JP4319568B2 - Hygroscopic exothermic animal hair fiber product and method for producing the same - Google Patents

Description

  The present invention relates to an animal hair fiber product with improved hygroscopic heat generation and a method for producing the same.

  Animal hair fibers such as wool are well known as those having the highest moisture absorption exothermicity among natural fibers. Hygroscopic exothermicity is a property that heat is generated when the dried fiber absorbs moisture (moisture). For example, a futon applied to the sun in the daytime is taken into the room, and the temperature is the same as room temperature after several hours. It is also known as a phenomenon that makes you feel warm when you touch the human skin.

Conventionally, as a method for producing a hygroscopic exothermic fiber, the following Patent Document 1 discloses a highly hygroscopic fiber comprising a hydrazine crosslinking treatment of an acrylic fiber, a hydrolysis treatment, and a conversion of a carboxyl group into a salt type and a method for producing the same. Proposed. Patent Document 2 below proposes a wet exothermic fiber composition in which amines, hydroxyls, and carboxyl groups are introduced singly or as a functional group into fibers other than protein fibers, and a method for producing the same. However, these methods relate to synthetic fibers and could not be applied to animal hair fibers. Patent Document 3 below proposes a highly moist exothermic animal hair protein fiber in which a highly hygroscopic compound is fixed on the surface of the protein fiber and a method for producing the same. However, according to this method, since the properties of the fiber surface change, there is a problem that the water repellency and texture inherent to animal hair fibers are impaired. Patent Document 4 below proposes a hygroscopic exothermic fiber in which a fiber is swollen with water and crosslinked using a polyfunctional epoxy compound in a swollen state, and a method for producing the same. However, when animal hair fibers were treated by this method, the degree of swelling with water was not sufficiently large.
Japanese Patent Laid-Open No. 5-132858 JP-A-8-311767 JP 2002-13075 A JP 2002-115179 A

  The present invention provides an animal fiber product having improved heat retention by improving the conventional problems and improving the moisture absorption exothermic property without impairing the properties of the animal fiber surface, and a method for producing the same.

The hygroscopic exothermic animal hair fiber product of the present invention is an animal hair fiber product in which hygroscopic exothermic property is imparted to the animal hair fiber, and at least part of the disulfide (-SS-) bond in the animal hair fiber. Is reduced and cleaved in at least one reducing agent solution selected from mercaptosuccinic acid and salts thereof, cysteic acid and salts thereof, thiols, and phosphines, and sufficiently swollen to generate mercapto groups (—SH), By chemically bonding a reactive compound that forms an irreversible blocking group containing a hydrophilic group and a polyfunctional group to the mercapto group (-SH) , the molecular gap is widened to facilitate water vapor penetration. This is characterized in that the affinity for the water is increased and the molecular gap for water vapor to enter is stabilized .

The method for producing a hygroscopic exothermic animal hair fiber product of the present invention is a method for producing a hygroscopic exothermic animal hair fiber product in which a reactive compound is bound to an animal hair fiber, wherein disulfide (- S—S—) at least a part of the bond is reductively cleaved in at least one reducing agent solution selected from mercaptosuccinic acid and salts thereof, cysteic acid and salts thereof, thiols, and phosphines, and sufficiently swollen. By forming a mercapto group (-SH) and chemically bonding a reactive compound that forms an irreversible blocking group containing a hydrophilic group and a multifunctional group that reacts with the mercapto group (-SH) , the molecular gap is reduced. It is characterized by obtaining animal hair fibers that are spread and easily penetrated with water vapor, increase affinity with water vapor, and stabilize molecular gaps for water vapor to enter .

  In the present invention, the bond between animal hair fibers is chemically cut and blocked, thereby preventing rebonding and absorbing more moisture. As a result, it is possible to provide an animal hair fiber product with improved moisture absorption exotherm and high heat retention. That is, at least a part of disulfide (—S—S—) bond between animal hair fibers is reductively cleaved in a reducing agent solution to generate a mercapto group (—SH), which reacts with the mercapto group (—SH). The reactive compound is blocked by chemical bonding. Thereby, it does not return to a disulfide (-SS-) bond, there are many gaps between the fibers, and a bulky bulk structure that easily absorbs moisture is obtained. As a result, the moisture absorption exothermic property can be improved.

  Furthermore, the animal hair fiber of the present invention becomes bulky between the fibers due to the above-described effects, increasing flexibility and stretchability, and improving the texture.

