JPS5870800A - Production of anti-bacterial sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a method for producing a bacteriostatic sheet. The present invention relates to a method for producing a fungicidal sheet.

(Technical Background of the Invention) As a bacterium-resistant paper with permanent corrosion resistance, it can be used as agricultural paper such as mulch layer paper, soil-covering paper, seedling paper tube, fruit bag, packaging paper, and paper for building materials. , 8-oxyquinoline and its derivatives are known. (U.S. time, No. 2,
No. 848,842).

This 8-oxyquinoline and its derivatives have cationic properties due to their chemical structure, and have been developed and used as agricultural chemicals. However, because they are not hydrophilic, they are difficult to disperse into fine particles in water, so they are added during the paper-making process. In this case, there are disadvantages of poor dispersion and poor yield. As a way to solve this drawback, we proposed
Paper making method using a solution of 8-oxyquinoline dissolved in a water-soluble solvent such as diethylene glycol monomethyl ether or triethylphosphine (U.S. Patent No. 3)
, 033,865), a method in which polyethyleneimine, dicyandiamide, and a polymeric quaternary amine such as formaldehyde P-condensate are added together during papermaking (US Pat. No. 3,060,079, PT. Kosho 45-
No. 25845), a so-called in-situ method in which an 8-oxyquinoline solution is added to a nor-ξ slurry, and then a metal salt solution is added to form an 8-oxyquinoline metal salt on the nor-ξ to form paper. (Special Publication No. 47-84, U.S. Patent No. 3.=193,464
(specification), introduction of sulfo/group into 8-1,000,000-quinoline 1
2 to solubilize, then add sulfuric acid and sulfuric acid to lye/
A method for producing paper by producing water-insoluble copper 8-oxyquinoline on fibers by the Cyteille method (US Pat. No. 3.71)
3,963) have been proposed, but none of these methods are satisfactory in terms of yield improvement and the bactericidal resistance of the paper produced, and they are expensive. Na8
- Currently, the bacterium resistance of paper is maintained by increasing the amount of oxyquinoline17.

(Objective of the Invention) The object of the present invention is to obtain a germ-resistant sheet in which oki/quinoline, its derivatives, or its salts are fixed on the surface of a fibrous base material mainly composed of cellulose with a good yield. be.

Still another object of the present invention is to provide a highly economical method that uses less oxyquinoline or its derivatives, particularly 8-oxyquinoline or its derivatives, and causes less pollution.

(Structure of the Invention) The present invention provides a method for applying a mixture of humic acid salts and oxyquinoline salts or oxyquinoline derivative salts in water to at least one side of a fibrous base material mainly composed of cellulose. is a method for producing a bacteriostatic sheet characterized by impregnation.

Below, the constituent elements of the present invention will be individually explained in detail.

(Salts of humic acids) In the present invention, the humic acids constituting the salts of humic acids are brown to black amorphous acidic organic substances that are soluble in alkalis and insoluble in acids that exist in soil or coal with a low degree of coalification. Regenerated humic acid, humic acid, especially lignite, which exhibits acidity and is soluble in aqueous alkaline solutions, obtained when coal is gently oxidized using an oxidizing agent such as oxygen or nitric acid.

Nitrohumin is a dark brown amorphous powder obtained when nitric acid is applied to humic acid and hummus of low-carbon coal such as brown coal, together with carbon dioxide, oxalic acid, other volatile acids, and water-soluble aromatic acids. As salts of humic acids, alkali metal salts such as lithium salts, sodium salts, potassium salts, ammonium salts, and alkaline earth metal salts such as magnesium and calcium salts are used. The most common are sodium and ammonium salts.

(oxyquinoline, etc.) Examples of the oxyquinoline and the like used in the present invention include 8-oxyquinoline, 2-oxyquinoline, dibromo-quinoline, etc.
8-oxyquinoline, dichloro-8-oxyquinoline or their salts, such as sulfate, copper salt, zinc salt, aluminum salt, co-solt salt, manganese salt, nickel salt or iron salt, etc. Of these, 8-oxyquinoline steel is preferred. However, these oxyquinolenes can also be used as a mixture of f4.

