JPS6357559B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a method for producing a bacteriostatic sheet, and more specifically, to a method for producing a bacteriostatic sheet using salts of oxyquinoline or salts of oxyquinoline derivatives. The invention relates to a method of manufacturing.

(Technical Background of the Invention) As a bacterium-resistant paper that has permanent corrosion resistance, it can be used as agricultural paper such as mulch paper, soil-covering paper, seedling paper tube, fruit bag, packaging paper, and paper for building materials. Papers containing 8-oxyquinoline and its derivatives are known. (U.S. Pat. No. 2,848,842). 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, and when added during the papermaking process. has disadvantages of poor dispersion and yield. As a method to solve this drawback, a paper making method using a solution of 8-oxyquinoline dissolved in a water-soluble solvent such as dimethyl sulfoxide, diethylene glycol monomethyl ether, or triethylphosphine (U.S. Pat.
3033865), a method of adding polymer-type quaternary amines such as polyethyleneimine, dicyandiamide, and formaldehyde condensate together during paper making (US Patent No. 3060079, Japanese Patent Publication No. 1973-
25845), the so-called in situ method (Tokuko Sho) in which an 8-oxyquinoline solution is added to the pulp slurry, and then a metal salt solution is added to form the 8-oxyquinoline metal salt on the pulp to make paper. 47-84, U.S. Pat. No. 3,493,464), a sulfone group is introduced into 8-oxyquinoline to make it solubilized, and then copper sulfate and sulfuric acid are added to form a water-insoluble 8-oxyquinoline onto the fiber by an in situ method. −
Methods such as a method of producing paper by producing copper oxyquinoline (U.S. Pat. No. 3,713,963) have been proposed, but all of these methods have problems in terms of yield improvement and the bacterium resistance of the paper. The current situation is that the bactericidal resistance of paper is maintained by increasing the content of 8-oxyquinoline, which is unsatisfactory and therefore expensive.

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

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 or dispersing 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. This 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 soluble in alkalis and insoluble in acids that exist in clay or coal with a low degree of coalification. humic acid, a regenerated humic acid obtained when coal is gently oxidized using an oxidizing agent such as oxygen or nitric acid, and which is soluble in an alkaline aqueous solution; humic acid, especially lignite,
Nitrohumic acid is a cutlet-colored amorphous powder obtained when nitric acid is applied to humic acid and humus in low-carbon coal such as brown coal, along with carbon dioxide, oxalic acid, other volatile acids, and water-soluble aromatic acids. Salts of humic acids include alkali metal salts such as lithium salts, sodium salts, potassium salts, or ammonium salts, as well as magnesium,
Alkaline earth metal salts such as calcium salts are used, but preferred are the sodium and ammonium salts.

(Oxyquinoline, etc.) Examples of the oxyquinoline used in the present invention include 8-oxyquinoline, 2-oxyquinoline, dibrom-8-oxyquinoline, dichloro-
8-oxyquinoline or salts thereof such as sulfate, copper salt, zinc salt, aluminum salt, cobalt salt, manganese salt, nickel salt or iron salt, among which copper 8-oxyquinoline is preferred. be. Furthermore, several kinds of these oxyquinolines can also be used as a mixture.

(Fibrous base material) As the fibrous base material mainly composed of cellulose in the present invention, cellulose pulp paper such as wood-free paper, kraft paper, newsprint paper, etc. is used. However, it is not necessarily limited to the above, but includes synthetic pulp made mainly of cellulose pulp, natural fibers such as cotton and linen, chemical fibers such as rayon, polyvinyl alcohol fibers, polyester and polyacrylonitrile, polyethylene and polypropylene, etc. It may be a base material containing inorganic fibers such as asbestos, rock wool, and glass fibers. The base material may be paper-like (including paperboard and cardboard), nonwoven fabric, or cloth. 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 such as humic acid salts or oxyquinoline may be used. 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. They are organic salts of metals, and examples of organic bases include trimethylamine, ethylenediamine, polyethyleneimine, etc., but aluminum sulfate, iron sulfate, etc. are preferable in connection with the coating process in the papermaking process.

