JPH01254605A - Antibacterial composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent compatibility and forming a film having high strength, by reacting a quaternary ammonium salt with a homopolymer or copolymer of acrylic acid or methacrylic acid and using the resultant polymer quanternary ammonium salt as an active component. CONSTITUTION:The objective antibacterial agent contains, as an active component, at least one kind of a polymer quaternary ammonium salt (e.g., polyacrylic acid tetradecyl dimethylbenzyl ammonium salt) which is a reaction product of (A) a homopolymer or copolymer of acrylic acid or methacrylic acid (the polymerization degree is preferably 50-20,000) and (B) a compound of formula (R<1>-R<4> are aliphatic hydrocarbon groups; three of them are aralkyl, trialkylammoniumalkyl, etc., or each two of the groups form a ring; X is halogen). The composition has excellent compatibility with another resin to be used as a component of an antibacterial composition, has arbitrarily controllable polymerization degree and is hardly soluble or insoluble in water and soluble in organic solvent.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention relates to an antibacterial composition containing a polymeric quaternary ammonium salt as an active ingredient. The present invention relates to an antibacterial composition containing at least one quaternary ammonium salt as an active ingredient.

(b) Conventional technology and issues Quaternary ammonium compounds (such as tetradecyldimethylbenzylammonium chloride) formed by combining quaternary ammonium ions and acid groups are used as antibacterial agents that have bactericidal and antifungal properties. Are known. However, when these compounds are used as active ingredients in antibacterial compositions that have bactericidal and antifungal properties, many of these compounds are water-soluble, so they should not be used particularly in areas with high humidity or rainwater. Not suitable for use.

On the other hand, carboxymethyl cellulose (CM C
) are known as quaternary ammonium salts. That is, dimethyl laurylcetylammonium salt (West German Patent No. 1,103)
, 336), trimethyloctadecylammonium salt (U.S. Pat. No. 2,881,074), dodecyldimethyl(3,4-dichlorobenzyl)ammonium salt [De
ut, Apotheker Ztg, 106(35),
1206-8 (1966) Tetradecylpyridium Salt and Cetyltrimethylammonium Salt E Phar
m.

IndJ7. (2), 100 (1976)].

These quaternary ammonium salts are sparingly soluble or insoluble in water and soluble in organic solvents, but because they are cellulose derivatives, they have a unique hygroscopic property, and the strength of the film they form is weak, making it difficult for them to interact with the resin in the pond. Due to poor compatibility, it is difficult to use it as an active ingredient in antibacterial compositions. In addition, CMC has a narrow controllable degree of polymerization, and the range is 50
~3,000, but industrially it is generally 200 to 1,000, which has the disadvantage of narrowing the range of antibacterial compositions that can be produced using this.

(c) Means and effects for solving the problems This invention was made to improve the above problems, and includes a homopolymer or copolymer of acrylic acid or methacrylic acid,
A quaternary ammonium salt R1 represented by the following formula (wherein R'-R' is a straight-chain but branched saturated or unsaturated aliphatic hydrocarbon group of C+-Z, respectively; Three of R1 to R4 are the above-mentioned hydrocarbon groups, and one is an aralkyl group, a trialkylammonium alkyl group, and an arylokynealkyl group, or R'4
Two of R' are the hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy)alkyleneoxyalkyl groups, or two of R1 to R4 are likely the hydrocarbon groups. The remaining two are likely to form a heterocyclic ring with a nitrogen atom, and The present invention provides an antibacterial composition characterized by containing the antibacterial composition as an ingredient. The polymeric quaternary ammonium salt, which is the active ingredient of this composition, forms a strong film, has excellent compatibility with other resins used as a component of the antibacterial composition, and allows the degree of polymerization to be controlled arbitrarily. It is sparingly soluble or insoluble in water and soluble in organic solvents.

