JPS61266672A - Method for modifying fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a method for modifying fibers.

Conventional technology In recent years, a wide range of performance has been required of fibers.
It is difficult to obtain all of these performances from a single material. In general, natural fibers and synthetic fibers have different properties; for example, natural fibers are superior in water absorption, antistatic properties, and texture, while synthetic fibers are superior in mechanical properties. In order to combine the advantages of both, methods are being used to mix natural fibers and synthetic fibers.

These methods include blending synthetic fibers with natural fibers or regenerated cellulose fibers, blending them, twisting them together, weaving them, and knitting them together. However, these methods complicate the manufacturing process, cause deterioration of the mechanical properties of the original synthetic fibers, and cause problems in the dyeing process due to differences in dyeability between different Wi fibers when mixed. It has the drawbacks that it becomes complicated and causes a decrease in color fastness. In addition, as a means to improve the water absorption and antistatic properties of synthetic fibers, polyalkylene glycol or its derivatives are injected into the synthetic fibers during manufacture, and then adhered to the surface of the fibers during post-processing. There is. However, these methods have drawbacks such as difficulty in spinning, mechanical and thermal properties, and deterioration of the fastness of dyed products.

In addition, so-called resin processing is a means to improve the performance of natural fibers, especially main fibers, hemp fibers, and regenerated cellulose fibers. Resin processing has the effect of increasing the wrinkle resistance and shrink resistance of cellulose fibers, but at the same time has the disadvantage of reducing strength, elongation, etc. In addition, as a means to prevent wool from shrinking, there are methods of treating it with monopersulfuric acid, organic chlorine compounds, permanganates, and urethane polymers, but these also kill the elasticity of wool and reduce its strength and elongation. It has disadvantages such as causing

Problems to be Solved by the Invention The present inventors took into consideration the above-mentioned drawbacks of conventional processing methods, and have developed synthetic fibers that do not degrade the mechanical and thermal properties of the fibers, but have water absorbency, The present invention was arrived at as a result of research on methods for imparting antistatic properties and improving texture, as well as imparting shrink-proofing properties to natural fibers and regenerated cellulose fibers. That is, the present invention is economically advantageous and highly safe, imparts water absorption and antistatic properties to synthetic fibers, and improves the texture.

The purpose is also to provide shrink-proofing properties to natural fibers and regenerated cellulose fibers.

Means for Solving the Problems The present invention uses 0.3 to 5 weight parts of (I) cellulose soluble in the sodium hydroxide aqueous solution to 100 parts by weight of a 3 to 15 weight % sodium hydroxide aqueous solution. and (I) 0.3 of at least one cellulose derivative and/or at least one polymeric polysaccharide having no cellulose skeleton.
~5 parts by weight are dissolved in the sodium hydroxide aqueous solution, and the sodium hydroxide aqueous solution containing the above (I) and (II) is applied to the fibers, followed by neutralization, washing with water, and drying. This is a fiber modification processing method.

The present invention will be specifically explained below.

Cellulose that is soluble in a 3 to 15% by weight aqueous sodium hydroxide solution used in the present invention refers to cellulose in which the hydrogen of the hydroxyl group in the glucose residue has not been substantially replaced by a reaction such as esterification or etherification. In Although,
Among these, wood pulp obtained by acid hydrolysis and pulverized using a grinder such as a Zeel mill, and regenerated cellulose fibers with a relatively low degree of orientation are easily dissolved in an aqueous sodium hydroxide solution. In addition, the cellulose is easily dissolved when the sodium hydroxide concentration is 5 to 15% by weight, especially 8 to 15% by weight.
A concentration of 10% by weight is desirable because it has the highest solubility. (Hydroxide) If the IJium concentration is lower than the above range,
Cellulose has low solubility. Moreover, if it is higher than the above range, the solubility of cellulose will not be reduced, but the performance of the fiber will be deteriorated during processing.

In addition, the cellulose derivatives soluble in the sodium hydroxide aqueous solution used in the present invention include cellulose ethers such as calxoxymethyl perlulose, calxoxyethyl cellulose, hydroxyethyl cellulose, and methyl cellulose.
Deer is also soluble in 3-15% by weight of sodium hydroxide. Therefore, cellulose esters such as
Nitrocellulose, acetylcellulose, cellulose sulfate, etc. are hydrolyzed by sodium hydroxide, so
It cannot be used for the purpose of this invention. Further, the polymeric polysaccharides having no cellulose skeleton that are soluble in 5 to 15% by weight aqueous sodium hydroxide solution used in the present invention include starch, dextrin, 2-ligalactyuronic acid, 1-gum arabic, tragacanthotum, and guar. These include vegetable TMs such as TM, locust bean alginic acid, and vegetable mucilages. Also included are modified products of the above-mentioned polymeric polysaccharides, such as roasted starch and carboxymethylated starch.

