JP2002138368A - Protein fiber material having improved hygrothermal property and process for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modification process for improving the hygrothermal properties of a protein fiber material with excellent economy and good adaptability to environment and safety. SOLUTION: This invention relates to a modification process for improving the hygrothermal properties of a protein fiber material characteristically by treating the fiber material with a mono- or dihalogenotriazine bearing hydrophilic substituents. The material of protein fiber, for example, wool, silk, leather, animal hair, and the like, yarns, knitted fabrics, woven fabrics therefrom is modified by treating them with a hydrophilic mono- or dihalogeno-s-triazine derivative to improve the hygrothermal properties whereby the wearing comfortability, for example, warmth retention and stuffiness is increased to increase the added value to the protein fiber material and expand the function and use. This modification process is friendly to global environment, highly economical and largely improves the hygrothermal properties with high practical value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a modification of a fiber material characterized by processing a protein fiber material with a mono- or dihalogeno-triazine compound having a hydrophilic substituent and modifying the fiber material from the viewpoint of wet heat generation. Quality processing method. More specifically, the present invention provides a material for protein-based fiber materials such as wool, silk, leather, and animal hair by using a hydrophilic mono- or di-halogeno-S-triazine derivative represented by the general formula (1).
Processing and modifying yarns, knits, and woven fabrics to improve wet heat generation and improve the comfort of clothing such as heat retention and stuffiness, thereby increasing the added value of protein-based fiber materials. The present invention relates to a processing method aimed at expanding applications. (In the formula, one or two of XYZ represent a halogen atom such as chlorine, fluorine, and bromine. Two or one of the remaining XYZ is a sulfone group, a carboxyl group, a hydroxyl group, a thiol group, or an amino group. A substitution having a hydrophilic substituent such as an allylamino group, an allyloxy group, an allylmercapto group, an alkylamino group, an alkoxy group, or an alkylthio group having at least one hydrophilic substituent such as a tertiary amino group and a quaternary amino group; Group, or an alkali metal salt such as a hydroxy group or a thiol group, or an alkaline earth metal salt, or a triazinyloxy group, a triazinylamino group, or a triazinylthio group having a hydrophilic substituent. A weakly acidic, neutral to weakly alkaline and water-soluble substituent such as a triazinylaminostilbeneamino group having a sulfone group. What may be. In the case only one of XYZ is halogen, and the remaining two substituents may be different and may be the same)

[0002]

2. Description of the Related Art Conventionally, protein-based fiber materials, particularly wool, are known as typical fibers having a heat-generating property.
It is said that this is caused by the release of heat of adsorption generated when the hydrophilic substituents of the protein fiber material firmly capture and fix water molecules in the atmosphere. This greatly contributes to the warmth of clothes, prevention of stuffiness, and comfort. on the other hand,
Synthetic fibers have a poor wet exothermicity, and have a problem that they are easily stuffed because they have a weak power of adsorbing water molecules. Has already been put to practical use. However, even a protein fiber material is not perfect in terms of wet heat generation, heat retention, and stuffiness. In particular, clothing such as socks, tights, pajamas, mufflers, and sheets that come in direct contact with the skin, and clothing worn in places with remarkable sweating, such as innerwear, sportswear, and winter clothing, have insufficient moisture absorption, heat retention, and moisture dissipation. Despite its limited use, little research has been done in this area.

[0003]

As described above, there has been little research on the modification and improvement of protein-based fiber materials due to their inherent heat build-up properties.
In order to elucidate the mechanism of exothermic heat generation of wool, studies have been known that the amount of heat generated by wetting is reduced by eliminating or blocking amino groups or carboxyl groups. However, the wet heat build-up, heat retention, stuffiness, etc. of protein fiber materials are not yet sufficient. If improvements are made, it is thought that wearing comfort will be improved in the fields currently used, and use of these materials will be postponed. It can be used in certain fields, which will further increase demand. Attempts have been made to improve the wet heat generation of synthetic fibers made from petroleum resources, but synthetic fiber materials are inferior in biodegradability and recyclability to protein-based fiber materials, and have environmental problems such as waste. The present invention also leads to environmental measures when considering that it is easy to cause problems. In particular, the processing method of the present invention using a hydrophilic mono- or dichlorotriazine-based compound is notable for its environmental friendliness due to the fact that it is non-formalin and non-resin. That is, the present invention aims to improve and improve the wet heat generation property of a protein-based fiber material by a method that does not cause environmental problems, open up a wider range of uses, and improve comfort. Another object of the present invention is to provide a protein-based fiber material having improved wet heat buildup.

