JP2001040584A - Hygroscopicity processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject agent capable of imparting formed products including textile products, films and sheets with excellent hygroscopicity and its sustainability by designing itself to consist mainly of a specific hygroscopic monomer and a specific polyoxyethylene-based polyether. SOLUTION: This hygroscopicity processing agent is obtained by designing itself to consist mainly of a hygroscopic monomer of the formula [X is H, a 1-4C alkyl or phenyl; Y is H, a 1-4C alkyl or COOM (M is a metal atom); Z is H, a 1-4C alkyl or CH2COOM] and a polyoxyethylene-based polyether of the formula A[(R1O)1R2]k [A is an organic compound residue <=300 in molecular weight having 1-6 active hydrogen atoms; R1 is an alkylene based on ethylene group; R2 is (meth)acryloyl, a part thereof optionally being H or a lower alkyl; (l) is a positive integer; (k) is 1-6], contain 0.01-10 wt.% of a compound having sulfonic acid group but no radical-polymerizable functional group, have water as medium and have a cloud point of >=60 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-absorbing agent, and more particularly to a moisture-absorbing agent capable of imparting excellent hygroscopicity and durability to molded articles such as fibers, films and sheets.

[0002]

2. Description of the Related Art Synthetic resins such as polyesters and polyamides are widely used as molding materials for fibers, films, sheets and the like because of their many excellent properties.
However, since these resins are hydrophobic, their use in fields requiring hygroscopicity is limited.

[0003] Conventionally, attempts have been made to impart hygroscopicity to these synthetic resins, and many proposals have been made so far. For example, synthetic fibers such as polyester fibers and polyamide fibers, cotton, natural fibers such as hemp and chemical fibers such as rayon have a hygroscopic property, to improve the wearing comfort, etc. After graft polymerization of acrylic acid and methacrylic acid to fibers, a method of sodium salification, a method of post-processing natural proteins such as sericin and collagen on synthetic fibers, and further, polyalkylene glycol, polyvinylpyrrolidone, polyetheresteramide, etc. There have been proposed hygroscopic synthetic fibers in which a hygroscopic component is copolymerized or blended, or used as a core component of a core-sheath conjugate fiber. However,
With these methods, it is difficult to achieve a good balance between the hygroscopicity and the physical properties / fastness of dyeing, and it is not practical.

Japanese Patent Application Laid-Open Nos. 5-33978, 6-17372, and 6-17373 disclose the fineness of a porous hollow fiber having fine holes communicating from the fiber surface to the hollow portion. It is disclosed that natural proteins are impregnated in pores and hollows, crosslinked and insolubilized to improve hygroscopicity. However, the natural protein aqueous solution used here has a high viscosity, and the aqueous solution may be gelled, so that it is extremely difficult to impregnate the hollow portion through the communication hole, and to reduce the viscosity in order to lower the viscosity. When the concentration of the protein is reduced, the amount of the natural protein finally contained in the hollow portion is reduced, and there is a problem that sufficient hygroscopicity cannot be obtained in any case.

Further, JP-A-6-173167 discloses that a core-sheath type conjugate fiber is reduced in alkali, a core portion is dissolved and removed, and a through groove parallel to a fiber axis penetrating from a fiber surface to a hollow portion is provided. There is disclosed a hygroscopic fiber in which a hollow fiber is used and a hygroscopic agent formed from a monomer having a cloud point equal to or lower than the glass transition point of a polymer constituting the hollow fiber is adhered to a hollow portion of the hollow fiber. However, in such a fiber, a through-groove having an excessively large width and length is formed, and there has been a problem that the hygroscopic agent easily falls off through the through-groove due to washing or the like, resulting in poor durability.

