Fast acting disinfectant and cleaner containing a polymeric biguanide

A cleaning and biocidal composition in liquid form comprising a solvent, a polymeric biguanide, a single quaternary ammonium salt, a sequestrant, and at least one surfactant. The composition comprising the solvent including water, the polymeric biguanide including a polyhexamethylene biguanide hydrochloride, the quaternary ammonium salt including a didecyldimethyl ammonium chloride, the sequestrant including an amino acid chelating agent selected from the group consisting of: ethylenediaminetetraacetic acid, nitrilotriacetic acid, tetrasodium ethylenediaminetetraacetic acid, or mixtures thereof, the surfactant including a non-ionic surfactant and an amphoteric surfactant.

BACKGROUND OF THE INVENTION
 1. Technical Field
 The present invention relates generally to a composition that can be used
 for cleaning and disinfecting a hard surface in one step with a relatively
 short contact time. More particularly, it relates to a composition that
 will clean and disinfect a surface by killing 99.999% of bacteria in under
 five minutes. This is accomplished while still keeping the amount of
 expensive ingredients such as quaternary ammonium compounds and polymeric
 biguanide, each contained in the composition at low levels of at least 5
 ppm in a diluted form or when diluted from a concentrated form.
 2. Background Art
 The cleaning and disinfecting of hard surfaces is important in both
 residential and commercial settings. The increasing importance of hygiene
 combined with the fast moving pace of the modem world has created a need
 for products with fast cleaning and disinfecting action. The main concerns
 are to effectively reduce bacteria in the short span of time the product
 is permitted to contact the surface while still maintaining a reasonable
 cost for the product allowing it to be feasible for commercial use. The
 use of a cleaner disinfectant concentrate in a liquid form is beneficial
 in that cleaning a surface and additionally elimination of bacteria is
 achieved in one step. The one step process reduces the bacteria that could
 cause contamination of other items placed on the surface such as food.
 The European Union standard suspension test, European Norm 1276 (EN1276),
 is a standard test for evaluation of the effectiveness of biocides in the
 European Union. The test was designed to simulate dirty conditions
 allowing for the evaluation of results of a product, experienced with
 simultaneously cleaning and disinfecting. Organic soils and hard water are
 known to interfere with the activity of biocides, so the use of
 "interfering substances" namely, bovine albumin (0.3%) and hard water (300
 ppm), represent the soil likely to be found when cleaning. The use of
 these interfering substances in the presence of quantitatively and
 qualitatively known bacteria (pseudomonas aeruginosa, the most difficult
 bacteria to kill; esherichia coli; staphylococcus aureus; enteroccus hire;
 amongst others) ensures a rigorous test standard ("dirty conditions"). To
 pass EN1276 and to claim a disinfectant product, a log 5 reduction
 (99.999% kill) of the bacteria must be attained at 20.degree. C.
 The use of Cleaner Disinfectant Concentrates is widespread throughout the
 industry, the majority being based on quaternary ammonium compounds.
 However, the kill of 99.999% of bacteria is normally met with long contact
 times (5 minutes or more) and by the use of products that contain very
 high levels of biocidal actives (much more than 300 ppm each). The
 consequence of using either a quaternary ammonium chloride or a polymeric
 biguanide alone is that they must be used in higher quantities to even
 achieve a satisfactory result at a time over five minutes. Additionally,
 the use of higher quantities results in a higher cost that is not
 commercially feasible. Polymeric biguanide is a particularly expensive
 biocide. The use of combinations of biocides until now has been
 ineffective in reducing the time necessary to eliminate 99.999% of the
 bacteria in the EN1276 test. The kill times have remained 5 minutes, which
 is excessive for the elimination of bacteria in a commercial setting or
 domestic setting because normal contact time of a cleaning an disinfecting
 composition within the work place or home is under five minutes.
 U.S. Pat. No. 5,529,713 claims a cleaning and disinfectant solution that
 contains quaternary ammonium chlorides and biguanide hydrochloride. This
 patent teaches the use of two or more quaternary ammonium chlorides and
 biguanide hydrochloride. The patent also teaches the use of two different
 quaternary ammonium salts in combination and a biguanide hydrochloride in
 order to have an effective bacterial reduction after five minutes which is
 unacceptable in the settings the product will be used. This patent further
 teaches the use of isopropyl alcohol, which very volatile evaporating
 quickly and also extremely flammable. The patent lastly does not teach the
 use of a sequestrant in combination with the quaternary ammonium chlorides
 and the biguanide hydrochloride.