(Fibrous base material) As the fibrous base material mainly composed of cellulose in the present invention, high-quality paper, kraft paper, newsprint paper, etc., and e-rubber paper are used, but In connection with the use of paper, it is not necessarily limited to the above, but mainly consists of cellulose pulp, natural fibers such as cotton and hemp, rayon, polyvinyl alcohol fibers, chemical fibers such as polyester, polyacrylic roni, trill, etc. It may be a base material containing synthetic fibers such as polyethylene, polypropylene, etc., inorganic fibers such as asbestos, rock wool, and glass fibers. The base material may be paper-like (including paperboard and corrugated paper), or may be non-woven or C cloth-like. It is preferable for these products to be supported on the base material in advance by internally adding, coating, or impregnating a divalent or higher metal salt during production, but in some cases, a mixed solution of amine acid salts, oxyquinoline, etc. After coating the base material, a divalent or higher water-soluble polyvalent metal salt may be coated in the next step. Examples of divalent or higher metal salts that can be chelated with humic acid salts include water-soluble compounds such as iron, tin, zinc, copper, magnesium, calcium, and aluminum, such as sulfates, nitrates, acetates, chlorides, and polyvalent metal salts. It is an organic salt of a metal, and as an organic base (for example, trimethylamine, ethylenediamine, 7f-lyethylenimine, etc. can be mentioned, but in connection with the coating process in the papermaking process, suitable ones are aluminum sulfate or iron sulfate, etc.) (Mixed liquid) In the present invention, salts of humic acids and salts of oxyquinoline or salts of oxyquinoline derivatives are dispersed in water,
The mixture (dispersion) thus obtained is used for coating or impregnation. The solid content concentration in the mixed liquid is l-to
Approximately the amount of w is appropriate. The mixing ratio of humic acid salts and oxyquinoline is approximately 200:1 to 10:l.
It is particularly preferably around 100:1. At this mixing ratio, the fixing property to a fibrous base material mainly composed of cellulose such as oxyquinoline is good.

The above mixed liquid is applied to the frame of the fibrous base material mainly composed of cellulose by 0.5 ml/rr? It is coated and impregnated to a level of ~5 f/ll (in terms of solid content), and then dried. In the above range, the fixability of oxyquinoline and the like on the fibrous base material is good, and the tendency of oxyquinoline and the like to fall off is the lowest. In addition, if more complete adhesion and prevention of falling off are required, add water-soluble polyolefin resin emulsion, modified sBR emulsion, EvA resin emulsion, acrylic resin emulsion, etc. to the above mixture to an extent that does not impair bacterial resistance and properties. May be mixed with

(Operations and Effects of the Invention) Since the salts of humic acids used in the present invention have colloidal properties, they facilitate the dispersion of oxyquinoline and the like in water;
Since the amine acid salt itself is ultrafine particles with a size of angstrom unit, it easily penetrates into the cellulose fiber tissue, and forms an ionic bond with the active group of the cellulose fiber. It is thought that it reacts with the valent metal salt and adsorbs the chelate, and at the same time fixes oxyquinoline and the like on the fiber surface. Furthermore, since the chelate reactant becomes insoluble in water, the obtained base material is imparted with water resistance and oxyquinoline and the like are prevented from falling off.

In addition, humic acid salts permeate and disperse into the cellulose fiber structure, form a metal chelate, and become fixed, so the bond between the cellulose fibers becomes stronger, and at the same time, the spaces in the fiber structure are filled, thereby improving the strength of the paper. It increases tension, strengthens the lower back, and improves pulling strength.

Furthermore, the present invention has the following effects.