In view of such a situation, the present inventors have previously made a hollow fiber which is composed of a single polymer and has a high hollow ratio of at least 20%. Micro-grooves are present in a state of communicating with the hollow portion as a trace of removal, and a moisture-absorbing component such as sodium acrylate and a crosslinking agent such as polyoxyethylene-based polyether are polymerized and gelled in the hollow portion. A hygroscopic hollow fiber in which a water-insoluble polymer is present has been proposed (see JP-A-8-325945). According to this hollow fiber, while having a high degree of hygroscopicity, physical properties such as fiber strength,
Hygroscopic synthetic fibers which are excellent in dye clarity, heat resistance, light resistance, color fastness, abrasion resistance and the like, and which are excellent in the washing performance of these functions and performances are provided. Such a hollow fiber has a water-soluble monomer such as sodium acrylate and a cross-linking agent such as polyoxyethylene-based polyether in a monomer state in a hollow portion of a high hollow fiber having microgrooves communicating with the hollow portion. It can be obtained by polymerizing and gelling after filling.

However, as an industrial aspect of obtaining such a hygroscopic hollow fiber, when a hollow fiber is formed into a woven or knitted fabric and the hollow portion is filled, the level of hygroscopicity varies between the inner side and the lower side of the processing. Is large. In addition, it takes a long time to fill the hollow portion with the hygroscopic agent through the microgroove. That is, when increasing the production volume, a large amount of storage space is required, and in order to manage the filling completion time, it is necessary to maintain the storage space at a constant temperature, which is not suitable for mass production. Had occurred.

The present inventors have proposed a hygroscopic processing agent comprising a specific hygroscopic monomer, a specific polyoxyethylene-based polyether and a metal salt of styrene sulfonic acid in order to solve such problems. It has been found that the variation is small, but it has not yet reached a level that is sufficiently satisfactory as an industrial product.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the hollow filling process, so that there is no variation in the moisture absorption level between the inside and the inside of the work, and a large amount of water is absorbed. Provides a moisture-absorbing agent that can be industrially produced by a process applicable to production, and stably imparts excellent moisture-absorbing properties and its durability even when processed into molded products such as ordinary fibers, films and sheets. It is an object of the present invention to provide a moisture-absorbing agent.

[0010]

Means for Solving the Problems The present inventors have conducted various studies in an attempt to eliminate the problem of the variation in hygroscopicity in the hollow filling process. In conventional processing agent compositions, monomer metal salts such as sodium acrylate and cross-linking agents such as polyoxyethylene-based polyethers are both water-soluble to a high concentration by themselves, but they are both soluble in an aqueous medium. When mixed, a cross-linking agent such as polyoxyethylene-based polyether is easily precipitated due to salting-out action of the monomer metal salt to give a cloudy working fluid. When the fiber cloth is subjected to padding using the cloudy processing liquid, the composition of the processing liquid picked up by the fiber cloth when the stirring of the processing liquid in the dipping bath is insufficient is compared with the adjusted processing liquid composition. It was analyzed that more polyether crosslinker and less monomer metal salt were used.

On the other hand, when the working fluid in the dipping bath is sufficiently stirred, the composition of the working fluid picked up in the fiber cloth matches the adjusted working fluid composition. It has been found that the composition of the working fluid that is squeezed and removed from the fabric has less polyether crosslinking agent and more monomer metal salt than the adjusted working fluid composition. That is, it was found that the polyether crosslinking agent, which is a cloudy component in the working fluid, was selectively adsorbed on the fiber cloth. Further, it was verified that the phenomenon of the selective adsorption also occurs when the working fluid transfers to the hollow portion of the hollow fiber. The present inventors, based on these findings,
The present inventors have conducted intensive studies and elucidated that these selective adsorption phenomena have caused the problem of variation in the moisture absorption rate in the hollow filling process. This problem of selective adsorption was not solved even if the dispersion stability of the working fluid was improved by using a dispersant such as polyvinyl alcohol.

