JP2009074200A - Method for producing modified cellulosic fiber material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To open up wider applications by imparting functionality and shape stability including wet heat buildup properties of a cellulosic fiber material without using a toxic agent such as formalin according to a method without causing environmental problems and improving and raising comfortableness to wear and washability and to provide the cellulosic fiber material having improved functionality and shape stability fit for the object thereof. <P>SOLUTION: The method for producing the modified cellulosic fiber material includes reacting a cellulosic fiber material with an aminoethylating agent and then reacting the resultant material with a cationizing agent or simultaneously reacting the cellulosic fiber material with the aminoethylating agent and the cationizing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing a modified cellulosic fiber material that has been modified so as to enhance the wet exothermic property of the cellulosic fiber material.

Cellulosic fiber materials are excellent in hygroscopicity, but they have the disadvantage of poor wet heat generation and weak heat retention compared to protein fiber materials such as wool, and keep warm when used in underwear and innerwear. Because of its inferior properties, various researches have been made and patent applications have been made with the goal of developing a cellulosic fiber material with excellent wet heat generation.

For example, Patent Document 1 discloses a method of treating a keratin degradation product by an immersion method, a resin processing method, or a chemical bonding method. Patent Document 2 describes a method for improving by introducing an amino group or a carboxyl group, and Patent Document 3 introduces a cationic group into a cellulosic fiber using a quaternary ammonium compound to generate wet heat. A method for imparting sex is disclosed. However, according to the method of Patent Document 3 in which only a cationic group is introduced, there is a property that it has a property of absorbing anions, and stains become conspicuous when washing is repeated.
JP-A-8-35176 JP-A-8-311767 Japanese Patent Laid-Open No. 10-251969

As described above, studies have been made to improve the stability of the cellulosic fiber material while improving its functionality, including wet exothermicity, but there are also many problems in terms of economy, safety and quality. , Has not yet reached full-scale practical use. Attempts have also been made to improve wet heat generation of synthetic fibers produced from petroleum resources, and some have been put to practical use, but synthetic fiber materials are particularly comfortable to wear when used as innerwear compared to natural fiber materials. In addition to being extremely inferior, the biodegradability and recyclability are inferior, and there are many problems such as environmental problems such as waste problems.

That is, the present invention imparts functionality and form stability including wet exothermic property of cellulosic fiber materials in a manner that does not cause environmental problems without using harmful drugs such as formalin, and wear comfort. By improving and improving the washability, a wide range of uses is cultivated, and an object of the present invention is to provide a cellulosic fiber material having improved functionality and shape stability in accordance with the purpose.

The present invention relates to a modified cellulose characterized by reacting a cellulose fiber material with an aminoethylating agent and then reacting with a cationizing agent, or reacting an aminoethylating agent and a cationizing agent simultaneously. (1).
Moreover, this invention is a manufacturing method of the modified cellulose fiber material of Claim 1 characterized by using 2-aminoethyl sulfuric acid as an aminoethylation agent (Claim 2).
Furthermore, the present invention uses, as a cationizing agent, a compound containing a quaternary ammonium group as a cation group and having an epoxy group or a chlorohydrin group as a reactive group. It is a manufacturing method of the modified cellulose fiber material in any one (Claim 3).

Furthermore, in the present invention, the cellulosic fiber material is selected from cotton, hemp, viscose rayon, cupra rayon, lyocell, tencel, modal and cellulose acetate. A method for producing a modified cellulose fiber material according to claim 4 (Claim 4).
Next, the present invention is a modified cellulosic fiber material produced by the method according to any one of claims 1 to 4 (claim 5).

As can be seen from the catchphrase of non-formalin, the method for producing the modified cellulosic fiber material of the present invention is environmentally friendly and economical, and can provide functionality such as a moist exothermic effect in terms of quality. In addition, it is noted that excellent shape stability can be imparted.

That is, according to the present invention, functionality and shape stability including wet exothermic property of cellulosic fiber material can be imparted by a method that does not cause environmental problems, thus improving wear comfort and washability. -By improving, it is possible to cultivate a wider range of applications, and it is possible to provide a cellulosic fiber material with improved functionality and form stability in accordance with the purpose. In particular, the method of Patent Document 3 in which only a cation group is introduced has a property of absorbing an anion group, and the effect is reduced by half in a masking state. However, according to the present invention, the disadvantage is compensated by aminoethylation. Has a unique effect.