 PCT patent publication WO 98/47359 describes a biocide composition without
 cleaning capabilities. The patent teaches the use of one quaternary
 ammonium chloride in over one percent and an amount of biguanide or
 another quaternary ammonium three percent or over in order to reduce
 bacteria in over five minutes. The patent also teaches the use of a high
 level of the biguanide or quaternary ammonium chloride is used without a
 sequestrant, in order to reduce a broad spectrum of bacteria that may be
 present.
 Sales information distributed by Zeneca Biocides, 1800 Concord Pike
 Wilmington, Del. 19850, suggests the combination of quaternary ammonium
 salts and a polymeric biguanide compound at a high percentage and at a
 ratio of 2:1 in order to have broad range bacterial reduction. The
 information is presented in relation to their product "Vantocil" that is a
 biguanide solution.
 SUMMARY OF INVENTION
 The present invention relates to disinfecting a hard surface in a reduced
 amount of time. The preferred embodiment relates to the simultaneous
 cleaning and disinfecting of a hard surface in a reduced amount of time.
 The invention comprises a composition that provides bacterial kill in the
 order of 99.999% in less than five minutes by incorporating an effective
 combination of a polymeric biguanide and a quaternary ammonium in
 effective amounts of at least 5 ppm and most preferably at 100 ppm to 300
 ppm each of the total composition, with a sequestrant all in diluted form.
 In addition the invention is a broad range disinfectant that kills 99.999%
 of bacteria, including pseudomonus aeruginosa, passing the EN1276 bacteria
 test method under "dirty" conditions in just 30 seconds.
 One aspect of the invention relates to a composition that contains a
 biocide and a cleaner in a liquid form that comprises a solvent, a
 polymeric biguanide, a quaternary ammonium compound, a sequestrant, and
 one or more surfactants. The preferred composition employs a solvent that
 includes water, a polyhexamethylene biguanide as the polymeric biguanide,
 and a didecyldimethylammonium as the quaternary ammonium. The composition
 also includes a sequestrant that is an acetic acid derivative selected
 from the group consisting of ethylenediaminetetraacetic acid (EDTA),
 nitrilotriacetic acid (NTA), Tetrasodium EDTA, or mixtures thereof. The
 surfactants contained in this composition comprise a linear alcohol
 ethoxylate and an amphoteric betaine. The composition contains the
 polymeric biguanide, quaternary ammonium salt, and a sequestrant of
 ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA),
 Tetrasodium EDTA or a mixture thereof in a ratio of 1 to 3:1 to 3:1 to 3
 most preferred in a ratio of 1:1:1.
 Another aspect of the invention comprises a composition that contains a
 biocide with a cleaner in a diluted liquid form that comprises water as a
 solvent, a polymeric biguanide that is at least 5 ppm of the total
 composition, a quaternary ammonium salt that is at least 5 ppm, of the
 total composition, sequestrant that is at least 5 ppm of the total
 composition, one or more surfactant that is at least 5 ppm of the total
 composition. The polymeric biguanide, preferably polyhexamethylene
 biguanide, and the quaternary ammonium salt, preferably
 didecyldimethylammonium, are contained in approximately equal amounts and
 preferably each presented in at least 100 ppm in the total composition.
 The invention also comprises a composition containing a biocide and a
 cleaning composition in a diluted liquid form containing a solvent of
 water, a polyhexamethylene biguanide and a didecyldimethylammonium
 chloride in approximately equal amounts of at least 5 ppm each of the
 total composition, a tetrasodium EDTA in at least 5 ppm of the total
 composition, a 9 carbon atom-11 carbon atom linear alcohol ethoxylate
 containing 6 moles ethylene oxide and an alkyl amido propyl dimethyl amine
 betaine in a combination in at least 5 ppm of the total composition. The
 composition incorporates a method for cleaning and disinfecting a hard
 surface that reduces kill time of pseudomonas aeruginosa bacteria to 30
 seconds: wherein the concentrated composition is diluted 1:100, then
 applied to a hard surface allowed to stand for fewer than 5 minutes and
 then the composition is removed eliminating 99.999% of bacteria, including
 the pseudomonas aeruginosa, on the surface.