On the basis of the above findings, the present inventors believe that the only solution to this problem is to obtain a solution other than converting the working fluid into a transparent solution. Na, K, Li) and polyethylene glycol dimethacrylate (molecular weight of polyethylene glycol: 400, 6) as a polyether crosslinking agent.
(00, 1000), an attempt was made to make a working solution composed of a system using water as a transparent solution. As a result, surprisingly, despite the system in which the polyether cross-linking agent cannot be dissolved only by adding a small amount of the polyether cross-linking agent to the transparent aqueous solution of the monomer metal salt and becomes a cloudy processing liquid, When the addition amount of the polyether crosslinking agent was further increased, it was found that there was a concentration region in which the solution was turned into a transparent solution again. This is thought to be due to some interaction between the monomer metal salt and the polyether crosslinking agent. As a result of successive experiments, it was found that the concentration range for forming the transparent solution was such that the metal species of the monomer metal salt was changed from Na to K to Li, and the polyethylene glycol molecular weight of the polyether crosslinking agent was changed from 400 to 600 to 1000. It was found that it was expanded by making it larger.

Further, the present inventors have proposed a process which can solve the problems such as the hollow filling process described above, when filling a hollow portion of a hollow fiber having a communicating hole from a fiber surface to a hollow portion with a gel, First, after introducing a liquid having a gel-type performance into the hollow portion of the hollow fiber through the communication hole under heating,
Introducing a liquid gel initiator having the gel-form performance, and then gel filling the liquid having the gel-form performance of the hollow portion into a hollow fiber characterized by gel filling method, '' In this process, the temperature at the time of filling the hollow fiber with the moisture absorbing agent is 50 to 170 ° C., preferably,
60-150 ° C is specified, the liquid composition can be set so that the cloud point of the hygroscopic agent exceeds the temperature at the time of filling, and it is a hygroscopic processing agent suitable for performing hollow filling processing in the above process. . Even when the moisture-absorbing agent of the present invention is processed into ordinary solid fibers, films or sheets, uniform processing becomes possible, the level of hygroscopicity is higher, the variation in moisture absorption rate is smaller, and the hygroscopicity is lower. Was found to be more excellent in washing durability and water resistance.

The present inventors have previously proposed a moisture-absorbing agent comprising the above-mentioned specific hygroscopic monomer as a specific polyoxyethylene-based polyether and further a metal salt of styrene sulfonic acid. This time, the present inventors arrived at the present invention as a result of intensive studies on a compound having a sulfonic acid group having no functional group capable of radical polymerization.

That is, it has a hygroscopic monomer represented by the following general formula (1) and a polyoxyethylene-based polyether represented by the following general formula (2) as main components and does not have a radically polymerizable functional group. A moisture absorbing agent containing 0.01 to 10% by weight of a compound having a sulfonic acid group and containing water as a medium, wherein the moisture absorbing agent has a cloud point of 60 ° C. or higher. .

[0016]

Embedded image

(Wherein X is a hydrogen atom and has 1 to 4 carbon atoms)
Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a -COOM group, Z is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or -CH ₂ COO.
M group, M represents a metal)

[0018]

Embedded image

Wherein A is an organic compound residue having an active hydrogen of 1 to 6 and having a molecular weight of 300 or less, R ¹ is an alkylene group mainly composed of an ethylene group, R ² is an acryloyl group or a methacryloyl group; Part may be a hydrogen atom or a lower alkyl group, l is a positive integer, and k is an integer of 1 to 6.)

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The hygroscopic monomer used in the present invention is represented by the general formula (1). In the general formula (1), X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and among the alkyl groups, a methyl group is preferable. Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a -COOM group, and among the alkyl groups, a methyl group is preferable. Z is a hydrogen atom, an alkyl group or a -CH ₂ COOM group having 1 to 4 carbon atoms, a hydrogen atom or -CH ₂
Preferably, it is a COOM group. M is a metal, and particularly when an alkali metal such as Na, K, and Li is used,
It is preferable because the moisture absorption rate can be significantly improved,
Further, Li and K are more preferable in that the composition range in which the cloud point of the hygroscopic processing agent is 60 ° C. or higher is wide.
i is most preferred. Part of M, preferably (COO
H) / {(COOM) + (COOH)} may be a hydrogen atom in a proportion of 30 mol% or less, which is rather preferable in terms of washing durability and water resistance.