[0004]

Means for Solving the Problems The inventor of the present invention has solved the above-mentioned various problems in terms of quality and the environment, and as a result of intensive studies on a method of modifying a protein fiber material which is friendly to the global environment. It has been found that when a mono- or dihalogeno-S-triazine-based compound having a hydrophilic substituent represented by the formula (1) is processed under the condition of reacting with a fiber material, the wet heat generation is greatly improved. (In the formula, one or two of XYZ represent a halogen atom such as chlorine, fluorine, and bromine. Two or one of the remaining XYZ is a sulfone group, a carboxyl group, a hydroxyl group, a thiol group, or an amino group. A substitution having a hydrophilic substituent such as an allylamino group, an allyloxy group, an allylmercapto group, an alkylamino group, an alkoxy group, or an alkylthio group having at least one hydrophilic substituent such as a tertiary amino group and a quaternary amino group; Group, or an alkali metal salt such as a hydroxy group or a thiol group, or an alkaline earth metal salt, or a triazinyloxy group, a triazinylamino group, or a triazinylthio group having a hydrophilic substituent. A weakly acidic, neutral to weakly alkaline and water-soluble substituent such as a triazinylaminostilbeneamino group having a sulfone group. Further, when only one of XYZ is halogen, the remaining two substituents may be the same or different.) Represented by the general formula (1) Conditions for reacting with a protein fiber material using a mono- or dihalogeno-S-triazine-based compound having a hydrophilic substituent can be processed under conditions similar to those of a mono- or dichlorotriazine-based reactive dye. Since the compound of the present invention has a small molecular weight and poor directivity, it cannot be processed efficiently under exactly the same conditions as in the case of the dye, so that a device for improving the directivity is required. As a result, a reduction in the amount of chemicals used, energy saving and a reduction in wastewater load can be achieved, and economic efficiency and environmental adaptability can be significantly improved.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to improving the heat generation property of a fibrous material containing a protein-based fiber material having a reactive substituent in its molecular structure as a main component, such as wool, silk, leather, and animal hair. By using a mono- or dihalogeno-S-triazine-based compound having a hydrophilic substituent to react by a covalent bond, a hydrophilic substituent is chemically imparted to provide excellent wet heat generation, anti-stuffiness, and wear. It is an object of the present invention to provide a protein fiber material having comfort.

The mono- or dihalogeno-S-triazine compound having a hydrophilic substituent which can be used in the present invention is a water-soluble compound represented by the general formula (1). (In the formula, one or two of XYZ represent a halogen atom such as chlorine, fluorine, and bromine. Two or one of the remaining XYZ is a sulfone group, a carboxyl group, a hydroxyl group, a thiol group, or an amino group. A substitution having a hydrophilic substituent such as an allylamino group, an allyloxy group, an allylmercapto group, an alkylamino group, an alkoxy group, or an alkylthio group having at least one hydrophilic substituent such as a tertiary amino group and a quaternary amino group; Group, or an alkali metal salt such as a hydroxy group or a thiol group, or an alkaline earth metal salt, or a triazinyloxy group, a triazinylamino group, or a triazinylthio group having a hydrophilic substituent. A weakly acidic, neutral to weakly alkaline and water-soluble substituent such as a triazinylaminostilbeneamino group having a sulfone group. What may be. In the case only one of XYZ is halogen, and the remaining two substituents may be different and may be the same)

