JP2001064874A - Production of cellulose-based processed fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing cellulose-based processed fiber products having sufficiently morphological stability, shrink resistance, tear strength, hygroscopicity, feeling, etc., by means of chemicals not containing formaldehyde. SOLUTION: This method for producing cellulose-based processed fiber products features imparting a processing liquid comprising a monomer having at least COOX [X is hydrogen atom, or an atom or atomic group capable of becoming n(-COO-)Xn+; n is a positive number] and at least one unsaturated bond, a polymerization initiator and an ester-forming catalyst to cellulose-based fiber-containing fibers or fabrics and then heat-treating the fibers or fabrics. The method may feature imparting a processing liquid comprising a monomer having at least COOX [X is hydrogen atom, or an atom or atomic group capable of becoming n(-COO-)Xn+; n is a positive number] and at least one unsaturated bond and a polymerization initiator to cellulose-based fiber-containing fibers or fabrics, then heat-treating the fibers or fabrics, and immediately (or after an optional treatment) imparting a processing liquid comprising at least an ester-forming catalyst and heat-treating the resultant product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a formaldehyde-free form-stable processing method for cellulosic fibers and / or fabrics.

[0002]

2. Description of the Related Art In textile products, cellulosic fibers represented by cotton are widely used because of their excellent hygroscopicity, heat retention and tactile sensation. However, on the other hand, it has drawbacks such as easy shrinkage and wrinkling when washed as it is. For example, clothes such as dress shirts have to be ironed. In order to remedy this drawback, blending with polyester fiber is carried out, or because it is still insufficient, cross-linking between hydroxyl groups of cellulose by glyoxal resin treatment or formaldehyde gas phase treatment, etc., leads to form stability and shrinkage prevention. It has been done to impart the property.

However, it is known that formaldehyde is contained in glyoxal resin and the like as a matter of course in the gas phase treatment of formaldehyde, and this formaldehyde remains in the fibers. Since formaldehyde is a harmful substance, it is required that formaldehyde does not remain in the fiber. Therefore, it is a fact that the system is operated within the standard after taking measures such as washing and using a medicine having a low formaldehyde content even though the effect is slightly inferior.

On the other hand, for example, Japanese Patent Publication No. Hei 7-26321
As disclosed in Japanese Unexamined Patent Application Publication No. Hei 8-27666, a method of treating with a polycarboxylic acid is disclosed. According to this method, formaldehyde is not contained in the drug, and no formaldehyde is generated by the reaction with the fiber, so that the fiber product does not contain formaldehyde at all.

However, according to these methods, the tear strength is lower than that of a fiber product treated with a formaldehyde-containing agent such as glyoxal resin, even though its form stability and shrinkage resistance are further inferior. There is a problem that it is about the same as that processed in.

Furthermore, the treatment with the above-mentioned glyoxal resin or gaseous formaldehyde imparts morphological stability by causing a cross-linking reaction between hydroxyl groups involved in the development of hygroscopicity of cellulose, so that hygroscopicity is lost. When wearing clothing, you may feel stuffy or hot.

[0007]

DISCLOSURE OF THE INVENTION In view of the state of the prior art, the present invention relates to a cellulosic compound which is excellent in form stability, shrinkage resistance, tear strength, hygroscopicity, texture, etc. by a formaldehyde-free drug. It is intended to provide a method for producing a processed fiber product.

[0008]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the method for producing a processed cellulose fiber product of the present invention comprises at least -COOX (X is a hydrogen atom or n
(—COO ⁻ ) X ^{n +} atom or atomic group; n is a positive number) and a treatment solution containing a monomer having an unsaturated bond, a polymerization initiator and an ester-forming catalyst, into a fiber or fiber structure containing cellulosic fibers. It is characterized in that it is applied to an object and heat-treated.

[0009] In the method of manufacturing cellulosic fibers processed products of the present invention, at least -COOX (X is a hydrogen atom or ⁿ (-COO ^-) X n ⁺ a will be atom or group;
n is a positive number) and a treatment liquid containing a monomer having an unsaturated bond and a polymerization initiator is applied to a fiber or a fiber structure containing a cellulosic fiber and heat-treated, and then immediately or after any treatment And applying a treatment liquid containing at least an ester-forming catalyst and performing heat treatment.

