KR19990037686A - Biological lethal composition and microbial remediation method using the same - Google Patents

Abstract

Treatment of biotic lethal hard surfaces

The present invention relates to an aqueous solution, suspension or dispersion of a copolymer comprising a biocidal agent and a chain unit of formula (1) and a chain ester unit of formula (2), wherein the molar ratio of unit 1 to 2 is from 1:10 to 3000: 1, Compositions suitable for application to hard surface or fabric surfaces having a molecular weight of from 1000 to 100,000 and methods of using such compositions from microbial remedies are provided.

Formula 1

-OC _n H _2n -

(2)

In this formula,

n is 2 or 3,

R is a hydrophobic group.

Description

Biological lethal composition and microbial remediation method using the same

Known biolytic compositions generally have the disadvantage of not having a lasting effect. That is, after applying this to the surface, especially when the surface is washed, the biocidal effect decreases rapidly.

The present invention relates to a biotic lethal composition and a method for remedying microorganisms using such a composition.

According to the present invention there is provided a composition suitable for application to a hard surface or fabric surface comprising an aqueous solution, suspension or dispersion of a biodegradable polymer and a copolymer comprising a chain unit of formula (1) and a chain ester unit of formula (2) , The molar ratio of units 1 to 2 is 1:10 to 3000: 1 and the copolymer has a molecular weight of 1000 to 100,000):

-OC _n H _2n -

In this formula,

n is 2 or 3,

R is a hydrophobic group.

R is preferably an alkylene group, a cycloalkylene group, or an arylene group. The alkylene group preferably has 6 or more carbon atoms, the cycloalkylene group preferably has 4 to 10 carbon atoms, especially the cyclohexylene and arylene groups are preferably meta- or para-phenyl Or a naphthylene group. The R group may be optionally substituted. Suitable substituents include, for example, C _1-6 -alkyl, such as methyl, or a hydrophilic group such as, for example, sodium sulfo-3,5-phenylene, in the form of a sulfonic acid group, optionally an alkali metal salt.

The copolymer preferably has a molecular weight of 2000 to 30,000. The molar ratio of unit 1 to 2 is preferably from 1: 1 to 100: 1.

Such copolymers include hydrophobic moieties that impart some adhesion to the surface to resist removal by water and weak surfactant solutions, and hydrophobic moieties that transfer the biolent agent to the surface of the polymer, particularly when rinsing the surface with water or aqueous solution It is estimated to possess a hydrophilic moiety. Chain ester unit 2 is hydrophobic while chain unit 1 is generally hydrophilic.

The copolymer used preferably comprises a chain unit of the formula 3, in particular a polyoxyethylene terephthalate unit, and a chain unit of the formula 4, in particular a polyethylene terephthalate unit:

In this formula,

m represents an integer of 12 to 230,

n and R are as defined above.

Preferred polymers have a molar ratio of units 3 and 4 of from 1:10 to 10: 1, preferably from 1: 2 to 1: 6. Unit 3 has a molecular weight of 500, preferably 1000 to 10,000, especially about 3400 (OC_nH_2n)_m Group is preferable. The polymer preferably has a total molecular weight of 1000 to 100,000, preferably 15,000 to 35,000, particularly preferably about 20,000. m is preferably an integer of 14 to 110, and particularly preferably about 75. [

Typical copolymers that can be used are:

(i) a copolymer derived from ethylene terephthalate and polyethylene oxide terephthalate in a molar ratio of about 1: 10 to 10: 1, said polyethylene oxide terephthalate having an ethylene oxide unit having a number average molecular weight of about 500 to about 10,000 And the polymer has a number average molecular weight of about 1,000 to 100,000.

(ii) a polymer derived from propylene terephthalate and polyethylene oxide terephthalate in a molar ratio of about 1: 10 to about 10: 1, said polyethylene oxide terephthalate having an ethylene oxide unit with a number average molecular weight of about 500 to about 10,000 And the polymer has a number average molecular weight of about 1,000 to 100,000.