The general formula (1) used in the present invention
More specifically, the modifying agent for a protein fiber material represented by the following formula: trihalogeno-S-triazine, preferably cyanuric chloride, is used as one raw material, and a carboxyl group, a hydroxyl group, a thiol group, an amino group, and a sulfamino group are used. ,
A single substance or a mixture of anilines, phenols, thiophenols, naphthylamines, naphthols, amino acids, triazines and the like having a water-soluble or hydrophilic substituent such as a sulfonic acid group is added in an amount of 1 to 1 mol of cyanuric chloride.
It is obtained by condensing 2 moles of neutral to weak alkali in the presence of an acid binder, or by alkaline hydrolysis of cyanuric chloride using sodium bicarbonate, sodium carbonate, sodium hydroxide, sodium hydroxide, calcium hydroxide, or the like. These compounds need not be pure,
The mixture of two or more of the above and cyanuric chloride may be reacted, or it may be preferable to mix a purely prepared product later and use it as a multi-component system. The compound having a hydrophilic substituent capable of reacting with trihalogeno-S-triazine, preferably cyanuric chloride, is specifically the following compound. As the hydrophilic substituent, a carboxyl group, an amino group, and a hydroxyl group are particularly important.

[0008] D-alanine, β-alanine, D-glutamic acid, L-glutamic acid, glycylglycine, L-aspartic acid, D-aspartic acid, γ-aminobutyric acid,
L-arginine, L-cystine, L-leucine, metanylic acid, sulfanilic acid, 2,5-disulfanilic acid, naphthonic acid, anthranilic acid, m-aminobenzoic acid, p
-Aminobenzoic acid, phenolsulfonic acid, dioxychlorotriazine, cyanuric acid, pyrocatechin, hydroquinone, pyrogallol, phloroglucinol, amidole, protocatechuic acid, C acid, G acid, J acid, γ acid, H
Acid, 4,4-diaminostilbene-2,2-disulfonic acid, salicylic acid, dithiochlorotriazine, aminooxychlorotriazine, aminodioxytriazine, ethanolamine, propanolamine, N- (2-aminoethyl) ethanolamine, N -Methylethanolamine, ammonia, methylamine, ethylamine, allylamine, methoxypropylamine, 3- (dimethylamino) propylamine, thiosalicylic acid, thioacetamide, thiocarbohydrazide, thioglycolic acid, 1-
Thioglycerol, thiodiglycol, triglycol dimercaptan, ethylene glycol, diethylene glycol, glycerin, bis (2-mercaptoethyl) sulfite, α-hydroxyisobutyric acid, melamine, urea, thiourea and the like, and salts thereof.