 Another aspect of the invention relates to a biocide and cleaning
 composition containing a polymeric biguanide, a quaternary ammonium salt,
 in a ratio of approximately 1:1 and, tetrasodium EDTA, in amounts
 effective to reduce pseudomonas aeruginosa bacteria in 30 seconds or less,
 using the EN1276 test method under "dirty" conditions.
 The invention further comprises a concentrated composition that contains a
 biocide with a cleaner in a liquid form that comprises water as a solvent,
 a polymeric biguanide that is at least 5 ppm when diluted, quaternary
 ammonium salt that is at least 5 ppm when diluted, sequestrant that is at
 least 5 ppm when diluted, one or more surfactant that is at least 5 ppm
 when diluted.
 The biocide elements of the composition that are the quaternary ammonium,
 the polymeric biguanide, and the sequestrant, are contained in a ratio
 about 1:1:1 respectfully. The ratio of the biocides is maintained in a
 concentrated form or a diluted form.
 DETAILED DESCRIPTION OF THE INVENTION
 The purpose of the invention is to produce a composition for a concentrated
 cleaner disinfectant for the purpose of cleaning and disinfecting hard
 surfaces, in a shorter period of time (demonstrated through fast kill
 times in the EN1276) than known to date, while still meeting the
 commercial and regulatory requirements by using lower levels of biocides.
 The problem in prior compositions was the kill time was over five minutes
 and any attempts to lower this time involved the use of large amounts of
 the biocides which were unacceptable for their increased in cost.
 In the present invention the purpose was accomplished while simultaneously
 meeting the commercial and regulatory requirements while still maintaining
 low amount of biocide in the composition. Using a combination of a single
 quaternary ammonium salt with a single polymeric biguanide and a single
 sequestrant solved the problem described above, on which the invention is
 based. The combination of these elements in lower concentration provides a
 synergy that allows for the exponential increase in effectiveness and
 speed of bacterial elimination. This increased efficacy is enough to
 reduce the kill time from 5 minutes to 30 seconds while still reducing
 pseudomonas aeruginosa and other bacteria by 99.999% in the EN1276 test
 under dirty conditions. This effect is not seen when either of the
 biocides are used alone or if the combination of the two or more biocides
 are used without the sequestrant. The combination of all three compounds
 is the key factor in the invention. An illustration of the benefits of the
 claimed composition over standard compositions is detailed below.
 The present composition of the invention solves the problem by
 incorporating a polymeric biguanide having the general structure of:
 ##STR1##
 Where R1 is an alkyl, or an aminoalkyl radical, R2 is a hydrogen atom or an
 alkyl radical and n is an integer from 1-6. The amount of the biguanide is
 at least 5 ppm in the diluted form. The preferred range is 100 ppm to 300
 ppm in the diluted form. The reason for the preferred range is because the
 level is low enough to make the composition economically feasible and
 cause no environmental hazard while still reducing the kill rate to 30
 seconds. The ranges of the polymeric biguanide in the concentrated form is
 an effective amount of at least 5 ppm when diluted. The preferred
 biguanide is polyhexamethylene biguanide and has the structure with n
 being 12:
 ##STR2##
 The biguanide is contained in the amount of at least 5 ppm of the total
 diluted composition and more preferred at a level of 100 ppm to 300 ppm
 when diluted. The preferred amount and specific biguanide allows for the
 greatest effectiveness with the other products contained within the
 claimed invention.
 The present composition of the invention also claims a quaternary ammonium
 salt that has the general structure of:
 ##STR3##
 Where R1 and R2 are a CH3 or alkyl group containing 6 to 22 carbon atoms.
 R3 and R4 are alkyl groups which can be either an aromatic ring or a
 straight or branched carbon chain containing 6 to 22 carbon atoms and X is
 an anion selected from the following group: halogen, acetate, phosphate,
 nitrate, and sulfate. The amount of the biguanide is at least 5 ppm in the
 diluted form. The preferred range is 100 ppm to 300ppm in the diluted
 form. The reason for the preferred range is because the level are low
 enough to make the economically feasible and cause no environmental hazard
 while still reducing the kill rate to 30 seconds. The ranges of the
 quaternary ammonium in the concentrated form is at least 5 ppm when
 diluted. The preferred quaternary ammonium is didecyldimethylammonium that
 has the structure:
 ##STR4##
 Where there are two methyl groups and there are two decyl groups (10 carbon
 atoms). The quaternary ammonium is contained in the composition in at
 least 5 ppm of the total composition and at the more preferred range of
 100 ppm to 300 ppm. The preferred quaternary compound and its preferred
 amount allows for the greatest effectiveness with the other products
 contained within the claimed invention when within the range of the
 invention.
