JPS5917223B2 - Manufacturing method for special fiber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing specialty fiber products consisting of polyester fibers and/or natural and man-made cellulosic fibers.

Many attempts have already been made to chemically process conventional textile products to impart new properties.

For example, techniques for manufacturing silky-like synthetic fibers by treating polyester fibers with alkali to reduce their weight have already been put into practical use.

However, in this weight reduction process, it tends to shrink and harden.

Textile products subjected to weight reduction processing have the disadvantage of poor drapability and lack of soft texture.

Therefore, a technique has been proposed in which some of the constituent fibers are dissolved and removed to impart appropriate bulk and drape properties.

For example, a method of interweaving soluble fibers with similar thermal shrinkage behavior to suppress deterioration of texture due to shrinkage while imparting appropriate bulkiness and drapability (Japanese Patent Publication No. 48-3
2318) or methods such as blending and interweaving polyoxymethylene fibers and then decomposing and removing the fibers (Japanese Patent Publication No. 1973-
24200), but these fibers are relatively stable both chemically and thermally, and the removal conditions themselves must be harsh, making it difficult to improve the fiber properties of the resulting product. The reality is that they are making sacrifices.

It is also possible to use fibers such as water-soluble polyvinyl alcohol or acetone-soluble cellulose acetate, but the former is difficult to adjust to the optimal range of heat shrinkage performance and to perform moist heat treatment, so it is difficult to use ordinary blended fibers. , unable to interweave.

Furthermore, it is difficult to apply glue to protect the warp threads during weaving.
In the latter case, there is a great risk of explosion and fire, and it is difficult to use it industrially.

In addition, cellulose-based natural fibers such as cotton are used in a wide range of applications, including underwear, due to their excellent hygroscopicity and dyeability, but there are many points that need to be improved. Chemical processing methods such as form stabilization processing and mercerization make cotton products less prone to wrinkles and give them form stability.

Although these methods have been developed with the aim of imparting a silk-like appearance, the drawback is that the texture and drape properties are likely to be impaired.

Additionally, it is generally possible to dissolve a portion of textile products with strong acids or strong alkalis.

For example, when rayon or cotton is treated with a strong acid (for example, concentrated sulfuric acid), it is decomposed and removed.

However, the use of strong acids can deteriorate the entire textile product, and there are restrictions on processing equipment due to corrosion, so in reality it takes about 24 hours to dissolve acrylic fibers at room temperature. It has also been proposed to dissolve the acrylic spinning solvent in an acrylic spinning solvent, but this is a special solvent that can easily cause environmental problems, it is relatively difficult to remove the solvent, and if the solvent cannot be completely dissolved, the texture may deteriorate. It has the disadvantage of being coarse and hard.

The present invention was completed as a result of research and study aimed at providing a fiber product that can maintain excellent texture while taking advantage of the respective characteristics of chemical processing in the field of synthetic fibers and natural fibers.

That is, the present invention uses acrylonitrile fibers copolymerized with a vinyl monomer having a carboxylic acid group in an amount of 0.18 to 2.2 milliequivalents/g as a carboxylic acid group, and a polyester and/or
Alternatively, a blended, twisted, interwoven, or interwoven fiber product made of natural and artificial cellulose fibers is treated with an alkaline aqueous solution to selectively dissolve and remove the acrylonitrile fibers.

Here, dissolution by alkaline aqueous solution treatment in the present invention means that when treated with an alkaline aqueous solution, the reduction rate with respect to the original weight of the fiber is 30 times or more.

The mixed fibers of the present invention are decomposed and dissolved in a relatively weak alkaline aqueous solution during scouring, bleaching, or dyeing and finishing processes.

On the other hand, polyester fibers and natural or artificial cellulose fibers have poor solubility in such relatively weak alkaline aqueous solutions, but it is necessary that they do not dissolve at a factor of 30 or higher as specified in the present invention.

Furthermore, the above mixed fibers are easy to remove after dissolution and are highly safe, making them suitable for spinning.

It combines easy solubility, safety, and textile performance with strong elongation and shrinkage characteristics that allow it to be easily mixed with other materials in processes such as knitting and weaving.

The easily soluble acrylic fiber of the present invention has a vinyl monomer having a carboxylic acid group with a carboxylic acid group of 0.18 to
It is produced from an AN-based polymer copolymerized at a rate of 2.2 milliequivalents/g.