[0010] In the method for producing a processed cellulose fiber product of the present invention, the hygroscopicity before treatment by the above-described production method is ΔΔ.
When MR1 and the hygroscopicity after treatment are ΔMR2, at least ΔMR2 / ΔMR1 is 70% or more.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The object of the present invention is to provide a method for producing a processed cellulosic fiber product having sufficient form stability, shrinkage resistance, tear strength, hygroscopicity, texture and the like by using a formaldehyde-free drug. About
When treated with a system containing the three requirements of a monomer having an unsaturated bond with COOX, a polymerization initiator, and an ester forming catalyst, it was surprisingly found that such a problem was solved at once. It is.

As the cellulosic fiber in the present invention,
For example, cotton, natural cellulose fibers such as hemp, rayon,
Regenerated cellulose fibers such as polynosic and cupra, and purified cellulosic fibers such as "TENCEL" and "Lyocell" can be used, but are not limited thereto.

The term "fiber containing cellulosic fiber" as used in the present invention may be used as long as the cellulosic fiber is contained in an amount of 1% by weight or more, and also includes 100% by weight cellulosic fiber. The shape of the fiber is not particularly limited, and may be, for example, a blended product with another fiber such as a synthetic fiber, or a covered yarn of a cellulosic fiber to another fiber. In addition, the fiber structure refers to a yarn containing the cellulosic fiber in an amount of 1 to 100% by weight, a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric, a garment made by sewing the fabric, and a curtain, for example. Refers to non-clothing sewing products.

The hygroscopicity (ΔMR) referred to in the present invention is:
The moisture absorption (%) at a temperature of 30 ° C. and a humidity of 90% Rh is represented by M
When the moisture absorption rate (%) at RH, a temperature of 20 ° C., and a humidity of 65% Rh is defined as MRL, hygroscopicity (ΔMR) = MRH−MRL. The moisture absorption is obtained by leaving a completely dried sample to stand in the above-mentioned atmosphere for 24 hours, and expressing the weight of the obtained sample as a weight increment from the completely dried state in%.

[0015] -COOX used in the present invention (X is a hydrogen atom or ⁿ (-COO ^-) X n ⁺ a will be atom or group; n is a positive number) a monomer having an unsaturated bond,
Although not particularly limited, for example, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, aconitic acid,
Acetylenedicarboxylic acid, allylmalonic acid, angelic acid, isocrotonic acid, itaconic acid, undecenoic acid, α-
Ethyl crotonic acid, elaidic acid, erucic acid, oxaloacetic acid, oleic acid, glutaconic acid, crotonic acid, chloroacrylic acid, chlorocrotonic acid, chlorofumaric acid, chloromaleic acid, citraconic acid, dihydroxycinnamic acid,
Tiglic acid, triacontenic acid, hydroxycinnamic acid,
Phenylbutenoic acid, phenylpropiolic acid, phenylpentadienoic acid, butyric acid, brandinic acid, furylacrylic acid, propiolic acid, bromocinnamic acid, hexadienedioic acid, behenolic acid, benzylidenemalonic acid, benzoylacrylic acid, metaconic acid, methylcinnamic acid , Methoxycinnamic acid and the like can be used. The carboxyl group contained therein may be in an acid form to which a hydrogen atom is bonded, for example, alkali metals such as potassium and sodium, alkaline earth metals, other metal ions, ammonium and triethanolamine, etc. May be used as a salt of a quaternized nitrogen compound. Further, for example, for those capable of forming an anhydride such as maleic acid, the anhydride may be used. Among these, water-soluble ones are preferably used, and among them, acrylic acid, methacrylic acid, and salts thereof are preferably used.

The amount of the monomer to be applied to the fiber structure is as follows:
It is preferably from 3 to 60% by weight, more preferably from 5 to 50% by weight, based on the cellulosic fibers in the fibrous structure.
40% by weight is particularly preferred.

The polymerization initiator used in the present invention may be any of those generally used in radical polymerization and the like, for example, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide and peroxides. Peroxides such as benzoyl, and azo compounds such as azobisisobutyronitrile, azobisamidinopropane dihydrochloride, and azobiscyanovaleric acid can be used. Among these, a water-soluble substance is more preferably used.

The amount of the polymerization initiator applied to the fiber structure is 0.5 to 10% by weight based on the amount of the monomer.
Is preferable, 1 to 7% by weight is more preferable, and 2 to 5% by weight is particularly preferable.

