JPH10331071A - Production of fiber material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber material with durable hygroscopicity, shrink- resistance, wrinkle-resistance and form-stability by copolymerizing a specific treating liquid containing vinyl carboxylic acid or vinyl sulfonic acid on surface of a fiber material containing cellulosic fiber and subjecting it to crosslinking treatment. SOLUTION: This fiber material is obtained by applying a treating liquid comprising (A) vinyl carboxylic acid or vinyl sulfonic acid, (B) vinyl monomer of the formula (R is H or a 1-6C alkyl; (n) is an integer of 1 to 8), and (C) polymerization initiator to a fiber material containing cellulosic fiber for copolymerization thereof on the surface of the fiber material, making the fiber material adsorb formaldehyde gas and catalyst and subjecting it to heat treatment, thus forming crosslinkages between the fiber materials, between the copolymers, and between the fiber material and copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fibrous material which imparts durable hygroscopicity, shrinkage resistance, wrinkle resistance and form stability simultaneously.

[0002]

2. Description of the Related Art It has been widely known that a formaldehyde gas is adsorbed on a cellulosic fiber material in a gas phase and a heat treatment is performed to form crosslinks, thereby giving excellent shrinkage resistance, wrinkle resistance and form stability. Have been. However, in this processing method, since the hydroxyl group of the cellulosic fiber is reduced by the reaction with formaldehyde, there is a disadvantage that the hygroscopicity is reduced, and improvement is desired.

[0003]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention maintains excellent durability, excellent moisture absorption, and simultaneously satisfies excellent shrinkage resistance, wrinkle resistance, and form stability. It is intended to provide a method for producing a fibrous material.

[0004]

The present invention employs the following means in order to solve the above-mentioned problems. That is, in the method for producing a fiber material of the present invention, a fibrous material containing a cellulosic fiber is represented by the following general formula [1] and at least one monomer A selected from vinyl carboxylic acid and vinyl sulfonic acid. Vinyl monomer B
In addition, a treatment liquid comprising a polymerization initiator is applied and copolymerized on the surface of the fibrous material, and then formaldehyde gas and a catalyst are adsorbed on the fibrous material and heat-treated to crosslink.

[0005]

Embedded image

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a fiber material which retains the above-mentioned problems, that is, durable and excellent hygroscopicity, and which simultaneously satisfies excellent shrinkage resistance, wrinkle resistance and form stability. As a result of intensive studies, after adding a copolymer comprising a specific monomer A and a specific monomer B to a fiber material containing a cellulosic fiber, the fiber material is further filled with formaldehyde, between the copolymer and between the fiber material and the copolymer. It has been found that the above-mentioned problems can be solved at once by cross-linking.

[0007] As the monomer A used in the present invention, vinyl carboxylic acid and / or vinyl sulfonic acid are selected. Specific examples of vinyl carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, butenetricarboxylic acid and the like. Specific examples of vinylsulfonic acid include 2-acrylamido-2-methylpropanesulfonic acid (hereinafter, AMPS), 2-allyloxy-2-hydroxypropanesulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, allylsulfonic acid, and methallylsulfonic acid. Acids and the like. In the present invention, two or more of these monomers may be used at all. In particular, in terms of polymerization efficiency and hygroscopicity, acrylic acid, methacrylic acid,
-Acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid are preferred.

The monomer B used in the present invention has the general formula [1]
Are used, and among these, n
= 2 or 3, R = H or CH ₃ monomers are preferably used.

The mixing ratio of monomer A and monomer B is preferably in the range of 1:10 to 10: 1 by weight. If the weight ratio is less than 1:10, sufficient hygroscopicity cannot be obtained. On the other hand, when the ratio exceeds 10: 1, the crosslinking reaction with formaldehyde does not sufficiently proceed, so that good durability cannot be obtained. The amounts of the monomers A and B are not particularly limited, and may be arbitrarily determined according to the purpose of the processing.