In the present invention, (I) 0.3 to 5 parts by weight of the above cellulose and at least one of the above cellulose derivatives are added to 100 parts by weight of an aqueous sodium hydroxide solution of 3 to 15 parts by weight. .3 to 5 parts by weight are dissolved in the sodium hydroxide aqueous solution, or (2) the above cellulose 0
．． 3 to 5 parts by weight and at least XS or more of the above-mentioned polymeric polysaccharide are dissolved or
(a) At least one or more of the cellulose derivatives and polymeric polysaccharides are mixed and 0.3 to 5 parts by weight of the cellulose and 0.3 to 5 parts by weight of the cellulose are dissolved.

The solution to be applied to the fibers may be any of the solutions (I) to (3) above. The concentration of the polymer in these solutions is 3 to 15 weight - sulfur hydroxide + 7 um aqueous solution 10
The amount of the polymer substance is 0.6 to 10 parts by weight relative to 0 parts by weight. When this solution is applied to fibers, neutralized with an acid aqueous solution, and washed with water, antinodes of these polymeric substances are formed on the fibers or in the gaps between the fibers, thereby improving the performance of the fibers. In this case, the amount contained in the solution of the polymeric substance is 3 to 15% by weight of hydroxide solution 100
When the amount is less than 0.6 parts by weight, there is almost no improvement in the performance of the fiber. If the amount exceeds 10 parts by weight, the performance of the fibers will improve, but the hand will become significantly hard. Considering the performance, texture, and stability of the solution, the concentration of the polymeric substance is preferably 1 to 7.

The substances to be applied to the fibers used in the present invention are at least one of (I) cellulose and (2) cellulose derivatives and/or a polymeric polysaccharide having no cellulose skeleton that is soluble in the aqueous sodium hydroxide solution. One or more types,
It is. Although cellulose alone has the effect of improving the antistatic properties and water absorption properties of synthetic fibers, it is possible to further improve these properties by using the above-mentioned cellulose derivatives and polymeric polysaccharides in combination with cellulose. Furthermore, the shrink resistance of natural fibers and regenerated cellulose fibers can also be improved.

Sodium hydroxide aqueous solution (Soluble cellulose derivatives and polymeric polysaccharides are generally water-soluble, with the exception of some cellulose derivatives, and if fibers are processed with only these, fiber performance can be temporarily improved, but It has a high rate of shedding when washed and has very low durability. The ratio of cellulose and a cellulose derivative, cellulose and a polymeric polysaccharide that does not have a cellulose essence, or cellulose and a cellulose derivative and/or a polymeric polysaccharide in combination is 1 part cellulose to 0.06 parts of the other polymer substance. ~15 times is appropriate, but
For good durability against washing, it is preferable to use cellulose 1 to 0.1 to 2 times that of other polymeric substances. Since cellulose is originally water-insoluble, when it is attached to fibers, it is less likely to come off when washed.

Therefore, when water-soluble polymeric polysaccharides and cellulose derivatives are attached to fibers at the same time as cellulose, they are far less likely to fall off during washing than when cellulose is not used in combination. Moreover, if such a combination is used, the water absorption performance and antistatic performance will be improved compared to when cellulose is used alone. That is, most of the hydroxyl groups in cellulose molecular chains, which are responsible for the water absorption of cellulose, are blocked by hydrogen bonds between or within cellulose molecules, resulting in high sludge and crystallinity. Due to steric hindrance caused by substituents, the cellulose derivative used in the present invention has significantly fewer hydrogen bonds and lower crystallinity than cellulose. Furthermore, the polymeric polysaccharides used in the invention that do not have a cellulose skeleton have very few hydrogen bonds and are mostly amorphous compared to cellulose. Therefore, when it is attached to fibers, its water absorbency is superior to that of cellulose.

Next, the method of the present invention will be explained in more detail.

