JP2002371472A - Finishing agent for fiber, fiber structure by using the same, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fiber finishing agent capable of imparting a moisture-absorbing polymer in a shape of a uniform film to the surface of the fiber, and capable of providing a high moisture-absorbing properties while suppressing the hardening of the feeling to minimum, and further to provide the fiber structure by using the finishing agent and a method for producing the fiber structure. SOLUTION: This finishing agent includes a urethane divinyl monomer having polyethyleneglycol parts on both ends of a hydrophobic part through urethane bondings and unsaturated double bonds on the both ends.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treating agent for improving the hygroscopicity of a fiber structure, a fiber structure treated with the same, and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, in order to improve the hygroscopicity of a fibrous structure such as a woven or knitted fabric, studies on modifying a polymer compound constituting the fiber or imparting a hydrophilic compound to the fibrous structure have been widely conducted. Has been done. In particular, as for the modification related to the hydrophilicity of the polyester fiber structure, an attempt is made to graft polymerize a hydrophilic monomer to the polyester fiber (Japanese Patent Application Laid-open No. Sho 60-2).
No. 46869, JP-A-63-105181, etc.), attempts to impart a hydrophilic polymer compound, or impart a hydrophilic monomer to polymerize (JP-A-6-15)
No. 8545, Japanese Unexamined Patent Publication No. 9-256278, etc.)
There are examples.

[0003]

However, in the above method of graft-polymerizing a hydrophilic monomer, monomers capable of efficiently graft-polymerizing polyester fibers are limited to those having a carboxylic acid such as acrylic acid.
There is a problem that the strength is greatly reduced after the metal salting treatment necessary for improving the hygroscopicity and after long-term use. In addition, in a method in which a hydrophilic polymer compound is applied to a fiber structure, or a method in which a hydrophilic monomer is applied and polymerized is used, when the applied amount is increased in order to obtain sufficient moisture absorption performance, the hydrophilic compound is converted into a fiber. Since the fibers are concentrated in the gaps and adhere to each other, there is a problem that the texture is greatly hardened and the commercial value is reduced.

In view of such circumstances, an object of the present invention is to attach a hydrophilic compound to the fiber surface so as not to cause a decrease in strength, but the texture is not significantly impaired by curing as in the conventional method. As described above, it is an object of the present invention to provide a fiber treating agent capable of imparting a hydrophilic compound in a film shape uniformly covering the fiber surface without concentrating the hydrophilic compound in the inter-fiber voids.

[0005] Another object of the present invention is to provide a fiber structure treated with the above-mentioned fiber treating agent.

[0006]

The present invention employs the following means in order to solve the above-mentioned problems.

That is, the fiber treating agent of the present invention is a fiber containing a urethane divinyl monomer having a polyethylene glycol moiety at both ends of a hydrophobic part via a urethane bond and further having an unsaturated double bond group at both ends. Treatment agent.

The fiber treating agent of the present invention may further contain a polymerizable hygroscopic monomer, or the fiber treating agent may be an aqueous solution further containing 1 g / l or more of a salt. In addition, the fiber structure of the present invention is obtained by treating with the above-mentioned fiber treating agent.

Further, the method for producing a fibrous structure according to the present invention comprises:
This is a method of treating a fiber structure in a fiber treating agent containing a urethane divinyl monomer having an ethylene glycol moiety at both ends of a hydrophobic part via a urethane bond and further having an unsaturated double bond group at both ends. And a treatment in a water-based bath containing the fiber treating agent at a temperature of 40 ° C. or more and 140 ° C. or less for 10 minutes to 90 minutes.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the above-mentioned objects are provided.
In other words, to prevent the texture from being significantly impaired by the curing, we will concentrate on the hydrophilic compound in the inter-fiber voids and intensively study a fiber treatment agent that can provide the hydrophilic compound in a film that uniformly covers the fiber surface. As a result, it has been found that such a problem can be solved by including a specific urethane divinyl monomer having a specific structure having good adhesion to the fiber structure and a self-crosslinking property in the fiber treatment agent. Things.

The urethane divinyl monomer used in the present invention is a urethane divinyl monomer having an ethylene glycol moiety at both ends of a hydrophobic part via a urethane bond and further having an unsaturated double bond group at both ends. The urethane divinyl monomer is preferably selected from diisocyanates that form a hydrophobic part, so that a fibrous structure,
In particular, the feature is that the hydrophobic portion can be designed in a wide range so as to have adhesion to the hydrophobic fiber structure, and the efficiency of adhesion to the fiber structure can be greatly improved.