Examples of carboxylic acid group-containing vinyl monomers include acrylic acid, methacrylic acid, itaconic acid, ethacrylic acid, crotonic acid, maleic acid, isocrotonic acid, fumaric acid, mesaconic acid, citraconic acid, butenetricarboxylic acid, and especially acrylic acid. It is preferable to use methacrylic acid and itaconic acid alone or in combination.

Copolymerization ratio of carboxylic acid group-containing vinyl monomer or the AN
It is necessary to adjust the amount of carboxylic acid groups present in the polymer in an amount of 0.18 to 2.2, preferably 0.5 to 19 milliequivalents/g.

If the carboxylic acid group in the AN-based polymer is less than O,l 8 miIJ equivalent/g, the solubility of the AN-based fiber obtained by spinning in an alkaline aqueous solution will decrease, and if the carboxylic acid group is less than 2.2 miIJ equivalent/g If it exceeds this value, fibers tend to adhere to each other during spinning of the AN polymer, and the physical properties of the fibers deteriorate, making it difficult to obtain good fibers.

As the AN-based polymer used here, a polymer mainly composed of an AN of 70 weight percent or higher and the above-mentioned carboxylic acid group-containing vinyl monomer is preferably used, but other vinyl monomers may be copolymerized.

Such copolymerization components include vinyl acetate, methyl or ethyl ester of acrylic acid or methacrylic acid, styrene, vinyl chloride, and vinylidene chloride.

Sulfonic acids such as acrylamide, methacrylonitrile, allylsulfonic acid, methyl)lylsulfonic acid, styrenesulfonic acid and their ammonium.

Examples include one or more of sodium, potassium salts, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and vinylpyridine derivatives.

These copolymers can be obtained by conventional methods such as aqueous polymerization or solution polymerization.

The preferably used solvent is dimethyl sulfoxide (DM
SO), organic solvents such as dimethylformamide and dimethylacetamide, and inorganic aqueous solutions such as nitric acid, zinc chloride, and rhodanates, but organic solvents are more preferred.

Spinning is carried out in a dry or wet manner, and after spinning, the fibers are made into fibers through various steps such as stretching, washing with water, and drying, followed by mechanical crimping and heat treatment.

Carboxylic acid group-containing AN-based fibers are more likely to cause adhesion between sheep fibers during the drying or crimping process than AN-based fibers that do not contain carboxylic acid groups, so high molecular weight cationic fibers are added to the gel-like yarn after washing with water. It is preferred (and practiced) to attach a surfactant or/anionic surfactant.

Specifically, polyethylene polyamine oils, stearic acid shedo sulfate, behenic acid amidoamine derivatives,
A higher alcohol having a molecular weight of 0.8 or higher and a higher alcohol ethylene oxide adduct having a mole of ethylene oxide added of 10 or higher is most preferably used.

Further, the AN-based fibers are given the same shrinkage as normal AN-based fibers, but preferably have a number of crimping stripes of 2 to 8 peaks/cm.
3.5 to 6 threads/cfrL, and good spinnability is obtained when the degree of shrinkage is within the range of 5 to 20, preferably 10 to 18.

The fineness of the AN fiber containing carboxylic acid waste is preferably 15 to 10 deniers, preferably 2.5 to 7 deniers.

If the denier is outside the above range, even if the AN-based fibers are blended, twisted, woven, or knitted and treated with an alkaline aqueous solution to remove the AN-based fibers, a sufficient texture improvement effect may not be obtained. Hateful.

In addition, regarding the strength and elongation properties of the AN fiber, the dry strength is 2.0g/
d preferably 2.5 g/d or more, dry elongation ro% preferably 20 modulus or more, which satisfies the performance required as a textile fiber, and achieves uniform blending in terms of shrinkage characteristics, denier range, etc. Excellent texture can be obtained through dissolution treatment.

Since the AN-based fiber of the present invention has excellent solubility in aqueous alkali solutions, it does not require severe conditions for dissolution and decomposition by alkali. When treated, the strength retention rate of the polyester fiber is 80φ or more, and furthermore, it has an excellent effect of 90 modulus or more.

Furthermore, depending on the dissolution conditions, it is possible to almost eliminate changes in the physical properties of polyester fibers.

In the present invention, the AN fiber is mixed with polyester and/or cellulose fiber, and cellulose fibers include vegetable fibers such as cotton and hemp, recycled fibers such as rayon and cupro, and semi-semi-fibers such as triacetate. Synthetic fibers and polyester fibers are preferred.