The conditions to be met by these compounds are that they have a substituent that reacts with the halogenotriazine and at the same time they are hydrophilic compounds that have a hydrophilic substituent. However, this is not always the case when used in combination with a compound having a hydrophilic substituent. The point is that the processing agent used in the present invention may be entirely hydrophilic. Specific examples of a product obtained by reacting a halogenotriazine with these hydrophilic compounds include a single substance or a mixture of the following compounds. 2-chloro-4,6-bis (α-carboxyethylamino) -S-triazine 2-chloro-4,6-bis (β-carboxyethylamino) -S-triazine 2-chloro-4,6-bis ( γ-carboxypropylamino) -S-triazine 2-chloro-4,6-bis (α-carboxy-γ-carboxypropylamino) -S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(Β-carboxyethylamino) -S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(Γ-carboxypropylamino) S-triazine 2-chloro-4 (α-carboxyethylamino) -6
Hydroxy-S-triazine 2-chloro-4 (β-carboxyethylamino) -6
Hydroxy-S-triazine 2-chloro-4 (β-hydroxyethylamino) -6
Hydroxy-S-triazine 2-chloro-4 (2-hydroxyethylamino) ethylamino-6-hydroxy-S-triazine 2-chloro-4 (γ-hydroxypropylamino) -6
-Hydroxy-S-triazine 2-chloro-4 (3-sulfoanilino) -6-hydroxy-S-triazine 2-chloro-4 (2-carboxyanilino) -6-hydroxy-S-triazine 2-chloro-4 ( 4-carboxyanilino) -6-hydroxy-S-triazine 2-chloro-4,6-dihydroxy-S-triazine 2-chloro-4,6-dimercapto-S-triazine 2-chloro-4-hydroxy-6 Amino-S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(3-Sulfoanilino) -S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(4-sulfoanilino) -S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(4-carboxyanilino) -S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(2-carboxyanilino) -S-triazine 2-chloro-4 (α-carboxyethylamino) -6
(3-hydroxyanilino) -S-triazine 2-chloro-4,6-bis (3-sulfoanilino)-
S-triazine 2-chloro-4,6-bis (4-sulfoanilino)-
S-triazine 2-chloro-4,6-bis (2-sulfoanilino)-
S-triazine 2-chloro-4,6-bis (2,5-disulfoanilino) -S-triazine 2-chloro-4- (3-sulfoianilino) -6- (4
-Sulfoanilino) -S-triazine 2-chloro-4- (3-sulfoanilino) -6
(2,5-disulfoanilino) -S-triazine 2-chloro-4,6-bis (3-carboxyanilino)
-S-triazine 2-chloro-4,6-bis (4-carboxyanilino)
-S-triazine 2-chloro-4,6-bis (2-carboxyanilino)
-S-triazine 2-chloro-4- (3-sulfoanilino) -6- (4
-Carboxanilino) -S-triazine 2-chloro-4,6-bis (4-sulfophenoxy)
-S-triazine 2-chloro-4,6-bis (3-carboxyphenoxy) -S-triazine 2-chloro-4,6-bis (2-carboxyphenylthio) -S-triazine 2-chloro-4,6 -Bis (3-hydroxyphenoxy) -S-triazine 2,6-dichloro-4- (α-carboxyethylamino) -S-triazine 2,6-dichloro-4- (β-carboxyethylamino) -S-triazine 2,6-dichloro-4- (γ-carboxypropylamino) -S-triazine 2,6-dichloro-4- (α-carboxy-γ-carboxypropylamino) -S-triazine 2,6-dichloro-4- (2-carboxyphenylthio) -S-triazine 2,6-dichloro-4- (carboxymethylthio) -S
-Triazine 2,6-dichloro-4- (3-sulfoanilino) -S
-Triazine 2,6-dichloro-4- (4-sulfoanilino) -S
-Triazine 2,6-dichloro-4- (2-sulfoanilino) -S
-Triazine 2,6-dichloro-4- (2,5-disulfoanilino) -S-triazine 2,6-dichloro-4- (3,5-disulfoanilino) -S-triazine 2,6- Dichloro-4- (3-sulfo-4-oxy-
5-carboxyanilino) -S-triazine 2,6-dichloro-4- (3-carboxyanilino)-
S-triazine 2,6-dichloro-4- (4-carboxyanilino)-
S-triazine 2,6-dichloro-4- (2-carboxyanilino)-
S-triazine 2,6-dichloro-4- (4-sulfophenoxy)-
S-triazine 2,6-dichloro-4- (3-sulfophenoxy)-
S-triazine 2,6-dichloro-4- (2-sulfophenoxy)-
S-triazine 2,6-dichloro-4- (4-carboxyphenoxy)
-S-triazine 2,6-dichloro-4- (4-carboxyphenylthio) -S-triazine 2,6-dichloro-4- (3-sulfophenylthio)
-S-triazine 2,6-dichloro-4- (3,6-sulfo-8-oxynaphthalen-1-ylamino) -S-triazine 2,6-dichloro-4- (4,8-sulfonaphthalene-2 -Ylamino) -S-triazine 2,6-dichloro-4-oxy-S-triazine Na salt 2,6-dichloro-4-oxy-S-triazine K salt 2,6-dichloro-4-oxy-S-triazine Li salt 2,6-dichloro-4-oxy-S-triazine Mg salt 2,6-dichloro-4-thio-S-triazine Na salt 2,6-dichloro-4 (4-oxy-6-chloro-S-
Triazin-2-yloxy) -S-triazine Na salt 2,6-dichloro-4 (4-thio-6-chloro-S-triazin-2-ylthio) -S-triazine Na salt 2,6-dichloro-4 ( 4,6-dioxy-S-triazin-2-yloxy) -S-triazine Na salt 2,6-dichloro-4 (3,5-dioxyphenyloxy) -S-triazine 2,6-dichloro-4 (3 -Oxyphenyloxy)-
S-triazine 2,6-dichloro-4 (4-oxyphenyloxy)-
S-triazine 2,6-dichloro-4 (4-carboxymethoxy) -S
-Triazine Na salt 2,6-dichloro-4 (4-sulfoethylamino)-
S-triazine Na salt 2,6-dichloro-4 (4-carboxymethylthio)-
S-triazine Na salt 2,6-dichloro-4 (4-sulfonyloxyethylamino) -S-triazine Na salt 4,4'-bis (4,6-dichloro-S-triazine-
2-ylamino) -stilbene-2,2'-disulfonic acid Na salt 2,6-dichloro-4 (4,6-diamino-S-triazin-2-ylamino) -S-triazine 2,6-dichloro- 4-carbamoylamino-S-triazine 2,6-dichloro-4-thiocarbamoylamino-S-
Triazine 2-chloro-4,6-dicarbamoylamino-S-triazine 2-chloro-4,6-dithiocarbamoylamino-S-
Triazine Mono- or dihalogenotriazines having a hydrophilic substituent can be considered to be many other effective compounds, and the present invention is not limited to these specific examples. A compound having a group,
The point is to have at least one active halogen atom or a similar reactive group. In addition, the above-mentioned compounds include cases where the water-soluble substituent is an alkali metal salt or an alkaline earth metal salt in all cases.