■ Since salts of humic acids act as dispersants and fixatives, oxyquinoline and other substances can be prepared as a dispersion with simple stirring operations, and compared to conventional internal addition methods and coating methods, it is still easier to use than impregnation methods. 1. This is an economical method since the amount of oxyquinoline used is extremely small.■ Humic acid salts contain oxyquinoline and stick to the fiber surface, making the product itself insoluble in water, resulting in lower product quality. Since the water resistance is improved, it is advantageous as a bacteriostatic sheet with permanent corrosion resistance for agricultural paper, packaging paper, and paper for building materials.

(2) Since monosalts of humic acids are colored brown to black, the antibacterial sheet according to the present invention is also colored brown to black and has excellent weather resistance and light shielding properties.

(Examples) Examples are shown below to explain the present invention in more detail, but the following examples do not limit the present invention.

Example 1 Sodium salt of aromatic humic acid (C manufactured by Chill Night Co., Ltd.)
HO2) was diluted with water, and 8-oxyquinoline copper (
Manufactured by Organic Synthetic Pharmaceutical Industry Co., Ltd., dust product name "Nikire" C!D
-50J) to cause crosstalk.

At this time, the mixing ratio of the sodium salt of recycled humic acid and the 8-oxyquinoline steel was 100:1 by weight to prepare a mixed solution having a concentration of 5%. Using this adjustment liquid, weighed 45 f/lp? On one side of unbleached kraft paper,
Using a coater, apply the above adjustment solution in a wet amount of 10f/
- It was coated uniformly, placed in a constant temperature hot air dryer at 60°C, and dried for about 1 minute to form a product.

As a comparative sample, a sample treated in the same manner as in Section -F except that the sodium salt of recycled humic acid was not used was produced (
Comparative example 1).

The 6-bacterial paper produced in Example 1 and Comparative Example 1 was stored on the 5th floor of a glass greenhouse belonging to the hand core industry cooperative association, Akabane-machi, Atsumi-gun, Aichi Prefecture.
Example 1: It was used as a cover paper for the roots of a prince melon culture for about 3 months from June 28, 1156 to September 21, 1156, during which time watering and drying were repeated.
No damage or rot was observed in the paper of Comparative Example 1, but the bacterium-resistant paper of Comparative Example 1 showed breakage after about 2 months, and corrosion was observed on the entire surface of the paper after 3 months, making it unsuitable for use as mulch paper. It is no longer possible to use it.

Example 2 Ammonium salt of nitrofumic acid (coN-07 manufactured by Chill Night Co., Ltd.) was diluted with water, and 8-oxyquinoline copper was added to it! The mixing ratio of ammonium salt of nitrofumic acid and copper 8-oxyquinoline at this time was 50:1 by weight to prepare a mixed solution having a concentration of 5%. Using this preparation, weigh 470 j/n?
Apply the above prepared solution to both sides of unbleached kraft paper using an off-machine roll coater in a wet amount of 109/n? Apply it evenly and let it dry to create a finished product.

As a comparative material, a sample was produced in the same manner as above except that the ammonium salt of nitrofumic acid was not used (Comparative Example 2).

The bacteriostatic papers obtained in Example 2 and Comparative Example 2 were buried in fertilized soil with a moisture content of 40%, and after being left at 30° C. for 4 weeks, the weight of the remaining paper was measured. Weight residual rate of paper of Example 2 (
d was 43%, whereas the weight residual rate of the paper of Comparative Example 2 was 26%. From this result, it can be seen that the bactericidal paper of the present invention is superior to the paper of the comparative example.

Out 11ji' 4 people Representative of Oji Paper Co., Ltd. Patent attorney Paige Isaka Husband

Claims (1)

[Claims] It is characterized by applying or impregnating at least one side of a fibrous base material mainly made of cellulose with a mixture of humic acid salts and oxyquinoline salts or oxyquinoline derivative salts dispersed in water. Method for manufacturing a bacteriostatic sheet.