Further, in order to impart other functions to these natural fibers, artificial cellulose fibers, and polyester fibers, other natural fibers or synthetic fibers may be used in combination.

These fibers can be used alone or in a mixture of two or more types.

In the present invention, the above-mentioned mixed fibers and natural and artificial cellulose fibers and/or polyester fibers are blended, twisted, knitted and woven, but the form and means thereof are not limited.

Although the mixed fibers can be blended with natural and artificial cellulose fibers and polyester fibers in any proportion, it is preferable to blend the mixed fibers in a proportion of 5 to 45 parts by weight, preferably 10 to 30 parts by weight.

In the present invention, it is possible to make a knitted fabric using only the blended yarn, but it is also possible to mix and weave other fibers such as polyester spun yarn or long fibers in the warp or weft.

The mixed fibers of the present invention can also be used as long fibers or processed yarns thereof.

In this case, it is mixed and woven with polyester spun yarn or long fibers.

If necessary, use it as a twisted yarn with polyester fiber.

The textile product thus obtained is treated with an alkaline aqueous solution, and such aqueous alkaline solutions include, for example, aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.

A relatively low concentration alkaline aqueous solution for treating the textile products of the present invention is sufficient, and an aqueous solution having an o, ooi-to weight ratio is usually sufficient.

Processing conditions depend somewhat on the fiber being processed;
Generally, the above concentration is preferably 60 to 110°C, preferably 70 to 100°C, for an aqueous solution of 0.1 to 5 weight molecules of alkali.
Conditions may be appropriately set so that the easily soluble AN-based fibers constituting the textile product are selectively dissolved under the conditions in the following range, and other fibers constituting the product are not dissolved.

The treatment temperature is generally 0.1 to 120 minutes, preferably 1 to 60 minutes.

It is most preferable to selectively dissolve the easily soluble AN fibers at a temperature of 70 to 100°C using a solution of 0.1 to 5 weight molecules of sodium hydroxide while preventing other fibers from dissolving. .

Under these processing conditions, the acrylic fibers are dissolved while shrinking during the melting process, resulting in weaving crimps and a uniquely good texture.

Such shrinkage during alkali treatment is also an important feature of the present invention.

Certain additives may be added to this alkaline processing solution.

For example, adding quaternary ammonium salts or amines makes it easier to partially dissolve polyester fibers.
It is possible to impart a distinctive appearance, and the polyester fiber products of the present invention subjected to such treatment are very soft, have good drape properties, and exhibit moderate bulkiness.

It also has excellent dimensional stability and is resistant to wrinkles.

In the case of cotton fiber products, it is preferable to add an anionic activator or an anionic activator as an auxiliary agent to the treatment solution, and the cotton products treated with such a treatment solution also have excellent bulk properties,
It has drapability and also has a silky texture.

If irregular cross-section yarn is used as the polyester fiber, the texture and appearance can be further improved and silk-like fibers can be obtained.

Such irregular cross-section threads include Y-shaped and T-shaped threads having a square to octagonal cross section.

Furthermore, the polyester fiber used in the present invention may be made of a low polymerization degree polymer, or may be improved by using a special copolymer or the like to form a pile or antistatic property, if necessary.

As described above, in the present invention, the above-mentioned specific mixed fibers are subjected to dissolution treatment, but as a final product, 30 to 100% by weight, preferably 60% by weight, of the blended fibers are removed. The purpose of the invention can be achieved.

The special fiber products obtained by the method of the present invention have excellent drapability, flexibility, and bulkiness.
It is a fiber material with excellent texture and appearance, and its range of applications is extremely wide.

When mixed with polyester fiber, it is used, for example, in clothing applications such as thin high-quality fabrics.

When used in combination with cotton, it is suitable as a material for inner and outer clothing for spring and summer.

The present invention will be further explained below with reference to Examples.

Example 1 A spinning stock solution was prepared by solution polymerizing AN93 mol and 7 mol of acrylic acid in dimethyl sulfoxide.

This stock solution was discharged into an aqueous coagulation bath, and after completion of coagulation, it was stretched 6 times in hot water at 98°C.

The fiber obtained by washing with water, drying, and crimping has a single yarn fineness of 3. It had physical properties of Od, strength of 3.1 g/d, elongation of 21 factors, Ken line number of 4.2 peaks/cm, and Ken shrinkage of 12 factors.