Preferred examples of the hygroscopic monomer include Li, K and Na salts of acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Can be given. The hygroscopic monomer may be used alone or in combination of two or more.

In the moisture-absorbing agent of the present invention, in addition to the above-mentioned moisture-absorbing monomer, it acts as a cross-linking agent at the time of polymerization of the moisture-absorbing monomer, and gives the finally obtained polymer bulk or polymer film a washing durability and a like. To impart water resistance,
The polyoxyethylene-based polyether represented by the general formula (2) is contained as an essential component.

In the general formula (2), A is a residue of an organic compound having an active hydrogen of 1 to 6 and a molecular weight of 300 or less, and methanol, propanol, butanol, phenol, ethylene glycol, bisphenol A, propylene glycol, Butylene glycol, butanediol,
Residues of hydroxyl-containing compounds such as neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, diglycerin, pentaerythritol, sorbitol and residues of primary and secondary amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine And the like. Among them, a hydroxyl group-containing compound is preferable.

[0024] R ¹ is mainly composed of ethylene, partially within polyoxyethylene polyether represented by the general formula (2) is a water soluble may be a propylene group or a butylene group, R ² Represents an acryloyl group or a methacryloyl group, and a part thereof may be a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. k is an integer of 1 to 6 corresponding to the number of active hydrogen atoms of the organic compound that forms A. l is a positive integer and may be the same or different between or within molecules. If the value of l is too large, the viscosity of an aqueous solution increases, and it may be difficult to perform uniform processing. Therefore, it is preferable that the value of k × l is 80 or less.

Preferred examples of such polyoxyethylene polyethers include polyethylene glycol (average molecular weight: 400) di (meth) acrylate, polyethylene glycol (average molecular weight: 600) di (meth) acrylate, and polyethylene glycol (average molecular weight: 600). (Average molecular weight: 1000) di (meth) acrylate, methoxypolyethylene glycol (average molecular weight: 1320) mono (meth) acrylate, bisphenol A ethylene oxide 30 mol adduct di (meth) acrylate, glycerin ethylene oxide adduct di (meth) acrylate A) acrylate, tri (meth) acrylate of glycerin ethylene oxide adduct, di (meth) acrylate of trimethylolpropane ethylene oxide adduct, trimethylolpropane ethylene oxide Tri Side adduct (meth)
Acrylate, di (meth) acrylate of sorbitol ethylene oxide adduct, tri (meth) acrylate of sorbitol ethylene oxide adduct, tetra (meth) acrylate of sorbitol ethylene oxide adduct, penta (meth) acrylate of sorbitol ethylene oxide adduct and Hexa (meth) acrylate of sorbitol ethylene oxide adduct and the like can be mentioned.

As the moisture absorbing agent of the present invention, those having a cloud point of 60 ° C. or more as shown below are used.
Among the above compounds, polyethylene glycol (average molecular weight: 1000) di (meth) acrylate can be cited as the most preferred embodiment in view of a wide composition range in which the temperature is 0 ° C. or higher. Further, such polyoxyethylene-based polyethers may be used alone or in combination of two or more.

Further, in the moisture absorbent according to the present invention,
It is important that a compound having a sulfonic acid group having no functional group capable of radical polymerization, which functions as a cloud point control agent, is contained as an essential component. Examples of such a compound having a sulfonic acid group include a metal salt of an alkylbenzenesulfonic acid, a metal salt of an alkylnaphthalenesulfonic acid, a metal salt of a melaminesulfonic acid, a metal salt of a dialkylsulfosuccinic acid, and a metal salt of an alkylsulfoacetate. Here, as the alkyl group, an alkyl group having 1 to 40 carbon atoms can be preferably exemplified. Among them, metal salts of alkylbenzenesulfonic acid and metal salts of dialkylsulfosuccinic acid which are small in amount and have a large cloud point increasing effect are particularly preferred. Such compounds may be used alone or in a combination of two or more.