(iii) a polyethylene derived from ethylene terephthalate and / or propylene terephthalate in an optional proportion and a polymer derived from polyethylene oxide and / or polypropylene oxide in any ratio, the polyethylene terephthalate added with propylene terephthalate to polypropylene oxide added with polypropylene oxide Oxide is from about 1:10 to about 10: 1, the ethylene oxide units and propylene oxide units each have a number average molecular weight of from about 250 to about 10,000, and the polymer has a number average molecular weight of from about 1,000 to about 100,000 .

In one embodiment, the ends of the polymer are capped with hydrophilic groups to impart some ionic properties, or increased hydrophilicity, to the polymer. Suitable hydrophilic groups include, for example, (MO ₃ S) (C ₆ H ₄ ) C (O) - or (MO ₃ S) (CH ₂ ) _x (CH ₂ CH ₂ O) (C _n H _2n O) _y -phosphorus group (where M is a suitable cation such as an alkali metal ion, particularly sodium, x is 0 or 1, y is 0 to 4, n is as defined above), ethylene glycol Monoester or propylene glycol. They can be added during the production of the base polyester. Generally, the molar amount of the hydrophilic group in the total molar amount of the units 2 used in this preparation is 0 to 15%.

A-4,770,666, US-A-4,116,885, US-A-3,962,152, GB-A-2,196,013, US-A-4,702,857, US- 4,713,194, US-A-3,416,952, US-A-4,427,557 and US-A-4,201,824, and also describes well known methods for their production.

The polymer is used as an aqueous solution, suspension or dispersion. Optionally in the presence of a solubilizing agent or dispersing agent, in particular a fatty alcohol ethoxylate such as a C ₁₂ or C ₁₄ alkyl ethoxylate, such as a nonionic surfactant. Since such formulations will be better adhered to the surface than the solution, it is generally preferred to use them as dispersions or suspensions.

Biodegradable agents that can be used in the compositions of the present invention include:

(a) Quaternary Ammonium and Phosphonium Biological agents:

Cocoalkylbenzyldimethylammonium chloride; _C12 / ₁₄ -alkylbenzyldimethylammonium chloride; Lauryl C _12/14 -alkyl-benzyldimethylammonium chloride; Coco-alkyl 2,4-dichlorobenzyldimethylammonium chloride; Tetradecylbenzyldimethylammonium chloride; Diisobutylphenoxy-ethoxy-ethyldimethyl-benzylammonium chloride; Laurylpyridinium chloride; C 12/ ₁₄ -alkyl-benzylimidazolinium chloride; Myristyl trimethyl ammonium bromide; Cetyltrimethylammonium bromide; Didecyldimethylammonium chloride; Dioctyldimethylammonium chloride; And myristyltriphenylphosphonium bromide.

(b) amphibian lethal agent:

N- (N'- _C8-18 -alkyl-3-aminopropyl) -glycine derivatives such as (dodecyl) (aminopropyl) glycine; N- (N '- (N "-C _8-18 -alkyl-2-aminoethyl) -2-aminoethyl) -glycine derivatives such as (dodecyl) (di-ethylenediamine) glycine; And N, N-bis (N'- _C8-18 -alkyl-2-aminoethyl) -glycine derivatives.

(c) Amine:

N- (3-aminopropyl) -N-dodecyl-1,3-propanediamine.

(d) Phenols:

O-cresol, p-cresol, o-phenyl-phenol, 4-chloro-m-cresol, chloroxylenol, 6-n- Amyl-m-cresol, resorcinol, resorcinol monoacetate, p-tert-butylphenol and o-benzyl-p-chlorophenol or water-soluble salts of these biologically active compounds, Metal salts.

(e) chlorhexidine and salts thereof such as, for example, chlorhexidine gluconate.

(f) Iodophor, hypochlorite and chlorine releasing agents such as sodium dichloroisocyanurate.

(g) Polysaccharide Ammonium:

(Dimethylimino) methylene dichloride], poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride], poly [hydroxyethylene (dimethylimino) ) -2-hydroxypropyl (dimethylimino) methylene dichloride] and polymers of (chloromethyl) oxirane and 1H-imidazole.

