JPS62281805A - Mildew-proofing fungicidal process - Google Patents

Abstract

PURPOSE:To easily impart durable mildew-proofing fungicidal activity to an object to be treated, by coating the object with an active component comprising a solution of a specific quaternary ammonium salt of a carboxymethylcellulose hardly soluble or insoluble in water and soluble in an organic solvent. CONSTITUTION:A quaternary ammonium salt of a carboxymethylcellulose expressed by formula I [R is H or quaternary ammonium salt of carboxymethyl group; n is 10-1,000; the substitution degree of carboxymethyl group per one glucose anhydride unit is 1.5-3.0; the quaternary ammonium salt of carboxymethyl group is expressed by formula II (R<1>-R<4> is 1-20C straight or branched saturated or unsaturated aliphatic hydrocarbon group or three of R<1>-R<4> are said hydrocarbon group and one is aralkyl, trialkylammonium alkyl, etc.] and especially hardly soluble or insoluble in water is dissolved in an organic solvent or in a mixture of an organic solvent and a small amount of water. The obtained solution is applied to an object by coating or immersion and the solvent is removed from the applied solution.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field This invention relates to the use of quaternary ammonium salts of carboxymethylcellulose (hereinafter abbreviated as CMC), which has a high degree of substitution of carboxymethyl groups per anhydroglucose unit, especially in water. The present invention relates to a method of imparting fungicidal and bactericidal properties to an object using a poorly soluble or insoluble material that has fungicidal and bactericidal properties.

(b) Conventional technology - Various devices, equipment, and materials for household, industrial, and medical use, whether inorganic or organic, are contaminated by microorganisms, such as the growth of mold or harmful bacteria, or microorganisms. Deterioration is occurring over a wide range of areas.

Most of the anti-mold and sterilization methods conventionally used to combat this problem use water-soluble fungicides.
Since disinfectants are leached out 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 satisfy the above-mentioned needs, and is a fungicidal and sterilizing method using CMC quaternary ammonium salt. is known, but the method of the present invention is not disclosed.

That is, Antibacterial and Antifungal, Vol. 7, No. 11, pp. 7-14,
1979, and the same magazine, Volume 12, No. 11, No. 5
pp. 61-571, 1984, using CMC as a carrier, quaternary ammonium compounds benzalkonium chloride, cetyltrimethylammonium bromide, cetylpyridinium chloride, laurylpyridinium chloride, dimethylphenylbenzylammonium chloride, tetradecyldimethyl Although it has been disclosed that benzyl ammonium chloride is immobilized and sterilized by passing a liquid through the layer of the obtained immobilized product, C.
Methods using MC quaternary ammonium salts are not disclosed.

Furthermore, West German Patent No. 1.103,336 discloses dimethyl laurylcetylammonium salt of CMC, and U.S. Patent No. 2
, No. 881,074 discloses that CMC trimethyloctadecylammonium salt, Q eutsche A pothek
er-zeituna), No. 106 JJ, No. 35, pp. 1206-1208, C-IC in 1966.
Dodecyldimethyl(3,4-dichlorobenzyl)ammonium salt,
harm, Ind, ).

Volume 37, No. 2, Page 100, CM in 1975
C cetyltrimethylammonium salts are each disclosed. However, these documents do not even suggest the method of the present invention.

These quaternary ammonium salts of CMC are used for applications that utilize the properties of CMC as a soluble polymer substance and the properties of the quaternary ammonium group. However, CMC, which is the raw material for these CMC quaternary ammonium salts, does not specifically describe the degree of conversion of carboxymethyl group per anhydroglucose unit (hereinafter abbreviated as DS), so generally commercially available DS
is considered to be less than 1.0. Since the quaternary ammonium group is bonded at the carboxymethyl ratio of CMC, the number of quaternary ammonium groups that can be introduced is less than 1.0 molecules per glucose unit, and the characteristics of the quaternary ammonium group, which is higher than this, can be utilized. Can not do it. These conventional CMC quaternary ammonium salts are generally water-soluble (insoluble in organic solvents) when the molecular weight of the quaternary ammonium group is small, but become water-insoluble when the molecular group of the quaternary ammonium group becomes large. It also does not dissolve sufficiently in polar solvents such as alcohol and acetone, or in non-polar solvents such as triene. Therefore, it is difficult to use it as a solution of a solvent.

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

(2) Means and effects for solving problems with conventional low D
As mentioned above, CMC quaternary ammonium salt using CMC of S is difficult to use as a solution in an organic solvent, but the inventors of the present invention found that it has a high A quaternary ammonium salt of CMC of OS, which has a particularly high fi
This invention was accomplished by finding something that is soluble or insoluble in water but soluble in organic solvents.