Further, in the hygroscopic processing agent of the present invention,
As described above, the cloud point needs to be 60 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher. When the cloud point is lower than 60 ° C., uniform and reproducible processing cannot be performed, and the surface of moisture absorption level, the surface of uneven moisture absorption, the washing durability of moisture absorption, the surface of water resistance, and the feeling What is satisfactory in terms of surface cannot be obtained.

In the moisture absorbing agent of the present invention, the above cloud point is 6
The type and concentration of each of the hygroscopic monomer, the polyoxyethylene-based polyether, and the compound having a sulfonic acid group may be appropriately selected so as to be 0 ° C. or higher. The concentration of the hygroscopic monomer is preferably in the range of 10 to 60% by weight, more preferably 15 to 50% by weight. The concentration of the polyoxyethylene-based polyether is preferably in the range of 10 to 60 wt%, more preferably in the range of 12 to 50 wt%.
The concentration of the compound having a sulfonic acid group having no functional group capable of radical polymerization is 0.01 to 10 w
Those in the range of t% are preferably used, and more preferably in the range of 0.1 to 8 wt%. When the concentration of the compound having a sulfonic acid group is less than 0.01 wt%, the effect of increasing the cloud point cannot be sufficiently obtained, and even when the concentration of the compound exceeds 10 wt%, The effect of increasing the cloud point is not obtained, and not only the viscosity of the liquid increases, but also a foaming phenomenon occurs, which makes processing difficult, which is not preferable. In addition, the moisture absorbing agent of the present invention uses water as a medium, and can be safely used in a general processing plant because an organic solvent or the like is not used.

The moisture-absorbing processing agent of the present invention may contain a polymerization initiator, if necessary, and this is rather preferable for performing a sufficient polymerization crosslinking reaction during processing. Examples of such a polymerization initiator include peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide, and benzoyl peroxide; cerium ammonium salts such as ceric ammonium sulfate and ceric ammonium nitrate; '-Azobisisobutyronitrile and the like.

The moisture-absorbing agent of the present invention is intended for fibers, films, sheets, and the like.
It can be applied at any stage such as yarn, woven or knitted fabric. As a processing method, a conventionally known processing method such as an immersion method, a pad drying method, a pad steam curing method, a coating method, a laminating method, and a heating method in a bath can be arbitrarily adopted. In particular, Japanese Patent Application Laid-Open No. H8-3259
No. 45, and the hollow filling method disclosed by the present inventors further proposes "when filling a gel into the hollow portion of a hollow fiber having a communication hole from the fiber surface to the hollow portion, first, After the liquid having a gel forming ability is introduced into the hollow portion of the hollow fiber through the communication hole under heating, the gel initiator of the liquid having the gel forming ability is introduced, and thereafter, the gel initiator is introduced into the hollow portion. A particularly great effect is obtained when the composition of the moisture-absorbing agent of the present invention is applied to a "gel filling method of hollow fibers for gelling a liquid having a gel-forming ability".

[0032]

The moisture absorbing agent of the present invention has a cloud point of 60
Since it is a transparent solution at a temperature of at least ℃ C, for example, there is no problem such as selective adsorption between the hygroscopic monomer component and the polyoxyethylene-based polyether in the processing step such as padding. Also in the hollow filling method disclosed in Japanese Unexamined Patent Publication No. 8-325945, there is no variation in the moisture absorption rate during processing, during processing, etc., and a high moisture absorption rate and its washing durability can be achieved.
It can be used in processes that allow mass production. In addition, even when processing is performed on molded products such as ordinary fibers, films, sheets, etc., there is no problem of selective adsorption and the like, so that excellent hygroscopicity and durability thereof can be stably provided.

