JP3385389B2 - Natural cellulose fiber having pleating property, fiber product thereof, and production method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a natural cellulose fiber having excellent pleating properties, a fiber product obtained by using it as a fiber raw material, and a method for producing them.

[0002]

2. Description of the Related Art Natural cellulose typified by cotton is widely used due to its many advantages such as hygroscopicity and touch, but has the drawback that significant deformation (wrinkles) occurs in the sewn fabric by washing. In particular, when natural cellulose is used as clothing, its improvement is required.

As a technique for improving such wrinkle resistance,
A method is known in which cellulose is impregnated with a neutralized aqueous solution of polycarboxylic acids, and the cellulose is heated for esterification (US Pat. No. 3,526,048).

On the other hand, the above-mentioned property is called wash and wear property (W & W property), and is an index intended to be worn after washing and drying without ironing, and as a standard for evaluating the degree of washing. The "DP Index" (AATCC Test Method 124-1967) is often used.

However, considering the convenience of actual wearing, it is not possible to sufficiently evaluate the W & W property of clothing by the DP index alone.

A pleating property is an extremely important item for solving such an evaluation problem. Here, with the pleating property, for example, after sewing, hot pressing is performed,
When a vertical stripe or collar is formed, the shape does not disappear due to washing, and the stripe or collar retains its original shape.

As a method for improving the pleat property, for example, a method in which formalin gas is allowed to act on sewn and pressed clothing, or a method in which a formalin derivative such as urea formalin resin is adhered and sewn and then hot pressed is known. There is.

However, when formalin or its derivative is applied, the phenomenon that the formalin remains after the treatment is remarkable. Formalin is known as a carcinogenic substance in addition to its peculiar malodor, and it is feared that not only the working environment in the fiber treatment step but also the consumer as a product will be affected.

[0009] Further, recent demands on clothing from consumers are strict, and a standard of shape memory clothing is required, and not only simple washing, but also W & W property having a pleat property in a practical sense. If you don't have your own clothes, you will not be able to accept them.

That is, in the present clothing field, there is a demand for natural cellulose fibers having not only wrinkle resistance but also excellent pleating properties without using formalin and its derivatives.

[0011]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide wrinkle-resistant natural cellulose fibers with improved pleating properties, natural cellulose fiber products obtained by using the fibers as raw materials, and methods for producing them. To do.

[0012]

Means for Solving the Problems The inventors of the present invention have made earnest studies to meet those demands, and as a result, the following (1) to (4)
Based on the findings, the present invention has been completed.

(1) Although natural cellulose fibers crosslinked by esterification with polycarboxylic acids are effective in improving wrinkle resistance, they are not sufficient in terms of pleating property and have a W & W property in a practical sense. In addition,
There is room for improvement.

(2) The same applies to the natural cellulose fiber modified by an ester composed of polycarboxylic acid and polyol (JP-A-5-247843).

(3) Even if natural cellulose fibers are impregnated with a treatment liquid containing a polycarboxylic acid and a polyol and then heated, it is difficult to obtain a predetermined effect.

(4) By preparing natural cellulose fibers preliminarily crosslinked with polycarboxylic acids, impregnating the treated fibers with a polyol solution, and then heat-treating the fibrils, not only wrinkle resistance but also excellent pleats are obtained. A fibrous material having properties can be obtained.

That is, the modified natural cellulose fiber according to the present invention is obtained by binding a polyol to a natural cellulose fiber which has been modified with a polycarboxylic acid in advance.

The natural cellulose fibers according to the present invention include cotton, hemp, rayon and mixed-spun fibers containing these fibers, and the fiber products thereof include yarns, woven fabrics, knitted fabrics, non-woven fabrics and the like obtained from the fibers. The product is exemplified.

The natural cellulose fibers modified with polycarboxylic acids (hereinafter referred to as "modified fiber raw materials") are natural cellulose fibers obtained by crosslinking polycarboxylic acids on natural cellulose fibers.

The modified fiber raw material is, for example, the above-mentioned US Pat. No. 3,526,048 and Japanese Patent Application Laid-Open No. 5-247843 and Japanese Patent Application Laid-Open No. 5-247843 previously proposed by the present inventors.
A fiber material obtained by treatment by the method described in Japanese Patent No. 247850, and specifically selected from the group consisting of polycarboxylic acids and, if necessary, alkali metal salts and lower amine salts with respect to natural cellulose fibers. It is prepared by impregnating a treatment liquid containing one or more kinds of salts described above and heating this.