The amount of carboxylic acid groups in the fiber was 1.33 IJ equivalents/g.

A spun yarn of 32 Sl yarn was produced by blending the acrylic fiber (20 wt.) with 80 wt.

A plain woven fabric was woven using this blended yarn for the warp and weft.

Then, at 98-100°C in a 3.0% caustic soda aqueous solution.
for 5 minutes.

In the plain woven fabric after the treatment, the acrylic fibers satisfying the copolymer composition and dissolution treatment requirements specified in the present invention were completely removed, while most of the polyester fibers remained.

Furthermore, the treated plain woven fabric had a soft texture and good wrinkle resistance.

Example 2 A spinning stock solution was prepared by solution polymerizing 96 moles of AN and 4 moles of itaconic acid in dimethyl sulfoxide.

Using this stock solution, the fibers obtained by spinning in the same manner as in Example 1 had a single yarn fineness of 3. Od, strength 2.9g/d, elongation 2
It had physical properties of 3 layers, Ken wire number of 4.5 peaks/cm, and Ken shrinkage of 13%.

The amount of carboxylic acid groups in the fiber was 1.38 IJ equivalents/g.

The above acrylic fiber 25 and polyester staple 7
5 were blended to obtain a spun yarn.

At this time, the materials shown in Table 1 were used in place of the above acrylic fibers, and each material was blended with polyester to obtain spun yarns in the same manner.

Weave to create a plain weave, and soak in the caustic soda aqueous solution of section 1.
Table 1 summarizes the dissolution state and texture of the resulting product after treatment at 00°C for 10 minutes.

Note that almost all the polyester fibers remained.

Rayon, cotton, nylon, acrylic ('"Trelon"
It was observed that most of the lint remained, and in particular, the plain woven fabric made of ordinary acrylic (Trellon) blended material had a rough and hard texture and was inferior.

The plain woven fabric made of the blended material of acrylic fibers of the present invention has a unique structure in which the acrylic fibers are completely removed when the copolymer composition and dissolution treatment requirements specified in the present invention are satisfied, and the fabric is bulky and has excellent drapability. It showed the texture of

This is because the dissolution behavior of the acrylic fiber of the present invention, that is, it is easily soluble in aqueous alkaline solutions, and the fiber dissolves without shrinkage during the dissolution treatment is different from conventional acrylic fibers. This shows that it has a positive effect on changes in texture.

In addition, water-soluble polyvinyl alcohol fibers ("Tsurubron", manufactured by Nichibi (Gyosha)) were also completely removed by dissolution treatment, but the shrinkage behavior during dissolution treatment was different from that of the acrylic fibers of the present invention, so it was difficult to remove. No effect on improving texture was observed.

In other words, the acrylic fiber of the present invention swells and contracts when it dissolves, causing weave crimp in the fabric, giving it a unique texture that is bulky and has excellent drapability, whereas polyvinyl alcohol fibers do not dissolve easily. It is considered that the texture improvement effect is small because it may be too rapid and dissolves without any weave crimp occurring.

Furthermore, water-soluble polyvinyl alcohol fibers have poor crimping properties, perhaps because they are water-soluble, and have difficulty in mixed spinning, whereas the acrylic fibers of the present invention exhibited good spinnability.

Example 3 20 parts of the acrylic fiber obtained in Example 1 and 80 parts of cotton were blended to obtain a spun yarn of 4oS yarn.

A plain woven fabric was woven using this blended yarn for warp and weft yarns.

After weaving, the acrylic fibers were dissolved and removed by treatment at 98° C. in a 2-layer caustic soda aqueous solution.

It was then washed with water and subjected to a bleaching process.

The obtained product exhibited a soft texture and good drapability.

Claims (1)

[Claims] 1 Blend, twist, or weave of acrylonitrile fibers copolymerized with a vinyl monomer having a carboxylic acid group as a carboxylic acid group with an equivalent weight of 0.18 to 2.2 + J equivalents/J, and polyester and/or natural and artificial cellulose fibers. , the interlaced fiber product is prepared under conditions such that the acrylonitrile fibers constituting the product are selectively dissolved and the other constituting fibers are not dissolved, the concentration is o, oot to lO weight ratio, and the temperature is 60 to 110 ° C. A method for producing a special textile product, characterized by treating it with an alkaline aqueous solution.