[0033]

According to the moisture-absorbing agent of the present invention, high hygroscopicity excellent in washing durability and water resistance can be stably imparted to fibers, films, sheets and the like. , Innerwear that requires wearing comfort and moisture absorption,
It is extremely useful to use it for clothing such as nighties, blouses, shirts, sportswear and the like and for non-clothing applications such as water-related products.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples, parts and% indicate parts by weight and% by weight, respectively, and the moisture absorption and washing durability were measured by the following methods.

(1) Moisture Absorption Rate The moisture absorption rate (unit:%) was determined by preliminarily drying a sample at a temperature of 50 ° C. for 2 hours and then absolutely drying the sample at a temperature of 105 ° C. for 2 hours (the weight at this time was designated as W ₀ ). Do). Then, 2 hours put weight after in a thermo-hygrostat of RH 35 ℃ × 95%: was calculated moisture absorption by the following equation by measuring the W _1. Moisture absorption (%) = [(W ₁ −W ₀ ) / W ₀ ] × 100

(2) Washing Durability Washing was repeated 30 times in accordance with JIS L-1018-77 6.36H method, and the moisture absorption was measured and evaluated by the method of (1).

Example 1 Melt spinning was performed using a spinneret having a spinning hole having an arc-shaped opening in which four circular slits were closed, and polyethylene terephthalate (dioxide) having an intrinsic viscosity of 0.61 was used. An undrawn yarn of hollow fiber composed of titanium: 0.07%) is drawn according to a conventional method, and a multifilament yarn having a hollow hollow section with a hollow ratio of 40% (35 denier / 12 Filament). A tricot half knitted fabric of 36 gauge is knitted by using the multifilament yarn having a round hollow section, refined according to a conventional method, and then treated in an aqueous solution of sodium hydroxide: 50 g / liter at a temperature of 105 ° C. for 10 minutes. The fabric was dyed under the following conditions (Table 1) (unprocessed cloth).

[0038]

[Table 1]

After dyeing, soaping was performed, and then drying was performed at a temperature of 100 ° C. for 5 minutes. The multifilament yarn was taken out from the obtained knitted fabric, and its surface was observed with a scanning electron microscope. The length in the fiber axis direction was 100 μm.
Hit, width: 1.0-1.5 μm, length: 50-150
At least one μm slit (communication hole) was present.

Next, the knitted fabric was immersed in a working liquid (clear at room temperature, cloud point: 81 ° C.) having the following composition (Table 2), and the amount of the working liquid was reduced to 100% with respect to the knitted fabric. It was then squeezed using a mangle, and then sealed in a polyethylene bag and then allowed to stand at 30 ° C. for 2 days.

[0041]

[Table 2]

After a lapse of 2 days, the knitted fabric was taken out of the polyethylene bag, immersed in hot water of 100 ° C. for 5 minutes while rocking, and dried continuously, and then dried at a temperature of 120 ° C.
For 1 minute and then a final set at a temperature of 180 ° C. for 1 minute. The weight increase of the knitted fabric by such a series of hollow filling processing, that is, the filling rate is 15%.
As a result of observing the knitted fabric with a scanning electron microscope, the solid content was present only in the hollow portion of the hollow fiber, and did not adhere to the outer surface of the fiber, the interfiber voids, or between the tissues. I didn't. For this reason, the resulting fabric exhibited a soft feel and touch as soft as the unprocessed fabric. Average value of moisture absorption rate when this series of hollow filling processing is repeated 10 times
The results of (n = 10) and R (maximum value−minimum value) are as shown in Table 10, and the variation in the moisture absorption was very small.