As the polycarboxylic acids, various linear aliphatic polycarboxylic acids, branched aliphatic polycarboxylic acids,
Examples thereof include alicyclic aliphatic polycarboxylic acid and aromatic polycarboxylic acid, which may have a hydroxyl group, a halogen group, a carbonyl group, or a carbon-carbon double bond.

Specific examples of such polycarboxylic acids include linear aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid. Branched fatty acids of these polycarboxylic acids, unsaturated dibasic acids such as maleic acid and fumaric acid, alicyclic dibasic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrahydrophthalic acid and nadic acid. , Tricarballylic acid, aconitic acid, tribasic acid such as methylcyclohexentricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, tetrabasic acid such as ene adduct of methyltetrahydrophthalic acid and maleic acid , Hydroxy fatty acids such as malic acid, tartaric acid and citric acid, o- m- or p- phthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and aromatic polycarboxylic acids such as diphenylsulfone tetracarboxylic acid.

Of these polycarboxylic acids, water-soluble carboxylic acids such as tricarballylic acid, aconitic acid, citric acid and butanetetracarboxylic acid are preferable because of their good workability, and particularly water-soluble and tetrabasic acids are preferable. The natural cellulose fiber using the butanetetracarboxylic acid is most excellent in the pleating property of the present invention.

Examples of the alkali metal salt include alkali metal hydroxides, carbonates, bicarbonates, formates, acetates and other monocarboxylic acid salts, phosphates, borates, ammonia, and secondary amines. And tertiary amines, quaternary ammonium salt hydroxides, and the like, and specifically, sodium hydroxide, sodium bicarbonate, sodium borate, sodium metaborate, sodium silicate, sodium metasilicate, sodium phosphate. , Sodium metaphosphate, sodium polyphosphate, sodium pyrophosphate, sodium phosphite, sodium hypophosphite, sodium formate, sodium acetate and the like. Further, salts of volatile lower amines such as potassium, ammonium, methylamine, dimethylamine, trimethylamine and triethylamine can be used in place of the above sodium, and these salts can be used alone or in combination of two or more kinds. .

The crosslinking treatment by heating is 100 to 250.
10 seconds to 1 under the condition of ℃, preferably 120 to 200 ℃
Done in time. Natural cellulose fibers that have been heat-crosslinked under milder conditions than this are insufficient in the crosslinking of polycarboxylic acids, and cause deterioration of the fibers under too severe conditions. Is not preferable.

The amount of the polycarboxylic acid ester-crosslinked with the natural cellulose fiber can be appropriately selected depending on the kind thereof, but is usually 0.1 to 50% by weight, preferably 0.5 to the natural cellulose. Is about 20% by weight. If it is less than this range, the pleating property of the present invention is insufficient, and even if it is used in a large amount, the effect corresponding to the amount used cannot be obtained, which is not economical.

Prior to the subsequent polyol treatment, natural cellulose fibers cross-linked by heating are washed with water or hot water to remove unreacted polycarboxylic acids and alkali metal salts, thereby preventing yellowing of the final product and providing a good texture. It is preferable because a product can be obtained. However, depending on the type of product, the polyol treatment may be performed with these chemicals attached for the purpose of shortening the process.

In the present invention, the polyol treatment is carried out by impregnating the modified fiber raw material with a solution of a polyol having a predetermined structure and heating it.

The polyol treatment may be carried out as a series of treatments following the polycarboxylic acid treatment, or natural cellulose fibers obtained by impregnating the modified fiber raw material with the polyol treatment liquid of the present invention are prepared in advance, This may be performed by heating separately.

The polyols used in the present invention are alcohols containing at least two alcoholic hydroxyl groups, and specifically, the following (1) to
Various polyols exemplified in each group of (4) are exemplified.

(1) Alcohol containing two alcoholic hydroxyl groups: ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, etc. 2-12 diols; branched diols such as neopentyl glycol, methylpentanediol, trimethylpentanediol; polypropylene glycol, 1,2-
Polymers of butylene oxide, polyether alcohols such as poly (1,4-butylene glycol).