In the method for producing the modified cellulose fiber material of the present invention, the cellulose fiber material is reacted with an aminoethylating agent and then reacted with a cationizing agent, or the aminoethylating agent and the cationizing agent are simultaneously used. It is made to react.

The method for producing the modified cellulosic fiber material of the present invention is preferably a method in which an aminoethylating agent and a cationizing agent are reacted simultaneously with the cellulosic fiber material. It is also preferable in some cases to react the agent.

As the aminoethylating agent referred to in the present invention, 2-aminoethylsulfuric acid is preferably used from the viewpoint of safety and economy, but in addition to this, an aminoethylating agent such as ethyleneimine can be used.

As the cationizing agent referred to in the present invention, a compound containing a quaternary ammonium group as a cation group and having an epoxy group or a chlorohydrin group as a reactive group is used. Examples of the cationizing agent referred to in the present invention include, for example, the trade magazine “Processing Technology” Vol. 26, No. 12 (1991) “Cationizing agents and their applications”, page 802, Table 1, low molecular weight compounds can be used. Specific examples include 3-chloro-2-hydroxypropyltrimethylammonium chloride, one molecule of the corresponding epoxy compound dechlorinated from 3-chloro-2-hydroxypropyltrimethylammonium chloride, chlorohydrin group, epoxy group or cationic group. The polyfunctional cationizing agent etc. which have 2 or more in it can be mention | raise | lifted. Among them, a polyfunctional cationizing agent having two or more cationic groups in one molecule, specifically, for example, Kathionone UK (one side multifunctional cationizing agent manufactured by Yushi Kogyo Co., Ltd.) is more preferably used.

Examples of the cellulosic fiber material that is the material to be processed of the present invention include alcohols in the molecular structure such as a cellulosic fiber material selected from cotton, hemp, viscose rayon, cupra rayon, lyocell, tencel, modal and cellulose acetate. A cellulosic fiber material or regenerated fiber material having a functional hydroxyl group is preferably used. Of these, viscose rayon, cupra rayon, lyocell, tencel, modal and the like are more preferably used.

The cellulosic fiber material modified by the production method of the present invention may be a single product or a mixed product, and may be a composite fiber including a so-called synthetic fiber. Moreover, it is a raw material or woven or knitted fabric whose main component is the cellulosic fiber material or recycled fiber material. These materials can be processed at the stage of cotton, loose hair, yarn, knitting, or half-finished product. These materials to be processed may be composites with petroleum-based synthetic materials such as polyester, polyamide, polyvinyl alcohol, polyacrylonitrile, and polypropylene.

As an example of the processing conditions for the cellulosic fiber material of the present invention, an outline in the case of processing a yarn (cheese) will be described. The cheese dyeing machine is charged with water 5 to 20 times the amount of yarn, and into it at room temperature. The antifoaming agent (specifically, for example, Taspon SN-1 (manufactured by LANXESS) 0.1 to 5% owf, as well as the inside / outside difference preventing agent (specifically, For example, Milleran QJ (manufactured by Ciba Specialty Chemicals) is 1 to 10% owf, aminoethylating agent is 10 to 50% owf, cationizing agent is 10 to 50% owf, and alkaline agents such as caustic soda are 10 to 50% owf. The temperature is raised to 120 to 160 ° C. at 1 to 2 ° C./min, and the solution is circulated while keeping the temperature at the same temperature for about 1 to several hours, then drained, washed with water, acid neutralized, Wash in hot water at 50-80 ° C for 5-10 minutes , Washed with water and dried.

As described above, when the aminoethylating agent and the cationizing agent are reacted at the same time, the reaction of the present invention is performed at a temperature of 120 to 160 ° C, more preferably at a temperature of 125 to 145 ° C, for 1 to 8 hours. Preferably it is performed in about 2 to 5 hours.

On the other hand, when the aminoethylating agent is reacted in a stepwise reaction with a cationizing agent, the aminoethylating agent is first carried out at 100 ° C. or lower, preferably 90 ° C. or lower, and then 120-160 ° C., A method of reacting by raising the temperature to 125 to 145 ° C is preferable.