  The animal hair fiber product of the present invention refers to a product containing hair fibers such as wool, cashmere, mohair, and camel. Although it may be mixed with other fibers, in order to obtain sufficient moisture absorption exothermicity, it is preferable that the mixing ratio of animal hair fibers is 30% or more. Examples of the product form include raw cotton, top, yarn, woven fabric, knitted fabric, felt, and non-woven fabric.

The reducing agent used in the present invention refers to a general drug used for setting a woolen fabric or hair or reducing treatment. Specifically, Ji o glycolic acid and salts thereof, mercaptosuccinic acid and its salts, cysteine acid and salts thereof, 2-mercaptoethylamine, 2-mercaptoethanol, thiols etc., tributylphosphine, hydroxymethyl phosphonium chloride, tris Examples include phosphines such as -3-hydroxypropylphosphine.

In the present invention, the irreversible blocking group refers to a linking group in which a mercapto group (—SH) does not return to a disulfide (—S—S—) bond under normal use conditions. The reactive compound used for this purpose is a compound containing a functional group that reacts with a mercapto group. Although a functional group may be individual, it is preferable to contain multiple functional groups. Specific examples include reactive dyes and compounds containing functional groups represented by the following general formula.
(1) α-Bromoacrylamide (R-NHCOCBr = CH ₂ )
(2) Sulfatoethylsulfone (R-SO ₂ CH ₂ CH ₂ OSO ₃ H)
(3) N-methyl taurine ethyl sulfone (R—SO ₂ CH ₂ CH ₂ —NCH ₃ —CH ₂ CH ₂ —SO ₃ H)
(4) vinyl sulfone _{(R-SO 2 -CH = CH} 2)
(5) Difluorochloropyrimidine represented by the following formula (Chemical Formula 1)

（６）下記式（化２）で示されるジクロロピリミジン

(6) Dichloropyrimidine represented by the following formula (Formula 2)

（７）下記式（化３）で示されるトリクロロピリミジン

(7) Trichloropyrimidine represented by the following formula (Formula 3)

（８）下記式（化４）で示されるモノクロロトリアジン

(8) Monochlorotriazine represented by the following formula (Formula 4)

（９）下記式（化５）で示されるジクロロトリアジン

(9) Dichlorotriazine represented by the following formula (Formula 5)

（１０）イソシアナート(R-N=C=O)
（１１）イソチオシアナート(R-N=C=S)
（１２）下記式（化６）で示されるエポキシ化合物

(10) Isocyanate (RN = C = O)
(11) Isothiocyanate (RN = C = S)
(12) Epoxy compound represented by the following formula (Formula 6)

（１３）ブンテ塩 (R-S-SO₃ ^-)（参考例）
（１４）酸無水物(R-CO-O-CO-R)
（１５）下記式（化７）で示される環状酸無水物

(13) Bunte salt (RS-SO ₃ ^-) (Reference Example)
(14) Acid anhydride (R-CO-O-CO-R)
(15) A cyclic acid anhydride represented by the following formula (Formula 7)

（１６）下記式（化８）で示されるマレイミド

(16) Maleimide represented by the following formula (Chemical Formula 8)

R in the general formula is an alkyl group, an aryl group, a chromophore group, etc., and is not particularly limited.
Furthermore, a compound containing one or more hydrophilic groups in R is preferred. Hydrophilic groups include —OH, —NH ₂ , —COOH, —COONa, —SO ₃ H, —SO ₃ Na, — (RO) n— (where R is an alkyl group, —COO—, —CO—NH -) Etc. are mentioned.

  The animal hair fiber product of the present invention with improved moisture absorption and exothermicity is obtained by reducing and cleaving disulfide bonds in animal hair fiber in a reducing agent aqueous solution, sufficiently swelling, and then reacting the resulting mercapto group with a reactive compound. Can be obtained. It is preferable that 1% or more of the disulfide bond in the animal hair fiber is reductively cleaved in an aqueous reducing agent solution, and then the reactive compound is reacted with the generated mercapto group.

  The treatment device for the reduction treatment and the reactive compound treatment may be any device capable of immersion treatment, and a general dyeing machine such as a top dyeing machine, a yarn dyeing machine, or an anti-dyeing machine should be used according to the form of the product. Can do. It is economically preferable that the bath ratio is as low as possible within the range in which the processing apparatus operates.

  The concentration of the reducing agent used varies depending on the reducing power of the reducing agent used, but is preferably in the range of 0.1% owf (owf is an abbreviation for on the weight of fiber) to 80% owf. A range of 30% owf is more preferred.