When preparing a solution containing the above-mentioned cellulose, cellulose derivatives, and polymeric polysaccharides, (I) first, an 8 to 11% by weight aqueous sodium hydroxide solution is preferably cooled to 4°C or less to add the required amount of cellulose. dissolve. Next, a required amount of cellulose derivative or polymeric polysaccharide is added to this solution and dissolved. Or (2) First, an 8 to 11% by weight aqueous sodium hydroxide solution is preferably cooled to 4° C. or lower to dissolve the required amount of cellulose. Separately, a high molecular weight polysaccharide or cellulose derivative is dissolved in water or a hydroxide solution at an appropriate concentration. Next, these two solutions are mixed, and the concentration of sodium hydroxide is 3 to 15% by weight, and the cellulose is hydrated).IJum aqueous solution 1
Note 0 A solution with a composition such that the lulose derivative and/or the polymeric polysaccharide without a cellulose skeleton is α3ν5 parts by weight is prepared. Either method (I) or @) above may be used, but when dissolving cellulose, use 8 methods as described above.
Solubility is poor unless an aqueous solution of ~11% by weight is used. Furthermore, using method (2) is effective in lowering the sodium hydroxide concentration. However, when the sodium hydroxide concentration is diluted to less than 3 TK, cellulose precipitates. (
When method 2) is used, the sodium hydroxide concentration is 3% by weight.
The reason why cellulose does not easily precipitate when it is less than 15% by weight is that cellulose and cellulose derivatives or cellulose and high molecular weight polysaccharides are uniformly dispersed in molecular form in the solution due to the apparent interaction, It is believed that solubility is improved even at sodium hydroxide concentrations outside the range of 8-11% by weight.

A method for attaching the solution obtained in this way to fibers is to immerse fibers in various forms, such as threads, fabrics, non-woven fabrics, etc., in the solution, and then squeeze the solution using a mangle, centrifugal dehydrator, etc. Neutralize the fibers by immersing them in an aqueous acid solution such as sulfuric acid, hydrochloric acid, or acetic acid.

The most common method is to continue washing with water and drying.

Other methods include spraying the solution onto the fiber surface, applying it to the fabric using a coating machine, or printing the solution onto the fabric surface using a printing screen. Next, neutralize, wash with water, and dry.

When neutralized using an acid aqueous solution, the cellulose in the solution attached to the fibers is deposited on the fibers or in the interstices between the fibers. In addition, some cellulose derivatives, such as calxoxymethylcellulose and calxyethylcellulose, have a low degree of substitution, and the 100 O contained in them
The solubility of the Na group becomes lower when it becomes a 1000H group; similarly, it is deposited on the fibers or in the interstices of the fibers. Among the polymeric polysaccharides that do not have a cellulose skeleton, alginic acid also has 1000 Na groups that are modified to -COO and deposits on the fibers or in the fiber gaps. In addition, the alkali-soluble and water-soluble cellulose derivatives or high-molecular polysaccharides used in the present invention are also adsorbed on the cellulose deposited on the rutted fibers and in the interstices of the fibers by neutralization. Between the fibers 1! During the subsequent drying process, it coexists with cellulose and deposits on the fibers and in the interstices of the fibers. In this way, cellulose derivatives and polymeric polysaccharides deposited in coexistence with KL, TE, and cellulose are much less likely to fall off during washing than in the case where they are not coexisting with cellulose, and the fiber modification effect is high.

Next, a method for measuring the measured values shown in Examples will be described.

[Water retention rate]

The sample was immersed in distilled water at 20°C for 5 minutes, and then dried in a centrifugal dehydrator for 3 minutes.
Dehydrate for 5 minutes under an acceleration of 000G.

It is the difference between the weight of the sample after dehydration and the bone dry weight divided by the bone dry weight, expressed as a percentage.

[Half-life]

According to JIS L 1094-1980 [Rubbing fastness in wet state] According to JIS L 0849-1971.

[Fabric shrinkage rate]

According to JIS L 1042-1983.

Next, the present invention will be explained in detail with reference to examples.

Example 1 100 g of purified cotton linters were dissolved in 9000 g of Shu/Itssa's reagent (copper ammonia solution). This cellulose solution was cast onto a glass plate and left at room temperature for 48 hours to evaporate ammonia and water. Next, the obtained thin film was immersed in a 4% by weight aqueous sulfuric acid solution to extract the copper in the thin film, and then dried. The cellulose obtained is soluble in alkali. Add 20g of this cellulose. It was dissolved in 1000 g of a 1 wt. sodium hydroxide aqueous solution. On the other hand, 10 g of calxoxymethylcellulose with a degree of substitution α5 was dissolved in 1000 g of a 0.9% by weight sodium hydroxide aqueous solution, and 10 g of sodium alginate was dissolved in 0.9% by weight of sodium hydroxide aqueous solution.
A solution dissolved in 1000 g of a sodium hydroxide aqueous solution of % by weight was prepared. Solution of the above three nutrients and water, 10% by weight
Solutions with seven types of compositions shown in Table 1 were prepared using an aqueous sodium hydroxide solution.