[Comparative Example 1] The procedure of Example 1 was repeated except that the transparent working fluid (cloud point: 44 ° C) having the following composition (Table 3) was used instead of the clear working fluid (cloud point: 81 ° C) used in Example 1. Example 1
The same was done. The evaluation results of the obtained fabric are also shown in Table 10.

[0044]

[Table 3]

[Comparative Example 2] Instead of the transparent processing liquid (cloud point: 81 ° C) used in Example 1, a processing liquid (cloud point: 24 ° C) having the following composition (Table 4) which became cloudy at room temperature was used. Except using, it carried out similarly to Example 1. The evaluation results of the obtained fabric are also shown in Table 10.

[0046]

[Table 4]

Example 2 In place of the transparent processing liquid (cloud point: 81 ° C.) used in Example 1, a transparent processing liquid (cloud point: 93 ° C.) having the following composition (Table 5) at room temperature was used. Except using, it carried out similarly to Example 1. The evaluation results of the obtained fabric are also shown in Table 10.

[0048]

[Table 5]

Example 3 In place of polyethylene glycol (average molecular weight: 1000) dimethacrylate in the transparent working fluid (cloud point: 81 ° C.) used in Example 1,
The procedure was performed in the same manner as in Example 1 except that the same amount of NP bioisomer P10W (a 60% aqueous solution of polyethylene glycol (average molecular weight: 1000) dimethacrylate) manufactured by ISC UK was used as polyethylene glycol (average molecular weight: 1000) dimethacrylate. . The cloud point of this working fluid is
84 ° C. The evaluation results of the obtained fabric are also shown in Table 10.

Example 4 In place of the transparent processing liquid (cloud point: 81 ° C.) used in Example 1, a transparent processing liquid (cloud point: 93 ° C.) having the following composition (Table 6) at room temperature was used. Except using, it carried out similarly to Example 1. The evaluation results of the obtained fabric are also shown in Table 10.

[0051]

[Table 6]

Example 5 Using the tricot half knitted fabric which had been dyed and used in Example 1 and having the following composition (Table 7), a transparent working liquid at room temperature (cloud point: 82 ° C.)
After immersion in the knitted fabric, the amount of the working fluid
Pressure squeezing to 0%, then 1 at normal pressure steamer
Heat treatment was performed at a temperature of 00 ° C. for 5 minutes. Thereafter, a 5% aqueous solution of potassium persulfate (first grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was sprayed onto the knitted fabric at a rate of 20 g / m ² .

[0053]

[Table 7]

After leaving at room temperature for 30 minutes,
After being immersed in hot water of 5 ° C. for 5 minutes while rocking, and subsequently air-dried, it was dried at a temperature of 120 ° C. for 1 minute, and then subjected to a final set at a temperature of 180 ° C. for 1 minute.
Weight increase of the knitted fabric by such a series of hollow filling processing,
That is, the filling factor was 14% (vs. unprocessed cloth). As a result of observing the knitted fabric with a scanning electron microscope, the solid content was present only in the hollow portion of the hollow fiber, the outer surface of the fiber, and the inter-fiber voids. No adhesion was found between the tissues. For this reason, the resulting fabric exhibited a soft feel and touch as soft as the unprocessed fabric. Table 10 shows the results of the average value (n = 10) and R (maximum value-minimum value) of the moisture absorption rate when such a series of hollow filling processing was repeated 10 times. Was very small.

Example 6 A multifilament yarn obtained by spinning and drawing a polyester made of polyethylene terephthalate having an intrinsic viscosity of 0.61 (containing titanium dioxide: 0.07%) (cross section: solid solid, 50 denier) / 2
4 filaments), and the fabric was scoured and preset according to a conventional method, and then dyed (unprocessed cloth) under the following conditions (Table 8).