Thus, this invention has the following formula: [wherein R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000.

However, the degree of substitution of the carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of the carboxymethyl group is D[formula: (wherein, R1-R4 are each of Cl-2a It is a linear or branched saturated or unsaturated aliphatic hydrocarbon group, or three of R1 to R4 are the above hydrocarbon groups and one is an aralkyl group, trialkylammonium alkyl, or aryloxyfurkyl group, or RL -, -R'
two of the above hydrocarbon groups and the remaining two are auroxy and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or R1-
One or two of R4 is the hydrocarbon group, and the remaining two or three form a heterocyclic ring with the nitrogen atom)]
Applying a solution of carboxymethylcellulose quaternary ammonium salt, which is expressed as n-soluble or insoluble in water, in an organic solvent or a mixture of an organic solvent and a small amount of water to the object to be imparted with fungicidal and bactericidal properties. The object of the present invention is to provide a fungicidal and sterilizing method, which comprises imparting fungicidal and sterilizing properties to the object by removing the solvent after soaking or impregnating the object.

Examples of the C-IC quaternary ammonium salt used in this invention include those in which the quaternary ammonium group in the formula 01 is as follows.

(i) RL-R' is a linear or branched saturated or unsaturated aliphatic hydrocarbon group each having C1-2°.

lauryltrimethylammonium, cetyltrimethylammonium, stearyltrimethylammonium, trioctylmethylammonium, dimethyldistearylammonium, dimethyloleyllinolyl ammonium,
Trimethylmonobhenylammonium, methyltrilauryl ammonium groups, etc. 0) Three of R1 to R4 are the above hydrocarbon groups and one is an aralkyl, trialkylammonium alkyl, or aryloxyalkyl group.

Tetradecyldimethylbenzylammonium, (trimethylammoniumhexyl)trimethylammonium,
(trimethyl-ammoniumdecyl)trimethylammonium [i.e. decamethonium], laurylphenoxydimethylammonium, etc. @ Two of R1-R' are the above hydrocarbon groups and the remaining two are aralkyl groups and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups something that is.

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

(f) One or two of R″ to R4 are the above hydrocarbon groups, and the remaining two or three form a heterocyclic ring together with the nitrogen atom.

laurylpyridinium, cetylpyridinium, laurylisoquinolinium, laurylpyridinium, laurylquinalsium group, etc.

Preferred quaternary ammonium salts of C to IC used in this invention are lauryltrimethylammonium salt, tetradecyldimethylpendylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, laurylpyridinium salt, cetylpyridinium salt, and benzethonium salt. salts, methylbenzethonium salts, laurylphenoxyethyldimethylammonium salts, laurylisoquinolinium salts, etc.

The CMC quaternary ammonium salt used in this invention consists of a solution of carboxymethylcellulose or a salt thereof having a degree of substitution by carboxymethyl groups per anhydroglucose unit of 1.5 to 3.0, and a corresponding quaternary ammonium compound or a solution thereof. It is produced by mixing and reacting the carboxymethylcellulose quaternary ammonium salt and purifying the resulting carboxymethylcellulose quaternary ammonium salt.

CMC used as a raw material for the CMC quaternary ammonium salt used in this invention needs to have a DS of 1.5 to 3.0 in view of the solubility of the quaternary ammonium salt in organic solvents. Such CMC having a high degree of substitution can be produced by, for example, the multistage etherification method described in JP-A-58-176202.

For CMC, an alkali metal salt such as sodium salt or potassium salt is usually used. Alkaline earth metal salts such as calcium salts, acid forms, and partially acid forms can also be used, but the sodium salt is most preferred.

-5 The quaternary ammonium compound must have antifungal and bactericidal properties.
When forming a quaternary ammonium salt of CMC of 0, m solvent or at least 5
A material that dissolves in an organic solvent solution of about 0% or more is selected.

From these viewpoints, suitable quaternary ammonium compounds include the quaternary ammonium ion in the above-mentioned sub-formation, halogen ions such as chlorine, bromine, and fluorine, @ acid ions, [
Examples include quaternary ammonium compounds bound to 1 ion and anions such as phosphate ions.

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

In the present invention, a solution of CMC quaternary ammonium salt as described above dissolved in an organic solvent as described above is applied to the surface of equipment/equipment to be imparted with fungicidal and bactericidal properties, and then the surface is dried by regular methods such as vacuum drying. This can be carried out 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 sterilizing properties and removing the solvent in the same manner as above.