As the polymerization initiator for monomer A and monomer B used in the present invention, a usual radical initiator can be used. For example, inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, and hydrogen peroxide;
Organic polymerization initiators such as azobis (N, N-dimethyleneisobutyramide) dihydrochloride and 2- (carbamoylazo) isobutyronitrile can be used. Further, a water-insoluble polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile can be used by emulsifying it with a surfactant such as an anion or nonion. In terms of cost and ease of handling, ammonium persulfate is preferably used. Further, in order to increase the polymerization efficiency, a so-called redox-based initiator using a peroxide and a reducing substance together can be used as a polymerization initiator. As the peroxide, for example, ammonium persulfate or potassium persulfate can be used. As the reducing substance, for example, a reaction product of sodium sulfoxylate and formalin or hydrosulfite can be used. The concentration of the polymerization initiator used depends on the monomer concentration used and the processing conditions,
0.1 to 3% by weight is preferred.

The treatment liquid used in the present invention comprises monomer A, monomer B and a polymerization initiator. However, a copolymer obtained by previously copolymerizing monomer A and monomer B separately may be used. If necessary, a finishing agent such as a water repellent, a softener, a flame retardant, an antibacterial deodorant or the like may be added.

As a method of applying the treatment liquid to the fiber material, a commonly used means can be applied. For example, a padding method, a spray method, a kiss roll coater, a slit coater and the like can be mentioned. After applying the treatment liquid by these methods, it is also preferable to adjust the applied amount by, for example, treating with a vacuum dehydrator.

In the present invention, as a method of copolymerizing monomer A and monomer B on the fiber surface, various methods used for radical polymerization, such as dry heat treatment, steam treatment, immersion method, cold batch method, microwave Processing, ultraviolet processing, etc. can be adopted. The microwave treatment is to generate heat by irradiating a high-frequency object having a wavelength of 2450 MHz or 920 MHz. These treatment means may be applied alone, or in order to increase the heating efficiency, for example, a microwave treatment or an ultraviolet treatment may be used in combination with steam treatment or dry heat treatment. In the case of dry heat treatment, microwave treatment, and ultraviolet treatment, it is preferable to perform treatment in an inert gas atmosphere, since the polymerization hardly proceeds when oxygen in the air is present, and in the case of the cold batch method, It is preferable to seal with a sealing material.

Among these polymerization methods, steam treatment is preferably used from the viewpoints of polymerization efficiency and treatment stability. The steam treatment may be any of normal pressure steam, overheated steam, and high pressure steam, but from the viewpoint of cost, normal pressure steam or overheated steam is preferable. The steam treatment temperature is 80 to 180 ° C, more preferably 1 to 180 ° C.
The temperature is preferably from 00 to 160 ° C, and the steam treatment time is from 1 to 160 ° C.
Conditions of about 10 minutes are preferably used.

In the method of the present invention, before the copolymerization of the monomers A and B on the fiber surface, it is also preferable to carry out preliminary drying by air drying or a drier.

In the present invention, the amount of the polymer of the treatment liquid is preferably 1 to 20% by weight based on the fiber material from the viewpoint of improving the moisture absorption performance and preventing the rough curing of the texture. .

After the copolymer of monomer A and monomer B is applied to the fiber material, the present invention adsorbs formaldehyde gas and a catalyst to the fiber material and heat-treats the fiber material to crosslink between the fiber material, between the copolymer and between the fiber material and the copolymer. Let me know.
In this treatment, various processing methods using a generally known formaldehyde gas can be applied.

The formaldehyde gas concentration in the gas processing apparatus is preferably in the range of 1 to 20%, and if it is less than 1%, the crosslinking reaction becomes insufficient, and if it exceeds 20%, no further effect can be expected. .

The catalyst for the cross-linking reaction may be prepared by padding the fiber material with a catalyst solution in advance, or by adsorbing the catalyst solution or the liquefied catalyst by vaporizing or mist.

Regarding the type of catalyst, when the catalyst is padded in advance to the fiber material, the same catalyst as used in conventional resin processing, for example, a metal salt of an acid such as zinc nitrate, Lewis acid, or Bronsted acid may be used. it can. When vaporizing in the form of a mist, it is preferable to use a volatile and low-boiling acid such as hydrogen chloride.

