JPH06166958A - Production of modified hydrophilic fiber - Google Patents

Abstract

PURPOSE:To form a water-insoluble or scarcely soluble organic compound metal salt in a hydrophilic fiber and obtain the subject fiber having improved yield of the organic compound in the formation of a sheet. CONSTITUTION:A hydrophilic fiber, especially preferably pulp fiber for paper- making use, is immersed in an aqueous solution containing a water-soluble organic compound (e.g. p-aminoacetophenone, anthranilic acid, 8-quinolinol) reactive with a watersoluble metal salt to form a water-insoluble or scarcely soluble metal salt of the organic compound. After impregnating 60-40% owf of the aqueous solution in the fiber, the fiber is immersed in an aqueous solution containing a metal salt reactive with the organic compound (e.g. sulfate, nitrate, chloride, etc., of Fe, Zn, Cu, Ag, etc.) to form and support a water-insoluble or scarcely soluble organic compound metal salt in the fiber or on the surface of the fiber. A modified hydrophilic fiber having high yield of the organic compound in the formation of a sheet can be produced by this process in high efficiency at a low cost.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for modifying hydrophilic fibers. More specifically, the present invention is to strongly support an organic compound that is insoluble or sparingly soluble in water on the surface of the hydrophilic fiber, the lumen, and the inside of the substance, so that when the sheet is formed, It is a method for producing a modified hydrophilic fiber that improves the yield. 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 of 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 2
Technology for adding metal salts of valency or more (Japanese Patent Publication No. 63-2512)
No. 0) is known, but 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. Technique for generating (Japanese Patent Publication No. 47-84, U.S. Pat.
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 (Tomizaki Norio, Paper and Paper Cooperative Magazine 4
5 (9): 30 (1991), Allan, GG, Balaban, C., et al.Tappi
J. 74 (1): 83 (1991)), but this method
This technique is completely different from the present invention in that an organic solvent is used.

[0005]

DISCLOSURE OF THE INVENTION The present invention modifies a hydrophilic fiber by efficiently and firmly supporting an organic compound having a special function on the hydrophilic fiber to provide an additional function,
For example, the present invention is intended to provide a method for obtaining a hydrophilic fiber which is added with functions such as antibacterial property and antibacterial property and further improves the yield of an organic compound when a sheet is formed.

[0006]

The method for producing a modified hydrophilic fiber of the present invention comprises at least a method of reacting with a water-soluble metal salt to produce a metal salt of an organic compound insoluble or sparingly soluble in water.
60 to 400 of the weight of the hydrophilic fiber is immersed in the first aqueous solution containing the water-soluble organic compound of the species.
% Of the first aqueous solution, and then immersing the hydrophilic fiber containing the first aqueous solution in a second aqueous solution containing a metal salt capable of reacting with the water-soluble organic compound, It is characterized in that a metal salt of the above-mentioned organic compound which is insoluble or hardly soluble in water is produced and carried on the inside and the surface.

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.

As the organic compound used in the present invention,
It is soluble in water having a pH of 2 to 12 and reacts with at least one metal salt to form a salt or chelate precipitate that is insoluble or sparingly soluble in water. Examples of such organic compounds include p-aminoacetophenone, aluminone, anthranilic acid, tetraphenylarsonium chloride, galloyl gallic acid, potassium xanthate,
8-quinolinol, α-quinolinecarboxylic acid, cuperon, sodium 4-chloro-3-methyl-5-nitrobenzenesulfonate, sodium diethyldithiocarbamate, thiourea, sodium tetraphenylborate, thenoyltrifluoroacetone, nitroso R salt , Neocuberone, bismuthiol II, vilogallol, phenylthiohydantoic acid, beryllon II, benzenearsonic acid, gallic acid, 2-mercaptobenzothiazole, trimethylphenylammonium iodide, sodium rhodizonate,
Rhodamine B etc. are mentioned.