The protein-based natural material modified and processed in the present invention may be a single product or a mixed product, and may be a composite fiber including so-called synthetic fiber. Specifically, it is a material or a woven knit mainly composed of wool, silk, leather, animal hair, or the like. These materials can also be processed at the stage of cotton, rose wool, yarn, woven or knitted, or at the stage of semi-finished products during the process. These are protein-based organic natural materials having a reactive group capable of reacting with a mono- or dihalogenotriazine-based compound having a hydrophilic substituent. The materials to be processed may be composites with petroleum synthetic materials such as polyester, polyamide, polyvinyl alcohol, polyacrylonitrile, and polypropylene.

The processing agent of the present invention is disclosed in German Offenlegungsschrift 23
No. 57252, or US Pat.
The compounds can be synthesized according to a known synthesis method as described in the above publications, and the outline is as follows. For example, 1.00 mol of cyanuric chloride is charged into ice water at 5 ° C. or lower, and then, for example, 1.00 mol of P-aminobenzoic acid and about 1 mol of sodium carbonate are gradually charged with good stirring. It takes about 3 hours to maintain pH = 7 ~ 8 and temperature 5 ± 2 ° C.
Stirring is continued until almost all of the cyanuric chloride disappears, as analyzed by LC, and the reaction is completed by further heating and stirring for 1 hour. During this period, the pH is maintained at 7 to 8, and the composition is analyzed by HPLC. When the unreacted substances have completely disappeared, the reaction is terminated. After the reaction, the pH is raised slightly to remove a small amount of insoluble matter by filtration, and finally the pH is adjusted to 7. In this way,
6-dichloro-4- (4-carboxyanilino) -S-
An aqueous solution of Na salt of triazine is obtained in high yield. In the case of monohalogeno system, the corresponding amines, alcohols, etc.
The reaction may be carried out by raising the secondary reaction temperature to 30 to 40 ° C. using about twice the molar ratio and sodium carbonate.

The processing conditions for the protein fiber material of the present invention are as follows:
Unlike mono- or dichlorotriazine-based reactive dyes or vinylsulfone-based reactive dyes, the dyes have low molecular weight, lack linearity and flatness, and have poor affinity and directness to fibers. Simply applying the above processing conditions does not provide sufficiently satisfactory results. The outline of the processing conditions is as follows.
10% (pure owf), bath ratio 1: 2-3
0, the fiber material is immersed in a dye bath in which 1 to 20% (owf) of anhydrous sodium carbonate, sodium bicarbonate or caustic soda, and if necessary, 1 to 100 g / l of sodium sulfate are added and mixed, In the case of a dihalogeno system while circulating the liquid, the primary reaction temperature is 20 to 70 ° C. for 0.5 to 2 hours, and the secondary reaction temperature is 6
After reacting at 0 to 100 ° C for 0.5 to 2 hours, soaping and washing are carried out. In the case of a monohalogeno system, the reaction is carried out at a reaction temperature of 60 to 100 ° C for 0.5 to 2 hours, followed by soaping and washing with water. The purpose can be achieved by the method of doing. It is also possible to carry out the primary reaction treatment within the heating time by allowing sufficient heating time.