(2) Alcohol containing three or more alcoholic hydroxyl groups: Aliphatic polyol such as glycerin, diglycerin, triglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol; cyclohexane Alicyclic diols such as diol, cyclohexanedimethanol, hydrogenated bisphenol A, spiroglycol and geometric isomers thereof; reducing sugars such as xylitol, sorbitol, mannitol and erythritol, xylose,
Sorbose, arabinose, ribose, erythrose,
Monosaccharides such as galactose and sorbitin, disaccharides such as lactose, sucrose and maltose; saponified products of polyvinyl acetate and ethylene-vinyl acetate.

(3) Alkylene oxides (ethylene oxide, propylene oxide) of compounds having two or more active hydrogens such as amines, phenols and alcohols
Adduct: As amines, ammonia, carbon number 1 to 2
2 monoalkylamine, alkylenediamine, alkylenetriamine, aniline, o-, m- or p-phenylenediamine, xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, diaminodiphenylketone, polycondensation product of aniline and formalin. Etc. are illustrated. As phenols, hydroquinone, resorcin, catechol,
Examples include bisphenol A, bisphenol S, phenol novolac, and cresol novolac. Examples of the alcohols include various polyols described in the groups (2) and (3).

Of these polyols, compounds having three or more primary alcoholic hydroxyl groups are particularly effective in enhancing the pleating property. In addition, the aliphatic polyol is effective in maintaining the texture of products such as clothing. Further, a compound containing no amino group is preferable in that the product is prevented from being colored during processing.

Therefore, preferable alcohols as raw materials for adding alkylene oxides include trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

The alcoholic hydroxyl group is preferably a primary alcohol. If a co-adduct of propylene oxide and ethylene oxide is used, the polyol with the ethylene oxide addition last is preferred.

The molecular weight of the polyol is 200 to 1000.
The range of 00 is preferable. When the molecular weight is less than 200, when it is used alone, the fibers produced tend to be hard, which causes a problem in terms of texture. On the other hand, if the molecular weight exceeds 100,000, the hot pressing conditions tend to become strict, which may cause a decrease in productivity and fiber deterioration, which is not preferable.

These polyols may be used alone or in admixture of two or more. When two or more kinds of polyols are mixed and used, even if the molecular weight is 200 or less, the above-mentioned compound containing active hydrogen should be used as it is or as a mixture with a small number of moles of ethylene oxide added. You can also

(4) Polyester polyol of the polyol and an aliphatic dicarboxylic acid or aromatic dicarboxylic acid having 2 to 12 carbon atoms, or a polyester polyol obtained by esterifying the polyol and the polycarboxylic acid in advance: polyester used in this case It is not preferable that the polyol is a crosslinked gel, and it is preferable that the polyol is at least soluble in a solvent, and preferably in an aqueous solution. Even if it is insoluble in water, one that can be emulsified and solubilized by using a surfactant can be used.

As the aliphatic dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and their branched fatty acids, maleic acid, unsaturated dibasic acids such as fumaric acid, Examples thereof include alicyclic dibasic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrahydrophthalic acid and nadic acid. Examples of aromatic dicarboxylic acids include o-, m- or p-phthalic acid, biphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, benzophenone dicarboxylic acid and naphthalenedicarboxylic acid.

In the present invention, the glycidyl ether of the above-mentioned polyol can be mentioned as a substance which substantially forms the polyol in the treatment liquid and has the same effect. However, even if the amount of these compounds is extremely small, the fiber products obtained from such fibers are not preferable because they may induce skin disorders.

The amount of the polyols used in the present invention is usually 0.1 to 1 with respect to the natural cellulose to be processed.
It is 00% by weight, preferably 1 to 50% by weight. 0.1
When it is less than 10% by weight, it is difficult to obtain satisfactory pleating properties, and even when it is used in excess of 100% by weight, the effect corresponding to the amount used cannot be obtained, which is not economical. The polyol concentration of the treatment liquid may be set to a concentration calculated from the squeezing ratio of the treatment liquid and the required amount of supporting.

In the present invention, when a water-soluble salt is added to such a treatment liquid, the pleating property tends to be more remarkably improved. Such water-soluble salts include, for example, sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium borate, sodium metaborate, sodium borohydride, sodium sulfate, sodium thiosulfate, sodium silicate, sodium metasilicate, Sodium phosphate,
Examples include sodium metaphosphate, sodium polyphosphate, sodium pyrophosphate, sodium phosphite, sodium hypophosphite, sodium formate, and sodium acetate. In the present invention, volatile lower amine salts such as potassium, ammonium, methylamine, dimethylamine, trimethylamine and triethylamine may be used in place of the above-mentioned alkali sodium. These salts may be used alone or in combination of two or more. The amount of these salts used is usually 0.1 to 10% by weight as the treatment liquid concentration. If it is less than this range, the effect cannot be obtained, and if it is more than the range, the effect beyond the range cannot be obtained, which is not economical.

