JPH08311767A - Wet exothermic fiber composition and method for producing the same - Google Patents

Abstract

(57) [Summary] [Purpose] Since the heat-and-wetness characteristic of protein fibers is due to the chemical structure of protein fibers, especially amino groups and carboxyl groups, these functional groups are used for other fibers, especially synthetic fibers Provided is a wet heat-generating fiber composition introduced into cellulose fibers and a method for producing the same. A wet exothermic fiber composition containing amine, hydroxyl and carboxyl groups as functional groups, alone and / or in combination.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a method for basically improving the heat retaining property of textiles. This composition can effectively utilize the fiber composition not only in the field of clothing but also in the field of industrial use where heat insulating effect is required.

[0002]

2. Description of the Related Art The heat retention of clothing is essential for the survival of humankind. Based on this as one criterion, humankind has selected and used the present protein fibers from natural materials. A major feature of this fiber is that it generates heat when adsorbing water, which has been used because it has a great effect on protecting the human body from changes in temperature and humidity of the outside air. In recent years, many chemical fibers have been developed and used as fibers to replace silk and wool, but fibers possessing this property of silk have not been developed. About 10 years ago, nylon using a light-heat conversion material was developed as a method of imparting heat generation to fibers. This fiber is a core-sheath fiber in which zirconium carbide is inserted into the core portion of nylon fiber, and by generating heat with light,
It is to improve the heat retention effect. The drawback of that fiber is
It does not generate heat when absorbing moisture like protein fibers, but rather absorbs heat. Since then, the development in this field has been advanced, and recently, since the amount of cotton fibers is small, but the properties are similar to these, products taking advantage of their effects have been developed. However, a fiber material having this property of protein fiber has not been developed.

[0003]

