JP3073153B2 - Method for producing cool and deep-colored modified cellulose acetate fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cool, deep-colored modified cellulose acetate fiber. More particularly, the present invention relates to a method for producing a refreshing and deep-colored modified cellulose acetate fiber having a refreshing sensation having excellent fine crater-like concave portions on its surface.

[0002]

2. Description of the Related Art In the field of garment textiles, various modifications of various natural fibers and chemical fibers have been made due to diversification and upgrading of consumer needs. For example, in the case of polyester fibers, in order to obtain a dry feeling and deep color, a technique of forming a fine crater-like concave portion on the fiber surface by alkali treatment of a raw yarn kneaded with silica-based fine particles to reduce the weight is used. Are known. In this technique, the fibers around the silica-based fine particles are easily decomposed specifically by alkali, and the fine particles fall off to form fine crater-like irregularities on the fiber surface (Japanese Patent Publication No. 9205/1992). etc).

[0003] Various methods for changing the fiber surface of cellulose acetate fibers have also been proposed. For example, when spinning cellulose acetate fiber, dry spinning is performed in a steam atmosphere to form voids on the fiber surface (Japanese Patent Application Laid-Open No. 54-6918). A method of forming only irregularities by dissolving only the very surface layer by immersion treatment (Japanese Patent Laid-Open No. 55-93)
814) has been reported, but the obtained fiber has a markedly reduced strength and elongation and large unevenness in treatment and the like, and has a practically difficult surface.

In addition, a method for controlling the fiber forming process at the time of spinning, specifically, setting the discharge linear speed and winding speed of the spinning stock solution at the spinning nozzle to appropriate conditions, and imparting complicated irregularities to the fiber surface. Method (Japanese Patent Publication No. 3-36928)
The cellulose acetate fiber obtained by the method has large irregularities, and it is difficult to obtain fine crater-like irregularities on the fiber surface by such a method.

Furthermore, a method of subjecting cellulose acetate fiber to biochemical treatment to form irregularities on the fiber surface, specifically, using a cellulose acetate fiber alone or an alkali compound in combination with a quaternary ammonium salt After the treatment, the fiber surface layer is converted into cellulose, and then the cellulose converted portion is decomposed and removed with a cellulolytic enzyme (Japanese Patent Laid-Open No.
JP-A-27067, JP-A-7-26471) or a method in which cellulose acetate fibers are alkali-treated to convert the fiber surface to cellulose, and then the cellulose-containing portion is decomposed and removed with a disinfectant (JP-A-6-264364). ) Is proposed, but the fine irregularities similar to those in the polyester fiber have not yet been formed.

Also, irregularities are formed on the surface by a method in which fine particles of an inorganic material having an average particle size of 0.01 to 0.3 μm are mixed in advance with a cellulose acetate fiber in a spinning solution (Japanese Patent Application Laid-Open No. 7-97713). Although a method is known, in such a method of simply dispersing the fine particle inorganic substance throughout the fiber, in order to form a sufficient unevenness on the surface,
It is necessary to incorporate a very large amount of fine particle inorganic material inside the fiber, and as a result, the fiber strength which is originally lower than that of other fibers is further reduced, and the glossiness unique to cellulose acetate fiber is significantly reduced. In addition, the formed irregularities are projected in a convex shape with respect to the fiber surface.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to form a large number of fine crater-like recesses on the surface of cellulose acetate fiber to provide a refreshing sensation and deep-colored color, which have not been achieved before, and to provide a sufficient color. It is an object of the present invention to provide a method for producing a cool, deep-colored modified cellulose acetate fiber having an appropriate practical fiber strength.