The concentration of the catalyst is preferably in the range of 0.1 to 3% when treated with a gas. If the gas concentration is 0.1% or less, the crosslinking reaction becomes insufficient, and if the gas concentration is 3% or more, further effects cannot be expected, and the strength of the fiber material may be reduced.
When the catalyst solution is attached to the fiber material by padding, the catalyst concentration is preferably in the range of 5 to 100 g / l. When the concentration is less than 5 g / l, the crosslinking reaction becomes insufficient,
If the amount exceeds 100 g / l, no further effect can be obtained, and there is a possibility that the fiber strength may be excessively reduced.

The heat treatment after adsorbing the formaldehyde gas is carried out at a temperature in the range of 100 to 180 ° C. and 0.5 to 10 ° C.
Minutes.

The cellulosic fibers referred to in the present invention are natural fibers such as cotton and hemp, and regenerated cellulosic fibers such as viscose rayon and polynosic. As the fiber material of the present invention, polyester, nylon, acryl, silk, wool, vinylon, and the like, in addition to these cellulosic fibers, can be used by blending, blending, weaving, and weaving. Fibers include filaments, staples, woven and knitted fabrics,
Any form such as a nonwoven fabric may be used. In particular, when the content of the cellulosic fiber is 10% or more, and more preferably 30% or more, it is preferable from the viewpoint of form stability and the durability of the copolymer.

[0024]

The present invention will be described in more detail with reference to the following examples. In addition, the measurement of various performances described in the examples is based on the following method.

[Resin adhesion amount] Resin adhesion amount (% owf) = [(A−B) / B] × 100 where A: fabric weight after processing B: fabric weight before processing Is 24 in a 20 ° C x 65% RH atmosphere.
Weight when left for a while.

[Hygroscopicity] ΔMR (%) = MR ₂ −MR ₁ Here, MR ₁ refers to a moisture absorption rate when left in an atmosphere of 20 ° C. × 65% RH from a completely dry state for 24 hours. This corresponds to the state of being in a dance, that is, the environment before wearing. Also, MR ₂ is 30 ° C x 90% RH from a completely dry state.
It refers to the moisture absorption when left for 24 hours in an atmosphere, and substantially corresponds to the environment in clothes under exercise conditions.

The △ MR are those represented by the value obtained by subtracting the value of the MR ₁ from MR _2, when motion from wearing clothes, equivalent to or absorb much stuffiness in the garment, Δ It can be said that the higher the MR value, the more comfortable. In general,
Polyester ΔMR is 0%, nylon is 2%, cotton is 4%
% And 6% wool.

[Wrinkle resistance] Judgment was made based on the AATCC 124-1984 5-step replica method. Grade 5 (good)-Grade 1 (poor) [Washing shrinkage] Measured according to JIS L-1042.

For the test cloth of the embodiment, a greige machine of polyester / cotton (45% by weight / 55% by weight) woven fabric (count 45 × 45 / density 110 × 76 / inch) was refined and set to dry heat. Was.

Example 1 The above-mentioned test cloth was immersed in a treatment liquid having the following composition, squeezed with a mangle having a squeezing rate set so that the resin adhesion amount was 6% owf, and dried with a dryer at 120 ° C. × 2 minutes.

AMPS 130 g / l Monomer B with R = H and n = 2 in General Formula 1 43 g / l Ammonium persulfate 3 g / l After drying, the mixture is treated with a saturated steam steamer at 100 ° C. for 3 minutes, washed with hot and cold water, and dried. did. Then, after setting in a dryer at 180 ° C. for 1 minute, formaldehyde gas processing was performed using a gas processing apparatus under the following conditions. Table 1 shows the evaluation results.

Injection amount of formalin gas 3724 ml Injection amount of sulfurous acid gas (catalyst) 454 g From Table 1, it can be seen that a fiber material having excellent hygroscopicity, shrinkage resistance and wrinkle resistance excellent in washing durability can be obtained.

Example 2 A sample was prepared in the same manner as in Example 1 except that the treatment liquid had the following composition. The results are shown in Table 1.