The term "ester-forming catalyst" as used herein means a catalyst for forming an ester bond between the carboxyl group of the monomer and the hydroxyl group of cellulose. As a catalyst for forming an ester bond, for example, alkali metal hypophosphite such as sodium hypophosphite, alkali metal phosphite such as sodium phosphite, borate and the like can be used. The applied amount is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, and particularly preferably from 15 to 35% by weight, based on the amount of the monomer.

The treatment liquid containing at least the above-mentioned monomer and polymerization initiator, or at least the above-mentioned monomer, polymerization initiator and ester-forming catalyst, preferably uses water as a main medium. An oily solvent may be appropriately contained, or the oily solvent itself may be the medium.

When the treatment liquid contains an appropriate amount of a polymerization inhibitor, for example, quinones such as p-methoxyphenol and hydroquinone, and mercaptans, the storage stability of the treatment liquid is ensured. It is preferred. The amount to be applied is 100 to 4000 p with respect to the monomer.
pm is preferable, 300 to 3000 ppm is more preferable, and 500 to 2000 ppm is particularly preferable.

The processing solution may further contain a fluorescent whitening agent, a dye, a pH adjuster, a surfactant,
A softening agent such as a silicone-based resin, and a tear strength lowering inhibitor such as a polyethylene-based resin can be included.

The method of applying to the processing solution employed in the present invention is as follows.
There is no particular limitation, and any method may be used as long as it has substantially the same effect. For example, a padding method, a spraying method, various coating methods, and the like may be appropriately employed so as to be convenient in manufacturing.

The heat treatment method employed in the present invention is not particularly limited, and may be any of dry heat treatment such as curing, and wet heat treatment such as steaming or high-temperature superheated steaming, or if necessary, both. Can be used. The purpose of this heat treatment is to cause the monomer to undergo a polymerization reaction and to allow the carboxyl group to react with the cellulose. By these two reactions, good morphological stability aimed at by the present invention is developed. In particular, wet heat treatment is more suitable for a polymerization reaction, and dry heat treatment is more suitable for a reaction between a carboxyl group and cellulose. Further, for example, it is also preferable to perform heating while applying pressure, such as calendering using an iron or a hot roll. The heating temperature of the dry heat treatment is preferably from 80 to 200C, more preferably from 120 to 180C, and particularly preferably from 140 to 180C. In the case of wet heat treatment, the temperature range of dry heat treatment may be used.
A sufficient effect appears at 0 to 110 ° C. Furthermore, after the treatment liquid is applied, heat treatment may be performed in one step, but according to the knowledge of the inventors, the reason is not clear, but two steps or three steps.
It is more preferable to perform the heat treatment of the step. In this case, the heat treatment temperature in the first stage is positioned in the drying step for convenience from the second stage, and is preferably 50 to 150 ° C., and 70 to 1 ° C.
30 ° C is more preferable, and 80 to 100 ° C is particularly preferable. In the case of the three-stage treatment, it is a preferable state that drying is performed in the first stage, wet heat treatment is performed in the second stage, and dry heat treatment is performed in the third stage. In another preferred embodiment, a processing method in which the second and third stages are interchanged can be used.

In the present invention, two types of manufacturing methods can be selectively used. One is a method in which a heat treatment is performed after applying a treatment liquid containing a monomer, a polymerization initiator and an ester forming catalyst simultaneously, and the other is a heat treatment after applying a treatment liquid containing a monomer and a polymerization initiator, and then immediately ,
Alternatively, after performing a predetermined treatment, a treatment liquid containing an ester forming catalyst is applied, and then heat treatment is performed. Of these methods, the former method is preferable because the number of steps is small, but the latter method is also preferable.

That is, for example, when acrylic acid is used as a monomer, if acrylic acid remains in the acid form in the former method, the efficiency of monomer utilization may deteriorate due to the property of volatilizing during the drying and heat treatment stages. is there. Therefore, polymerization is first performed using a treatment solution of non-volatile sodium acrylate and a polymerization initiator, and then treated in an acidic bath to convert sodium polyacrylate present in the fiber into acid-type polyacrylic acid. If a method of treating with a treatment liquid containing an ester forming catalyst is adopted, the monomer can be used with high efficiency.