Examples of the diisocyanate for forming the hydrophobic portion include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated Xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate methyl ester, tetramethylhexamethylene diisocyanate and the like can be mentioned, and an appropriate one may be selected from these or other isocyanates according to the application.

The hydrophobic portion of the urethane divinyl monomer used in the present invention may be a polymer diisocyanate in which isocyanate groups are bonded to both ends of a polymer compound. In particular, it is effective to use a polymer diisocyanate containing an aliphatic or aromatic polyester in order to increase the affinity with the polyester fiber. The polymer used herein has a molecular weight of 1,000 or more,
Desirably less than 100,000. The degree of polymerization of ethylene glycol in the polyethylene glycol portion of the urethane divinyl monomer used in the present invention is desirably 3 or more and 20 or less, and more preferably 5 or more and 10 or less.
The reason is that when the degree of polymerization is less than 3, the hygroscopicity becomes small, and when the degree of polymerization is more than 20, the hydrophilicity becomes too large and the adhesion to the fiber structure tends to decrease. is there. From this, the number average molecular weight of the urethane divinyl monomer of the present invention is about 4
It is preferably in the range of 00 to 2000, more preferably 50.
0 to 1,200.

As the unsaturated double bond group of the urethane divinyl monomer used in the present invention, an acrylate group, a methacrylate group, or another functional group having a double bond may be used.

The urethane divinyl monomer of the present invention includes a compound having an isocyanate at both terminals of the compound forming the hydrophobic part (diisocyanate) and a compound having an ethylene glycol moiety bonded to the unsaturated double bond group (containing polyethylene glycol). (A vinyl monomer).

Specific examples of the urethane divinyl monomer include a reaction product of any of the above diisocyanates with a polyethylene glycol-containing vinyl monomer containing an ethylene glycol moiety having various degrees of polymerization. A reaction product of tolylene diisocyanate or hexamethylene diisocyanate with a polyethylene glycol-containing vinyl monomer is preferred because of its high cost and availability.

In the present invention, it is also advantageous that the urethane divinyl monomer can be designed to have good biodegradability and to be designed so that the degraded product does not adversely affect the living body, by appropriately selecting the hydrophobic part. This feature is extremely effective in overcoming a situation in which compounds that are difficult to use as fiber processing agents are increasing due to the recent increase in environmental awareness.

The fiber treating agent of the present invention desirably contains a polymerizable hygroscopic monomer in addition to the urethane divinyl monomer in order to obtain higher hygroscopicity. Examples of the polymerizable moisture-absorbing monomer, acrylic acid, organic carboxylic acids such as methacrylic acid, 2-hydroxyethyl acrylate, hydroxyalkyl acrylates such as 2-hydroxyethyl methacrylate or hydroxyalkyl methacrylates, amide compounds such as acrylamide, Methylol compounds such as N-methylolacrylamide; tertiary amine-containing compounds such as dimethylaminoethyl methacrylate; quaternary amine-containing compounds such as dimethylaminomethyl methacrylate quaternary compound; 2-acrylamide-2-methylpropanesulfonic acid; styrene Sulfonic acid group-containing compounds such as sulfonic acid or salts thereof, phosphate group-containing compounds such as 2-methacryloyloxyethyl acid phosphate or salts thereof, polyethylene glycol Polyethylene glycol moiety-containing compounds such as call dimethacrylate, sugar chain-containing compounds such as glucosyl methacrylate, N- vinylpyrrolidone, N- vinylacetamide, and the like N- vinylformamide. Among them, acrylic acid or methacrylic acid is preferably used in the present invention.

In the present invention, the amount of the polymerizable moisture-absorbing monomer is 50 to 50 parts with respect to the urethane divinyl monomer.
% Or less, and more preferably 30% or less. The reason for this is that if the amount of the polymerizable moisture-absorbing monomer is too large, the hydrophilicity of the moisture-absorbing polymer produced as a result of the copolymerization becomes too high, and the adhesion to the fiber structure decreases.

The fiber treating agent of the present invention has a content of 1 g / l or more,
An aqueous solution containing a salt at a concentration of 20 g / l or less is desirable. The reason is that when the salt concentration is higher than this, the solubility of the hygroscopic polymer produced as a result of the polymerization in water decreases, and the polymer easily adheres to the fiber structure.
Here, as the salt, chlorides such as sodium chloride, potassium chloride, ammonium chloride, magnesium chloride, aluminum chloride, and barium chloride, and similar bromides, iodides, sulfates, carbonates, phosphates, and the like can be used. However, from a practical point of view, sodium sulfate,
It is desirable to use barium sulfate, aluminum sulfate, or the like.