The objects on which the curator applies the paint to form a film include the inner walls of pure water containers, the inner walls of bathrooms that are prone to moisture and mold, and the inner walls of reinforced concrete houses that are prone to water droplets, especially in the winter. Painted or unpainted surfaces, such as glass or plastic surfaces, may be mentioned. Furthermore, the quaternary ammonium salt itself or the solution described above may be mixed with the paint applied to these surfaces.

Examples of the materials to be impregnated with the latter include all materials that can be impregnated with the organic solvent solution of the quaternary ammonium salt, such as paper, fibers, nonwoven fabrics, leather, sponges, carpets, and wood. Also, items that are not washed often or 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.), chests of drawers, etc. Furniture, porous insulation, filters, books/documents, shoes, etc. will also have anti-fungal properties.

The content of the quaternary ammonium salt in the solution depends on the desired fungicidal and bactericidal properties, but is usually about 0.01 to 30%. Depending on the type of quaternary ammonium salt, a mixture of an organic solvent and 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) Example CMC quaternary ammonium field Production example 1 1% aqueous solution of various CMC sodium salts as shown below 20
0g, each f' shown in Table 1 below in excess of 10% from the current amount
! Quaternary ammonium (arsenic compound) was added and stirred for 1 second.

The formed precipitate was filtered, thoroughly washed with water, and then vacuum dried at room temperature to obtain each CMC quaternary ammonium salt.Table 1 shows the solubility of these products.

Note that the CMC quaternary ammonium salt prepared in the same manner as above using dimethyl distearyl ammonium chloride as the quaternary ammonium compound has a CMC DS of 2.
In the case of No. 84, it was soluble in hydrocarbons such as benzene.

(1) CMC sodium field DS used Polymerization degree 1% aqueous solution viscosity (C1)S) 1.27 10
00 17521.37 1000
1724-1.46 1050 -182
01.50 1100 20001.58
980 16001.94 5
50 2762.41480 203 2.84 250 84 (margin below,
Continued on next page) CMC quaternary ammonium salt production example 2 To 200 g of a 1% aqueous solution of CMC sodium salt of manure,
Equivalent amounts of aqueous solutions of various quaternary ammonium compounds listed below were added and quenched. The generated precipitate was filtered, thoroughly washed with water, and then vacuum dried at room temperature to obtain each CMC quaternary ammonium salt. The solubility of these products is shown in Table 2. Both were insoluble in water but soluble in lower alcohols.

(1) CMC sodium salt DS used Degree of polymerization 1% aqueous solution layer (cps) 2.41 700
610(n) Quaternary ammonium compounds used Benzethonium chloride Methylbenzethonium chloride Cetylpyridium chloride (Continued in the margin below, next page) Example VA1 [) By the reaction of the CMC sodium salt of 32.15 with tetradecyldimethylpenzyl ammonium chloride The following experiment was conducted using the obtained CMC-tetradecyldimethylbenzyl ammonium salt.

CMC-tetradecyldimethylbenzyl ammonium salt 0.25g 31! Dissolved in methanol with an inner diameter of 18M.
, to form a uniform thin film on the inner surface of a 180 mm long glass test tube, and methanol was distilled off under reduced pressure to form a film of CMC-tetradecyldimethylbenzyl ammonium salt on the inner surface of the test tube. Antibacterial tests were conducted using the test tubes thus obtained and blank (untreated) test tubes. That is, a suspension of various bacteria at a fixed concentration was placed in a test tube, and the number of bacteria was measured 30 minutes later. The results are shown in Table 3.

(Margins below, continued on next page) Example 2 The CMC-tetradecyldimethylbenzyl ammonium salt obtained in Example 1 was dissolved in methanol, and after uniformly coating the inner surface of a 2ρ glass container, the methanol was distilled off under reduced pressure. A film was formed. 1Q of ion-exchanged water was added to this glass container and the same untreated glass container (blank), and the containers were left in a 30° C. incubator, and the number of native plants in the water was determined by the agar plate dilution method using a standard agar medium. As shown in the results shown in Table 4, water in a glass container whose inner surface was coated with CMC-quaternary ammonium salt was able to repeatedly maintain sterility over a long period of time.

(The following margins are continued on the next page) Table 4 Example 3 The paint surface of a test piece obtained by temporarily applying acrylic emulsion paint to a 3A11 square board made of straight steel was coated with C~ obtained in Example 1. A film of CMC quaternary ammonium salt was formed by spraying a solution of IC-tetradecyldimethylbenzyl ammonium in methanol and evaporating the methanol.