The former method, that is, a method of treating with a treatment solution containing sodium acrylate, a polymerization initiator and an ester forming catalyst simultaneously, may be adopted. Since the formation proceeds efficiently only under acidic conditions, the efficiency decreases.

After the heat treatment, it is preferable to wash the fiber or the fibrous structure with hot water or water, since the unreacted monomer or its polymer can be surely removed if there is any. This hot water washing or water washing liquid may appropriately contain a penetrant, a surfactant and the like. Further, the pH of the hot water or water washing solution is more preferably alkaline from the viewpoint of washing efficiency. In addition, since it may be yellowed by heat treatment,
In that case, it is also preferable to add an appropriate bleaching agent such as a peroxide type or a chlorine type.

According to the production method of the present invention described above, the obtained cellulose fiber processed product has a higher moisture absorption (ΔMR2) than the hygroscopicity (ΔMR1) before the series of treatments of the present invention. (ΔMR2 / ΔMR1) is maintained high, and it is difficult to feel discomfort when worn as clothing. For that purpose, the retention is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

Further, it is more preferable to use water containing an amount of a metal salt having a pH of 9 or more in the above-mentioned step of washing with hot water or water. Still more preferably, it is a salt of an alkali metal such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. Surprisingly, when treated with a liquid containing such a metal salt, the retention of hygroscopicity may be 100% or more. For example, it is very suitably used for a cellulosic fiber or the like in which a polyester having low hygroscopicity is blended.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The morphological stability was evaluated by comparing with an AATCC wrinkle replica after hanging home washing 20 times and then hanging and drying. In addition, the judgment of the class that is not in the replica,
It is a value evaluated by interpolating between replicas of each class sensuously.

The morphological stability and tear strength of each of the examples and comparative examples are summarized in Table 1. Untreated cloth 1 Refined 45th cotton / polyester blend yarn (60
/ 40% by weight) (fabric weight 110 g / m ² )
Was used. Example 1 Untreated cloth 1 was immersed in the following treatment solution by the padding method,
Squeezed (squeezing rate 70%).

Treatment liquid formulation Acrylic acid 20% by weight Ammonium persulfate 0.6% by weight Sodium hypophosphite 5% by weight Polyethylene resin emulsion 1.5% by weight Next, dried at 85 ° C. for 5 minutes, and then at 180 ° C. for 90 seconds Dry heating was performed.

Further, the fabric was washed with hot water at 50 ° C. to obtain a fiber structure (fabric) according to the production method of the present invention. Comparative Example 1 Untreated cloth 1 was treated with the following treatment liquid, and the same procedure was followed as in Example 1 including drying.

Treatment liquid formulation Acrylic acid 20% by weight Ammonium persulfate 0.6% by weight Polyethylene resin emulsion 1.5% by weight Comparative example 2 Untreated cloth 1 was treated with the following processing liquid, and only drying and dry heating were performed. The same was done (no hot water washes).

Treatment liquid formulation Sodium acrylate 20% by weight Ammonium persulfate 0.6% by weight Polyethylene resin emulsion 1.5% by weight Example 2 The cloth obtained in Comparative Example 2 was treated with an acetic acid-sodium acetate buffer solution of pH = 3. For 3 hours.

Next, the mixture was treated with the following treatment solution, followed by drying, dry heating and hot water washing in the same manner as in Example 1.

Treatment Solution Formulation Sodium Hypophosphite 5% by Weight Comparative Example 3 Untreated cloth 1 was treated with the following treatment solution, and thereafter the same procedure as in Example 1 was performed, including drying.

Treatment liquid formulation Glyoxal resin 20% by weight Magnesium chloride 5% by weight Polyethylene resin emulsion 1.5% by weight Comparative example 4 Untreated cloth 1 was treated with the following treatment liquid, and thereafter dried and treated as in Example 1. Performed similarly.

Treatment liquid formulation Butanetetracarboxylic acid 20% by weight Sodium hypophosphite 5% by weight Polyethylene resin emulsion 1.5% by weight Example 3 Untreated cloth 1 was immersed in the following processing liquid by the padding method.
Squeezed (squeezing rate 70%).

Treatment liquid formulation Methacrylic acid 20% by weight Ammonium persulfate 0.6% by weight Sodium hypophosphite 5% by weight Polyethylene resin emulsion 1.5% by weight Next, dried at 85 ° C. for 5 minutes, and then at 180 ° C. for 90 seconds Dry heating was performed.