[Problems to be Solved by the Invention] It is humanity's dream to create the same fiber as silk. Humanity is 19 to realize this dream
It has been active since the latter half of the century. As a result, several kinds of fibers having similar properties have been industrialized, and about half of the present fibers can be covered with this, and a rich clothing life has become possible. Especially in recent years due to the physical modification of polyester,
In terms of texture, clothing products and new synthetic fibers that are almost the same as silk have come into practical use, but the basic performance of silk / wool fibers such as dyeability, hygroscopicity, and heat-absorption characteristics as clothing is It was totally ignored. The present invention is intended to develop a fiber product in which the basic performance of this clothing, particularly wet heat generation property, is imparted to existing chemical fibers and the like. As a result, the performance, which has hitherto been the shortcoming of chemical fibers and the like, is improved, and at the same time, the dyeability is also solved.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a fiber composition and a method for producing the same which solve the above problems. That is, a fiber composition obtained by introducing a single and / or a plurality of quaternary amine groups, hydroxyl groups, and carboxyl groups into a fiber-forming polymer has a wet exothermic property. To be presented. The target fibers for modification according to the present invention are applied to existing fibers other than protein fibers and polymers having a fiber-forming ability, but preferably nylon, polyester, acrylic, vinylon, polypropylene in synthetic fibers, Polyethylene is particularly preferable, but acrylic and polyester are not limited thereto. Acrylic fibers are usually composed of acrylonitrile and other monomer copolymers. Among the copolymer components used in this case, those containing halogen and / or quaternary ammonium salt alone or both, and the halogen being chlorine are preferable, but not limited thereto. In the copolymer component constituting the acrylic fiber, the halogen-containing monomer is preferably vinyl chloride or vinylidene chloride, but is not limited thereto. In the copolymer component constituting the acrylic fiber, the quaternary amine-containing monomer is preferably vinyl pyridine, but is not limited thereto. As a method for introducing an amino group into the acrylic fiber, an existing method that has already been proposed, for example, a method of treating with polyethylene polyamine, a method of treating with hydrazine hydrate, etc. can be applied, but the method is not limited thereto. The polyester used in the present invention is represented by the following formula, but is not limited thereto. 1) acid component HOOC-R-COOH alcohol component HO- R'-OH to wherein _{R; (- CH 2 -)} n (8 ≧ n ≧ 2) φ-A φ = C 6 H 5 A = H, SO 3 Na, CH
₂ Cl R ′; Polycondensate of monomer consisting of (—CH ₂ —) _n (6 ≧ n ≧ 2) 2) HOOC-R—OH R; Polycondensate of monomer consisting of the same as the above R However, it is not limited. Particularly preferred polyesters are polyethylene terephthalate and its derivatives, but not limited thereto. The present invention is applicable to natural fibers, especially hemp and cotton, but is not limited thereto. The production method of the fiber composition according to the present invention is the existing fiber,
Alternatively, these functional groups may be introduced into a polymer having a fiber-forming ability. Any of the methods already proposed can be used and the method is not limited. Among these methods, particularly preferable methods in the present invention are described below, but the present invention is not limited thereto. In the case of cotton, hemp, rayon, and cupra, which are fibers of cellulose yarn, a compound (binder) having a reactive group that reacts with a hydroxyl group and a group that reacts with ammonia and its derivative, and ammonia and its derivative with alkali 1 in the presence or absence
A method of reacting at 00 ° C or lower is preferable. Preferred binders used in this case include, for example, those represented by the following general formula, but the binder is not limited thereto. _{Y = CH 2 -Z-CH 2} Y ' here Y; Cl, Br, I, Y'; epoxy group, sulfite group _{Z; -C n H 2n - (} 1 ≧ n ≧ 4) -C n H 2n _{-D-C n H 2n - (} n = 1,2) D; -S -, - NH 2 -, - SO -, - SO 2 -, examples of such compounds are epichlorohydrin, glycidol, 1,3 -Dichloropropan-2-ol, etc., but is not limited thereto. Examples of ammonium or its derivative used in the present invention include, but are not limited to, ammonia, ethylenediamine, triethylenetetramine, polyethyleneimine, and the like. When these alkylating agents and amines such as polyethyleneimine are used to synthesize wet fibers, the mixing ratio is 100 to 100 amines, and the alkylating agent is 0.01 to 2.0, preferably 0.1 to. It is 1.0, but is not limited to this. In the present invention, as a method for introducing a primary amine into the cellulosic fiber, there is a method utilizing an amino acid, but the method is not limited to this. The method for producing wet fibers when using vinylon in the present invention is basically the same as the method for producing cellulosic fibers. The preferred production method for using polyester in the present invention is a treatment method with ammonia at low temperature plasma. There is. In this case, a method in which the polyester is subjected to low-temperature plasma treatment in a nitrogen atmosphere reduced to several millitorr or less is preferable, but the method is not limited to this. It is considered that the obtained fiber composition has a heat absorption and exothermic property for the following reason. Up to now, it was well known that protein fiber has such performance, but the reason for this has not been clarified. The inventors were interested in this, and as a result of diligent study on the mechanism, surprisingly, the heat of reaction when a functional group contained in a protein, particularly a primary amine and a carboxyl group, binds to a water molecule, and then It was clarified that the heat of condensation of water that occurred in It was thought that this kind of phenomenon requires the presence of many amide bonds in the molecular chain like protein fibers, but surprisingly, even with hydrophobic polymers, amino groups and carboxyl groups were present. It has been revealed that the same exothermic phenomenon occurs when a hygroscopic functional group such as is present. The present invention is based on the discovery of such a phenomenon. The invention will be explained in more detail in the examples described below.