A mold resistance test was conducted using two test pieces: this test piece and a blank on which no CMC quaternary ammonium salt coating was formed. That is, a test piece was placed in the center of a potato dextrose agar medium, and Aspergillus niger (A 5per (li I 1usniqer)
ATCC6275, Aspergillus fu77'),
(Asl)erQillus rlaVus > AT
CC9643, Penicillium luteum (penic
iI liumluteum ) ATCC9644
, Trichoderma T-1A
Spray inoculation with four types of mold spore suspension of TCC9645,
After culturing at 30°C, the growth state of the mold was measured by iA. As a result, as shown in Table 5, no mold growth was observed on the paint surface coated with the CMC quaternary ammonium field.

5 Table 1: No mold growth observed on the test piece surface 2: Slight mold growth observed on the test piece surface 3: Mold growth observed on 1/3 of the test piece surface 4: Test piece Mold growth is observed on 2/3 of the surface 5: Mold growth is observed on the entire surface of the test bead Preparation of paint; Add a thickener to an acrylic emulsion consisting of 70 parts of ethyl acrylate and 30 parts of methyl methacrylate. , clay, riluc, sodium tripolyphosphate, a surfactant, etc. were added to prepare a paint stock solution, and a pigment paste was added to the stock solution.

Example 4 Tetradecyldimethylbenzylammonium salt and dodecyltrimethylammonium salt of CMC obtained by reaction of CMC sodium salt of [)32.15 with tetradecyldimethylbenzylammonium chloride and dodecyltrimethylammonium chloride and C of O82,41
The following experiment was conducted using cetylpyridinium salt, benzethonium salt, and methylbenzethonium salt of CMC obtained by the reaction of MC sodium salt with cetylpyridinium chloride, benzethonium chloride, and methylbenzethonium chloride.

Dissolve 0.25Q of the quaternary ammonium salt of the above CMC in 31 mm of methanol, and prepare a powder with an inner diameter of 18 mm and a length of 180 mm.
CM was poured so as to form a uniform thin film on the inner surface of a mm glass test tube, and methanol was distilled off under reduced pressure.
A film of C4 ammonium salt was formed on the inner surface of the test tube. Antibacterial tests were conducted using the test tubes thus obtained and blank (untreated) test tubes.

In other words, 10a/1! Elysia coli (E.
5 Cherichia coli) solution was placed in a test tube, and the number of bacteria was measured 30 minutes later.

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.

1-2 [CMC Tetradecyldimethylbenzyl ammonium salt Okotsu 110MC
Dodecyltrimethylammonium salt 00MC cetylpyridinium salt 00MC benzethonium salt
00MC Methylbenzethonium [0 Example 5 CMC obtained in CMC quaternary ammonium salt production example
Mold resistance test method (J Is Z-2911-198+) for tetradecyldimethylbenzylammonium salt of (DS 2.41) using the following two types of molds
A mold prevention test was conducted in accordance with .

The ammonium salt was dissolved in ethanol at 50 mm
A 50 mm filter paper was impregnated and dried to prepare the samples shown in Table 6.

Place the sample on a plate medium and pour the mold spore suspension 11! ItJ evenly! The cells were incubated with a lid at 30°C for 2 hours. The results obtained and the method of expressing the mold resistance are shown in Tables 7 and 8, respectively.

The spore suspension was obtained by culturing the test bacteria on a potato dextrose agar slant medium and dispersing the resulting spores in sterile water supplemented with 0.005% dioctyl sodium sulfosuccinate.

The composition of the plate medium is as follows.

Purified water 10 Q Q y! Potassium chloride o, 2 sg Ammonium nitrate 3.09 @ferrous acid o, oo 2 g Potassium phosphate 1.0 g Agar 250 Magnesium sulfate o, sg Table 6 (The following margins continue on the next page) Table 7 Resistance to mold paper Test results (below margins, continued on next page) Table 8 Method of displaying test results (f) Effects of the invention

Claims (1)

[Claims] 1. The following formula: ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000. However, the degree of substitution of the carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of the carboxymethyl group has the sub-formula: ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, R ^1~R^4 are respectively C_1_-_2_
0 linear or branched saturated or unsaturated aliphatic hydrocarbon groups, or three of R^1 to R^4 are the above hydrocarbon groups and one is an aralkyl group, trialkylammonium alkyl, or aryloxy is an alkyl group, 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 R^4 one or two of which are the hydrocarbon groups and the remaining two or three form a heterocyclic ring with the nitrogen atom)], in particular of carboxymethyl cellulose quaternary ammonium salts that are sparingly soluble or insoluble in water, A solution of an organic solvent or a mixture of an organic solvent and a small amount of water is applied or impregnated onto an 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.