  The temperature of the reduction treatment is preferably 40 ° C. or higher and 106 ° C. or lower. When the treatment temperature is too low, the production of mercapto groups is small, and when the treatment temperature is too high, the quality of the animal hair fibers deteriorates. The pH of the reduction treatment is preferably 4 or more and 11 or less. When the pH is too low, the production of mercapto groups is small, and when the pH is too high, the quality of animal hair fibers deteriorates. Further, as disclosed in JP-A-2002-155467, when the reducing agent is selected from thiol compounds containing carboxylic acid (for example, thioglycolic acid and its salt, mercaptosuccinic acid and its salt, etc.) It is preferable to change the pH from acidic to alkaline. The reduction treatment time is preferably 10 to 60 minutes. If it is too short, the production of mercapto groups is small, and if it is too long, the cost increases economically.

  The reactive compound treatment is preferably carried out following the reduction treatment without going through the drying step. When the drying step is interposed, the mercapto group generated by air oxidation is re-bonded to the disulfide bond, so that the reaction rate of the reactive compound is reduced.

  The concentration of the reactive compound used varies depending on the molecular weight and reactivity of the compound, but is preferably in the range of 0.1% owf to 80%, and more preferably in the range of 1% owf to 30% owf in view of the effect and cost.

  The treatment temperature is preferably 40 ° C. or higher and 106 ° C. or lower. If the temperature is low, the reaction rate decreases, and if it is high, the quality of the animal hair fibers deteriorates. The treatment pH is preferably 4 or more and 11 or less. If the pH is low, the reaction rate is poor, and if it is high, the quality of the animal hair fibers deteriorates. The treatment time is preferably 10 to 60 minutes. If it is short, the reaction rate is bad, and if it is long, the cost increases economically.

  The reason why the moisture absorption exothermic property of animal hair fibers is improved by the present invention has not been fully elucidated, but is generally considered as follows. That is, regeneration of disulfide bonds is suppressed by cleaving disulfide bonds of animal hair fibers and reacting the generated mercapto groups with reactive compounds. For this reason, the binding force between the fiber molecules due to the disulfide bond is weakened, and the interstices are widened, so that water vapor easily penetrates. As a result, it is thought that moisture absorption exothermic property improves. Further, if the reactive compound has a hydrophilic group, the affinity with water vapor is increased, and it is considered that it advantageously works to improve the hygroscopic exothermic property. Further, if the reactive compound is a polyfunctional compound, the reaction rate with the mercapto group is increased, and a part of the crosslink is formed, so that the molecular gap for water vapor to enter is stabilized.

  The fiber product of the present invention may be of any kind, but is preferably at least one selected from cotton, top, yarn, woven fabric, knitted fabric, felt and non-woven fabric. Further, the textile product may be sports clothing, underwear, a suit, a uniform, gloves, socks, a hat, an inside cotton clothing, or a futon.

The animal hair fibers of the present invention include animal hair fibers that have been subjected to treatments such as shrinkage reduction, descaling, stretching, and electric discharge, and also include fibers that have not been subjected to the aforementioned treatment. Examples of the shrink-proofing method include the chlorination method, oxidation method, chlorination / resin method and the like described in the following non-patent document (1) and the ozone method and the like in the following non-patent document (2). As the descaling process, a method according to the following document (3) can be mentioned. Examples of the stretching treatment include the stretching / setting method described in Non-Patent Document (4) below. Examples of the discharge treatment include corona discharge and low-temperature plasma discharge methods described in Non-Patent Document 5 below.
(1) `` Dyeing Industry '' Vol. 41, No. 7, pp. 350-363, 1993, Michinobu Kaimori
(2) "Journal of the Textile Machinery Society" Vol.55, N0.9, 340-344, 2002, Tadashi Karagawa, Ryo Umehara
(3) `` Dyeing Industry '' Vol. 41, No. 11, pp. 566-569, 1993, Michinobu Kaimori
(4) "Journal of the Textile Machinery Society" Vol.52, No.8, pp.348-351, 1999, Norio Nagasawa
(5) `` Dyeing Industry '' Vol. 41, No. 11, pp. 569-575, 1993, Michinobu Kaimori

  Next, the present invention will be described specifically by way of examples. The present invention is not limited to the following examples.

(1) Hygroscopic exothermic evaluation test A temperature sensor is attached to the surface of the sample fabric, placed in a constant temperature and humidity device, and conditioned for 2 hours at 30 ° C. and a relative humidity of 40% RH. Next, measurement of the surface temperature (data collection at intervals of 20 seconds) was started. After 30 minutes, the temperature and humidity were changed by 30 ° C. and 90% RH, and measurement was continued for another 60 minutes.