[0008]

According to the present invention, a cellulose acetate fiber kneaded with inorganic fine particles alone or a composite yarn composed of cellulose acetate fiber kneaded with inorganic fine particles and other fibers is alkali-treated with an alkali compound. At least the surface of the cellulose acetate fiber is made into cellulose, and then subjected to an enzymatic treatment with a cellulose-decomposing enzyme to decompose and remove the cellulose-formed portion, thereby forming a fine crater-like recess on the surface of the cellulose acetate fiber. A gist of the present invention is a method for producing a cooled and deep-colored modified cellulose acetate fiber, characterized by performing alkali treatment by using a quaternary ammonium salt in combination with alkali treatment by an alkali compound.

The cellulose acetate fiber used in the present invention may be cellulose triacetate having an acetylation degree of 56.2% to 62.5% or cellulose diacetate having an acetylation degree of 48.8% to 56.2%. The shape may be any of filament and staple.

In the cellulose acetate fiber used in the present invention, it is necessary that the fine particle inorganic substance is kneaded and contained in a so-called fiber which is obtained by adding a fine particle inorganic substance to a spinning solution. Examples of such a fine particle inorganic substance include calcium carbonate, silicon dioxide, and titanium oxide. Furthermore, this fine particle inorganic substance is more than cellulose acetate,
If high specific gravity, preferably, the specific gravity of the fine particle inorganic material,
If it is 3.5 or more, improvement in drape property can be expected.
In addition, by using an inorganic substance having a refractive index of 1.3 to 1.9, preferably 1.4 to 1.7 as the fine particle inorganic substance, it is possible to suppress a decrease in glossiness. That is, since the inorganic substance having such a refractive index is close to the refractive index of cellulose acetate, it is possible to suppress a decrease in glossiness, and the refractive index is 1.3 to 1.
When the ratio is outside the range of 9, the glossiness and the good coloring property, which are the characteristics of the cellulose acetate fiber, may be impaired. As an inorganic material satisfying such specific gravity and refractive index, specifically,
For example, barium carbonate (refractive index 1.53, specific gravity 4.
4), barium sulfate (refractive index 1.64, specific gravity 4.1),
Zinc oxide (refractive index 1.9, specific gravity 5.6) and the like. In particular, barium sulfate is very preferable in terms of increasing the specific gravity and glossiness, and further affecting the human body (chemical and physical stability).

[0011] In addition, depending on the size of the aggregate (aggregate) of the fine inorganic particles contained in the cellulose acetate fiber, a difference in the physical properties of the fiber appears, which affects the spinnability, the post-process passability, and the like. It is preferable that the average particle diameter of the fine particle inorganic substance as an aggregate is 1.5 μm or less, more preferably, the average particle diameter of the aggregate is 1 μm or less. If it is larger than this, the fiber properties are significantly reduced, and the spinnability, the post-process passability, etc. are extremely deteriorated.

In order to reduce the average particle size of the aggregate to 1.5 μm or less, it is preferable that the primary particle size (average particle size) of the inorganic fine particles to be added is 0.5 μm or less, more preferably 0.1 μm or less. 05 μm. If it is larger than this, the average particle diameter of the aggregates of the inorganic fine particles becomes large, and the physical properties of the fiber are liable to be extremely deteriorated. Further, troubles such as thread breakage in the fiber formation, for example, in a spinning step, occur frequently.

The content of the inorganic fine particles in the cellulose acetate fiber is 5 to 30% by weight, preferably 5 to 20% by weight. When the content is less than 5% by weight, the cellulose acetate fiber is alkali-treated with an alkali compound to give the cellulose acetate. By converting at least the surface of the fiber into cellulose, and then treating with a disinfectant to decompose and remove at least a part of the cellulose-containing portion, it becomes difficult to form many fine crater-like concave portions on the fiber surface, It is difficult to obtain a sufficient refreshing feeling and deep color. On the other hand, if it exceeds 30% by weight, the strength and elongation of the fiber may be significantly reduced, which may cause practical problems.