The polymer compound used in the production of the polymeric quaternary ammonium salt, which is the active ingredient of the present invention, is an alkali metal salt, such as a sodium salt, of a homopolymer or copolymer of acrylic acid or methacrylic acid. The term "copolymer" refers to a copolymer of acrylic acid and methacrylic acid, a monomer copolymerizable with these monomers, and a copolymer of the seven monomers mentioned above. Examples of monomers that can be copolymerized with methacrylic acid, such as acrylic acid, include methacrylic acid alkyl esters, acrylic acid alkyl esters, vinyl acetate, vinyl chloride, acrylonitrile, and styrene.

On the other hand, the quaternary ammonium compound used in the production of the polymeric ammonium salt of the active ingredient of the present invention is such that the quaternary ammonium group in the above formula is the following group, and x'-1 is chlorine, bromine, or fluorine. Examples of such ions include halogen ions, sulfate ions, nitrate ions, and phosphate ions.

(i) R'=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 group, etc. (ii) Three of R' to R4 are the above-mentioned hydrocarbon groups, and one is an aralkyl group, and the trialkylammonium alkyl group is an arylokynerualkyl group.

Tetradecyldimethylbenzylammonium, (trimethylammoniumhexyl)trimethylammonium,
(trimethyl-ammoniumdecyl) trimethylammonium [i.e. decamethonilamco, laurylphenoxydimethylammonium group, etc.

(iii) Two of R'=R' are the above-mentioned hydrocarbon groups, and the remaining two are an aralkyl group and dialkylphenoxy (
or an alkylphenoxy)alkoxyalkyl group.

(p-1,1,3,3-tetramethylbutylphenoxy)ethoxyethyldimethylbenzylammonium], (methyl(p-1,1,3,
3-tetramethylbutylphenoxy)ethoxyethyldimethylbenzylammonium group [i.e., methylbenzethonium group, etc.

(iv) One or two of R' to R' are the above-mentioned hydrocarbon groups, and the remaining two, probably three, form a heterocyclic ring together with the nitrogen atom.

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

The polymeric quaternary ammonium salt used in the present invention can be obtained by reacting an alkali metal salt, such as a sodium salt, of the above-described polymer with a corresponding quaternary ammonium halide in approximately equimolar amounts in an aqueous solution. In addition, as an alkali metal salt of polyacrylic acid, polymethacrylic acid, or a copolymer thereof, the degree of polymerization (osmotic pressure method) is about 50 to 2.
0,000 can be used. Note that this degree of polymerization is appropriately selected depending on the use of the antibacterial composition.

The product of the above reaction is sparingly soluble or insoluble in water,
The reaction results in a precipitate. This precipitate is filtered, for example, and purified if necessary. Purification can be carried out by simply washing with water or using an organic solvent containing a small amount of water (approximately 10% or less) (e.g., lower alcohols such as ethanol, isopropanol, ketones such as methyl isobutyl ketone, benzene derivatives such as xylene, etc.). This can be done by reprecipitation method by dissolving and adding water.

The antibacterial composition of this invention can be used in articles such as textile products (interiors such as carpets and curtains, clothing such as socks, gloves, and work clothes), building materials (floors, wall materials, etc.), and sheet materials (tents, campuses, etc.). It can be used to impart antibacterial properties.

The composition of the present invention can be used by coating or impregnating the above articles, and the composition may be in the form of a solution, paste or emulsion. For example, a composition for coating an article may include one in which the active ingredient of the present invention is dissolved in an organic solvent and a binder is added thereto. When such a composition is applied to the surface of an article or impregnated into the article and then the solvent is removed, the active ingredient remains on the surface of the article and exhibits antibacterial properties.

The solvent used in the composition of the present invention is appropriately selected from those that dissolve the quaternary ammonium salt used, and includes lower alcohols such as methanol, ethanol, propatool, isopropanol, isobutylene alcohol, A mixture of a small amount of water (approximately 10% or less) with an organic solvent such as acetone, methyl ethyl ketone, dimethyl sulfoxide, benzene, xylene, or chloroform is used.

As the binder used in this invention, it is generally preferable to use one having low compatibility with the above-mentioned active ingredients, and the following may be mentioned.

Thermoplastic resins such as polyvinyl acetate, polyacrylic acid ester, vinyl acetate-acrylic acid copolymer, polyethylene, polypropylene, polystyrene, cellulose acetate, etc., plasticizer-containing polyvinyl chloride, synthetic rubber butadiene styrene rubber (SBR), nitrile Butadiene rubber (NBR)
There are thermosetting resins such as epoxy resin, phenol/formaldehyde resin, and melamine/formaldehyde resin.

