JPS62277303A - Antifungal sterilization - Google Patents

Abstract

PURPOSE:To readily impart sustained sterilizing property to apparatuses, equipment and materials requiring antifungal sterilizing property, by using a specific alginic acid quaternary ammonium salt particularly insoluble or sparingly soluble in water. CONSTITUTION:A solution of an alginic acid quaternary ammonium salt, having each carboxyl residue of D-mannuronic acid and L-guluronic acid which are constituent units of alginic acid expressed by the formula (1-3 of R<1>-R<4> are 1-10C straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group and the residual 1.2 are aralkyl, etc.; the residual 2-3 together with N form a heterocyclic ring) and particularly sparingly soluble or insoluble in water in an organic solvent or a mixture thereof with a small amount of water is applied or impregnated into an object, e.g. apparatus, equipment, etc., in which the antifungal sterilizing property is imparted. The solvent is then removed by a normal means, e.g. vacuum drying, etc., to impart improved antifungal sterilizing property to the above-mentioned object by a simple means.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial field of application This invention uses a quaternary ammonium alginate salt, particularly one that is poorly soluble or insoluble in water and has fungicidal and bactericidal properties, to impart fungicidal and bactericidal properties to objects. Regarding the method of granting.

(b) Various equipment, equipment, and materials used in conventional engineering, industrial, and pharmaceutical use, whether unfilled or exposed, are contaminated by microorganisms, such as mold and harmful bacteria. Deterioration due to proliferation or microorganisms is occurring extensively.

Most of the anti-mold and sterilization methods conventionally used to combat this problem use water-soluble fungicides.
Since disinfectants are eluted by water such as rainwater and are not sufficiently effective in preventing the growth of mold and harmful bacteria, there is a strong need for effective countermeasures.

This invention was made to meet the above-mentioned needs, and is a fungicidal and sterilizing method using quaternary ammonium alginate as described above. The method of the present invention is not disclosed, only what is known.

i) JP-A-59-187001 describes an example of a method for producing a water-insoluble film-like acidic polysaccharide by gently adding an aqueous solution of benzalkonium chloride, a quaternary ammonium compound, to an aqueous solution of sodium alginate. A method is disclosed for forming a water-insoluble thin film of a water-insoluble benzalkonium alginate salt at the interface of the water-insoluble benzalkonium alginate. However, there is no disclosure of a method using a solution of quaternary ammonium alginate salts as in the present invention, and there is no disclosure at all about the solubility of these salts in organic solvents.

b) West German Patent No. 1103336 discloses dimethyl laurylcetylammonium salt, abiethylammonium salt and laurylpyridium salt of alginic acid;
In addition, German Che Abote Power--Zeitzung (DeuL)
sche ApoLheker-Zeitung), Vol. 106, No. 35, pp. 1206-1208, 19
In 1966, a dodenyl dimethyl, 3.4 dichlorobenzylammonium salt of alginic acid was disclosed, but a method similar to the present invention was not disclosed.

(c) Problems to be Solved by the Invention The purpose of the present invention is to easily impart antifungal properties to various devices, equipment, and materials.

(d) Means for Solving the Problems The inventors of the present invention have discovered that a quaternary ammonium salt of alginic acid, which is obtained by reacting a quaternary ammonium compound with excellent fungicidal and bactericidal properties with alginic acid, is sparingly soluble in water. Others are insoluble but soluble in organic solvents such as ethanol, and if the solution is applied to the surface of equipment or equipment, or impregnated into materials, then the solvent is evaporated and removed. The inventors have discovered that it has bactericidal properties and long-lasting properties, leading to the creation of this invention.

This invention is a quaternary ammonium salt of alginate,
D-mannuronic acid and L, which are the structural units of alginic acid
- The carboquino residue of each guluronic acid has the following formula: R1 is an unsaturated aliphatic hydrocarbon group, three of R1 to R' are the above-mentioned hydrocarbon groups, and one is an aralkyl group, a trialkylammonium aryloxyalkyl group, or R1 −
Two of R4 are the above hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R
'-R' is represented by two of the above hydrocarbon groups and the remaining two or three forming a heterocyclic ring with the nitrogen atom, especially quaternary ammonium alginate which is sparingly soluble or insoluble in water. A solution of a salt in an organic solvent or a mixture of an organic solvent and a small amount of water is applied to or impregnated onto the object to be imparted with fungicidal and bactericidal properties, and then the object is treated with fungicidal properties by removing the solvent. The object of the present invention is to provide a fungicidal and sterilizing method that involves imparting bactericidal properties.

Alginic acid is the main component of algin, a natural polysaccharide extracted from seaweed, and has a chemical structure in which D-mannuronic acid and L-guluronic acid are linked in a chain.

Examples of the quaternary ammonium alginic acid salt used in the present invention include those in which the quaternary ammonium group in the above formula is as follows.

i) R'=R' or C2~, respectively. linear or branched saturated or unsaturated aliphatic hydrocarbon groups.