 The combination of quaternary ammonium with the polymeric biguanide allow
 for the broad spectrum of bacterial elimination of gram negative and gram
 positive bacteria. The broad spectrum is not at the efficiency level that
 is needed to product results in a short period of time. To increase the
 efficiency a sequestrant is added to the formulation to increase the
 elimination ability and speed of the biocides. The sequestrant that can be
 used has the general structures:
 ##STR5##
 The amount of the sequestrant is at least 5 ppm in the diluted form. The
 preferred range of the sequestrant at 100 ppm to 1000 ppm in the diluted
 form. The reason for the preferred range is because the level is high
 enough to assist in the formulation and increase the efficacy of the
 biocides reducing the kill rate to 30 seconds. The ranges of the
 sequestrant in the concentrated form is an effective amount of at least 5
 ppm when diluted. The preferred sequestrant is tetrasodium
 ethylenediaminetetraacetic acid that has the structure:
 ##STR6##
 The combination of a single quaternary ammonium, the polymeric biguanide
 and the sequestrant allow for the broad spectrum of bacterial elimination
 of gram negative and gram positive bacteria and additionally dramatically
 reduce the kill time require for the bacterial elimination. The
 composition further includes surfactants that are added so that there is a
 combined cleaning and disinfecting process. The surfactants are selected
 from group that allows for the maximum cleaning effect and minimal
 interference with the ability of the biocides to work properly. The
 surfactant is one or more from the following general structures.
 ##STR7##
 Where R is an alkyl derivative containing a reactive hydrogen atom for
 example an alkyl phenol, alcohol, amine, fatty acid, ester, glyceride or
 amide. The carbon chain length can vary from 6 carbon atoms to 18 carbon
 atoms. Also, n is 3 to 5 moles of ethoxylation or propoxylation, x is 3 to
 15 moles ethoxylation and y is 2 to 4 moles propoxylation.
 ##STR8##
 Where R is an alkyl group having 10 to 16 carbon atoms, R1 and R2 are
 identical or different alkyl groups but are often CH3.
 ##STR9##
 Where R1 is an alkyl group having 10 to 16 carbon atoms, R2 and R3 are
 identical or different alkyl groups having 1 to 4 carbon atoms, n is
 integers from 1 to 18.
 ##STR10##
 Where R1 is an alkyl group having 10 to 16 carbon atoms, R2 and R3 are
 identical or different alkyl groups having 1 to 4 carbon atoms, n is
 integers from 1 to 18.
EQU RNHCH.sub.2 CO.sub.2 H glycinate 7)
 Where R is an alkyl group having 1 to 4 carbon atoms. The surfactants have
 an amount of at least 5 ppm of the total composition in diluted form. The
 preferred range of 5 ppm to 3000 ppm, which allows for the most effective
 cleaning while still not interfering with the effectiveness of the
 biocides to kill bacteria. If the surfactants are used in too high
 quantities then the will inhibit the effectiveness of the biocides and the
 sequestrants and reduce or eliminate their bacterial reduction effects.
 The ranges of the surfactant in the concentrated form is an effective
 amount of at least 5 ppm.
 The solvent in the present invention can be a liquid that is
 environmentally acceptable, non-irritating to humans, will dissolve the
 ingredients and is not so volatile that it will evaporate before allowing
 the ingredients to clean the surface. The solvent is added to present
 composition of the invention to bring it up to 1,000,000 ppm or 100% in
 its concentrated state and diluted state. The solvent can be water,
 alcohol (ethanol, isopropyl), or glycols. The preferred solvent is water
 because it does not interfere with the effectiveness of the surfactants or
 the biocides and sequestrant.