Furthermore, depending on the intended use, additives may be added to the composition of the present invention in addition to the above-mentioned three components (for example, pigments in the case of paint).

The antibacterial compound is used in an amount sufficient to impart antibacterial properties to the article. For example, when coating the surface of an article, the antibacterial compound is used in an amount of about 0.1 to 15.0% by weight of the composition. It will be done.

(d) Examples The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 18.8 g of sodium polyacrylate with a degree of polymerization of 300 (
0.2 moυ in 1 g of separable 3-day flask
0112 was added to water and heated and stirred to completely dissolve at 40°C. Separately, an equivalent amount of various quaternary ammoniums shown in Table 1 below was dissolved in 370 Mura water, and this aqueous solution was gradually added to an aqueous sodium polyacrylate solution while stirring,
The mixture was stirred for 30 minutes.

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

Table 1 shows the solubility of these products in solvents and their compatibility with resins.

Elemental analysis results, infrared absorption spectra, and 'HNM of the obtained polyacrylic acid tetradecyldimethylbennolammonium salt and polyacrylic acid penzethonium salt.
The main absorptions of the R spectrum are as follows.

(i) Polyacrylic acid-tetradecyldimethylbenzylammonium salt! R (KBr): 3400,286
0~2930.1570.1450.1400.730
and 707 cm-'' II-NMR (ppm) + 0.9 (9), 1.3
(D, 1.85(e), 2.2-2.7(d).

3.1-3.35(c), 4.6(b), 4.95(H
zO), and 7.5-7.6(a)(ii) Polyacrylic acid-benzethonium salt IR (KBr): 340
0.2860~3010.1570~1585.141
8.1415~1460.1395~1410,136
5,1245,1190.1128.985,902,
832°770 and 720cm''0'I14MR (ppm); 0.6g (m), 1.3
((2), 1.7(k), 2.5(D, 3.1(i).

3.35o1v, (methano1/H*O), 3.
65 (h), 3.9 (g), 4.1 ('').

4.65(e), 4.9(HtO) and 6.8(d)
Example 2 Polyacrylic acid tetradecyldimethylbenzyl ammonium salt was selected from among polymeric quaternary ammonium salts, and an antibacterial test was conducted to obtain the results shown in Table 2.

This antibacterial activity test was conducted under the following conditions.

Vj strain used Staphylococcus aureus (Staphylococcus a)
ureus FDA 209P)
Bacillus 5ubtilis IFO300
7) Escherichia coli IF
O3301) Pseudomonas ae
ruginosa IFO3445) Black koji mold (A
spergillus niger ATCC6275
) Aureobasidium pu
llulans; laboratory-preserved mold) Test method: Add 0.5% of the test substance solution to a sterile tube. Dispense 9.5 iC of sterilized agar medium and mix uniformly and solidify to prepare a test plate with a test substance concentration of 1500 μ9/R (l) to 23.4 μ9/l (l) in a 2-fold dilution series. did.

Agar medium: Trypto Soya agar medium for bacteria (Nissui Pharmaceutical) Potato dextrose agar medium for mold (Nissui Pharmaceutical)
The number of bacteria on the prepared test plate was approximately 107 bacteria/j! (The test bacterial solution prepared in 2 was inoculated using a platinum loop.

The plates inoculated with bacteria were cultured at 37°C for 48 hours, and the plates inoculated with mold were cultured at 30°C for 7 days, and then the presence or absence of bacterial growth was observed. The lowest concentration at which no bacterial growth was observed was defined as the minimum growth-inhibiting concentration. In order to examine the influence of the solvent in which the test substance was dissolved, the test bacteria were inoculated into a medium containing only the solvent, and the growth status was examined.

As a result, the solvent had no effect on the test bacteria.