Lauryltrimethylammonium, cetyltrimethylammonium, stearyltrimethylammonium, trioctylmethylammonium, trimethyldistearylammonium, dimethyloleyllinolyl ammonium,
trimethylmonobhenylammonium, methyltrilauryl ammonium groups, etc. 1i) Three of R'=R' are the above-mentioned hydrocarbon groups and one or more of them are aralkyl, trialkylammonium alkyl or aryloxyalkyl groups.

Tetrazonoltzmethylbennolammonium, (trimethylammonium hequinol)trimethylammonium,
(trimethyl-ammoniumdecyl) trimethylammonium [i.e. decamethonium], laurylphenoxydimethylammonium group, etc.

1ii) Two of R'=R' are the above hydrocarbon groups and the remaining two are an aralkyl group and a noalkylphenoquine (or alkylphenoquine) alkyleneoxyalkyl group.

Diisobutylphenoquinethoquinethyldimethylbenzylammonium [i.e., benzethonium], (diisobutyl)methylphenoxyethoxyethyldimethylbenzylammonium group [i.e., methylbenzethonium group], and the like.

iv) One or two of R'-R' is the hydrocarbon group and the remaining two or three form a heterocyclic ring together with the nitrogen atom.

laurylpyridium, cetylpyridinium, laurylisoquinolium, laurylpyridium, laurylpyridium group, etc.

Preferred quaternary ammonium salts of alginic acid used in this invention are lauryltrimethylammonium salt, tetradecyldimethylbenzylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, laurylpyridinium salt, cetylpyridinium salt, and benzethonium salt. , methylbenzethonium salt, laurylphenoxyethyldimethylammonium salt, laurylisoquinolinium salt, etc.

The quaternary ammonium salt of alginic acid used in the present invention can be obtained by contacting and reacting a salt (for example, a metal salt) of alginic acid with a corresponding quaternary ammonium compound in the form of a combined liquid. Filter the precipitate,
Obtained by washing with water and drying under reduced pressure at room temperature.

In particular, it is preferable to add an aqueous solution of a quaternary ammonium compound to an aqueous solution of an alginic acid salt and react with the aqueous solution, and this reaction can usually be easily carried out near room temperature.

It is preferable to introduce the quaternary ammonium compound into the alginic acid in an excessive amount, which is equivalent to the carfoquinol group of the alginic acid to be reacted, in order to obtain a strong antifungal and bactericidal property. The alginic acid used as the raw material for the quaternary ammonium alginic acid salt used in the present invention may be, for example, a commercially available one with a molecular weight of 10,000 to 500,000, and in the case of a salt of alginic acid, sodium salt, potassium salt, etc. Examples include alkaline earth metal salts such as alkali metal salts and calcium salts, but sodium salts are usually preferred.

On the other hand, quaternary ammonium compounds have antifungal and bactericidal properties, and when quaternary ammonium alginic acid salts are formed, they can be used in organic solvents or at least 50% or more. The solvent that dissolves in the aqueous solution is selected.

From these viewpoints, suitable quaternary ammonium compounds include the quaternary ammonium ion in the above formula, halogen ions such as chlorine, bromine, and fluorine ions, and anions such as sulfate ions, nitrate ions, and sulfate ions. Included are bound quaternary ammonium compounds.

The organic solvent used in this invention is preferably one that can be dissolved and has a low boiling point, but it can be selected as appropriate depending on the type and purpose of the quaternary ammonium salt to be dissolved, such as methanol, ethanol, isopropanol, etc. Examples include lower alkyl alcohols such as acetone, toluene, and benzene.

This invention involves applying a solution of the quaternary ammonium alginate salt dissolved in the organic solvent described above to the surface of equipment/equipment that is to be imparted with fungicidal and bactericidal properties, and then applying the solution by a normal method such as vacuum drying. This is carried out either by removing the solvent and forming a film of quaternary ammonium salt on the surface, or by impregnating the material to be imparted with fungicidal and bactericidal properties and removing the solvent in the same manner as above.

The objects on which the coating is applied include the inner walls of pure water containers, the inner walls of bathrooms where mold is likely to grow due to high humidity, and the inner walls of reinforced concrete houses that are particularly susceptible to water droplets in the winter. For example, glass or plastic surfaces may be coated or unpainted. Furthermore, the quaternary ammonium salt itself or the solution described above may be mixed with the paint applied to these surfaces.

The latter can be impregnated with any material that can be impregnated with the organic solvent solution of the quaternary ammonium salt, such as paper, fibers, nonwoven fabrics, leather, sponge, rattan, and wood. Items that are rarely washed or that are difficult to wash, such as futons, tatami mats, wallpaper, wallboards, various sports equipment (balls for volleyball and basketball, gloves for baseball, protective gear for kendo, etc.), furniture such as chests of drawers, etc. Products, porous insulation, filters, books, documents, shoes, etc. will also have anti-fungal properties.

The amount of the quaternary ammonium salt used depends on the desired antifungal and sterilizing properties and is about 0.01 to 30%. Depending on the type of quaternary ammonium salt, a mixture of an organic solvent and a small amount of water may be used as the solvent.

The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

(E) Examples Production of quaternary ammonium salts of alginate To 200 g of an approximately 2% aqueous solution of sodium alginate, approximately 10% aqueous solutions of the following various quaternary ammonium salts equivalent to carboxyl groups were added at room temperature and stirred.