In addition to the above-mentioned polyols and water-soluble salts, known softening agents such as polyethylene emulsion, dimethyl silicone emulsion, and modified silicone for fibers are added to the polyol treatment liquid to improve texture and sustainability. Can be granted. Such a softening agent may be added to the polyol bath or may be added at the stage of producing natural cellulose fibers cross-linked with polycarboxylic acids which are a processing material.

Examples of the modified silicone for fibers include compounds having a basic skeleton of dimethylpolysiloxane containing at least one aliphatic hydroxyl group, epoxy group and amino group in the molecule, and generally, amino modified silicone and polyether. It is a compound which is called as modified silicone or epoxy modified silicone and is sold. The treated cloth may be colored depending on the type and composition of the amino-modified silicone, and the polyether-modified silicone is preferable. These silicones are available as a raw material or an emulsion solution and can be used as they are.

The amount of these fabric softeners used is 0.01 to 50% by weight, based on the natural cellulose fibers to be processed.
It is preferably 0.1 to 10% by weight.

Although an organic solvent can be used as a solvent constituting the polyol treatment liquid of the present invention, water is preferably used as the solvent in consideration of safety and cost.

The modified fiber raw material is immersed in the treatment liquid prepared as described above to impregnate the polyols.

As the method of impregnating the modified fiber raw material with the polyol treatment liquid, a dipping method, a pad method, a spray method,
Known methods such as a coating method can be exemplified. The permeation rate of the polyol treatment liquid into the modified fiber raw material is sufficiently high, and the dipping time and bath temperature are not particularly limited. Usually, the immersion time is 0.5 to 300 seconds, and the bath temperature is 10 to 40 ° C.

After impregnation, squeezing is performed if necessary, and then drying is performed. The drawing depends on the product to be processed, and an appropriate drawing method and drawing ratio can be adopted for each. Usually, it is preferable to perform the drawing rate at 30 to 200%. The drying temperature is 4
The temperature may be 0 to 150 ° C., and the drying time may be selected according to the temperature.

The fabric or thread produced by the above method may be the fabric as it is, but it is preferable to give the necessary form as a textile product such as clothing clothing by sewing or cutting. The form may be the entire garment or a part such as a collar, sleeves, or placket.

By subjecting both the cloth and the thread to the treatment according to the present invention during sewing, the puckering property can be improved in addition to the pleating property. Here, the puckering property is a phenomenon in which the threads of the collar and sleeves are wavy due to washing, and is a very important performance when pleating property and actual W & W property are required. However, regarding the yarn to be used, even if the yarn is not according to the present invention, puckering property can be obtained by combining with the fabric of the present invention.

The heat treatment in the present invention can be performed by hot pressing as well.
It may be heating in the chamber. When heat-treated by hot pressing, a pleat property is improved by forming pleat lines. In the heat treatment by hot pressing, the dough that was heat-treated as it was without forming pleats was compared with the dough cross-linked with polycarboxylic acids, which is the material of the present invention, and the wash represented by the DP index I will be improved. When heated in the chamber, the product retains the sewn form.

That is, the effect of improving the pleating property in the present invention is to fix the shape of the cloth impregnated with the polyol by heat-treating the shape such as a fold or a flat surface, and the performance is not lost by washing. Is one manifestation of.

The heat treatment temperature in the polyol treatment of the present invention is 100 to 250 ° C., preferably about 120 to 200 ° C., and the treatment time is about 1 second to 1 hour. Under milder conditions, the pleating and puckering properties of the work cloth are less likely to be exerted, and too strict conditions cause deterioration of the fibers, which results in a decrease in strength and yellowing of the fibers.

The fabric manufactured by the above method is a product as it is if it is heat-treated after the whole is sewn,
If it is partially heat-treated, add the necessary sewing to make the product.

[0057]

EXAMPLES The present invention is described in detail below with reference to examples. In addition, the pleating property is evaluated by AATTC test method 88.
According to C-1973, the following method was used.