In the case of the padding method, the drawing ratio is 50 to 3
The fiber material impregnated with the aqueous drug solution at 00% is subjected to a primary treatment temperature of 20 to 60 ° C, a heat treatment time of 30 to 360 minutes, a secondary treatment temperature of 60 to 130 ° C, and a secondary heat treatment time of 5 to 120.
What is necessary is just to process by adopting processing conditions such as minutes. In general, a drug having a highly reactive halogen is preferably treated at a low temperature, and a drug having a less reactive halogen is preferably treated at a high temperature. These processing conditions are not limited to the above conditions according to the type of the protein material and the processing purpose. For example, in order to enhance the processing effect, the amount of the chemical used is increased and the processing conditions are strengthened. Can be changed to

[0014]

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.

Example 1 1k of 1 / 48th wool yarn off-scaled on a squeeze tester
g, and at a bath ratio of 120, 2,6-dichloro- obtained by reacting 1 mol of sodium L-glutamate with 1 mol of cyanuric chloride in a water solvent at 0-5 ° C. with sodium carbonate.
600 g of a 10% aqueous solution of 4- (α-carboxy-γ-carboxypropylamino) -S-triazine is added at 30 ° C.
Prepare with. After 5 minutes, add 1 kg of sodium sulfate, and after 5 minutes, add 200 g of sodium carbonate and check the pH after 10 minutes. If necessary, add sodium carbonate to adjust the pH to 9.8 or more and 10.5 or less. keep. The temperature is raised to 70 to 80 ° C at 1 ° C / minute. The temperature is maintained at 70 to 80 ° C. for 60 minutes, and the completion of the reaction is confirmed by the absence of pH fluctuation. After draining, washing with water is performed, followed by washing with hot water at 90 ° C. for 10 minutes. The wet calorific value of the wool-processed yarn thus obtained was measured using a Shimadzu differential scanning calorimeter. Text. Mach.
Soc. Japan, Vol. 52, no. 7, P38
(1999). as a result,
481 mj / mg as the average of three measurements of the heat generation value
High value was obtained. Since the measured value of the wet heat value of the same unprocessed yarn was 300 to 350 mj / mg, it was clearly confirmed that the processing effect of increasing the wet heat value by the method of the present invention was extremely large. In addition, an environmental tester, a temperature and humidity tester ETACHI manufactured by Ettack Engineering Co., Ltd.
The measurement condition of the tester was set to 2 using FLEX FX206C.
The measurement was performed at 6 ° C. and 90% RH. The container containing the sample dried under a certain condition is mounted in the tester, and the sample with the temperature and humidity inside the sample container of 26.7 ° C. and 13% RH is opened in the tester, and the tester is stopped. The temperature change was recorded.
Heat generation starts and a temperature rise curve is obtained, but after reaching the saturation point, a gradually falling curve is drawn. Comparing the temperature difference at the peak time between the processed product and the unprocessed product, the processed product having a temperature of 2 to 3 ° C. shows a higher value, and data supporting that the wet heat generation effect is large also by this test method was obtained. . When the socks were knitted with the processed yarn of this example and subjected to a wearing test, it was confirmed that wearing comfort such as heat retention and stuffiness was significantly superior to unprocessed products.

Example 2 1k of 1 / 48th wool yarn off-scaled on a scab tester
g in a bath ratio of 125, and 2-mol-4 obtained by coexisting sodium mol-sodium L-glutamate in an aqueous solvent at 0 to 30 ° C. with sodium carbonate at a bath ratio of 125 to 1 mol of cyanuric chloride.
1500 g of a 10% aqueous solution of 6-bis (α-carboxy-γ-carboxypropylamino) -S-triazine was added to 3
Charge at 0 ° C. After 5 minutes, add 1 kg of glass nitrate, and
After 120 minutes, 120 g of sodium carbonate was added, and the pH after 10 minutes was confirmed. If necessary, sodium carbonate was added to adjust the pH to 9.8.
It is kept at not less than 10.5. The temperature is raised to 70 to 80 ° C at 1 ° C / minute. After keeping the temperature at 70 to 80 ° C. for 60 minutes, draining and washing with water, then washing with 90 ° C. for 10 minutes, washing with water, and then finishing with a flexible treatment. The wet calorific value of the wool yarn thus obtained was measured in the same manner as in Example 1. as a result,
455 mj / mg as an average of three measurements of the heat generation value
High value was obtained. Since the measured value of the wet heat value of the same unprocessed yarn was 300 to 350 mj / mg, it was clearly confirmed that the processing effect of increasing the wet heat value by the method of the present invention was large. In addition, when a heat generation test using an environmental tester was performed in the same manner as in Example 1, the temperature difference at the peak showed a higher value in the processed product at 1 to 2 ° C. when compared between the processed product and the unprocessed product. This test method also provided data supporting a large moist heat generation effect.