The generated precipitate was filtered, thoroughly washed with water, and then vacuum dried at room temperature to obtain each quaternary ammonium alginic acid salt.

1) Sodium alginate used Kamogawa Kasei Duck Algin NSPM 2) Quaternary ammonium compound used Dodenyltrimethylammonium chloride Tetradenyldimethylbenzylammonium chloride Cetylpyridinium chloride Benzethonium chloride Methylbenzethonium chloride The following table shows the solubility in solvents.

(Left below) Bactericidal test A bactericidal test was conducted on each quaternary ammonium alginate salt produced in the first production example.

0.25 each of each alginate quaternary ammonium salt
Dissolve g in 3 mQ of methanol and make an inner diameter of 18 mm.
A film of quaternary ammonium alginic acid salt was formed in the test tube by flowing the mixture so as to form a uniform thin film on the inner surface of a glass test tube having a length of 180 mm, and methanol was distilled off under reduced pressure. A sterilization test was conducted using the test tubes thus obtained and blank (untreated) test tubes. i.e. 10
'/mQ Escherichia coli (Escherichia coli)
A coli) solution was put into a test tube, and the number of bacteria was measured 30 minutes later by the agar plate dilution method. In the case of no treatment, there was almost no change in the number of bacteria. The number of bacteria on the coated samples is as follows.

Bacterial count tetradeci, gong methylbenclammonium salt
O Dodecyltrimethylammonium salt O Cetyl bilinonium salt
O bacteria count benzethonium salt
0 methylbenzethonium salt
0 Mildew Resistance Test 1 The following acrylic emulsion paint was coated on a 3 cm square board made of straight material.The paint surface of the test piece was coated with about 10% of the tetradecyldimethylbenzyl ammonium alginate obtained in the above production example. A methanol solution was sprayed overnight, and then the methanol was evaporated to form a film of the quaternary ammonium alginic acid salt.

A mildew resistance test was conducted using two test pieces: this test piece and a blank without a quaternary ammonium alginate coating. That is, a test piece was placed in the center of a potato dextrose agar medium, and Aspergillus n!ger A
TCC6275, Aspergillus flavus (Aspe
rgillus flavus) ATCC9643, Penicillium lu
teum) ATCC9644, Tricoble? (Tri
choderma) T-I ATCC9645 @ suspension (J[S Z-29LL, 1981i
, , prepared accordingly) was spray inoculated and cultured at 30°C.

As a result, as shown in the following table, no mold growth was observed on the paint surface coated with quaternary ammonium alginate.

1) No mold growth was observed on the heather surface 2.
I think there is a slight growth of mold in 3: 1 of 3
/3 Mold growth observed 4 〃 Mold growth observed on 273 of 5:〃 Preparation of paint with mold growth observed on the entire surface. It is prepared by adding additive clay, talc, sodium tripolyphosphate, surfactant, etc. to make a paint stock solution, and adding pigment and paste to this.

Mold Resistance Test 2 Mold resistance test method (
A mold resistance test was conducted according to JIS Z-2911-1981).

The ammonium salt was prepared as a methanol solution at 50 m m
It was impregnated into a 50mm x 50mm numb paper and then dried to prepare the samples shown in Table 1.

Place the sample on a plate medium, and place the mold spores @fA on top.
1 mC of the solution was evenly sprayed on the plate, the plate was covered with a lid, and the plate was incubated at 30°C twice. The results obtained and the method of expressing mold resistance are shown in Tables 2 and 3, respectively.

The spore suspension was made using potato dextrose cold 0.00
It was obtained by dispersing it in sterile water supplemented with 5% dioctyl sodium sulfosuccinate.

The composition of the plate medium is as follows.

Purified water 100100O, potassium chloride [1.25g
.

Ammonium nitrate 3.0g.

Ferrous sulfate 0.002g, potassium phosphate 1.0
g agar 25g and magnesium sulfate 0.5g.

(The following margins continue on the next page) Table 1 Table 2 Mold resistance test results Table 3
It is possible to easily impart time-honored anti-fungal and sterilizing properties to vessels, equipment and materials.

Claims (1)

[Claims] 1. A quaternary ammonium salt of alginic acid, in which the carboxyl residues of D-mannuronic acid and L-guluronic acid, which are the constituent units of alginic acid, have the following formulas: ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 to R^4 are C_1_-_2_
0 is a linear or branched saturated unsaturated aliphatic hydrocarbon group, or three of R^1 to R^4 are the above-mentioned hydrocarbon groups and one is an aralkyl group or a trialkylammonium alkyl group. is an aryloxyalkyl group, or two of R^1 to R^4 are the above hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R^1 to One or two of R^4 is the above-mentioned hydrocarbon group and the remaining two or three form a heterocyclic ring with the nitrogen atom. A solution of an organic solvent or a mixture of an organic solvent and a small amount of water is applied to or impregnated onto the object to be imparted with fungicidal and bactericidal properties, and then the solvent is removed to impart fungicidal and bactericidal properties to the object. A fungicide-preventing sterilization method consisting of imparting.