(Mixed liquid) In the present invention, salts of humic acids and salts of oxyquinoline or salts of oxyquinoline derivatives are dispersed in water, and the thus obtained mixed liquid (dispersion) is used for coating or impregnation. The solid content concentration in the liquid mixture is suitably about 1 to 10% by weight. The mixing ratio of humic acid salts and oxyquinoline is in the range of about 200:1 to 10:1, 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 at least one side of the fibrous base material mainly composed of cellulose in an amount of 0.5 g/m ² to 5 g/m ²
(based on solid content) and 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. 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. May be mixed.

(Operations and Effects of the Invention) The salts of humic acids used in the present invention have colloidal properties and thus facilitate the dispersion of oxyquinoline and the like in water, but the salts of humic acids themselves are ultrafine particles with a size of angstrom unit. Therefore, it penetrates well into the cellulose fiber structure, ionically bonds with the active groups of cellulose fibers, and reacts with internally added water-soluble polyvalent metal salts of divalent or higher valence to adsorb chelate, and at the same time, it absorbs oxyquinoline etc. It is also thought that the particles are fixed 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, which strengthens the bonds between the cellulose fibers and at the same time fills the spaces in the fiber structure, thereby increasing the paper's strength. Increases tension, strengthens the waist and improves tensile strength.

Furthermore, the present invention has the following effects.

Since salts of humic acids act as dispersants and fixing agents, oxyquinoline and other substances can be prepared as a dispersion liquid with simple stirring operations, and it is more effective than conventional internal addition, coating, or impregnating methods. This is an economical method as the amount of oxyquinoline used is extremely small.

Humic acid salts, including oxyquinoline, etc., stick to the fiber surface and become insoluble in water, improving the water resistance of the product, so it can be used permanently as agricultural paper, packaging paper, and paper for building materials. It is advantageous as a bacteriostatic sheet with excellent corrosion resistance.

Since salts 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 Regenerated sodium salt of humic acid (CH02, manufactured by Ternite Co., Ltd.) was diluted with water, and 8-oxyquinoline copper (manufactured by Organic Chemical Industry Co., Ltd., trade name "Euchlate CD-50") was added to this. Knead. At this time, the mixing ratio of sodium salt of regenerated humic acid and copper 8-oxyquinoline was 100:1 by weight to prepare a mixed solution with a concentration of 5%. Using this adjustment liquid, use a bar coater to uniformly apply the above adjustment liquid at a wet amount of 10g/m ² to one side of unbleached kraft paper weighing 45g/m ² , and then dry it with constant temperature hot air at 60°C. The product was placed in a container and dried for about 1 minute.

A sample for comparison was produced in the same manner as above except that the sodium salt of regenerated humic acid was not used (Comparative Example 1).

The bacteriostatic papers obtained in Example 1 and Comparative Example 1 were stored in a glass greenhouse belonging to the Agricultural Cooperative Association of Akabane Town, Atsumi District, Aichi Prefecture for approximately three months from June 28, 1980 to September 21 of the same year. When the paper of Example 1 was used as a mulch paper for prince melon cultivation and repeatedly watered and dried, no damage or rot was observed in the paper of Example 1, but the bacterium-resistant paper of Comparative Example 1 was used for about 2 months. After three months, corrosion was observed on the entire surface of the paper, and it could no longer be used as mulch paper.

Example 2 Ammonium salt of nitrofumic acid (CHN-07 manufactured by Ternite Co., Ltd.) is diluted with water, and copper 8-oxyquinoline is added thereto and kneaded. The mixing ratio with copper was 50:1 by weight to prepare a mixed solution with a concentration of 5%. Using this prepared solution, the above prepared solution was uniformly coated on both sides of unbleached kraft paper weighing 70 g/m ² using an off-machine roll coater in a wet amount of 10 g/m ² and dried to obtain a 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. The residual weight of the paper of Example 2 was 43%, while the residual weight of the paper of Comparative Example 2 was 26%. This result shows that the bactericidal paper of the present invention is superior to the paper of the comparative example.

Claims (1)

[Claims] 1. A resistant material 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 producing fungal sheet.