In the case of the cloth pad steaming method, the fiber material is padded with a dye bath similar to the dipping method and impregnated with the chemical aqueous solution at a drawing ratio of 50 to 200%. Steaming at 120 ° C. to 160 ° C., preferably 130 ° C. to 150 ° C. in a humidified state, for 30 minutes to 5 hours, preferably about 30 minutes to 3 hours, and then soaping and drying by a conventional method .

These processing conditions are not limited to the above conditions depending on the type of cellulosic material and the purpose of processing. For example, in order to enhance the processing effect, it is free to increase the amount of chemicals used and strengthen the processing conditions. Needless to say, it can be changed.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples,% means% by weight, and part means part by weight.

Example 1
30 /-(30 single yarn) rayon 100% yarn 1kg cheese set in cheese dyeing machine, water 12kg, antifoam taspon SN-1 (manufactured by LANXESS) 10g, inside / outside prevention agent Milleran QJ (Ciba Specialty Chemicals) 30g, 2-aminoethylsulfuric acid 300g, Kathionon UK (one side oil and fat industry polyfunctional cationizing agent) 200g, and caustic soda 300g were added while liquid circulation at room temperature, and the temperature increased at 1.5 ° C / min. Warm to 135 ° C. The solution is kept at 135 ° C. for 4 hours and circulated, then drained, washed with water, neutralized with acid, further washed with hot water at 60 ° C. for 5 minutes, washed with water and dried.

A knit fabric was knitted using the rayon yarn obtained by processing in this way, and thermographic surface temperature analysis was performed. That is, the environmental humidity around the test product was changed as follows, and the temperature change on the surface of the fabric was observed.

The material of the example and the material of the comparative example (in the comparative example, the same rayon yarn was washed with hot water at 60 ° C. for 5 minutes, washed with water and dried) and then subjected to an absolute drying treatment at 105 ° C. for 24 hours. Then, the humidity was adjusted at 20 ± 2 ° C. and 65 ± 5% RH (standard state) for 48 hours, and then the test was performed.
Test environment condition 23 ± 2 ℃
The surface temperature of the dough when the humidity was stabilized at 30% RH (about 30 minutes) → 80% RH was observed and measured. As a result, the dough of the example showed a wet exothermic property that was 1.0 to 2.0 ° C. higher than the dough of the comparative example. The processed product of the present invention clearly has a temperature difference of 1 to 2 ° C. compared to the unprocessed product, which confirms that the exothermic sensitivity is large.

Using the yarn of this example, knitting, sewing innerwear, and wearing test, wearing comfort such as heat retention, steaming, and form stability are remarkably superior to the unprocessed product It was confirmed.

Example 2
When the same processing was performed using cotton yarn instead of the rayon yarn in Example 1, a cotton yarn having the same wet heat generation effect as in Example 1 was obtained.

The cellulosic fiber material modified by the method of the present invention has a higher wet calorific value than the unprocessed cellulosic fiber material, and as a result, the wearing comfort such as heat retention and steaminess is improved. In addition, an excellent reforming effect is obtained, for example, that the effect is durable.

Furthermore, the feature of the present invention is that it is possible to provide an excellent wet heat generation effect by using an inexpensive processing agent excellent in safety and environmental compatibility without using harmful agents such as formalin. With the improved economy and excellent economic efficiency, for example, the use of cellulosic fiber materials can be further expanded to fields where there have been many restrictions such as underwear, inner wear, socks, sports equipment, bedding, and lining, It has high practical value and contributes greatly to environmental problems.

Claims (5)

1. A modified cellulose fiber material characterized by reacting a cellulosic fiber material with an aminoethylating agent and then reacting with a cationizing agent or reacting an aminoethylating agent and a cationizing agent simultaneously. Production method.
2. The method for producing a modified cellulose fiber material according to claim 1, wherein 2-aminoethyl sulfate is used as the aminoethylating agent.
3. The modified cation according to any one of claims 1 to 2, wherein a compound containing a quaternary ammonium group as a cation group and having an epoxy group or a chlorohydrin group as a reactive group is used as the cationizing agent. For producing a cellulosic fiber material.
4. The cellulosic fiber material is selected from cotton, hemp, viscose rayon, cupra rayon, lyocell, tencel, modal, and cellulose acetate, The modified cellulose type according to any one of claims 1 to 3 A method for producing a fiber material.
5. A modified cellulosic fiber material produced by the method according to any one of claims 1 to 4.