It is desirable that the fiber treating agent of the present invention contains a polymerization initiator in order to polymerize the polymerizable hygroscopic monomer. The polymerization initiator refers to a substance which has a function of initiating a radical reaction and induces a crosslinking reaction of a hydrophilic polymer compound by a polymerizable moisture-absorbing monomer. Examples of the initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides such as benzoyl peroxide, and azo-based initiators such as azobisisobutyronitrile.

In the present invention, it is more effective if the above-mentioned initiator also has an adhesive property to the fibrous structure. In particular, examples of the initiator having an adhesive property to the hydrophobic fiber structure include a hydrophobic organic peroxide such as benzoyl peroxide, and a hydrophobic azo-based initiator.

Next, the fiber structure of the present invention and the method for producing the fiber structure will be described. The fibrous structure of the present invention is obtained by being treated with the above-mentioned fiber treating agent of the present invention. Further, the method for producing a fiber structure of the present invention comprises treating the fiber structure with the treating agent.

Examples of the fiber structure in the present invention include filaments, spun yarns, woven fabrics, knitted fabrics, and nonwoven fabrics of at least one of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers. As natural fiber,
Regenerated fibers such as cotton, animal hair fiber, silk, and hemp; regenerated fibers such as cellulosic regenerated fiber rayon (viscose rayon) and cupra (copper ammonia rayon); Also, as synthetic fiber, polyester,
Various fibers such as nylon, acrylic, and aramid can be used as fibers to be treated.

Among them, polyester fibers are the most important in practical use among general-purpose fibers which are strongly required to have improved hygroscopicity. Therefore, in the present invention, it is more effective to use a polyester fiber structure. In addition, since the hydrophobic part of the urethane divinyl monomer generally has an adhesive property to polyester fibers, it is advantageous to use a polyester fiber structure from this aspect as well. As a polyester fiber structure, besides those consisting of only polyester fibers, cotton,
Natural fibers such as wool, semi-synthetic fibers such as acetate, regenerated fibers such as rayon, and at least one of synthetic fibers such as nylon and polyester fibers mixed or twisted,
Includes cross-weaving and knitting. By treating such a fiber structure with the fiber treating agent of the present invention, a film that uniformly covers the fiber surface with the hygroscopic polymer can be formed. As described above, by using the fiber treating agent of the present invention particularly for a fiber structure, a hygroscopic fiber structure having excellent product characteristics can be obtained.

In the present invention, as a method of treating a fiber structure with a treating agent for fibers, a processing device such as a dyeing machine used in ordinary fiber processing is used to raise the temperature from normal temperature to a temperature of 40 ° C. or more and 140 ° C. or less. After the temperature is raised, the temperature may be maintained for about 10 to 90 minutes. At this time, in order to sufficiently increase the amount of the fibrous structure to be treated in one treatment, the ratio of the treating agent weight to the fibrous structure is desirably 50 times or less.

As another method for treating a fiber structure with the fiber treatment agent of the present invention, a fiber treatment agent is applied to the fiber structure using a resin processing machine used in ordinary dyeing. Thereafter, heat treatment may be performed at a temperature of 110 ° C to 200 ° C. This heat treatment may be performed in two stages, a heat treatment at a relatively low temperature for drying and a heat treatment at a relatively high temperature for sufficiently promoting the reaction between the divinyl monomer and the initiator. In addition, this heat treatment may be performed in the presence of steam in order to efficiently promote the reaction between the urethane divinyl monomer and the initiator.

In the present invention, in order to make the amount of the hygroscopic polymer formed by polymerization sufficient to adhere to the fiber structure,
The amount of the urethane divinyl monomer and the polymerizable moisture-absorbing monomer contained in the fiber treatment agent for the fiber structure is 5% or more and 20% or less, more preferably 10% or more and 15% or less by weight.
% Is desirable.

In order to sufficiently efficiently generate radicals from the monomer (the sum of the urethane divinyl monomer and the polymerizable hygroscopic monomer), the initiator is added in an amount of about 10% to 100% based on the monomer. I just need.

In the fiber structure of the present invention, it is desirable that the adhesion rate of the hygroscopic polymer formed by polymerization is 5% or more based on the weight of the fiber structure before adhesion. The reason is that if the adhesion ratio is smaller than this, it is difficult to obtain sufficient hygroscopicity. From the viewpoint of hygroscopicity, the larger the amount of the hygroscopic polymer attached, the better. However, if the amount is too large, the texture tends to be hardened. Further, particularly when the fiber structure is composed only of polyester fibers, ΔMR of the fiber structure after the hygroscopic polymer is attached is:
It is desirable that it is 2% or more, more preferably 4% or more and 12% or less. Further, it is desirable that the MR of the fiber structure is 1% or more and 8% or less.