Example 3 A 1 wt % ethanol solution of polyacrylic acid tetradecyldimethylbenzyl ammonium salt was prepared and impregnated onto a towel. Thereafter, the ethanol was removed to obtain a towel containing 1 m'' of polyacrylic acid tetradenol methylbenzyl ammonium salt 109. Similarly, a towel containing benzethonium polyacrylic acid salt (109/m
') got.

Using these towels, the antibacterial properties against Staphylococcus aureus were tested according to the shake flask method.

The results are shown in Table 3.

Example 4 Cetylpyridinium chloride 74.1 was used instead of tetradecyldimethylbenzylammonium chloride in Production Example 1.
9 (0.22 mol) was used in the same molar amount, but the corresponding polymeric quaternary ammonium salt 69.09
(0,184 mol) was obtained (yield 92%).

Example 5 The corresponding polymeric quaternary ammonium was prepared in the same manner as in Production Example 1, except that the same molar amount of todenrutrimethylammonium chloride 79.99 (0.22 mol) was used in place of tetradecyldimethylbenzylammonium chloride. 72.69 (0,182 mol) of salt was obtained (yield 91%).
) Example 6 Polymerization degree 400 polysodium methacrylate 21.69
(Q as carboxyl group equivalent, 2Iioρ) was added to 1ρ of water, heated to 40°C and stirred to completely dissolve.

Tetradecyldimethylbenzylammonium chloride 8
An aqueous solution of 1.09 (0.22 mof2) dissolved in 370x water (ff) was gradually added to the above while stirring up and down, and after the addition was completed, stirring was continued for 30 minutes. The formed precipitate was separated by filtration, thoroughly washed with water, and vacuum dried at room temperature. Polymethacrylic acid tetradecyldimethylammonium salt 76.99% was obtained (yield: 9
2%) Test Example I Table 4 shows the solubility of the polymeric quaternary ammonium salts obtained in Examples 4 to 6 in each solvent.

Test Example 2 Dissolve 0.259 of the various polyacrylic acid quaternary ammonium salts produced in Production Examples 4 to 6 in 8 m of methanol,
The mixture was poured so as to form a uniform thin film on the inner surface of a glass test tube having an inner diameter of 18 x m and a length of 180 H, and methanol was distilled off under reduced pressure to form a coating of quaternary ammonium salt of polyacrylic acid 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, 10'ko/! Escherichja cot of ρ
i) The solution was put into 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 material is as follows.

(Margin below)

[Brief explanation of the drawing]

Figures 1 and 2 are infrared absorption spectra of tetradecyldimethylammonium polyacrylate and benzethonium polyacrylate, respectively; Figures 3 and 4 are tetradecyldimethylammonium polyacrylate and polyacrylic acid, respectively. It is a 'H-N MR spectrum diagram of benzethonium.

Claims (1)

[Claims] 1. A homopolymer or copolymer of acrylic acid or methacrylic acid and a quaternary ammonium salt represented by the following formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^ 1 to R^4 are C_1_-_2_ respectively
0 is a linear or branched saturated but 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. The group is an aryloxyalkyl group, or two of R^1 to R^4 are the above-mentioned hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups, or One or two of R^1 to R^4 are the hydrocarbon groups, and the remaining two or three form a heterocyclic ring together with the nitrogen atom, and X
is a halogen atom) as an active ingredient. 2. The antibacterial composition according to claim 1, wherein the homopolymer or copolymer of acrylic acid or methacrylic acid has a degree of polymerization of 50 to 20,000. 3. The antibacterial composition according to claim 1, wherein three of R^1 to R^4 in the formula are methyl groups and the remaining one is dodecyl group. 4. The antibacterial composition according to claim 1, wherein in the formula, three of R^1 to R^4 are one tetradecyl group and two methyl groups, and the remaining one is a benzyl group. 5. In the above formula, two of R^1 to R^4 are methyl groups, and the remaining two are benzyl groups and (p-1, 1, 3,
The antibacterial composition according to claim 1, which is a 3-tetramethylbutylphenoxy)ethoxyethyl group. 6. In the above formula, one of R^1 to R^4 is n-
2. The antibacterial composition according to claim 1, wherein the remaining three cetyl groups or lauryl groups form a pyridinium group together with adjacent nitrogen atoms.