In the present invention, the cellulose acetate fiber containing the inorganic fine particles is treated with an alkali compound and a fourth compound.
At least the surface of the cellulose acetate fiber is treated with a treating agent containing a quaternary ammonium salt to convert the cellulose acetate fiber into cellulose. The cellulose conversion itself is mainly caused by the action of an alkali compound. When treated in combination, the rate of weight loss is greatly improved in the enzymatic treatment, which is a subsequent treatment, so that the cellulized portion is decomposed and removed in a short time, forming a fine crater-like concave portion on the fiber surface, and It will improve and give good results.

Further, when hydrogen peroxide is used in combination with the alkali compound and the quaternary ammonium salt, the rate of weight loss can be further improved in the enzymatic treatment which is a subsequent treatment, and good results can be obtained. .

Examples of the alkali compound used in the present invention include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium hydrogen carbonate, and carbonate. A conjugate salt of a strong alkali such as sodium and a weak acid is exemplified.

The quaternary ammonium salts to be used in combination are DYK-1125, DXY-10N (manufactured by one company), mercerin PES, marserin PEL, and mercerin PEF (manufactured by Meisei Chemical Co., Ltd.). ), Cathizole N
S-11conc (manufactured by Takamatsu Yushi Co., Ltd.), Neolate NCB
(Nichika Chemical Co., Ltd.), and cation-based auxiliaries available under trade names such as Silfine PE (Senka Co., Ltd.).

Further, as the hydrogen peroxide optionally used in the present invention, those generally used in the bleaching step of cotton products may be used, and examples thereof include industrial preparations (30 to 35% by weight). .

In order to obtain the modified cellulose acetate fiber and the modified cellulose acetate fiber composite yarn of the present invention,
A cellulose acetate fiber kneaded with inorganic fine particles of 1 to 20% by weight is mixed with an alkali compound of 0.5 to 40% by weight.
An aqueous solution containing (from cellulose acetate fiber) and a quaternary ammonium salt in an amount of 0.5 to 12 g / l is used as a treating agent, and alkali-treated by immersion at room temperature to 130 ° C. for 5 to 120 minutes. By the alkali treatment, at least the cellulose acetate fiber having a fiberized cellulose surface is subjected to an enzymatic treatment with a cellulose-decomposing enzyme to decompose and remove the cellulized layer, to drop inorganic fine particles on the fiber surface layer, and to finely coat the fiber surface. A crater-like concave portion is formed, and deep color is imparted.

The cellulolytic enzymes used in the present invention include those originating from filamentous fungi such as Trichoderma and Aspergillus. Onozuka R-10 (Yakult), Meiselase (Meiji Seika), Cellsoft ( It can be easily obtained with a trade name such as Novo. 1 to 50 g / l of these cellulolytic enzyme preparations, pH 3.5 to 7
By immersion treatment at 20 to 65 ° C. for 2 to 180 minutes in an aqueous solution of the above, the cellulized layer of the cellulose acetate fiber is decomposed and removed, whereby a fine crater-shaped concave portion can be formed on the fiber surface.

In the present invention, regarding the surface for improving the dry feeling, the surface layer of the fiber may be cellulosic, that is, the base cellulose acetate fiber,
The surface layer may be a cellulosic layer, the surface of which may be a fine crater-shaped recess, but if the cellulosic layer remains, the layer is not usually dyed with a disperse dye used for dyeing cellulose acetate fibers. Hinders the improvement of the deep color. Therefore, in the modified cellulose acetate fiber of the present invention, it is necessary to remove most of the cellulose in the surface layer by an enzyme treatment.

The modified acetate fiber of the present invention thus obtained has fine crater-like concave portions on the fiber surface, and fine crater-like concave portions having a crater size of 3 μm or less are randomly present on the fiber surface. Then, the cellulose acetate fiber is given a cool feeling and a deep color due to irregular reflection of light. However, from the viewpoint of further improving the cool feeling and the deep color, 300 fine crater-shaped concave portions are formed in 300 per 1 × 10 ^-2 mm ^2. It is preferable to have the above.

The modified cellulose acetate fiber of the present invention having fine crater-shaped concave portions on the fiber surface has a very refreshing feeling that is not seen in conventional cellulose acetate fibers due to its surface structure. Specular reflection is suppressed and it has deep color.

