JPH06192990A - Production of modified hydrophilic fiber - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a method for producing a modified hydrophilic fiber in which an organic compound is efficiently and strongly supported on a hydrophilic fiber. [Composition] An aqueous solution is prepared by dissolving an organic compound such as adrenaline, isonitroacetophenone, or xanthine, which is insoluble or hardly soluble in water, in an acid or an alkali.
A hydrophilic fiber such as a lignocellulosic material is immersed in this aqueous solution to impregnate it with an aqueous solution of 60 to 400% by weight of the hydrophilic fiber, and then the hydrophilic fiber containing the aqueous solution is neutralized with an acid or an alkali. A method for producing a modified hydrophilic fiber, wherein an insoluble or sparingly water-soluble organic compound is produced and carried inside and on the surface of the hydrophilic fiber.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a modified hydrophilic fiber. To elaborate further,
The present invention is a method for producing a modified hydrophilic fiber in which a water-insoluble or sparingly soluble organic compound is carried on the surface, lumen, and inside of the hydrophilic fiber. That is, the method of the present invention is a method of compounding while utilizing the functions of both the hydrophilic fiber and the organic compound carried by the hydrophilic fiber, and a raw material for papermaking, a molding material, and a fiber material useful as a functional material. The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art Techniques such as internal addition and coating are known as techniques for compounding an organic compound insoluble or poorly soluble in water with hydrophilic fibers, especially pulp for papermaking. In the above method, a water-insoluble or sparingly soluble organic compound is mixed as solid powder with pulp or coated on paper, which is clearly different from the method using a water-soluble substance. In the case of internal addition, since many organic compounds are not hydrophilic in general, they are difficult to disperse into fine particles in water, and when they are added in the papermaking process, there is a drawback that the dispersion and yield are poor.

As a method for solving this drawback, for example, in a method of making paper by adding 8-oxyquinoline metal salt to pulp slurry, after adding nitrohumic acid to the pulp slurry, further adding a metal salt having a valence of 2 or more. Technology (Japanese Patent Publication No. 63-25120) is known,
It is not satisfactory in terms of yield improvement.

As a technique for producing a metal salt precipitate of an organic compound in a pulp slurry, an 8-quinolinol solution is added to the pulp slurry, and then a metal salt solution is added to add a metal salt of 8-oxyquinoline. Generating Technology (Japanese Patent Publication No. 47-84, U.S. Pat. No. 3,394,464)
Specification) is known. In this method, since 8-oxyquinoline metal salt is liberated in the pulp slurry, there is a problem that the loss from papermaking wire is large and the utilization efficiency thereof is low. The amount of 8-oxyquinoline metal salt deposited on the surface and carried within the fiber is small.

In addition, a technique of impregnating an organic solvent in which an organic compound such as aspirin is dissolved with a pulp previously substituted with the organic solvent and then evaporating the organic solvent to support the organic compound on the pulp (Yukio Tomizaki, Paper and Paper Cooperative Magazine 4
5 (9): 30 (1991), Allan, GG, Balaban, C., et al.Tappi
J. 74 (1): 83 (1991)) is known. This method is a completely different technique from the present invention in that an organic solvent is used.

[0006]

DISCLOSURE OF THE INVENTION The present invention intends to provide a method for efficiently modifying a hydrophilic fiber with an organic compound which is insoluble or sparingly soluble in water to obtain a hydrophilic fiber having an additional function. It is a thing.

[0007]

The method for producing a modified hydrophilic fiber according to the present invention comprises the steps of immersing a hydrophilic fiber in an aqueous solution prepared by dissolving an organic compound insoluble or hardly soluble in water in an acid or an alkali, 60 to 400% of the weight of hydrophilic fiber
And impregnating the hydrophilic fiber containing the aqueous solution with an acid or an alkali to generate and carry an organic compound insoluble or sparingly soluble in water inside and on the surface of the hydrophilic fiber. It is characterized by.

The hydrophilic fiber used in the method of the present invention is not particularly limited in its kind, and a fiber containing a hydrophilic synthetic polymer such as polyvinyl alcohol or polyacrylamide as a component, or a natural hydrophilic polymer such as ligno. Fibers made of a cellulosic material can be used. Among these hydrophilic fibers, those particularly suitable for the purpose of the present invention are fibers made of lignocellulose, and among them, pulp fibers used for papermaking purposes are particularly suitable.
Pulp fibers for papermaking consisting of lignocellulosic materials,
There are those derived from wood and those derived from herbs, and any of them can be used in the present invention. The method for pulping the lignocellulosic material is not particularly limited, and bleaching, beating, dyeing, and chemical treatment of these papermaking pulps can be used for the method of the present invention. is there.