The polymer is preferably used at a concentration of from 1 to 80% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 30% by weight, for example about 15%. The biocidal agent is preferably used in a concentration range of 0.1% to 20% by weight, preferably 1% to 10%, more preferably 1% to 5%, for example, about 2.5% by weight.

The treatable surface is a hard surface, for example a fabric or a flexible polymer surface or a coated surface. Therefore, the composition can be advantageously used during domestic or industrial laundry processes.

The amount of solid active component deposited on the hard surface per m < 2 > is typically from 0.01 to 10 g, preferably from 0.1 g to 1 g in the case of biotic agents and typically from 0.1 g to 20 g, preferably from 1 to 5 g to be. In the case of fabrics, the amount deposited by weight, based on the weight of the fabric, is typically from 0.001% to 10%, preferably from 0.01% to 5%, such as about 0.1%, for biodegradable agents, Is typically from 0.001% to 10%, preferably from 0.01% to 5%, such as about 0.2%.

A particular advantage of the compositions according to the invention is that they provide a sustained bioluminescence effect when applied to hard surfaces. This persistent effect is not affected even when cleaning the surface. The polymer used in the composition has the advantage of being biodegradable due to the ester bond present in the backbone of the polymer. Another advantage of the composition is that these compositions can be easily removed from the applied surface by using an alkali.

A further advantage of the composition is that the polymer need not contain cationic groups to enhance hydrophilicity. The presence of these groups, especially cationic nitrogen groups, tends to cause wastewater problems because polymers with these groups are often detrimental to fish.

Application to fabric surfaces extends the biocidal effect during normal use. Thus, the presence of the polymer hinders the removal of the biocide even when the fabric becomes damp or lightly sprayed or rinsed with water during use.

The composition can be applied to a variety of applications such as a sheet, a uniform of a nurse, a general hospital laundry including a doctor's gown, a doctor's white coat, a garment apron used in some sensitive industries such as the food industry, Hand towels, garments and uniforms worn during participation in energetic sports activities, and personal garments, especially those worn near the skin, such as socks and underwear.

It is convenient to apply the composition at the end of the laundry treatment to avoid possible fluorination between a general anionic detergent system and a biocide, for example, a secondary biocide. A typical method is shown below:

(a) Apply biodegradable material with added polymer during final water rinse.

(b) For example, if the secondary biocide is combined with a cation and an amphoteric softener, apply a biocide with a polymer added with a fabric softener.

(b1) It is convenient to add the biodegradable and softener formulations to which the polymer is added separately to the cleaner.

(b2) Instead, the polymer biased lysate may be incorporated into the fabric softener formulation itself.

(c) In some cases, minimal water may be added to the biocide added with the polymer in the separation step before drying. This ensures maximum movement to the fabric or sheet.

The extended bioluminescence effect will be best observed on common textile and polymer surfaces. Many biological agents such as quaternary ammonium basic products are naturally present on many such surfaces, but their effect is improved by the presence of the polymer. The fabrics include those made of natural fibers such as cotton and wool, natural products modified such as cellulose acetate, synthetic polymers such as polyester, polyamide and acrylic, and polyester coated with a coated fabric, for example PVC do.

The addition of the polymer types to protect the biocidal agent has a second benefit, especially on substrates such as polyesters and polyamides. Good soil release properties of this polymer can be confirmed during laundry washing.

Suitable fabric softeners include:

1. A simple dialkyl quaternary ammonium compound of the formula:

2. An alkylamido quaternary ammonium compound of the formula:

3. An alkyl imidazolinium compound of the formula:

4. Dialkyl imidazolinium compounds of the formula:

5. Dialkyl ester quaternary ammonium compounds of the formula:

In this formula,

R ₁ and R ₂ may be the same or different and each independently represent C ₁₆ -C ₁₈ , such as long chain aliphatic groups such as tallow, hydrogenated tallow, stearyl or oleyl.