In the alkali treatment of the present invention, the selection, concentration, temperature, time and the like of the alkali compound are adjusted depending on the degree of modification of the modified cellulose acetate fiber.
In the enzyme treatment, the treatment time and the like are adjusted depending on the amount of the cellulosic portion.

The cellulose acetate fiber into which the inorganic substance has been kneaded in the present invention can be composited with one or more other fibers to form a composite yarn. And natural fibers such as wool, and synthetic fibers such as nylon fibers, polyester fibers, acrylic fibers, and polyurethane fibers. The shape thereof may be any of filaments and staples. In addition, any known method such as air compounding, compound false twisting, and twisting can be applied to the compounding method.

In order to obtain the modified cellulose acetate fiber composite yarn of the present invention, it can be obtained basically by the same method as in the case of the above-mentioned modified cellulose acetate fiber, Accordingly, alkali treatment conditions and enzyme treatment conditions are appropriately changed within the above-mentioned ranges.

The modified cellulose acetate fiber composite yarn of the present invention has a cooling feeling based on cellulose acetate fibers having fine crater-shaped concave portions and a deep color, as well as the performance of other fibers.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.
To obtain the cellulose acetate fiber used in the present invention,
The following method is adopted. The flakes of cellulose triacetate or cellulose diacetate are dissolved in a single solvent such as methylene chloride or acetone or a mixed solvent such as methylene chloride and methanol to obtain a stock solution having a solution concentration of 15 to 30% by weight, preferably 18 to 27% by weight. Prepare.

In order to obtain a cellulose acetate fiber containing fine particles used in the present invention, a dispersion obtained by dispersing a fine particle inorganic material in a predetermined size of agglomerate in a solvent of cellulose acetate at the time of preparing a spinning dope is used. In a solution of cellulose acetate dissolved in an acetate solvent,
Addition, mixing, or directly adding the fine particle inorganic matter to a solution in which cellulose acetate is dissolved in a cellulose acetate soluble solvent, adding and mixing, and adjusting the size of the aggregate of the fine particle inorganic matter by predetermined dispersion conditions, etc. By the method, the inorganic fine particles are dispersed and contained in the spinning dope.

Here, it is important to prepare a spinning solution so that the average particle size of the aggregates does not increase. As a method for adjusting the average particle size of the aggregate, it is preferable to use a disperser. For example, when a horizontal sand mill is used as a dispersing machine, the disk peripheral speed and the bead diameter (0.8 to
1.0 mmφ), the bead filling ratio, the residence time in the vessel, and the like can be appropriately adjusted so that the average particle size of the aggregates does not increase.

The spinning solution containing inorganic particles thus obtained is supplied to a spinning nozzle device and spun by a dry spinning method in which the spinning solution is discharged into a high-temperature atmosphere. In addition, wet spinning may be performed instead of dry spinning.

The cellulose acetate fiber thus obtained is formed on a fabric. Alkali treatment and enzymatic treatment with the following alkali compound may be performed in a fiber state, that is, in a plastic bobbin winding state or a skein winding state, but industrially, weaving or knitting is preferably performed.

In general, after the fabric is formed, it is scoured and dried, and the scoured fabric is poured into an aqueous solution of an alkali compound such as sodium hydroxide containing a quaternary ammonium salt, and then heated at a high temperature (1%).
(00 ° C. or higher) to make the fiber surface of the cellulose acetate fiber cellulose. Next, this cloth is immersed in an aqueous solution of a cellulolytic enzyme, washed with water, and dried to obtain a cloth made of modified cellulose acetate fiber having good coolness and deep color.

[0034]

The present invention will be described below in more detail with reference to examples. The evaluation in the examples was based on the following method.