A 30 cm × 30 cm pressed pleated cloth was subjected to home washing (method 103) and tumble drying 10 times to obtain a test cloth. The judging method was AATTC test method 88C, pleating property class 1 to 5 grades.

Example 1 12% by weight of 1,2,3,4-butanetetracarboxylic acid (hereinafter referred to as "BTC") of a 100% plain-woven cotton shirting fabric having a basis weight of 120 g / cm ² (pleat type 1.0 grade) It was immersed in an aqueous solution containing 5% by weight of sodium phosphate monobasic, squeezed, dried at 60 ° C., and then cured at 170 ° C. for 150 seconds. This cloth was washed with water to prepare a modified fiber raw material. Pentalit EO (ethylene oxide) 2
Immersion in an aqueous solution (polyol treatment liquid) in which 3% by weight of 0 mol adduct and 3% by weight of monosodium phosphate are dissolved,
Squeezed and dried at 60 ° C. Fold this cloth in half and
A pleated cloth was obtained by pressing at 0 ° C. and 1 kg / cm ² for 20 seconds. When the pleating property of the obtained cloth was evaluated,
It was 4.0 grade.

Example 2 A 100% by weight twill-woven cotton uniform material having a basis weight of 250 g / cm ² (a pleating property of 1.0 grade) was used, and pentalit PO (propylene oxide) 20 mol EO 8 mol adduct 5 was used as a polyol treatment liquid. A pleated cloth was obtained in the same manner as in Example 1 except that an aqueous solution in which 1% by weight and 5% by weight of monosodium phosphate were dissolved was used. The pleating property of the obtained cloth was evaluated to be 3.5 grade.

Example 3 A pleat cloth was obtained in the same manner as in Example 1 except that 100% by weight plain weave cotton 100% by weight casual pants material having a basis weight of 200 g / cm ² (pleat property grade 1.5) was used. When the pleats of the obtained cloth were evaluated, it was 4.0 grade.

Example 4 A plain weave blended fabric (polyester / cotton = 50/50, weight basis) having a basis weight of 120 g / cm ² was used, and 40 mol of EO of pentalit was added as a polyol treatment liquid using a shirt fabric (class pleating property: 3.5). A pleated cloth was obtained in the same manner as in Example 1 except that an aqueous solution containing 5% by weight of the product and 5% by weight of sodium hypophosphite was used. When the pleating property of the cloth was evaluated, it was 4.0 grade.

Example 5 Twill weave blended fabric having a basis weight of 250 g / cm ² (polyester /
Cotton = 30/70) Uniform material (pleating 3.3)
12% by weight of BTC and sodium hypophosphite 5
It was immersed in an aqueous solution in which wt% was dissolved, squeezed, dried at 60 ° C, and then cured at 190 ° C for 90 seconds. This cloth was washed with water to prepare a modified fiber raw material. Then, 5 wt% of EO40 mol adduct of dipentalit as a polyol treatment liquid
A pleated cloth was obtained in the same manner as in Example 1 except that an aqueous solution containing 5% by weight of sodium hypophosphite was used. When the pleating property of the obtained cloth was evaluated, it was 4.0.
It was class.

Example 6 A plain weave having a basis weight of 200 g / cm ² (polyester / cotton =
30/70) Casual pants material (pleating 3.3)
A modified fiber raw material was prepared in the same manner as in Example 5 using Then, a pleated cloth was obtained in the same manner as in Example 1 except that an aqueous solution containing 5% by weight of a 15 mol adduct of trimethylolpropane EO and 5% by weight of sodium hypophosphite was used as the polyol treatment liquid. When the pleats of the obtained cloth were evaluated, it was 4.0 grade.

Example 7 A pleated cloth was obtained in the same manner as in Example 1 except that a plain weave rayon shirt fabric having a basis weight of 120 g / cm ² (pleatability grade 1.0) was used. The pleating property of the obtained cloth was evaluated to be 3.5 grade.

Example 8 A pleated cloth was obtained in the same manner as in Example 1 except that a plain weave hemp shirt fabric having a basis weight of 150 g / cm ² (pleat type 1.0 grade) was used. When the pleating property of the obtained cloth was evaluated, it was 3.3 grade.