X is a halide, preferably an anion such as chloride, or methosulfate (CH ₃ SO ₄ ), A is hydroxyl (OH) or amino (NH ₂ )

Or amido group to be.

Such softeners are usually present in a composition of from 2 to 20% by weight, preferably from 3 to 15% by weight, particularly preferably about 10% by weight.

Such softening formulations may optionally contain other ingredients such as coloring agents, flavoring agents, photoinitiators and stabilizing solvents such as isopropanol.

There is additionally provided a method of remedying microorganisms in such a site, including applying the biodegradable agent and copolymer as defined above to a site requiring remediation according to the present invention, for example in the form of a composition according to the invention . Suitable places include, but are not limited to, flexible surfaces, as well as hard surfaces such as glazed or unfabricated ceramics, glass, PVC, formica and other hard plastics, stainless steels or other painted or non- There is no timber.

It is preferable to use the method of the present invention in the form of a diluted solution of 20 to 500 times, preferably 50 to 100 times, the diluted solution of the composition according to the present invention. In laundry applications, the composition is typically diluted with the wash / rinse water.

Microorganisms that can be rescued by the method of the present invention include:

(i) Gram negative bacteria: Pseudomonas aeruginosa; Escherichia coli; And Proteus mirabilis.

(ii) Gram positive bacteria: Staphylococcus aureus; And Streptococcus faecium.

(iii) Other harmful food bacteria: Salmonella typhimurium; Listeria monocytogenes; Campylobacter jejuni; And Yersinia enterocolitica.

(iv) Yeast: Saccharomyces cerevisiae; And Candida albicans.

(v) Mycobacterium: Aspergillus niger; Fusarium solani; And Penicillium chrysogenum.

(vi) Algae: Chlorella saccharophilia; Chlorella emersonii; Chlorella vulgaris; And Chlamydomonas eugametos.

The microorganisms rescued by the method of the present invention are preferably Gram negative microorganisms, particularly Pseudomonas aeruginosa, Gram positive microorganisms, especially Staphylococcus aureus, and fungi such as Aspergillus niger.

The following examples illustrate the invention. In this example, the gram negative bacteria Pseudomonas erujino are known to be difficult to kill. The clear results obtained with the compositions of the present invention indicate that the compositions can be effective against a wide range of known microorganisms.

Example 1

Two bactericidal concentrates (DC1 and DC2) were prepared in the formulations shown in Table 1 below.

DC1 DC2 Biotic mortality 2.5% 2.5% polymer 14.25% 0 water 100% added 100% added

The biocidal agent used in the above table is C _12-14 -alkylbenzyldimethylammonium chloride and the polymer is of the following formula with a molecular weight of about 20,000 g / mol. Percentages shown in the table are percent by weight.

Pre-sterilized hard surfaces with an area of 25 cm 2 pre-sterilized with isopropyl alcohol are each diluted to a suitable dilution, for example 100-fold, with 3 ml of a bactericidal concentrate, then treated and dried at 45 ° C. The tiles are continuously washed with a water sprayer or sponge and dried again at 45 ° C. 0.25 ml of aqueous medium containing gram negative bacteria Pseudomonas aeruginosa approximately 10 ⁸ cfu / ml is spread on the treated hard surface. The surface is left as it is for the contact time shown in Table 2 below. This is the time it takes the biocide to migrate through the polymer layer to kill the bacteria on the surface. The surface is dried at 37 占 폚.

Surviving organisms are recovered using a sterile, cotton wool swab pre-moistened with a neutralizing medium. Carefully wipe the entire surface by wiping back and forth several times. Transfer the swab to 9 ml of neutralization medium containing 3% tween 80% and 2% soy lecithin, and platelet the nutrient agar using 10 serial dilutions. Plates are incubated at 37 ° C for 48 hours and the number of viable microorganisms counted.

Control tests are carried out using clean hard surfaces of the same area and the same method, except that no polyester or biosecurity is applied.