Further, the fabric was washed with hot water at 50 ° C. to obtain a fibrous structure (fabric) according to the production method of the present invention. Example 4 The fiber structure (fabric) obtained in Example 1 was immersed in a sufficient amount of a 0.1% aqueous solution of sodium hydroxide and stirred at 50 ° C. for 30 minutes. Thereafter, the same hot water washing as in Example 1 is performed again,
A fiber structure (fabric) was obtained by the production method of the present invention. Untreated cloth 2 A plain woven cloth (having a basis weight of 105 g / m ² ) consisting of 100% of scoured 50th-numbered cotton was used. Example 5 Untreated cloth 2 was immersed in the following treatment liquid by a padding method,
Squeezed (squeezing rate 70%).

Treatment liquid formulation Acrylic acid 20% by weight Ammonium persulfate 0.6% by weight Sodium hypophosphite 5% by weight Polyethylene resin emulsion 1.5% by weight Next, dried at 85 ° C. for 5 minutes and then at 105 ° C. for 60 seconds Moisture heat treatment was performed, followed by dry heating at 180 ° C. for 90 seconds.

Thereafter, the resultant was washed with hot water at 50 ° C. to obtain a fiber structure (fabric) according to the production method of the present invention. Comparative Example 5 The untreated cloth 2 was treated with the following treatment liquid, and the same procedure as in Example 4 was performed thereafter, including drying.

Treatment liquid formulation Glyoxal resin 20% by weight Magnesium chloride 5% by weight Polyethylene resin emulsion 1.5% by weight

[0047]

[Table 1]

As can be seen from Table 1, the fiber structures (Examples 1 to 4) according to the production method of the present invention were treated with a conventional formaldehyde-containing treatment (Comparative Examples 3 and 5) or a non-formaldehyde-based treatment (Comparative Examples 3 and 5). Compared with Comparative Example 4), it is very excellent in simultaneously satisfying good form stability and tear strength.

[0049]

Industrial Applicability According to the present invention, it is possible to produce a cellulosic fiber that achieves sufficient form stability, tear strength, shrinkage resistance, moisture absorption, texture, and the like, using a drug containing no formaldehyde.

Claims (8)

[Claims] 1. A least -COOX (X is a hydrogen atom or ⁿ (-COO ^-) X n ⁺ a will be atom or group;
n is a positive number) and a treatment liquid containing a monomer having an unsaturated bond, a polymerization initiator and an ester-forming catalyst is applied to a fiber or a fibrous structure containing cellulosic fibers and heat-treated. Manufacturing method of processed fiber products. Wherein at least -COOX (X is a hydrogen atom or ⁿ (-COO ^-) X n ⁺ a will be atom or group;
n is a positive number) and a treatment liquid containing a monomer having an unsaturated bond and a polymerization initiator is applied to a fiber or a fiber structure containing a cellulosic fiber and heat-treated, and then immediately or after any treatment A method for producing a processed cellulose fiber product, comprising applying a treatment liquid containing at least an ester-forming catalyst and performing heat treatment. Wherein the optional treatment, -COOX '(X' is ^{n (-COO -) X 'n} + and becomes capable atom or group;
3. The method for producing a processed cellulose fiber product according to claim 2, wherein (n is a positive number) is converted into -COOH. 4. The process for producing a processed cellulose fiber product according to claim 1, wherein the treatment liquid contains a polymerization inhibitor. 5. The process for producing a processed cellulose fiber product according to claim 1, wherein the monomer is acrylic acid or methacrylic acid. 6. The method for producing a processed cellulose fiber according to any one of claims 1 to 5, wherein the processed cellulose fiber is treated with water containing an amount of a metal salt having a pH of 9 or more. A method for producing a processed cellulosic fiber product, comprising: 7. A process for producing a processed cellulosic fiber product, wherein the metal salt according to claim 6 is an alkali metal salt. 8. A fiber or a fibrous structure containing a cellulosic fiber having a hygroscopicity ΔMR1 before treatment by the method for producing a cellulosic fiber processed product according to any one of claims 1 to 6,
When the hygroscopicity after the treatment is ΔMR2, at least ΔMR2
The method for producing a processed cellulosic fiber product according to any one of claims 1 to 7, wherein 2 / ΔMR1 is 70% or more.