Example 3 1k of 1 / 48th wool yarn off-scaled on a scab tester
g, and at a bath ratio of 120, 2,6-dichloro-4 (4,6-) obtained by reacting 1 mol of melamine with 1 mol of cyanuric chloride in a water solvent at 0-5 ° C. with sodium carbonate.
550 g of a 10% aqueous solution of diamino-S-triazin-2-ylamino) -S-triazine is charged at 30 ° C. 5
After 1 minute, add 1 kg of sodium sulfate, and after 5 minutes, add 85 g of sodium carbonate to check the pH after 10 minutes. If necessary, add sodium carbonate to maintain the pH at 9.8 or more and 10.5 or less. . The temperature is raised to 70 to 80 ° C at 1 ° C / minute. 70-8
Incubate at 0 ° C for 60 minutes, drain and rinse with water, then 90 ° C
After washing with water for 10 minutes, a softening finish is performed.
The wet heat value of the wool-processed yarn thus obtained was determined in Example 1.
The measurement was performed in the same manner as described above. As a result, a high value of 467 mj / mg was obtained as an average value of the measured values of the three heat generation values. The same calorific value of unprocessed yarn is 300-350mj
/ Mg, it was clearly confirmed that the processing effect of increasing the amount of heat generated by the method of the present invention was extremely large. In addition, when a heat generation test using an environmental tester was performed in the same manner as in Example 1, the temperature difference at the peak showed a higher value in the processed product at 2 to 3 ° C. when compared between the processed product and the unprocessed product. This test method also provided data supporting a large moist heat generation effect.

Example 4 1k of 1 / 48th wool yarn off-scaled on a squeeze tester
g, and at a bath ratio of 115, 2,6-dichloro-4-carbamoylamino-S- obtained by reacting 1 mol of urea with 1 mol of urea to 1 mol of urea per 1 mol of sodium carbonate in an aqueous solvent at 0-5 ° C. 832 g of a 10% aqueous solution of triazine was added to 30
Charge at ° C. After 5 minutes, add 1 kg of sodium sulfate, and after 5 minutes, add 250 g of sodium carbonate and check the pH after 10 minutes. If necessary, add sodium carbonate to adjust the pH to 9.8 or more and 10.5 or less. keep. The temperature is raised to 70 to 80 ° C at 1 ° C / minute. After keeping the temperature at 70 to 80 ° C. for 60 minutes, draining and washing with water, then washing with 90 ° C. for 10 minutes, washing with water, and then finishing with a flexible treatment. The wet calorific value of the wool yarn thus obtained was measured in the same manner as in Example 1. As a result, 4
Values as high as 55 mj / mg were obtained.

Example 5 1 / 48th wool yarn 1k off-scaled on a squeeze tester
g, and at a bath ratio of 1:20, 2,6-dichloro- obtained by reacting 1 mol of P-aminobenzoic acid with 1 mol of cyanuric chloride in a water solvent at 0-5 ° C. with sodium carbonate.
4- (4-carboxyanilino) -S-triazine 1
855 g of a 0% aqueous solution are charged at 30 ° C. After 5 minutes, add 1 kg of sodium sulfate, and after 5 minutes, add 200 g of sodium carbonate and check the pH after 10 minutes. If necessary, add sodium carbonate to adjust the pH to 9.8 or more and 10.5 or less. keep. 70
The temperature is raised at a rate of 1 ° C./min to ８０80 ° C. 60 at 70-80 ° C
It is kept warm for one minute, washed with water after draining, then washed with hot water at 90 ° C. for 10 minutes, and then subjected to a softening treatment. The wet calorific value of the wool yarn thus obtained was measured in the same manner as in Example 1. As a result, a high value of 435 mj / mg was obtained.