The hard surface is washed with a sponge prior to treatment with microorganisms using the method described above to determine the sustained bioluminescent effect of the composition of the present invention. Sponge handling involves the use of a Gardener-Scrub washer, which pushes a submerged sponge across a horizontally laid surface at a pressure of 5.6 g / cm2. For each " wash " in Table 2 below, the sponge is passed over the surface twice.

The results shown in Table 2 below were obtained:

Formulation Dilution used Contact time (h) Number of washes and log ₁₀ reduction obtained 0 One 2 4 DC1 100 times One 4.6 4.4 2.8 2.47 DC1 100 times 3 6.0 DC2 100 times One 6.0 1.82 0.3 0.10

Log ₁₀ reduction of bacterial counts is calculated as follows:

Log ₁₀ Decrement = Log ₁₀ (N / n)

Where N represents the number of bacteria recovered from the control (cfu / ml) and n represents the number of bacteria recovered from the test sample (cfu / ml). Log ₁₀ reduction 5 is particularly good for food contact areas and Log ₁₀ reduction 3 is satisfactory for general disinfection.

This result indicates that DC1 is very resistant to abrasive sponge treatment. There is still a Log ₁₀ reduction of about 3 after two washes. An increase in contact time from one hour to three hours gives a higher mortality rate, probably because the polymer coating slows down the action of the biocidal agent as the biotic agent must first diffuse through the polymer film before attacking the bacteria It is considered. If the contact time is longer, the Log ₁₀ reduction after twice washing will probably be more than 3.

Example 2

This example is carried out in the same manner as in Example 1 (100-fold dilution) except that the surface is not washed with a sponge, but the non-abrasive cleaning is performed with a water atomizer. This entails spraying 1 g of water onto the surface using a handheld trigger sprayer to place the surface vertically and wash each. The results shown in the following Table 3 are obtained:

Formulation Contact time (h) Number of water spray and Log ₁₀ reduction obtained 0 One 2 4 8 12 D.C.1 One 4.6 4.52 6.0 3.6 2.16 1.46 D.C.1 3 6.0 D.C.2 One 6.0 5.82 3.4 0.8 0.05 0.0

In the case of DC1 formulation, the reason for the low value in the case of 0 time and 1 time of washing for 1 hour is due to delayed biocidal action by polymer coating. The second wash removes a sufficient amount of polymer and the time delay is long enough to increase the biocidal action rate. The additional wash gradually removes the biocidal agent and the protective polymer, thus reducing the bacterial rate. If at least three drops of Log ₁₀ are provided, the film will still be protected even at least four water sprays.

Example 3

A bactericidal concentrate having the formulation shown in Table 4 below is prepared:

DC3 DC4 Biotic mortality 1.0% 1.0% polymer 14.7% 0% water 100% added 100% added

The bioluminescent agent used is poly [hydroxyethylene (dimethylimino) -2-hydroxypropyl (dimethylimino) methylene dichloride]. The polymer used is a polymer of formula (10) as in Example 1. Percent is weight percent.

This example is carried out in the same manner as in Example 2 except that the bactericide concentrates DC3 and DC4 are used. The results obtained are shown in Table 5 below:

Formulation Dilution used Contact time (h) Number of water spray and Log ₁₀ reduction obtained 0 One 2 4 DC3 100 times 24 6.0 6.0 4.9 0.19 DC4 100 times 24 6.0 2.96 2.02

Since the polymer quaternary ammonium biolabile is a relatively slow functional biocide, it is contacted for 24 hours before testing. When a polymer is present, the biolent agent is also resistant to at least two water sprays before the effect is significantly reduced.

Example 4

In the case of producing the bactericidal concentrate DC5, the same biocides and polymers as in Example 1 are used:

Biotic mortality 10% polymer 20% water 100% added

After a 100-fold dilution, 5 ml of the diluted formulation is added to the petri dish followed by a small area (5 cm x 5 cm) of polyester fabric with a weight of 0.2 g. The liquid is dried at 45 [deg.] C to deposit all the biocides added to the polymer presently present on the fabric.

Biotic mortality 2.5% w / w (2 gms per square meter of fabric) polymer 5.0% w / w (4 gms per square meter of fabric)

A control sample of the fabric is treated with 5 ml of water under the absence of biodegradation as described above.