In the general formula 1, 100 g / l of monomer B with R = CH ₃ and n = 3, 3 g / l of ammonium persulfate From Table 1, even if the type of monomer B and the mixing ratio of monomer A and monomer B are changed. It can be seen that a fiber material having excellent hygroscopicity, shrinkage resistance, and wrinkle resistance excellent in washing durability can be obtained as in Example 1.

Example 3 A sample was prepared in the same manner as in Example 2 except that the treatment liquid had the following composition. The results are shown in Table 1.

Sodium methacrylate 100 g / l In the general formula 1, R = CH ₃ , n = 3 monomer B 100 g / l ammonium persulfate 3 g / l From Table 1, monomer A is converted from vinyl sulfonic acid to vinyl carboxylate. Even if it changes, it turns out that the fiber material which is excellent in the washing durability similarly to Example 2 and has moisture absorption, shrinkproof property, and wrinkle resistance can be obtained.

Example 4 A sample was prepared in exactly the same manner as in Example 1 except that the treatment liquid had the following composition. The results are shown in Table 1.

With AMPS, in the general formula 1, R =
H, n = 2 monomer B 200 g / l copolymer (AM
PS: monomer B = 3: 1) As shown in Table 1, even when a treatment solution containing a copolymer prepared in advance is used, a fiber having excellent hygroscopicity, shrinkage resistance, and wrinkle resistance having excellent washing durability as in Example 1. It can be seen that the material is obtained.

Comparative Example 1 A sample was prepared in exactly the same manner as in Example 1 except that the treatment liquid had the following composition. The results are shown in Table 1.

AMPS 130 g / l Ammonium persulfate 3 g / l From Table 1, it can be seen that when monomer B is not added, the adhesion to the fiber surface becomes insufficient and sufficient washing durability cannot be obtained.

Comparative Example 2 A sample was prepared in exactly the same manner as in Example 2 except that the treatment liquid had the following composition. The results are shown in Table 1.

In the general formula 1, R = CH ₃ , monomer B with n = 3 100 g / l Ammonium persulfate 3 g / l From Table 1, it can be seen that when monomer A is not added, sufficient moisture absorption performance cannot be obtained. .

Comparative Example 3 A sample was prepared in exactly the same manner as in Example 1 except that no formaldehyde gas processing was performed. The results are shown in Table 1.

From Table 1, it can be seen that unless formaldehyde gas processing is performed, durable hygroscopicity, shrinkage resistance and wrinkle resistance cannot be obtained.

Comparative Example 4 A sample was prepared by performing only formaldehyde gas processing under the same conditions as in Example 1. The results are shown in Table 1.

From Table 1, it can be seen that in the case of only formaldehyde gas processing, sufficient moisture absorption performance cannot be obtained.

[0047]

[Table 1]

[0048]

According to the present invention, durable moisture absorption,
It is possible to stably provide a fiber material having excellent shrinkage resistance, wrinkle resistance and shape stability.

Claims (5)

[Claims] 1. A fibrous material containing cellulosic fibers,
A treatment liquid comprising at least one monomer A selected from vinyl carboxylic acid and vinyl sulfonic acid, a vinyl monomer B represented by the following general formula [1], and a polymerization initiator is applied, and copolymerized on the surface of the fiber material. A method for producing a fibrous material, comprising: adsorbing formaldehyde gas and a catalyst onto the fibrous material and heat-treating the fibrous material to cause crosslinking. Embedded image 2. The method for producing a fiber material according to claim 1, wherein the treatment liquid contains a copolymer of the monomer A and the monomer B. 3. The weight ratio of said monomer A and said monomer B is 1: 1:
3. The method for producing a fiber material according to claim 1, wherein the ratio is in the range of 10 to 10: 1. 4. The method for producing a fiber material according to claim 1, wherein said monomer B is a monomer of n = 2 or 3, R = H or CH ₃ . 5. The method for producing a fiber material according to claim 1, wherein said monomer A is at least one selected from vinyl carboxylate and vinyl sulfonate.