 The determination of bacterial kill of the cleaning and biocidal agent was
 evaluated using The European Union standard suspension test, European Norm
 1276 (EN1276). This is a standard test for evaluation of the effectiveness
 of biocides in the European Union. The test was designed to simulate the
 dirty conditions experienced when simultaneous cleaning and disinfecting
 occurs. Organic soils and hard water are known to interfere with the
 activity of biocides, so the use of "interfering substances" namely,
 bovine albumin (0.3%) and hard water (300 ppm), represent the soil likely
 to be found when cleaning. The use of these interfering substances in the
 presence of quantitatively and qualitatively known bacteria (pseudomonas
 aeruginosa; esherichia coli; staphylococcus aureus; enteroccus hire;
 amongst others) ensures a rigorous test standard ("dirty conditions"). To
 pass the EN1276 and to claim a disinfectant product, a log 5 reduction
 (99.999% kill) of the bacteria must be attained in five minutes at
 20.degree. C. The EN1276 test method can also be used to test the
 effectiveness of disinfecting products when using contact times shorter
 than 5 minutes.

EXAMPLE 1
 A cleaning composition was prepared according to the present invention
 containing water as a solvent and combining into the solvent first, 180
 ppm of tetrasodium ethylenediaminetetraacetic acid, second, 600 ppm linear
 alcohol ethoxylate and 30 ppm betaine, third, 180 ppm of polymeric
 biguanide, and finally 180 ppm of a quaternary ammonium. The composition
 was tested and passed the EN1276 under dirty conditions, on all bacteria
 including pseudomonas aeruginosa in just 30 seconds. (as shown in table
 1).
 EXAMPLE 2
 The composition used for example 2, contained 220 ppm polymeric biguanide
 as the only biocide (having a comparable cost to composition A) failed the
 EN1276, dirty conditions, on pseudomonas aeruginosa in 5 minutes. In order
 to attain a pass at 5 minutes, let alone 30 seconds the level of biguanide
 would need to be increased to a level that is unacceptable due to
 environmental issues and commercial feasibility. (as shown in table 1).
 EXAMPLE 3
 A composition containing 720 ppm of quaternary ammonium salt with no
 biguanide, was tested per the EN1276, on pseudomonas aeruginosa in 5
 minutes it failed as shown in table 1. Increasing this concentration up to
 960 ppm passed the EN1276, on pseudomonas aeruginosa in 5 minutes. Again
 to pass the EN1276 in 30 seconds the quaternary ammonium salt would need
 to be increased to a level to which commercial feasibility and
 environmental acceptability are reduced, other aspects of the composition
 optimized in composition A, such as cleaning, would be decreased by the
 increase in the biocide (as shown in table 1).
 The test is conducted in a controlled environment where the bacteria are
 cultured in bovine serum. After the bacteria is cultured there is a count
 made of the bacteria to establish if there is a large enough count to
 perform the testing. Once there is a sufficient count the composition is
 applied and removed allowing for testing at different time intervals.
 After the desired time has passed and the composition is neutralized or
 filtered, the resultant solution cultured and a final count is performed
 to establish if the bacteria count was reduced sufficiently for a passing
 result. To conclude there was a passing result the bacteria count must be
 lowered by a log 5 reduction, or 99.999%. The results in the EN1276
 testing at 30 seconds are as follow in table one.
 The compositions tested show the increases in the effectiveness and the
 reduction in the time needed for bacterial kill. The use of a quaternary
 ammonium salt, a polymeric biguanide with tetrasodium EDTA in combination
 is key to eliminating the need for higher levels of biocide to kill
 bacteria in a short contact time.
 TABLE I
 Results: EN1276 test under dirty conditions at a 1:100 dilution.
 EXAMPLE EXAMPLE EXAMPLE
 NAMES 1 2 3
 CONTENTS IN DILUTED
 FORM:
 BIGUANIDE (100%) 180 PPM 220 PPM 0 PPM
 QUATERNARY 180 PPM 0 PPM 720 PPM
 AMMONIUM (100%)
 TETRASODIUM EDTA 180 PPM 220 PPM 320 PPM
 (100%)
 LINEAR ALCOHOL 600 PPM 600 PPM 600 PPM
 ETHOXYLATE (100%)
 BETAINE (100%) 30 PPM 30 PPM 0 PPM
 DI WATER TO 100% TO 100% TO 100%
 EN 1276 TEST RESULTS PASS FAILED FAILED
 AT 30 SECONDS
 EN 1276 TEST RESULTS PASS FAILED FAILED
 AT 5 MINUTES