The adhesion rate of a hygroscopic polymer (a polymer of a urethane divinyl monomer and a polymerizable hygroscopic monomer) can be measured by a change in weight before and after the treatment for adhering the hygroscopic polymer. A method of removing and quantifying the hygroscopic polymer on the fiber surface by any method, estimating the amount of attached matter by a cross-sectional photograph of the fiber, and dissolving the entire fiber structure to determine the contained component may be used.

In the present invention, a dye may be contained in the fiber treating agent of the present invention, and the above-mentioned hygroscopic polymer may be attached to the fiber structure simultaneously with the dyeing. By using this method, the process of treating the fibrous structure can be further shortened, which is very advantageous in terms of improving production efficiency and reducing energy consumption.

Further, in the present invention, a processing agent for realizing other required functions in addition to the hygroscopicity may be contained in the fiber treating agent of the present invention. For example, water repellents, deep color processing agents, lightfast agents, antistatic agents, antifouling agents, flame retardants,
An antimicrobial agent or the like can be used in combination with the urethane divinyl monomer or the polymerizable hygroscopic monomer of the present invention.

[0034] The fibrous structure obtained by the present invention comprises a shirt,
Blouses, inners, pants, skirts, socks, stockings, coats, uniform clothing, sports clothing,
It is suitably used as a fabric for lining, interior, furniture, wallpaper, curtains, carpets, car seats and the like.

[0035]

[Example] <ΔMR> Fiber structure (sample) to which urethane divinyl monomer used in the example reacts and is fixed
Was measured by the following method. That is, the sample was put into a weighing bottle, left in a thermo-hygrostat adjusted to 20 ° C. and 65% RH for 24 hours and weighed. Then 30 ° C, 9
It was left in a thermo-hygrostat adjusted to 0% RH for 24 hours and weighed again. Finally, it was dried in a dryer at 110 ° C. for 1 hour to determine the absolute dry weight. The difference in the water content was calculated by the following equation. ΔMR (%) = ((W′−W) / W− (W ″ −W) /
W) × 100 W: Absolute dry weight of sample (g) W ′: Weight of sample at 30 ° C., 90% RH (g) W ″: Weight of sample at 20 ° C., 65% RH (g) When the treated sample was subjected to sodium salt treatment in order to increase the hygroscopicity, this measurement was performed after the treatment.

<Adhesion Ratio> The adhesion ratio of the polymer compound was calculated by the following equation by measuring the absolute dry weight of the fiber structure sample before and after the treatment. Adhesion rate (%) = 100 × (W1−W0) / W0 W0: Absolute dry weight of sample before treatment (g) W1: Absolute dry weight of sample after treatment (g) When performing a sodium salt treatment for increasing the hygroscopicity, the above measurement was performed before the treatment.

<Flexural rigidity increase rate> In order to quantify the change in texture of a fiber structure sample, a KES (Kawabata Evaluation System) generally used as a texture measurement system is used.
m) Using a measuring machine (Kato Tech), the average value B of the bending stiffness of the sample was measured before and after the treatment, and the rate of increase after the treatment compared to before the treatment was calculated.

Example 1 A urethane vinyl monomer (molecular weight: 1000) obtained by reacting polyethylene glycol methacrylate (polymerization degree of ethylene glycol = 8) with tolylene diisocyanate was used, and ammonium persulfate was used as a polymerization initiator. Was dissolved in water to prepare a fiber treating agent. The concentration of the urethane divinyl monomer was 5 g / l, and the concentration of the initiator was 0.5 g / l. Into 200 g of the aqueous solution, as a sample, a polyester taffeta cloth piece (a cloth after the intermediate setting at 180 ° C., using a yarn: warp and weft both having a total fineness of 83 dtex (75 denier) -36 multifilament), weaving density: warp 98 × weft 84 / inch basis weight: 70g / m ²⁾ 10g (urethane divinyl monomer content 10%) was immersed against fabric was treated at 100 ° C. 30 min. The adhesion rate of the hygroscopic polymer (urethane divinyl monomer polymer) to the sample by this treatment was 8.0%.
The ΔMR of the sample after the treatment was 0.8%. Also,
The rate of increase in bending stiffness after the treatment was 9.3%. As described above, a polyester fabric having hygroscopicity and low texture hardening was obtained by this method.