The metal salt used in the present invention forms a salt or chelate with the water-soluble organic compound and causes precipitation in the pH range of 2-12.
Examples of such metals include Li, Be, Na, M
g, Al, K, Ti, V, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ge, As, Rb, Zr, N
b, Mo, Tc, Ru, Pd, Ag, Cd, In, S
n, Sb, Te, Ta, W, Os, Pt, Au, Hg,
Tl, Pb, Bi, lanthanoids, Th, U and the like are exemplified, and any of these metal sulfates, nitrates, carbonates, chlorides, hydroxides, etc., which are water-soluble, can be used in the present invention. Can be used.

In the present invention, when the hydrophilic fiber is impregnated with the first aqueous solution containing the water-soluble organic compound, the solution permeates and is retained inside the fiber, and even after the liquid is drained, the aqueous solution remains inside the fiber. To remain. A hydrophilic fiber containing such an organic compound aqueous solution is added to the second layer containing the metal salt.
When it is impregnated with the aqueous solution of, a water-insoluble or sparingly soluble precipitate is formed inside the fiber, and the water-insoluble organic substance is firmly supported on the fiber, and as a result, when a sheet is produced using this fiber, The yield of the contained organic substances is remarkably improved. First containing organic compound used in the present invention
The concentration of each of the aqueous solution and the second aqueous solution containing a metal salt 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 in the first aqueous solution, the more the amount of the organic compound supported by the modified fiber increases. In the step of immersing the hydrophilic fiber in the first aqueous solution and the second aqueous solution, the treatment temperature may be any temperature between the freezing point and the boiling point of the aqueous solution. Also, the time for immersion is not particularly limited.

The amount of the first aqueous solution with which the hydrophilic fibers are impregnated in the impregnating step of the method of the present invention is adjusted to 60 to 400% based on the weight of the hydrophilic fibers. The amount of impregnation is adjusted by removing (delivering) the organic compound from the hydrophilic fiber impregnated with the organic compound. First
There is no particular limitation on the method of deliquoring the hydrophilic fiber material impregnated with the aqueous solution of (1), which is placed on a net and gravity deliquoring, suction deliquoring, centrifugal deliquoring, and press deliquoring. A conventional deliquoring method such as a method can be used. The degree of deliquoring, that is, the impregnated amount of the first aqueous solution affects the amount of the water-insoluble substance supported on the modified fiber.

[0012]

EXAMPLES The present invention will be specifically described below with reference to examples, but the following examples do not limit the present invention. The beating method for pulp in the examples is TAPPI.
It was carried out by the method of 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 softwood bleached kraft pulp beaten to a freeness of 550 ml was immersed in 200 ml of a distilled aqueous solution of anthranilic acid having a concentration of 5% for 2 hours 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 30 g. The pulp that had been deliquored was defibrated by a mixer in air and immersed in a zinc chloride aqueous solution having a concentration of 20% by weight. After standing for 1 hour in this state, the pulp was taken out from the zinc chloride aqueous solution. 1 part of this pulp in 1 liter of distilled water
After being left for a time, it was disintegrated in water with a disintegrator and washed with water on a 150 mesh wire. 8.9% by weight of this pulp
Of zinc anthranilate was supported.

Example 2 10 g of softwood bleached kraft pulp beaten to 450 ml of freeness was immersed in 200 ml of a distilled aqueous solution of anthranilic acid 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 is 32 g
was. The pulp that had been deliquored was defibrated by a mixer in air and immersed in an aqueous nickel sulfate solution having a concentration of 10% by weight. After leaving this state for 3 hours, the pulp was taken out from the nickel sulfate aqueous solution. This pulp was left in 1 liter of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 150 mesh wire. This pulp has 14.
6 wt% nickel anthranilate was supported.

Example 3 10 g of unbleached softwood kraft pulp beaten to a freeness of 550 ml was used as a distilled aqueous solution 2 of cuperone having a concentration of 5%.
It was immersed in 00 ml at room temperature for 3 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 deliquored pulp was defibrated by a mixer in air and immersed in an aqueous solution of iron (III) chloride having a concentration of 5% by weight. After leaving it in this state for 2 hours, the pulp is mixed with iron chloride (I
II) Removed from aqueous solution. This pulp was left in 1 liter of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 150 mesh wire. This pulp has 11.
6 wt.% Cuperon iron was supported.