(Crater formation state): Judgment from electron micrograph ◎: good ×: none

(Number of craters): Judgment from electron micrographs Pieces / 10 ^-2 mm ²

(Weight loss rate of enzyme treatment): [(weight of fabric before enzyme treatment−weight of fabric after enzyme treatment) / weight of fabric before enzyme treatment] × 100 (%)

(Deep color): Evaluated by L * value (measured by spectral colorimeter Juki JP7100)

(Examples 1 and 2) 18% by weight of barium sulfate
Five-ply satin woven fabric using a bright 80d / 20f made of cellulose triacetate fiber having a kneading degree of 61.3% as a weft and a bright 100d / 26f as a weft (200 density / inch, 87 density / inch)
Was refined and dried in a 6-tank continuous refiner. 7% by weight of sodium hydroxide with a bath ratio of 1:20 (based on the fabric)
And a quaternary ammonium salt mercerin PEF (manufactured by Meisei Chemical Co., Ltd.) in an aqueous solution containing 2 g / l.
The temperature was raised at a rate of ° C./min, and alkali treatment was performed at 120 ° C. for 60 minutes to convert the fiber surfaces of the constituent fibers into cellulose, thereby obtaining an alkali-treated fabric having an alkali reduction rate of 7.3%. Next, 6 g of cellosoft (cellulolytic enzyme preparation manufactured by Novo) was added to the woven fabric.
/ L, Bioassist MT (manufactured by Morirokusha) containing 5 g / l, was immersed in an aqueous solution having a pH of 4.8, 53 ° C and a bath ratio of 1:50, and subjected to an enzyme treatment with stirring for 60 minutes and 120 minutes, followed by washing with water and drying. The woven fabric obtained was measured for the formation status and number of crater-shaped recesses on the fiber surface of the constituent fibers, and the rate of weight loss by enzyme treatment, and then the enzyme-treated fabric was treated with Dianix Black TAN 20.
0% (Mitsubishi Kasei Hoechst) 6% owf, Disper TL (Meisei Chemical) 0.5g / l, Ultra MT-N
2 (manufactured by Onitsujima Chemical Co., Ltd.) in a dyeing bath containing 0.5 g / l.
The dyed fabric was dyed at 20 ° C. for 60 minutes, and the obtained dyed fabric was evaluated for deep color. The evaluation results are shown in Table 1.

(Comparative Examples 1-2) The same scoured fabrics as in Examples 1-2 were put into an aqueous solution containing 7% by weight (to fabric) of sodium hydroxide at a bath ratio of 1:20, and the temperature was changed from 30 ° C to 2 ° C /. Then, the fiber surface of the constituent fibers was converted to cellulose by alkali treatment at 120 ° C. for 60 minutes to obtain an alkali-treated fabric having an alkali weight loss rate of 7.1%. Next, this woven fabric was used in Example 1.
Enzyme treatment, staining, and evaluation were performed under the same conditions as in Examples 1 to 2 and the evaluation results are shown in Table 1.

(Comparative Example 3) The same scoured fabric as in Examples 1 and 2 was dyed under the same conditions as in Examples 1 and 2 without alkali treatment and enzyme treatment, and then the deep color was evaluated. It was shown to.

[0042]

[Table 1]

