), Wound up under the same conditions, and then scoured and dried. The speed increase rate was 7.5%, and the guide adjustment for leveling was constant at 12 °. At this time, the life of the metal plate and the filter was about 5 days.

The resulting yarn had a fineness of 68.2 denier and a dry strength of 1.23, a wet strength of 0.51, and was much lower than the control fine particle-free yarn. Then, the content of the fine particles increased with time, that is, as the inner layer was formed, and it was expected that the fine particles were suspended and separated in the concentrated liquid tank. That is, in both the direct dyeing and the dispersion dyeing, the innermost layer was dark and the (R) thereof was as large as 5.5 and 2.2. Table 2 shows the fineness, physical properties, dyeing concentration, and fine particle content of each layer of the cake yarn.

[0052]

[Table 2]

Example 4 Except that the polymer fine particles used in Comparative Example 1 were used, the addition ratio to cellulose was 15%, the nozzle was 0.07 mm × 30 holes, and the discharge rate was 6.47 cc / min. Produced a rayon cake yarn in the same manner as in Example 1. The life of the nozzle metal plate showing this spinning condition and the clogging of the filter occurred was about 5 days.

The resulting yarn had an average fineness of 70.
0 denier, dry strength 1.16 g / d, wet strength 0.45 g
/ D. The difference between the average value of the fine particle content and the content ratio between the inner and outer layers of the cake yarn is 14.5% and 1.4, respectively.
%, The difference in dye density between the inner and outer layers due to the disperse dye (R)
Is 1.0, and the dyeing density difference (R) is 5.5, which is remarkably reduced, compared to the dyeing density difference (R) of the direct dye of rayon of 5.5. In the direct dyeing, the innermost layer was the darkest color, whereas in the disperse dyeing, the innermost layer was not dark.

Comparative Example 2 Using the same semi-dal viscose as in Control Example 1 and spinning under the same spinning conditions as in Comparative Example 1 except that the discharge rate was 6.88 cc / min. When dyed with the direct dye, the dye density was 52.6 and the dye density difference R was 6.1. This value was a value close to R when the cake yarn obtained in Comparative Example 1 was dyed with the direct dye. there were.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsutomu Kawamura 892 Sakuhi-shi, Saijo-shi, Ehime Prefecture Kuraray Co., Ltd. Examiner Tadahiro Sanada (58) Field surveyed (Int.Cl. ⁶ , DB name) D01F 1/10 , 2/06

Claims (1)

(57) [Claims] 1 to 5% by weight of polymer fine particles dyeable with a disperse dye and having an average particle size of 0.05 to 5 μm.
A rayon cake yarn, wherein the difference in dyeing concentration (R) between the outer, inner and inner layers of the cake yarn with a disperse dye is 2.0 or less.