Example 2 The fiber treating agent of Example 1
Example 1 except that methacrylic acid was added as a polymerizable hygroscopic monomer at a concentration of 2 g / l (the amount of the urethane divinyl monomer and the hygroscopic monomer was 14% based on the fabric).
Was performed in the same manner as described above. As a result, the adhesion rate of the hygroscopic polymer (polymer of urethane divinyl monomer and polymerizable hygroscopic monomer) was 9.8%, and the ΔMR of the sample after the treatment was 3.3. The rate of increase in flexural rigidity was 13.8%. As described above, a polyester fabric having high hygroscopicity and low texture hardening was obtained by this method.

Example 3 The fiber treating agent of Example 2
The same procedure as in Example 2 was carried out except that sodium sulfate was added as a salt at a concentration of 5 g / l. As a result, the adhesion rate of the hygroscopic polymer (polymer of urethane divinyl monomer and polymerizable hygroscopic monomer) was 12.0%, and the ΔMR of the sample after the treatment was 4.4. The rate of increase in bending stiffness was 18.0%. As described above, a polyester fabric having high hygroscopicity and low texture hardening was obtained by this method.

Comparative Example 1 The procedure of Example 1 was repeated, except that polyethylene glycol dimethacrylate (degree of polymerization of ethylene glycol = 16) was used instead of the urethane divinyl monomer of Example 1. As a result, the adhesion rate of the crosslinked product of polyethylene glycol dimethacrylate to the sample was only 2.8%, the ΔMR of the sample after the treatment was 0.2, and a highly hygroscopic polyester fabric was not obtained.

Example 4 Example 4 was repeated except that urethane divinyl monomer obtained by reacting polyethylene glycol methacrylate (degree of polymerization of ethylene glycol = 8) with hexamethylene diisocyanate was used as the urethane divinyl monomer. Performed in a similar manner to 1. As a result, the adhesion rate of the hygroscopic polymer (polymer of urethane divinyl monomer and polymerizable hygroscopic monomer) was 6.9%.
The ΔMR of the processed sample was 1.2. The rate of increase in bending rigidity was 7.8%. As described above, a polyester fabric having high hygroscopicity and low texture hardening was obtained by this method.

Example 5 The procedure of Example 5 was repeated except that a urethane divinyl monomer obtained by reacting polyethylene glycol methacrylate (degree of polymerization of ethylene glycol = 12) with tolylene diisocyanate was used as the urethane divinyl monomer. Performed in a similar manner to 1. As a result, the adhesion rate of the hygroscopic polymer (polymer of urethane divinyl monomer) was 7.2%, and the ΔMR of the treated sample was 7.2%.
Was 1.5. The rate of increase in flexural rigidity was 8.5%. As described above, a polyester fabric having high hygroscopicity and low texture hardening was obtained by this method.

Example 6 The procedure of Example 1 was repeated except that benzoyl peroxide dissolved in dimethyl phthalate at a ratio of 50% was used as the polymerization initiator. As a result, the adhesion rate of the hygroscopic polymer (polymer of urethane divinyl monomer and polymerizable hygroscopic monomer) was 9.0%, and the ΔMR of the sample after the treatment was 1.5. The rate of increase in flexural rigidity was 8.5%. As described above, a polyester fabric having high hygroscopicity and low texture hardening was obtained by this method.

[0045]

According to the present invention, it is possible to obtain a fiber structure, particularly a polyester fiber structure, which has a small texture hardening and is excellent in product properties, despite having a good hygroscopic property due to adhesion of a hygroscopic polymer. Can be.

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Claims (8)

[Claims] 1. A fiber treatment wherein an ethylene glycol moiety is present at both ends of a hydrophobic part via a urethane bond, and a urethane divinyl monomer having an unsaturated double bond group at both ends is contained. Agent. 2. The fiber treating agent according to claim 1, further comprising a polymerizable hygroscopic monomer. 3. The fiber treating agent according to claim 1, wherein the fiber treating agent is an aqueous solution further containing 1 g / l or more of a salt. 4. A fibrous structure which is treated with the treating agent for fibers according to claim 1. 5. A fiber structure in a fiber treating agent containing an urethane divinyl monomer having an ethylene glycol moiety at both ends of a hydrophobic part via urethane bonds and further having an unsaturated double bond group at both ends. A method for producing a fibrous structure, comprising treating in a water-based bath containing the fiber treating agent at a temperature of 40 ° C or more and 140 ° C or less for 10 minutes to 90 minutes. 6. The method according to claim 6, wherein the fiber treating agent contains a polymerizable hygroscopic monomer. 7. The method according to claim 5, wherein the fiber treating agent is an aqueous solution containing 1 g / l or more of a salt. 8. The method for producing a fiber structure according to claim 5, wherein the fiber structure is a polyester fiber structure.