[0056]

[Table 8]

Next, the fabric was immersed in a transparent working fluid (cloud point: 81 ° C.) at room temperature and having the same composition as that used in Example 1, and the amount of the working fluid adhered to the fabric was 80%. %, Squeezed with a mangle, and dried with a dryer at a temperature of 120 ° C. for 2 minutes. After drying, it is treated with a normal pressure steamer at a temperature of 100 ° C. for 3 minutes, washed with hot water, dried, and then dried at 180 ° C.
For 1 minute. Weight increase of fabric by processing,
That is, the adhesion ratio was 7.0% (vs. unprocessed cloth).
The resulting woven fabric exhibited a good feel and touch comparable to the untreated fabric. The average value (n = 10) and R (maximum value-) of the moisture absorption rate when this series of hollow filling processing is repeated 10 times is performed.
The result of (minimum value) is as shown in Table 10, and the variation in the moisture absorption was very small.

[Comparative Example 3] Instead of the transparent working fluid (cloud point: 82 ° C) used in Example 5, a clear working fluid (cloud point: 45 ° C) having the following composition (Table 9) at room temperature was used. Except using, it carried out similarly to Example 5. The obtained work cloth had the average value of moisture absorption and R as shown in Table 10, and the texture of the work cloth was hard.

[0059]

[Table 9]

Comparative Example 4 A transparent working fluid (cloud point: 44 ° C.) at room temperature used in Comparative Example 1 was used in place of the transparent working fluid (cloud point: 82 ° C.) used in Example 6. Except for the above, the procedure was the same as in Example 6. The evaluation results of the obtained fabric are also shown in Table 10.

[0061]

[Table 10]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CH021 CH051 EG036 EG056 EV257 FD206 FD207 4L033 AC07 AC15 BA28 CA18 CA20 CA48 DA07

Claims (5)

[Claims] 1. A main component comprising a hygroscopic monomer represented by the following general formula (1) and a polyoxyethylene-based polyether represented by the following general formula (2), and having no radically polymerizable functional group. A moisture-absorbing agent containing 0.01 to 10% by weight of a compound having a sulfonic acid group and containing water as a medium, wherein the moisture-absorbing agent has a cloud point of 60 ° C. or higher. Embedded image (In the formula, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a -COOM group, Z is a hydrogen atom, 1 carbon atom. Or an alkyl group of —4 or —CH ₂ COOM group, M represents a metal) (Where A is an organic compound residue having an active hydrogen of 1 to 6 and a molecular weight of 300 or less, R ¹ is an alkylene group mainly composed of an ethylene group, R ² is an acryloyl group or a methacryloyl group, and a part is hydrogen. May be an atom or a lower alkyl group, l is a positive integer, and k is an integer of 1 to 6. 2. The moisture-absorbing agent according to claim 1, wherein the hygroscopic monomer is an alkali metal acrylate. 3. The moisture-absorbing agent according to claim 1, wherein the hygroscopic monomer is at least one selected from sodium acrylate, lithium acrylate, and potassium acrylate. 4. A polyoxyethylene polyether comprising polyethylene glycol di (meth) acrylate, di (meth) acrylate of glycerin ethylene oxide adduct, tri (meth) acrylate of glycerin ethylene oxide adduct, and trimethylolpropane ethylene oxide adduct. Di (meth) acrylate, trimethylolpropane ethylene oxide adduct tri (meth)
Acrylate, di (meth) acrylate of sorbitol ethylene oxide adduct, tri (meth) acrylate of sorbitol ethylene oxide adduct, tetra (meth) acrylate of sorbitol ethylene oxide adduct, penta (meth) acrylate of sorbitol ethylene oxide adduct and 4. At least one selected from the group consisting of hexa (meth) acrylate of sorbitol ethylene oxide adduct.
The moisture absorbing agent according to any one of the above. 5. The compound having a sulfonic acid group having no functional group capable of undergoing radical polymerization is at least one selected from the group consisting of a metal salt of an alkylbenzenesulfonic acid and a metal salt of a dialkylsulfosuccinic acid. 4
The moisture absorbing agent according to any one of the above.