[0067]

Example 10 The modified fiber raw material (pleat type 1.0 grade) of Example 1 was immersed in an aqueous solution in which 5% by weight of EO4 mol adduct of pentalit was dissolved, squeezed and dried at 60 ° C. The same pressing as in Example 1 was performed to obtain a pleated cloth. When the pleats of the obtained cloth were evaluated, it was 3.0 grade.

Example 11 Using the modified fiber raw material (pleatability 1.0 grade) obtained without washing with water in the step of preparing the modified fiber raw material,
A polyol treatment was carried out in the same manner as in Example 1 to obtain a pleated cloth. When the pleating property of the obtained cloth was evaluated, it was 4.0.
It was class.

Comparative Example 1 The modified fiber raw material of Example 1 (pleatability grade 1.0) was pressed as in Example 1 to obtain a pleated cloth. When the pleating property of the obtained cloth was evaluated, it was 1.0
It was class.

Comparative Example 2 Curing was performed in the same manner as in Example 1 except that an aqueous solution containing 12% by weight of BTC, 5% by weight of monosodium phosphate and 5% by weight of dipentalitate of 40 mol of EO was used as a treating solution, and a polyol-containing modification was carried out. Made fiber raw material. Heat pressing was performed as it was in the same manner as in Example 1 to obtain a pleated cloth.
When the pleating property of the obtained cloth was evaluated, it was 1.0 grade.

Comparative Example 3 A pleated cloth was obtained in the same manner as in Example 1 except that a cloth not subjected to BTC treatment (pleatability grade 1.0) was used. When the pleating property of the obtained cloth was evaluated, it was 1.0
It was class.

[0073]

The treatment according to the present invention makes it possible to obtain natural cellulose fibers having excellent wrinkle resistance and pleating properties. By using the treated fibers as a fiber material, wrinkle resistance and pleating properties can be improved. An excellent natural cellulose fiber product can be obtained.

Continuation of the front page (72) Inventor Hiroyuki Miura 175 Shinkai, Gotobiho-cho, Konan-shi, Aichi Prefecture (72) Inventor Hiroshi Tsujimoto 1-1-1, Takasu-cho, Nishinomiya-shi, Hyogo Prefecture Building No. 918 (56), Mukogawa housing complex No. 918 (56) Kaihei 5-247844 (JP, A) JP-A-5-247850 (JP, A) JP-A-2-84556 (JP, A) Special Table 3-503072 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) D06M 13/00-13/535

Claims (7)

(57) [Claims] 1. A natural cellulose fiber modified with a polycarboxylic acid and at least two alcoholic hydroxyl groups.
A method for producing a modified natural cellulose fiber , which comprises impregnating a polyol having a salt and heat-treating the same . 2. The modified natural cellulose fiber according to claim 1, wherein the polycarboxylic acid is butanetetracarboxylic acid.
Manufacturing method . 3. Natural cellulose fibers and polycarboxylic acids
Impregnated with a solution containing
Acid-treated natural cellulosic fibers are obtained and then the treated natural cell
At least two alcoholic hydroxyl groups on the lulose fiber
Impregnated with the polyols it has, and it is non-catalyst or cured
The heat treatment is carried out in the presence of a catalyst.
Or the method for producing the modified natural cellulose fiber according to item 2. 4. Natural cellulose fibers and polycarboxylic acids
And from the group consisting of alkali metal salts and lower amine salts
Contains a solution containing one or more selected salts
Soak and heat to heat the polycarboxylic acid-treated natural cellulose
Fiber, and then add less to the treated natural cellulose fiber.
Polyols having at least two alcoholic hydroxyl groups
And heat it in the presence of no catalyst or curing catalyst.
3. Reforming according to claim 1 or 2, characterized in that it is treated.
Method for producing natural cellulose fiber. 5. A polyol is impregnated and heat-treated.
When treating, heat treatment should be performed in the presence of water-soluble salt.
The modified natural cell according to any one of claims 1 to 4, characterized in that
Method for producing lulose fiber. 6. A polycarboxylic acid is modified to reduce the
Polyols having at least two alcoholic hydroxyl groups
Characterized by heating natural cellulose fiber impregnated with
The modified natural cellulose fiber according to claim 1 or 2.
Production method. 7. A method of modifying a polycarboxylic acid with a small amount
Polyols having at least two alcoholic hydroxyl groups
It is special to heat natural cellulose fiber products impregnated with
A method for producing a modified natural cellulose fiber product.