The organic compound used in the present invention is soluble in at least one of an acid and an aqueous alkali solution and, when neutralized, produces an insoluble or sparingly soluble precipitate in water. Examples of such organic compounds include adrenaline, aminomalonyl urea, allantoin, anthrone, isonitroacetophenone,
Xanthine, 8-quinolinol, 5-quinolinecarboxylic acid, guanine, copper citrate, chrysin, L-cystine,
Dithiooxasim, 5,7-dihydroxyflavonol, thioxanthene, 2,5-diphenylfuran, zinc oxalate, thiobenzanilide, thiobenzamide, terephthalic acid, 1,2,3-trioxyanthraquinone,
Examples thereof include p-nitroaniline, nitroacetanilide, nitroguanidine, 1-nitroso-2-naphthylamine, 2-hydroxyazobenzene, flavone and the like.

The acid used in the present invention may be any acid as long as the aqueous solution exhibits acidity, and examples thereof include aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid and the like. The alkali used in the present invention may be any as long as its aqueous solution shows alkalinity, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium hydroxide, lithium hydroxide, hydroxide. Examples thereof include aqueous solutions of magnesium and ammonia.

In the method of the present invention, when the hydrophilic fiber is impregnated with an aqueous solution in which the organic compound is dissolved in an acid or an alkali, the solution is permeated and retained inside the fiber, and even after the liquid is drained, the solution remains inside the fiber. The aqueous solution remains. When a hydrophilic fiber containing such an aqueous solution of an organic compound is neutralized, a water-insoluble or sparingly soluble precipitate is formed inside the fiber, and the water-insoluble substance is carried on the fiber. The concentration of the organic compound in the aqueous solution is not particularly limited, and a solution up to the saturated concentration of the compound can be used. Generally, the higher the concentration of the organic compound, the more the amount of the organic compound supported by the modified fiber increases.

In the step of immersing the hydrophilic fiber in the aqueous solution in which the organic compound is dissolved in acid or alkali, the treatment temperature may be any temperature between the freezing point and the boiling point of the aqueous solution. Further, the time for immersing the hydrophilic fiber in the aqueous solution in which the organic compound is dissolved in acid or alkali is not particularly limited.

The amount of the acid or alkali aqueous solution in which the organic compound impregnated in the hydrophilic fiber in the impregnating step of the method of the present invention is dissolved is 60 to 4 relative to the weight of the hydrophilic fiber.
It is adjusted to 00%. This adjustment of the impregnation amount is performed by removing (delivering) the organic compound from the hydrophilic fiber impregnated with the organic compound. There is no particular limitation on the method of deliquoring the hydrophilic fiber material impregnated with the aqueous solution in which the organic compound is dissolved in acid or alkali. Ordinary deliquoring methods such as the method, centrifugal deliquoring method, and press deliquoring method can be used. The degree of deliquoring, that is, the impregnated amount of an aqueous solution in which an organic compound is dissolved in an acid or an alkali affects the amount of the water-insoluble substance supported on the modified fiber.

An acid aqueous solution or an acidic gas is used as the acid for neutralizing the hydrophilic fiber impregnated with an aqueous solution of an organic compound dissolved in an acid or an alkali, for example, hydrochloric acid, sulfuric acid, a nitric acid aqueous solution, hydrochloric acid, or dioxide. Examples thereof include carbon gas. As the alkali to be neutralized, an alkaline aqueous solution or a basic gas is used, and for example, sodium hydroxide, potassium hydroxide, sodium carbonate,
Examples thereof include aqueous solutions of sodium bicarbonate, calcium hydroxide, lithium hydroxide, magnesium hydroxide, ammonia and the like, or ammonia gas.

[0015]

The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the present invention. The beating method for pulp in the examples is TAP
It was carried out by the method of PI Standard T200 "Pulp processing method in laboratory, beater method". The beating degree was measured according to the method of 227 “Freeness of pulp”.