  At this time, the comparative example and the example compared the data measured simultaneously. If the measurement is performed separately, accurate comparison cannot be made due to the effect of subtle temperature changes in the temperature and humidity.

(2) Sample The sample was a 2/2 twill fabric using 100% wool and a 48th double yarn. Examples 1 to 3 and Comparative Example 1 are undyed fabrics, Examples 4 to 5 and Comparative Example 2 are pre-dyed products, and Examples 6 and 3 are undyed croi processed (scale-removed products by shrink-proofing) fabrics. did.

Example 1
Mercaptosuccinic acid was treated with 2% owf and a bath ratio of 1:20 at 65 ° C. for 20 minutes, added with ammonia water 4% owf, and further treated at 65 ° C. for 20 minutes. Subsequently, the bath was changed, and Denacol EX313 (glycerol polyglycidyl ether (hydrophilic group-containing polyfunctional epoxy compound), Nagase ChemteX Corp.) 5% owf, bath ratio 1:20 at 90 ° C. for 30 minutes. After the treatment, a Hoffman press finish was performed to obtain a woven fabric with improved moisture absorption and heat generation.

(Example 2)
Mercaptosuccinic acid was treated with 2% owf and a bath ratio of 1:20 at 65 ° C. for 20 minutes, added with ammonia water 4% owf, and further treated at 65 ° C. for 20 minutes. Subsequently, the bath was changed, and a treatment was performed at 90 ° C. for 30 minutes at 5% owf of succinic anhydride and a bath ratio of 1:20. After the treatment, a Hoffman press finish was performed to obtain a woven fabric with improved moisture absorption and heat generation.

(Example 3)
Treated with ammonium bisulfite 10% owf, bath ratio 1:20, 65 ° C., 40 minutes. Subsequently, the bath was changed, and Denacol EX171 (lauryl alcohol (EO) ₁₅ glycidyl ether (hydrophilic group-containing epoxy compound), Nagase ChemteX Corporation) 5% owf, bath ratio 1:20 at 90 ° C. for 30 minutes. It was. After the treatment, a Hoffman press finish was performed to obtain a woven fabric with improved moisture absorption and heat generation.

(Comparative Example 1)
The sample untreated product used in Examples 1 to 3 was referred to as Comparative Example 1.

  The measurement results of the hygroscopic exothermic evaluation test of Example 1 and Comparative Example 1 of the present invention are shown in FIG. 1, and the measurement results of Examples 2, 3 and Comparative Example 1 are shown in FIG. As is clear from FIGS. 1 and 2, it was confirmed that Examples 1 to 3 all had a higher maximum temperature than Comparative Example 1 and the effect was maintained for 1 hour or more.

(Example 4)
Processing was carried out using a dyeing machine at the production site, and finishing was carried out in a normal process. The sample was a 2/2 twill fabric (dyed product) using 100% wool and 48th yarn.

  Using a meter dyeing machine, treated with mercaptosuccinic acid 2% owf, nonionic surfactant 0.1 g / L, bath ratio 1:20 at 65 ° C. for 20 minutes, added with ammonia water 4% owf, and further at 65 ° C. For 20 minutes. Subsequently, the bath was changed, and Denacol EX313 (glycerol polyglycidyl ether (hydrophilic group-containing polyfunctional epoxy compound), Nagase ChemteX Corp.) 3% owf, bath ratio 1:20 at 90 ° C. for 20 minutes. After the treatment, a normal finishing process was performed to obtain a woven fabric with improved moisture absorption and heat generation.

  The evaluation results are collectively shown in Table 1 later.

(Example 5 , Reference example )
Using a meter dyeing machine, Cobral M / M (ammonium bisulfite, Lamberti (Italy)) 20% owf, nonionic surfactant 0.1 g / L, bath ratio 1:20, 65 ° C., 40 minutes. Subsequently, the bath was changed, and Denacol EX313 (glycerol polyglycidyl ether (hydrophilic group-containing polyfunctional epoxy compound), Nagase ChemteX Corp.) 3% owf, bath ratio 1:20 at 90 ° C. for 20 minutes. After the treatment, a normal finishing process was performed to obtain a woven fabric with improved moisture absorption and heat generation.

(Comparative Example 2)
Without performing a reduction dyeing treatment of wool fiber and a meter dyeing machine for imparting a reactive compound for chemically bonding an irreversible blocking group, the rest was passed through the same finishing steps as in Examples 4 and 5, A fabric of Comparative Example 2 was obtained.