0.25 ml of an aqueous medium containing about 10 ⁸ cfu of gram-negative bacteria Pseudomonas erujinoja per ml is spread over the surface of both fabric samples. 15 ml of nutrient agar is poured onto two fabric samples and incubated at 37 ° C for 48 hours.

On the untreated control fabric, the bacteria grow extensively, while there are few bacteria that survive on the treated fabric.

Example 5

(a) Following the same procedure as in Example 4, but before the re-drying at 45 ° C, the fabric is continuously dipped in the treated area for 10 seconds in a water beaker, then the bacteria are added and covered with the nutrient agar as described above.

(b) Similar control treatments are carried out using biolytic agents without polymer.

Fungicide concentrate DC6:

Biotic mortality 10% water 90%

In this experiment, the bacteria grow more widely on the sample (b) without the polymer.

It is clear that the polymer helps to extend the effectiveness of the biocidal agent against mild rinsing with water.

Claims (21)

Aqueous solutions, suspensions or dispersions of copolymers and biodegradants containing chain units of formula (1) and chain ester units of formula (2), wherein the molar ratio of units 1 to 2 is from 1:10 to 3000: 1, A composition suitable for application to a hard surface or fabric surface having a molecular weight of 100,000. Formula 1 -OC _n H _2n - (2) In this formula, n is 2 or 3, R is a hydrophobic group. The composition of claim 1, wherein R is an alkylene group having 6 or more carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group. 3. The composition according to claim 1 or 2, wherein the copolymer has a molecular weight of from 2000 to 30,000. 4. The composition according to any one of claims 1 to 3, wherein the molar ratio of units 1 to 2 is from 1: 1 to 100: 1. The composition according to any one of claims 1 to 4, wherein the copolymer comprises a chain unit of formula (3) and a chain unit of formula (4). (3) Formula 4 In this formula, m represents an integer of 12 to 230, n and R are as defined above. 4. The composition according to any one of claims 1 to 3, wherein the polymer is end-capped with hydrophilic groups containing sulfo groups. 7. A composition according to any one of the preceding claims, in the form of a dispersion or suspension. The composition according to any one of claims 1 to 7, wherein the biocide is a quaternary ammonium or phosphonium biocide, an amphoteric biocide, an amine, a phenolic compound, a chlorhexidine, an iodophore or a poly- . 9. The composition according to any one of claims 1 to 8, comprising 5 to 50% by weight of the polymer and 1 to 10% by weight of biodegradation. 10. The composition of claim 9, comprising from 10 to 30% by weight of the polymer and from 1 to 5% by weight of biodegradation. 11. The composition according to any one of claims 1 to 10, further comprising a fabric softening agent. 12. The composition of claim 11, wherein the fabric softener is a dialkyl quaternary ammonium compound, an alkylamido quaternary ammonium compound, an alkyl imidazolinium compound, a dialkyl imidazolinium compound or a dialkyl ester quaternary ammonium compound. 13. A composition according to claim 11 or 12, wherein the fabric softener is present in an amount of from 3 to 15% by weight. 11. A method of remedying microorganisms in a location as claimed in claim 1, comprising applying the biolysis agent and the copolymer according to claim 1 to a site requiring remediation. 15. The method according to claim 14, wherein the biocidal agent and the copolymer are applied in the form of a composition according to any one of claims 1 to 13. 16. The method of claim 15, wherein the composition is diluted 50 to 100 times prior to use. 17. The method according to any one of claims 14 to 16, wherein the microorganism is a gram negative microorganism. 18. The method according to any one of claims 14 to 17, wherein the place is glazed or unsuitable ceramic, glass, PVC, hard plastic material, unpainted metal or unpainted wood. 18. The method according to any one of claims 14 to 17, wherein the location is a fabric material. 20. The method of claim 19, wherein the fabric material is washed and the composition is applied during rinsing. 20. The method of claim 19, wherein the fabric material is washed and the applied composition is the composition of any one of claims 11 to 13.