(Left below) A knitted fabric with a three-tiered double-sided structure (fabric weight 220 g/m") using false twisted yarns of polyethylene terephthalate fibers 150d/48f was separately immersed in these seven types of solutions.
The squeezing rate is 100% with 2 Zeurmangles, and the squeezing rate is 100%, immediately 2
It was neutralized by immersing it in a wt% aqueous sulfuric acid solution. Subsequently, washing in running water was repeated twice for 1 minute each, and drying was performed in a hot air dryer at 100° C. for 20 minutes. The water retention rates and half-lives of these knitted fabrics are shown in Table 1 together with the values for untreated fabrics. As shown in Table 1, experiments Nos. 1 to 5 according to the method of the present invention showed excellent results in both water retention and half-life compared to untreated fabrics. Further, superior results were obtained compared to the comparative example of Experiment No. 7 in which only cellulose was attached.

In Experiment No. 6, which is outside the scope of the present invention, the effect of improving both water absorption and antistatic properties was small compared to the untreated cloth.

Example 2 15 g of a nonwoven fabric made of regenerated cellulose fibers, Benliese (trade name, manufactured by Asahi Kasei Industries, Ltd.) was cooled to 4°C and hydroxylated)
It was dissolved in 1.000 g of a 10% by weight aqueous solution of IJum. Next, add 5g of hydroxyethylcellulose to this solution.
and 5 g of locust bean gum were added and dissolved. In this solution, acrylic fiber 1.5d×6 made from 35 cod raw cotton was added.
Double-sided smooth knitted fabric knitted using No. 4 single yarn is soaked,
The mixture was squeezed with two Zeurmaguru to a squeezing rate of well over 105, immediately neutralized in a 4% by weight acetic acid aqueous solution, washed with water and dried in the same manner as in Example 1. The water retention rate and half-life of this knitted fabric are shown in Table 2 in comparison with the untreated fabric.

As shown in Table 2, the method of the present invention significantly improves the water absorption and antistatic properties.

Example 3 Into the solution of Experiment No. 1 shown in Table 1 prepared in Example 1, a plain woven fabric of recycled fiber Bempelg (trade name, manufactured by Asahi Kasei Industries, Ltd.) [direct dye Sumilite Splat W 4BL Conc (direct dye) was added in advance.
Product name manufactured by Sumitomo Chemical Co., Ltd.) Dyed with 4% OWF]
was soaked, immediately squeezed with two dill mangles to a squeezing rate of 30 mm, and then neutralized in a 2% by weight acetic acid aqueous solution. Next, washing was repeated twice for 1 minute under running water, and then dried for 5 minutes in a hot air dryer at 80°C. For comparison, a patterned fabric was similarly treated with the solution of Experiment No. 7 of Example 1.

Table 3 shows the shrinkage percentage in the warp direction and the fastness to rubbing in a wet state of the fabrics treated with the 2ai solution and the untreated fabrics.

Table 3 Note that the fabric treated in Experiment No. 7 (comparative example) of Example 1 had a high concentration of hydroxide (IJ), so the texture was extremely rough and hardened, making it unusable for clothing. However, when processed using the method of the present invention, the fabric had a slightly firmer texture and a strange voluminous feel than the untreated fabric. Furthermore, as shown in Table 3, it can be seen that according to the present invention, the shrinkage rate and the fastness to friction in a wet state are also improved.

Effects of the Invention The present invention can safely and economically improve the lack of antistatic properties and water absorbency, which are the drawbacks of synthetic fibers, and can also make the texture close to that of cotton. It also has the effect of preventing shrinkage and fibrillation of natural fibers and regenerated cellulose fibers. Furthermore, it has the effect of improving the adhesion between fibers and other substances or between fibers, and improving the melting resistance of fibers that melt due to friction.

Claims (1)

[Claims] 0.3 to 5 parts by weight of (I) cellulose and (II) a cellulose derivative soluble in the sodium hydroxide aqueous solution to 100 parts by weight of a 3 to 15% by weight aqueous sodium hydroxide solution. and/or 0.3 to 5 parts by weight of at least one polymeric polysaccharide having no cellulose skeleton are dissolved in the aqueous sodium hydroxide solution to obtain the above (I) and (II). A method for modifying fibers, which comprises simultaneously applying an aqueous sodium hydroxide solution to the fibers, followed by neutralization, washing with water, and drying.