(Examples 3 and 4) 18% by weight of barium sulfate
Air-entangled composite yarn of 80d / 20f cellulose triacetate fiber Bright having a degree of acetylation of 61.3% kneaded and 20d / 12f polyester fiber semi-dal 20d / 12f, and five satin woven fabrics used for warp and weft (density 160 yarn / inch, (Weft density: 70 lines / inch) was scoured and dried by a 6-tank continuous scouring machine. This scoured fabric is put into an aqueous solution containing 5.5% by weight of sodium hydroxide (to fabric) at a bath ratio of 1:20 and mercerin PEF of quaternary ammonium salt (manufactured by Meisei Chemical Co., Ltd.) at 2 g / l. Temperature at 2 ° C / min.
The fiber surface of the constituent fibers was converted to cellulose by alkali treatment to obtain an alkali-treated fabric having an alkali weight loss rate of 5.6%. Next, the woven fabric was treated with 6 g / l of cell soft (cellulolytic enzyme preparation manufactured by Novo) and 5 g / l of Bioassist MT (manufactured by Moriroku) at pH 4.8, 53 ° C., and a bath ratio of 1:
The resultant was immersed in an aqueous solution of No. 50 and subjected to an enzyme treatment for 60 minutes and 120 minutes with stirring, washed with water, and dried. After measuring the state of formation of crater-shaped concave portions on the fiber surface of the constituent fibers, the number of the woven fabric, and the rate of weight loss by the enzyme treatment, the enzyme-treated fabric was treated with Dianix B.
Lack TAN 200% (Mitsubishi Kasei Hoechst)
6% owf, Disper TL (manufactured by Meisei Chemical Co., Ltd.) 0.5 g
/ L, 0.5 g of Ultra MT-N2 (manufactured by Minejima Chemical Co.)
The dyed fabric was dyed in a dyeing bath containing 120 g / l at 120 ° C. for 60 minutes, and the deep color of the obtained dyed fabric was evaluated. The evaluation results are shown in Table 2.

Comparative Examples 4-5 The same scoured fabric as in Examples 3-4 was prepared by adding 5.5% by weight of sodium hydroxide having a bath ratio of 1:20.
(To fabric), heated from 30 ° C. at a rate of 2 ° C./min, and alkali-treated at 120 ° C. for 60 minutes to convert the fiber surface of the constituent fibers into cellulose, and the alkali weight loss rate was 5.7.
% Of the alkali-treated fabric was obtained. Next, this fabric was subjected to an enzyme treatment, dyeing and evaluation under the same conditions as in Examples 3 and 4, and the evaluation results are shown in Table 2.

Comparative Example 6 The same scoured fabric as in Examples 3 and 4 was dyed under the same conditions as in Examples 3 and 4 without alkali treatment and enzyme treatment, and then the deep color was evaluated. It was shown to.

[0046]

[Table 2]

[0047]

According to the present invention, the cellulose acetate fiber kneaded with inorganic fine particles is treated with a treating agent containing an alkali compound and a quaternary ammonium salt and then treated with an enzyme to reduce the amount of enzyme compared to the conventional method. Since the speed is improved, the cellulized portion can be decomposed and removed in a short time, and the surface of the cellulose acetate fiber has fine crater-shaped concave portions, and it is possible to efficiently obtain a modified cellulose acetate fiber rich in deep color. it can. The modified cellulose acetate fiber has a very refreshing feeling due to the fine crater-like concave portions, suppresses the regular reflection of light, and has improved deep color. In a similar manner, the composite yarn composed of cellulose acetate fibers kneaded with inorganic fine particles and other fibers has the same performance as the cellulose acetate fibers having fine crater-shaped recesses on the surface of the cellulose acetate fibers. The modified cellulose acetate fiber composite yarn can be obtained efficiently.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI D06M 1/06 A Examiner Tadahiro Sanada (56) References JP-A-7-26471 (JP, A) JP-A-7-97713 (JP, A JP-A-5-311506 (JP, A) JP-A-3-394576 (JP, A) JP-A-7-138871 (JP, A) JP-A-64-61568 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) D06M 11/00-11/84 D06M 16/00

Claims (1)

(57) [Claims] At least the surface of a cellulose acetate fiber obtained by subjecting a cellulose acetate fiber kneaded with a fine particle inorganic substance alone or a composite yarn consisting of a cellulose acetate fiber kneaded with a fine particle inorganic substance and another fiber to an alkali compound with an alkali compound. The cellulose is then converted to cellulose, and then the cellulose-decomposed portion is decomposed and removed by enzymatic treatment with a cellulose-decomposing enzyme to form fine crater-shaped recesses on the surface of the cellulose acetate fiber. A method for producing a cool and deep-colored modified cellulose acetate fiber, characterized by performing an alkali treatment in combination with a quaternary ammonium salt.