Example 1 10 g of hardwood unbleached kraft pulp beaten to 650 ml of freeness was mixed with 3.5% of adrenaline having a concentration of 5%.
It was immersed in 100 ml of a hydrochloric acid aqueous solution at room temperature for 1 hour. The pulp that had been soaked was taken out of the liquid and drained for 3 minutes under the acceleration of gravity of 900 G. The weight of the impregnated pulp after deliquoring was 35 g. The pulp that had been drained was immersed in 120 ml of a 0.8% aqueous sodium hydroxide solution. After standing for 1 hour in this state, the pulp was taken out from the aqueous sodium hydroxide solution. This pulp was allowed to stand in 1 L of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 200 mesh wire. This pulp was loaded with 9.4% by weight of adrenaline.

Example 2 10 g of softwood bleached kraft pulp beaten to a freeness of 600 ml was immersed in 200 ml of a 4% aqueous sodium hydroxide solution of isonitroacetophenone having a concentration of 10% for 1 hour at room temperature. The pulp that had been soaked was taken out of the liquid and drained under a gravitational acceleration of 900 G for 5 minutes. The weight of the impregnated pulp after deliquoring was 28 g. The pulp that had been drained was immersed in 90 ml of a 0.7% hydrochloric acid aqueous solution. After leaving this state for 3 hours, the pulp was taken out from the aqueous hydrochloric acid solution. This pulp was allowed to stand in 1 L of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 150 mesh wire. The pulp was loaded with 7.8% by weight of isonitroacetophenone.

Example 3 10 g of softwood bleached kraft pulp beaten to a freeness of 550 ml was immersed in 300 ml of a 2% ammonia aqueous solution containing 15% xanthine at room temperature for 2 hours. The pulp that had been soaked was taken out of the liquid and drained for 1 minute under the acceleration of gravity of 900 G. The weight of the impregnated pulp after deliquoring was 40 g. The pulp that had been drained was immersed in 35 ml of a 5% sulfuric acid aqueous solution. After standing for 2 hours in this state, the pulp was taken out from the aqueous sulfuric acid solution. This pulp was allowed to stand in 1 L of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 150 mesh wire. The pulp was loaded with 13.6% by weight of xanthine.

Example 4 10 g of hardwood bleached kraft pulp beaten to 600 ml of freeness was mixed with 6% potassium hydrogen tartrate at a concentration of 10%.
% Aqueous nitric acid solution at room temperature for 3 hours. The pulp that had been soaked was taken out of the liquid and drained for 10 minutes under the acceleration of gravity of 900 g. The weight of the impregnated pulp after deliquoring was 25 g. The pulp that had been drained was immersed in 60 ml of a 2% aqueous potassium hydroxide solution. 3 in this state
After standing for a period of time, the pulp was taken out of the aqueous potassium hydroxide solution. This pulp was allowed to stand in 1 L of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 150 mesh wire. This pulp contained 12.3% by weight of potassium hydrogen tartrate.

Example 5 10 g of unbleached softwood kraft pulp beaten to a freeness of 500 ml was immersed in 200 ml of a 10% aqueous sodium hydroxide solution of terephthalic acid having a concentration of 5% at room temperature for 1 hour. Remove the soaked pulp from the liquid and
The liquid was drained for 15 seconds under a gravitational acceleration of g. The weight of the impregnated pulp after deliquoring was 45 g. The pulp that had been drained was immersed in 90 ml of a 3.5% hydrochloric acid aqueous solution. After standing for 1 hour in this state, the pulp was taken out from the aqueous hydrochloric acid solution. After leaving this pulp in 1 L of distilled water for 1 hour,
It was disintegrated in water with a disintegrator and washed with water on a 150 mesh wire. The pulp was loaded with 6.6% by weight of terephthalic acid.

[0021]

EFFECTS OF THE INVENTION According to the production method of the present invention, it has become possible to efficiently produce a hydrophilic fiber carrying a large amount of organic substances at a low cost by a simple process, which has been conventionally difficult to produce. . Furthermore, the production method of the present invention makes it possible to support and fix a large amount of organic substances not only on the surface of the fiber but also within the substance of the fiber.

Claims (1)

[Claims] 1. A hydrophilic fiber is immersed in an aqueous solution in which an organic compound insoluble or hardly soluble in water is dissolved in an acid or an alkali, and 60 to 400% by weight of the hydrophilic fiber is dipped in the hydrophilic fiber.
And impregnating the hydrophilic fiber containing the aqueous solution with an acid or an alkali to generate and carry an organic compound insoluble or sparingly soluble in water inside and on the surface of the hydrophilic fiber. A method for producing a modified hydrophilic fiber, comprising: