RU2254144C1 - Interpolymeric disinfecting agent - Google Patents

Abstract

FIELD: medicine, hygiene.

SUBSTANCE: invention relates to a disinfecting agent. Interpolymeric agent comprises the following ratio of components, wt.-%: polyguanidine base, 0.3-0.5; chlorine-containing polymer, 3.1-4.0; ethyl alcohol, 7-10; nefras, the balance. Polyalkylene guanidine base or polyoxyalkylene guanidine, or polyalkylene biguanide is used as a polyguanidine base. Mixture of chlorosulfonated polyethylene with chlorinated polyvinyl chloride taken in the ratio = (7.3-10.1):1 is used as a chlorine-containing polymer. Agent can be used for preventive prolonged disinfection in compartment with many people amount, for example, in medicine institutions, in objects of criminal-executive system, evacuation points, in apartments for culture-domestic aims, in homes, veterinary, food branch, trade, transport. Invention provides enhancing strengthening indices of polymeric cover and to expand field of its applying.

EFFECT: valuable properties of agent.

4 cl, 6 tbl, 14 ex

Description

The invention relates to disinfectants and can be used for preventive prolonged disinfection of rooms with large crowds and prolonged stay of people: in medical institutions, at the facilities of the penitentiary system, at evacuation centers, in premises for cultural and domestic purposes, at home, in veterinary medicine, in food industry, trade, transport.

Currently, all over the world refuse traditional disinfectants based on compounds containing active chlorine or phenol. These compounds are not stable, highly toxic, cause allergies; treatment of medical facilities with such disinfectants is permitted only in the absence of patients. The preparations are volatile, therefore, the period of their antimicrobial action is limited to several hours, after which the treated surfaces are re-cantaminated and their sanitization must be repeated.

Chlorative and phenol-containing compounds are increasingly being replaced by less toxic and more stable, non-aggressive drugs, in particular polyguanidines (PG), which are highly soluble in water, form a biocidal polymer film on the surface to be protected, which has a wide spectrum of biocidal action.

The valuable property of GHGs - water solubility - becomes their drawback when it is necessary to achieve long-term antimicrobial protection of walls, furniture and other equipment in medical institutions, where these surfaces are periodically wet-cleaned, since the GHG film is easily washed off by water, and it is also sticky and has low mechanical strength (hardness and impact strength - 0, tensile strength <0.5 MPa).

These disadvantages of GHG can be eliminated by using chemically crosslinked polymer compositions (interpolymers) as a disinfectant, consisting of GHGs in the form of a base and hydrophobic polymers, which simultaneously act as a film former and a crosslinking agent.

In the preparation of interpolymers, the guanidine groups in the macromolecules of the PG base enter into chemical interaction with the reactive functional groups of the film-forming polymer with the formation of interchain chemical bonds. Interpolymers form spatially structured interpolymer networks from a solution that are not washable from the surface to be protected with water, possessing biocidal properties and increased mechanical strength.

In order for interpolymers to be used as disinfectants, they must be soluble in organic solvents and their solutions must be stable; toxicity (hazard class) of the selected organic solvent is also very significant. All this requires a very careful approach to optimizing the qualitative and quantitative composition of the organosoluble polymer composition, proposed for use as a disinfectant.

Known biocidal polymer composition containing polyhexamethylene guanidine (PHMG), which contains polytrichlorobutadiene as a crosslinking agent and film-forming base, and chloroform as a solvent [A.S. USSR No. 1728264, cl. C 08 L 15/2, 1992, BI No. 15]. The composition is intended to protect against corrosion and biofouling of surfaces in the aquatic environment. However, it cannot be recommended as a disinfectant, since the resulting polymer coating has a black color, and the solvent used for its preparation (chloroform) has a narcotic effect. In addition, polytrichlorobutadiene is not currently available on an industrial scale.

Closest to the proposed invention is a biocidal composition, which contains a PHMG base as a biocidal component, chlorine-containing polyethylene as a crosslinking agent and a film-forming base, and a mixture of toluene with ethyl alcohol as a solvent; in addition, the composition contains carboxylic acid, various pigments [US Pat. RF 2169163, 1999, C 09 D 123/28; BI No. 17, 2001]. The composition is intended for repair and construction work. The disadvantages of the known composition include the fact that it cannot be used as a disinfectant, since it changes the color of the surface to be protected (depending on the pigment), and the main solvent of the composition (toluene) has high inhalation toxicity (class 3 moderately hazardous substances according to GOST 12.1 .007-76).

The technical problem solved by this invention is to reduce the toxicity of the solvent, increase the strength characteristics of the polymer coating based on a disinfectant, as well as expanding the scope of application of the disinfectant.

To solve the technical problem, an interpolymer disinfectant, including a polyguanidine base, a chlorine-containing polymer, an aromatic solvent, and ethanol, a polyalkylene guanidine base, a polyoxyalkylene guanidine base, or a polyalkylene biguanide base, and a chlorinated polychlorinated chloride-chlorinated polymerized polymer are used as the chlorinated polymer as aromatic solvent use nefras A-130/150 with the following component ratio, wt.%:

A polyalkylene guanidine base or a polyoxyalkylene guanidine base or a polyalkylene biguanide base 0.3-0.5 A mixture of chlorosulfonated polyethylene with chlorinated polyvinyl chloride 3.1-4.0 Ethanol 7-10 Nefras rest

In this case, the base of polyalkylene guanidine is a base of polyhexamethylene guanidine, or a base of polytetramethylene guanidine, or a base of polydedecamethylene guanidine, or a base of benzyl polyhexamethylene guanidine, or a base of octadecyl polyhexamethylene guanidine; as the base of polyoxyalkylene guanidine, a base of poly- (4,9-dioxadodecanguanidine) or poly- (3,7,10-trioxatridecanguanidine) is used.

As the base of the polyalkylene biguanide, a base of polyhexamethylene biguanide or a base of benzyl polyhexamethylene biguanide is used.

The ratio of chlorosulfonated polyethylene to chlorinated polyvinyl chloride is (7.3-10.1): 1.

Compositions of this composition can serve as an organically soluble disinfectant of prolonged action, the spectrum of biocidal action of which depends on the chemical nature of the selected GHG. After evaporation of the solvent, the disinfectant forms a colorless polymer coating containing 7-12% GHG, the rest is a mixture of chlorinated polymers. The coating is active against bacteria (including Mycobacterium tuberculosis), fungi of the genus Candida and Aspergilus; Coating activity persists for at least 18 months from the date of application to the surface. The coating is not washed off with water, has good adhesion and high strength characteristics.

The biocidal active substance of the disinfectant are GHGs of various compositions, converted to the base form.

The base of polyhexamethylene guanidine (PHMG) with MM = (2.5-10.0) · 10 ^{3 is} obtained by alkaline dehydrochlorination of PHMG chloride, as described in [A.S. USSR No. 1687261, class A 61 L 2/16, 2/18, 1991, BI No. 40]. PHMG base is a white solid, limitedly soluble in water, insoluble in organic solvents, except lower alcohols.

It should be noted that during alkaline dehydrochlorination of PG chlorides, the ion exchange reactions do not reach the end, and the resulting PG base is a copolymer of the basic and chloride forms:

Only dehydrochlorinated PG units react with the polymer binder (the chloride form is not involved in the reaction). As a result of the reaction between the macromolecules of PG and the polymer binder, a small number of interchain chemical crosslinking is formed, due to which the interpolymer retains solubility, as well as the specific properties inherent in both high molecular weight components.

The bases of polytetramethylene guanidine (PTMG) and polydodecamethylene guanidine (PDDMG) are also synthesized:

These are solid whitish polymers, the first of which is soluble in water and alcohol, and the second is insoluble in water, but soluble in chloroform and toluene.

The base of benzylpolyoxymethylene guanidine (BPHMG) and octadecylpolyhexamethylene guanidine (ODPHMG) is obtained by the action of alkali on aqueous solutions of their hydrochlorides:

Both bases are light yellow solids. The first is soluble in water and alcohol; the second is in chloroform, toluene and alcohol. BPHMG and ODPHMG have a strong virucidal and tuberculocidal effect.

Bases of polyoxyalkylene guanidines (POAG): poly-4,9-dioxadodecanguanidine (DODDG) and poly-3,7,10-trioxatridecanguanidine (TOTDG)

semi-liquid, pasty substances of yellow color. Both bases are soluble in water and alcohol, and have extremely low toxicity.

Bases of polyhexamethylene biguanide (PHMBG) and its benzyl derivative (BPHMBG): white solids soluble in water and alcohol.

The film-forming base of the disinfectant is a mixture of chlorinated polymers, consisting of chlorosulfonated polyethylene (ChSPE) and chlorinated polyvinyl chloride (CPVC). The ratio of HSPE to CPVC is (7.3-10.1): 1.

KhSPE - hydrophobic film-forming polymer with MM ~ 20,000, soluble in aromatic and chlorinated hydrocarbons; from a solution forms highly elastic, but relatively low-strength films; It is used, in particular, in the production of varnishes and enamels. It contains easily moving chlorine atoms, which enter into chemical interaction with the guanidine groups of PG in the form of a base. As a disinfectant, it serves as a crosslinking agent and an elastic component of the film-forming coating base.

CPVC is a hydrophobic film-forming polymer with an MM of ~ 40000-80000 soluble in aromatic and chlorinated hydrocarbons. CPVC films have increased hardness, elasticity, and impact resistance; used to obtain chemical and weatherproof coatings. The composition of the disinfectant is introduced to improve the strength characteristics of the film-forming coating base; in the interpolymer reaction with PG is not involved.

If the ratio of HSPE to CPVC is less than 7.3: 1, this will lead to a decrease in the mechanical strength of the coating. If this ratio is more than 10.1: 1, then this will lead to a decrease in the water resistance of the coating.

The disinfectant contains two solvents - ethyl alcohol and nefras. Nefras (GOST 10214-78) is a mixture of aromatic hydrocarbons obtained in the process of catalytic aromatization of oil (light fraction); according to GOST 12.1.007-76 refers to low-hazard substances of the 4th class; It is used as a non-toxic solvent for varnishes, paints and enamels. Ethyl alcohol - according to GOST 18300 or GOST 17299.

A disinfectant is prepared as follows.

Example 1. Two solutions are prepared: a mixture of 3.0 g of HSPE and 0.3 g of CPVC, dissolved in 89 g of nephras A-130/150; 0.3 g of base PHMG is dissolved in 7 g of ethyl alcohol. Both solutions are prepared at a temperature of 50-60 ° C and stirring, filtered through a dense cloth. Then, the PHMG base solution is added to the solution of a mixture of HSPE with CPVC and stirred at room temperature. Get 100 g of interpolymer disinfectant, which is a homogeneous, mobile liquid, light yellow in color with the smell of a solvent. The disinfectant solution is stable (does not phase out) if the dry residue (the sum of the polymers in the solution) does not exceed 4.5%. At higher solution concentrations, polymer deposition as a crosslinked gel may occur.

Table 1 shows the composition of the components of the disinfectant for the claimed compounds No. 1-7, as well as for compositions 8-13, beyond the stated limits. The composition of the components and their percentage are identified on the basis of numerous experiments and is optimal.

Before use, the interpolymer disinfectant is thoroughly mixed and applied with a brush, roller or pneumatic spray gun to clean, dry wall surfaces and other objects in rooms (except the floor). After evaporation of the solvent on the surface to be protected, an inconspicuous colorless polymer coating is formed, which is dried at room temperature; the room is ventilated until the smell of solvent disappears.

The polymer coating contains in its composition 7-12% GHG and ensures surface sterility for 18 months without additional treatment with disinfectants; it can be washed off with water.

The long-term antimicrobial effect of the polymer coating is due to the fact that GHG is “sewn” to CSPE with rare chemical bonds; however, most of the guanidine groups of PG do not participate in the reaction and, remaining free, provide biocidal properties of the coating. The presence of interchain chemical bonds between CSPE and GHG, as well as the presence of CPVC, gives the polymer coating increased mechanical strength and water resistance.

Table 2 shows the strength characteristics of a dry film and a polymer coating for the prototype and two interpolymer disinfectants of the present invention. It is obvious that the claimed composition forms a coating with high strength characteristics.

Tables 3-6 show the results of the disinfecting activity of polymer coatings. Microbiological and toxicological studies of the interpolymer disinfectant were carried out in accordance with the standards set forth in the list of “Normative indicators of the safety and effectiveness of disinfectants to be monitored during mandatory certification” No. 01-12 / 75 of 1997, as well as in accordance with the methods set forth in collection: "Test methods for disinfectants to assess their safety and effectiveness", Moscow, Ministry of Health of the Russian Federation, 1998, part I and II.

To determine the effectiveness of the polymer coating, S.aureus (pcs. 906), C.albicans fungi (pcs. 15), Mycobacterium B 5, Asp.niger were used as test microorganisms, and a surface 10 × 10 in size was used as test surfaces cm from wood, painted and not painted with oil paint. To neutralize the agent, a universal neutralizer containing tween-80, saponin, histidine, cysteine, and drinking water was used.

An interpolymer disinfectant was applied to the test surface with a brush; dried over a day. When studying the dependence of the antimicrobial activity of the interpolymer coating on the shelf life, a suspension of the test culture was applied to surfaces treated with a disinfectant in an amount of 0.5 ml and dried for an hour (until completely dry). At various intervals, washings were made with gauze napkins, which were placed in test tubes with beads containing 10 ml of neutralizing solution; shook them for 10 minutes Then 0.2 ml of flushing liquid was sown on solid nutrient media: in experiments with Staphylococcus aureus - on meat-peptone or casein agar; with candida albicans and aspergillus niger - on Saburo agar; with Mycobacterium B5 - on casein agar with glycerin and Petraniani medium. The control was a test surface made of a similar material, not treated with a disinfectant.

Tests of the effectiveness of the disinfectant obtained according to examples No. 1-7 showed that the culture of Staphylococcus aureus is 100% inactivated on the interpolymer coating after 30 minutes, the candida albicans culture after 120 minutes, and the culture of mycobacteria B 5 after 24 hours. On the surface treated with a disinfectant obtained according to control example No. 8, the culture of Staphylococcus aureus is inactivated by 90% in 60 minutes, therefore this example is beyond the scope of the claimed composition.

Laboratory tests have shown that the antimicrobial effect of the interpolymer coating against S.aureus, Mycobacterium B 5 and C. Albicans persists after repeated repeated contamination of the surface with test microorganisms for at least 6 months (table). The presence of 40% protein whey did not reduce the effectiveness of the interpolymer coating over the entire observation period.

Tests of the coating based on interpolymer disinfectant in practical conditions (prison cell, hospital ward, staff room) showed that the biocidal effect of the interpolymer coating remains for 18 months (for water-soluble PHMH chloride this period is 1 month).

Table 6 shows that the interpolymer coating also retains its properties with respect to the dried culture of Staphylococcus aureus, which is essential, for example, when the surface is contaminated by microorganisms that enter from the air together with dust particles.

When studying the fungicidal activity of the interpolymer coating, a black Aspergillus test culture was applied to unpainted wooden surfaces, dried, and then treated with an interpolymer disinfectant. Found that the development of mold under the coating is halted, although the culture remains viable.

table 2
Strength characteristics of a coating based on interpolymer disinfectant Name of indicator Prototype Example number in table 1 1 5 Stickiness is absent is absent Solubility in water HP HP Relative hardness according to M-3, conv. units (according to GOST 5233) 0.30 0.40 0.40 Breaking strength of a dry film, MPa 23 35 33 Impact strength according to U-1A, kgf · cm (according to GOST 4765) fifty 60 60 Bending elasticity according to ShG-1, mm (according to GOST 6806) 1 1 1 Adhesion, points (according to GOST 15140, section 2) 1 1 1

Table 3
The antimicrobial effect of the coating based on interpolymer disinfectant according to example No. 3 in table 1 (coating thickness 15-20 μκ) The multiplicity of surface contamination with test microorganisms (with an interval of 1 hour) Microorganism test S.aureus C.albicans Mycobacterium b 5 Control Some / cm ² Experience Koe / cm ² Efficiency% Control CFU / cm ² Experience, Koe / cm ² Efficiency% The control Experience 1 2400 0 100 2200 2 99,99 + - 2 2600 0 100 2800 1 99,99 + - 3 2480 0 100 2100 0 100 + - 4 2680 0 100 2600 0 100 + - 5 3150 0 100 2300 2 99,99 + - 6 3200 0 100 2500 1 99,99 + - Note 1: “control” - the surface of the sample without coating; “Experience” - the surface of the sample is treated with an interpolymer disinfectant.
Note 2: “+” means the growth of mycobacterium tuberculosis, “-” means no growth Table 4
The antimicrobial effect of the coating based on interpolymer disinfectant according to example No. 6 in table 1 (coating thickness 15-20 μκ) The multiplicity of surface contamination with test microorganisms (with an interval of 1 hour) Microorganism test C.albicans Mycobacterium b 5 Control CFU / cm ² CFU experience / cm ² Efficiency% The control Experience 1 120 0 100 + - 2 90 0 100 + - 3 110 0 100 + - 4 103 0 100 + - 5 71 0 100 + - 6 90 0 100 + - Note 1: “control” - the surface of the sample without coating; “Experience” - the surface of the sample is treated with an interpolymer disinfectant.
Note 2: “+” means the growth of mycobacterium tuberculosis, “-” means no growth

Table 5
The antimicrobial effect of the coating based on interpolymer disinfectant according to example No. 1 of table 1 (coating thickness 15-20 μκ) Duration of observation, weeks Microorganism test C. albicans Mycobacterium b 5 Control, CFU / cm ² Experience, Koe / cm ² Efficiency% The control Experience 2 209 0 100 + - 4 306 0 100 + - b 196 0 100 + - 8 250 0 100 + - 10 220 0 100 + - 12 180 0 100 + - 14 154 0 100 + - 16 295 0 100 + - eighteen 300 0 100 + - twenty 240 0 100 + - 22 220 0 100 + - 24 187 0 100 + - Note 1: “control” - the surface of the sample without coating; “Experience” - the surface of the sample is treated with an interpolymer disinfectant.
Note 2: “+” means the growth of mycobacterium tuberculosis, “-” means no growth Table 6
The antimicrobial effect of the coating based on interpolymer disinfectant for example No. 2 of table 1 in relation to the dried culture of Staphylococcus aureus Exposition, Hour Control, CFU / cm ² Experience, CFU / cm ² Efficiency% 1 2.1 × 10 ⁷ 0 100 2 1.3 × 10 ⁷ 0 100 3 1.9 × l0 ⁷ 0 100 24 2.4 × 10 ⁷ 0 100 Note 1: “control” - the surface of the sample without coating; “Experience” - the surface of the sample is treated with an interpolymer disinfectant.

Claims (4)

1. An interpolymer disinfectant comprising a polyguanidine base, a chlorine-containing polymer, an aromatic solvent and ethyl alcohol, characterized in that a polyalkylene guanidine base or a polyoxyalkylene guanidine base or a polyalkylene biguanide base is used as the chlorine-containing polyethylene chlorinated polymethylene chloride mixture in the ratio of 7.3-10.1: 1, nefras is used as an aromatic solvent in the trace the ratio of the components, wt.%: Polyalkylene guanidine base, or base polyoxyalkylene guanidine, or base polyalkylene biguanide 0.3-0.5 A mixture of chlorosulfonated chlorinated polyethylene polyvinyl chloride in the ratio of 7.3-10.1: 1 3.1-4.0 Ethanol 7-10 Nefras Rest. 2. The interpolymer disinfectant according to claim 1, characterized in that the base of polyalkylene guanidine is a polyhexamethylene guanidine base or a polytetramethylene guanidine base or a polydecamethylene guanidine base or a benzyl polyhexamethylene guanidine base or an octadecyl polyanhexamethylene base. 3. The interpolymer disinfectant according to claim 1, characterized in that the base of polyoxyalkylene guanidine is the base of poly- (4,9-dioxadodecane guanidine) or poly- (3,7,10-trioxatridecanguanidine). 4. The interpolymer disinfectant according to claim 1, characterized in that a polyhexamethylene biguanide base or a benzyl polyhexamethylene biguanide base is used as the base of the polyalkylene biguanide.