1 kg of 1/48 wool yarn off-scale was set in a skein test machine, and at a bath ratio of 120, 1 mol of anthranilic acid was added to 1 mol of anthranilic acid in an aqueous solvent at a bath ratio of 120.
855 g of a 10% aqueous solution of 2,6-dichloro-4- (2-carboxyanilino) -S-triazine obtained by a coexistence reaction with sodium carbonate at 30 ° C is charged at 30 ° C. Five minutes later, 1 kg of glass nitrate is added, and after another five minutes, sodium carbonate is added to 20 kg.
Check the pH 10 minutes after adding 0 g, and if necessary, add sodium carbonate to maintain the pH at 9.8 or more and 10.5 or less. The temperature is raised to 70 to 80 ° C at 1 ° C / minute. 70-80
After keeping the temperature at 60 ° C. for 60 minutes, draining and washing with water, then washing with 90 ° C. for 10 minutes and washing with water, and then finishing with a soft treatment. The wet calorific value of the wool yarn thus obtained was measured in the same manner as in Example 1. As a result, a high value of 415 mj / mg was obtained.

The fibrous material mainly composed of a protein-based organic natural material processed by the method of the present invention has a remarkably large amount of heat generated by heating as compared with an unprocessed protein-based fibrous material. In addition to the excellent modifying effect, such as improved wear comfort such as stuffiness, and durability, it also has excellent strength. In particular, the feature of the method of the present invention is that, without using harmful chemicals such as resin and formalin, using a safe and environmentally friendly and inexpensive processing chemical, it is possible to achieve a large moist heat generation effect. Practical value, with improved comfort and excellent economics, further expanding the use of protein-based fiber materials in areas of limited use, such as innerwear, socks, sports equipment, bedding, etc. And contribute greatly to environmental issues.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiromi Kashiwara 1 in Okamoto Co., Ltd., 150, Oaza, Koryo-cho, Kitakatsuragi-gun, Nara Prefecture F term (reference) 4L033 AA03 AC15 BA58

Claims (2)

[Claims] 1. A method for modifying a protein fiber material by reacting it with a hydrophilic halogenotriazine-based compound, wherein a mono- or di-halogeno-S-triazine derivative represented by the general formula (1) is used. A processing method for improving wet heat generation of a protein fiber material characterized by processing using a mixture. (In the formula, one or two of XYZ represent a halogen atom such as chlorine, fluorine, and bromine. Two or one of the remaining XYZ is a sulfone group, a carboxyl group, a hydroxyl group, a thiol group, or an amino group. A substitution having a hydrophilic substituent such as an allylamino group, an allyloxy group, an allylmercapto group, an alkylamino group, an alkoxy group, or an alkylthio group having at least one hydrophilic substituent such as a tertiary amino group and a quaternary amino group; Group, or an alkali metal salt such as a hydroxy group or a thiol group, or an alkaline earth metal salt, or a triazinyloxy group, a triazinylamino group, or a triazinylthio group having a hydrophilic substituent. A weakly acidic, neutral to weakly alkaline and water-soluble substituent such as a triazinylaminostilbeneamino group having a sulfone group. What may be. In the case only one of XYZ is halogen, and the remaining two substituents may be different and may be the same) 2. A mono- or di-halogeno-S-triazine derivative represented by the general formula (1) comprising a protein fiber material such as wool, silk, leather or animal hair as a main material to be processed. A protein fiber material that has been processed and has improved wet heat generation. (In the formula, one or two of XYZ represent a halogen atom such as chlorine, fluorine, and bromine. Two or one of the remaining XYZ is a sulfone group, a carboxyl group, a hydroxyl group, a thiol group, or an amino group. A substitution having a hydrophilic substituent such as an allylamino group, an allyloxy group, an allylmercapto group, an alkylamino group, an alkoxy group, or an alkylthio group having at least one hydrophilic substituent such as a tertiary amino group and a quaternary amino group; Group, or an alkali metal salt such as a hydroxy group or a thiol group, or an alkaline earth metal salt, or a triazinyloxy group, a triazinylamino group, or a triazinylthio group having a hydrophilic substituent. A weakly acidic, neutral to weakly alkaline and water-soluble substituent such as a triazinylaminostilbeneamino group having a sulfone group. What may be. In the case only one of XYZ is halogen, and the remaining two substituents may be different and may be the same)