Example 4 10 g of hardwood bleached kraft pulp beaten to a freeness of 600 ml was immersed in 200 ml of a distilled aqueous solution of galloyl gallic acid having a concentration of 10% for 3 hours at room temperature. 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 is 2
It was 8 g. The pulp that had been deliquored was defibrated by a mixer in air and immersed in an aqueous silver nitrate solution having a concentration of 20% by weight. After leaving this state for 3 hours, the pulp was taken out from the silver nitrate aqueous solution. 1 part of this pulp in 1 liter of distilled water
After being left for a time, it was disintegrated in water with a disintegrator and washed with water on a 150 mesh wire. This pulp was loaded with 12.5% by weight of galloyl silver gallate.

Example 5 10 g of unbleached softwood kraft pulp beaten to a freeness of 500 ml was immersed in 200 ml of a 10% strength 8-quinolinol dilute sulfuric acid aqueous solution at room temperature for 1 hour. 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 30 g. The pulp that had been deliquored was defibrated by a mixer in air and immersed in a copper sulfate aqueous solution having a concentration of 20% by weight. After standing in this state for 1 hour, the aqueous solution was neutralized and left for 1 hour, and then the pulp was taken out from the copper sulfate aqueous solution. This pulp was left in 1 liter 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 18.6% copper 8-oxyquinoline.

Example 6 10 g of unbleached softwood kraft pulp beaten to a freeness of 500 ml was immersed in 200 ml of a dilute sulfuric acid aqueous solution of 8-quinolinol having a concentration of 0.69% for 1 hour at room temperature.
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 30 g. The pulp that had been deliquored was defibrated by a mixer in air and immersed in a copper sulfate aqueous solution having a concentration of 20% by weight. After standing for 1 hour in this state, the aqueous solution was neutralized, and after further standing for 1 hour, the pulp was taken out from the copper sulfate aqueous solution. This pulp was allowed to stand in 1 liter of distilled water for 1 hour, disintegrated in water with a disintegrator, and washed with water on a 150 mesh wire. This pulp has 1.3% 8-
Oxyquinoline copper was supported. Next, using this pulp, a hand-made sheet of 60 g / m ² was prepared by a conventional method. The obtained sheet carried 1.0% copper oxyquinoline and had a yield of 77%. Then, the sheet obtained in the above step is buried in soil and the temperature is adjusted to 2
When left for 8 weeks under conditions of 5 to 30 ° C. and humidity of 30 to 85%, almost no corrosion was observed and there was little discoloration.
It was also extremely easy to remove from the soil.

Comparative Example 1 Copper oxyquinoline powder (2.3% by weight of pulp) was added to a pulp slurry of unbleached softwood kraft pulp beaten to a freeness of 500 ml, and 60 g / m 2 was added according to a conventional method.
^Two handmade sheets were prepared. The obtained sheet has 1.
0% copper oxyquinoline is supported and the yield is 43
%Met. Next, when the sheet obtained in the above step was buried in soil and left for 8 weeks under conditions of temperature of 25 to 30 ° C. and humidity of 30 to 85%, corrosion was observed on the surface of the sheet after 4 weeks and discoloration occurred. Was also observed, but it was easy to remove from the soil. However, after 8 weeks, both corrosion and discoloration were remarkably observed, and it was extremely difficult to take out from the soil.

[0020]

EFFECTS OF THE INVENTION According to the production method of the present invention, it becomes possible to firmly 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. Efficient hydrophilic fibers supporting organic substances,
It becomes possible to manufacture at low cost by a simple process, and further, by making a sheet using this fiber, it becomes possible to remarkably improve the yield of organic substances, and a fiber material having a special function is used. This is a very useful technique in the field.

Claims (1)

[Claims] 1. At least 1 which reacts with a water-soluble metal salt to form a metal salt of an organic compound which is insoluble or sparingly soluble in water.
60 to 400 of the weight of the hydrophilic fiber is immersed in the first aqueous solution containing the water-soluble organic compound of the species.
% Of the first aqueous solution, and then immersing the hydrophilic fiber containing the first aqueous solution in a second aqueous solution containing a metal salt capable of reacting with the water-soluble organic compound, A method for producing a modified hydrophilic fiber, characterized in that a metal salt of the organic compound which is insoluble or sparingly soluble in water is produced and supported on the inside and the surface thereof.