[0005]

【Example】

Examples 1-48, Comparative Examples 1-5 As commercially available acrylic fibers, Kashimilon (manufactured by Asahi Kasei), Bonnell (manufactured by Mitsubishi Rayon), Exlan (manufactured by Japan Exlan), Kanecaron (manufactured by Kanegafuchi Chemical Industry) Trelon (manufactured by Toray). used. These acrylic fibers were immersed in an aqueous solution of triethylenetetramine of various concentrations (bath ratio 1:20).
0), and treated at a temperature of 90 ° C. for 1 to 12 hours. After the treatment, it was washed with ion-exchanged water until the washing liquid became neutral, and then dried. The amino group of the treated fiber was determined from the equilibrium dyeing amount of Orange II by the Maclarren method. The heat of wetting of these samples was titrated by the following method. A differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) was used as a measuring machine. 2m for a sample that is fully dried and cut to 2mm or less
g It was inserted into a sample bottle and set without a lid. Nitrogen gas adjusted to a constant humidity is caused to flow into the measurement chamber, the sample is allowed to reach a thermal equilibrium state, and then nitrogen at a further increased humidity is flowed in. The total calorific value from the start of heat generation until the equilibrium was reached 5 minutes after was reached was the wet calorific value under the conditions.

Table 1 shows the results of measuring the amount of amino groups and the amount of heat generated by wetting in Examples 1-48 and Comparative Examples 1-5.

[0007]

[Table 1]

Examples 49-57, Comparative Example 6 Scoured and bleached hemp fibers were cut to a length of 10 mm, using only the treatment liquid of Table 2 and water as a comparison, and a bath ratio of 1:
50 was treated at 40 ° C. for the treatment time shown in Table 3.

[0009]

[Table 2]

[0010]

[Table 3]

The wet calorific value of the treated hemp fiber was measured in Example 1-
Measurement was carried out in the same manner as 48. Table 4 shows the results of the measurement of wet calorific value of Examples 49-57 and Comparative Example 6.

[0012]

[Table 4]

Examples 58-62, Comparative Example 7 Short fiber (2d) of polyester fiber was thoroughly scoured and dried, and 5 g of the dried fiber was sampled and inserted into a low temperature plasma treatment apparatus. After the pressure inside the processing apparatus was reduced to 1 mmHg or less, ammonia was inserted into the system and the pressure inside the tank was adjusted to 2 mmHg for plasma treatment. Wet calorific values of treated and untreated fibers are shown in Example 1-
The measurement was carried out in the same manner as in 48. Table 5 shows the plasma treatment time and the amount of heat generated by wetting.

[0014]

[Table 5]

[0015]

EFFECTS OF THE INVENTION The present invention is intended to impart to fibers other than wool and silk the same wet heat generation as wool and silk. By imparting such properties, it is possible to improve the comfort, which has hitherto been a drawback of synthetic fibers.
As a result, the synthetic fiber has come closer to the natural fiber, and its effect is immeasurable.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiromoto Uejima 4-1-1 Shimoda Higashi, Kashiba City, Nara Prefecture (72) Minoru Takewaki 141-3 Kisato, Nanbu-cho, Hidaka-gun, Wakayama Prefecture

Claims (11)

[Claims] 1. Wet exothermic fiber composition containing amine, hydroxyl and carboxyl groups as functional groups, alone and / or in combination. 2. The wet exothermic fiber composition according to claim 1, wherein the functional group is a primary and / or quaternary amine. 3. The wet exothermic fiber composition according to claim 1, wherein the fiber composition is a cellulosic fiber. 4. The fiber composition is polyester.
Wet exothermic fiber composition according to item 5. The wet heat-generating fiber composition according to claim 1, wherein the fiber composition is an acrylic fiber. 6. The functional group content is 0.1 mmol / g.
It is above, Preferably it is 0.2 mmol / g or more, The heat generating fiber composition of Claim 1 of Claim 1 7. A method for producing a wet heat-generating fiber composition, characterized in that the fiber composition contains amine, hydroxy group and carboxyl group as functional groups singly and / or in a proportion of 0.1 mmol / g or more. 8. The method for producing a wet heat-generating fiber composition according to claim 7, wherein the functional group is a primary and / or quaternary amine. 9. The method for producing a wet heat-generating fiber composition according to claim 7, wherein the fiber composition is a cellulosic fiber. 10. The method for producing a wet heat-generating fiber composition according to claim 7, wherein the fiber composition is polyester. 11. The method for producing a wet heat-generating fiber composition according to claim 7, wherein the fiber composition is an acrylic fiber.