  Table 1 shows the KES measurement values (texture values) of Examples 4 and 5 and Comparative Example 2 described above. Here, the KES measurement value (texture value) is a measurement method commonly used in the industry, edited by Home Economics Society of Japan, “Clothing Materials for Clothing and Resources”, pp. 57-84, December 10, 1989. , Published by Asakura Shoten.

  Moreover, the hygroscopic exothermic measurement result of Examples 4 and 5 and Comparative Example 2 is shown in FIG. As is clear from FIG. 3, it was confirmed that Examples 4 to 5 all had a higher maximum temperature than Comparative Example 2 and the effect was maintained for 1 hour or more.

  From Table 1, Examples 4 and 5 have flexibility because of low bending and shearing force compared to Comparative Examples, and both stretch and horizontal have high stretchability, and the texture is high due to high swelling. It was confirmed that there was an improvement.

(Example 6)
As a sample, 100% non-condensed wool by the Kroi / resin method, 48th yarn, 2/2 twill fabric was used, and reduced cut in a reducing agent solution as in Example 1 to generate a mercapto group (-SH). The compound which reacts with the mercapto group (-SH) to form an irreversible blocking group is chemically bonded.

(Comparative Example 3)
An untreated product of the same fabric as in Example 6 was designated as Comparative Example 3.

  The measurement results of the hygroscopic exothermic evaluation test of Example 6 and Comparative Example 3 are shown in FIG. As is clear from FIG. 4, it was confirmed that Example 6 had a higher maximum temperature than Comparative Example 3 and that the effect was maintained for 1 hour or more.

The graph which shows the measurement data of the hygroscopic exothermic evaluation test of Example 1 and Comparative Example 1 of the present invention. The graph which shows the measurement data of the hygroscopic exothermic evaluation test of Example 2, 3 of this invention, and the comparative example 1. FIG. The graph which shows the measurement data of the hygroscopic exothermic evaluation test of Examples 4 and 5 and Comparative Example 2 of the present invention. The graph which shows the measurement data of the hygroscopic exothermic evaluation test of Example 6 and Comparative Example 3 of the present invention.

Claims (6)

An animal hair fiber product in which moisture absorption heat generation property is given to animal hair fiber,
At least a part of the disulfide (—S—S—) bond in the animal hair fiber is contained in at least one reducing agent solution selected from mercaptosuccinic acid and salts thereof, cysteic acid and salts thereof, thiols, and phosphines. And reductively cleave with to sufficiently swell to produce a mercapto group (-SH),
By chemically bonding a reactive compound that forms an irreversible blocking group containing a hydrophilic group and a multifunctional group to the mercapto group (-SH) ,
A hygroscopic exothermic animal hair fiber product characterized by widening the molecular gap to facilitate water vapor permeation, increasing affinity with water vapor, and stabilizing the molecular gap for water vapor to enter .   The hygroscopic exothermic animal hair fiber product according to claim 1, wherein the reactive compound is at least one selected from an acid anhydride, isocyanate, isothiocyanate, vinyl sulfone, an epoxy compound, and an alkylene oxide compound. The hygroscopic exothermic animal hair fiber product according to claim 1 or 2 , wherein the fiber product is at least one selected from cotton, top, yarn, woven fabric, knitted fabric, felt and non-woven fabric. The hygroscopic exothermic animal hair fiber product according to any one of claims 1 to 3 , wherein the textile product is a sports apparel, an underwear, a suit, a uniform, a glove, a sock, a hat, an inside cotton apparel product or a futon. A method for producing a hygroscopic exothermic animal fiber product in which a reactive compound is bound to animal fiber,
At least a part of the disulfide (—S—S—) bond in the animal hair fiber is contained in at least one reducing agent solution selected from mercaptosuccinic acid and salts thereof, cysteic acid and salts thereof, thiols, and phosphines. And reductively cleave with to sufficiently swell to produce a mercapto group (-SH),
By chemically bonding a reactive compound that forms an irreversible blocking group including a hydrophilic group and a multifunctional group that reacts with the mercapto group (-SH) ,
Moisture- absorbing and exothermic animal hair fiber product characterized by widening the molecular gap to facilitate the penetration of water vapor, increasing the affinity with water vapor, and obtaining animal hair fibers with a stabilized molecular gap for water vapor to enter Manufacturing method. The method for producing a hygroscopic exothermic animal fiber product according to claim 5 , wherein the reactive compound is at least one selected from an acid anhydride, isocyanate, isothiocyanate, vinyl sulfone, an epoxy compound, and an alkylene oxide compound.

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