阅读说明：本技术 经稳定的过氧酸溶液 (Stabilized peroxyacid solutions ) 是由 G·梅伦克维兹 于 2019-08-01 设计创作，主要内容包括：通过选自膦基聚羧酸、聚(丙烯酸)-丙烯酰胺基烷基丙烷磺酸共聚物或聚(丙烯酸)-丙烯酰胺基烷基丙烷磺酸-磺化苯乙烯三元共聚物的聚合物稳定剂使过氧酸的水溶液稳定。该经聚合物稳定的过氧酸溶液可应用于对表面的无菌灭菌和消毒中。(The aqueous solution of peroxyacids is stabilized by a polymeric stabilizer selected from the group consisting of a phosphonopolycarboxylic acid, a poly (acrylic acid) -acrylamidoalkyl propane sulfonic acid copolymer, or a poly (acrylic acid) -acrylamidoalkyl propane sulfonic acid-sulfonated styrene terpolymer. The polymer stabilized peroxy acid solution is useful in the aseptic sterilization and disinfection of surfaces.)

1. An aqueous composition comprising

A peroxy acid; and

one or more polymeric stabilizers selected from the group consisting of:

a) a phosphonopolycarboxylic acid or a salt thereof, the phosphonopolycarboxylic acid having a molecular weight of from 1500 to 10,000 g/mol; and

b) polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromAnd optionally presentA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

2. The composition of claim 1, wherein the one or more polymeric stabilizers are selected from the group consisting of the phosphonopolycarboxylic acids or salts thereof.

3. The composition of claim 2, wherein the phosphonopolycarboxylic acid is of formula (I):

wherein

R²Is composed of

R³Is composed of

R⁴Independently at each occurrence is hydrogen or C_1-4An alkyl group; and is

m and n are each independently an integer, wherein m + n is an integer from 30 to 60.

4. Combination according to claim 3In which R is⁴Is hydrogen.

5. The composition of claim 3 wherein the phosphonopolycarboxylic acid has a molecular weight of 3300-3900 g/mol.

6. The composition of claim 1, wherein the one or more polymeric stabilizers are selected from polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

7. The composition of claim 6, wherein the polymer is derived from A plurality of monomer units of each of (a).

8. The composition of claim 1, wherein the one or more polymeric stabilizers are selected from polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

9. The composition of claim 8, wherein the polymer is derived from A plurality of monomer units of each of (a).

10. The composition of claim 1, comprising 0.1-1500ppm of the one or more polymeric stabilizers.

11. The composition of claim 1, wherein the peroxyacid is one or more of peracetic acid and peroxooctanoic acid.

12. The composition of claim 1, having a peroxyacid concentration of less than about 35% by weight.

13. The composition of claim 1 comprising 4-20% by weight peracetic acid, 5-40% by weight acetic acid, 1-30% by weight hydrogen peroxide, and water in chemical equilibrium between peracetic acid, acetic acid, hydrogen peroxide, and water.

14. The composition of claim 1 having ≤ 5ppm of chelating substances other than the one or more polymeric stabilizers.

15. A method of aseptically sterilizing or disinfecting a surface, comprising contacting the surface with the composition of claim 1.

16. The method of claim 15, wherein the surface is a surface of a packaging material.

17. The method of claim 15, which is washer cold sterilization.

18. The method of claim 15, wherein the surface is contacted with an aqueous solution prepared by diluting the composition with water to a peroxyacid content of about 0.001 to about 1% by weight.

Technical Field

The present invention relates to a stabilized aqueous peroxyacid solution, to a process for the preparation of said solution and to the use of said solution for the aseptic sterilization or disinfection of surfaces. The invention relates in particular to stabilized aliphatic peroxyacid solutions, in particular peracetic acid solutions.

Background

Aqueous solutions of peroxyacids have many applications in industry, including in particular as bleaching agents, reagents in chemical synthesis, and especially as disinfectants for domestic, industrial and environmental applications. Many of these applications are performed at a location remote from the location of peroxyacid production, and the peroxyacid is therefore advantageously stable at least during transport to the site of application. In very large amounts, the peroxyacid may also be stored for a considerable time, usually months or even years, e.g. in a warehouse before use.

The stability of peroxyacid solutions can be improved by avoiding the introduction of impurities (in particular transition metal ions) into the solution during its manufacture, which may make the peracid unstable. However, as a practical matter, it is virtually impossible to ensure that no such impurities are present. Furthermore, even if impurities are avoided during manufacture, there is still a possibility of introducing impurities during any subsequent packaging or transport of the solution. Therefore, it is desirable to stabilize peracid solutions from decomposition by such impurities. In addition to stabilizing the peracid solution during storage, the presence of a stabilizer in the peracid solution may have the additional benefit of improving the stability of the peracid solution in use and thus increasing the efficacy of the solution. The presence of the stabilizer may also reduce the deleterious properties of the solution.

Many systems have been proposed for use as stabilizers for peracid solutions. Among those found to have broad utility, including dipicolinic acids, such as disclosed in U.S. patent No. 2,609,391. Other compounds include phosphonates, particularly those disclosed in Henke's british patent No. 925,373. In some cases, combinations of stabilizers are used, such as the combinations of dipicolinic acid and phosphonate disclosed in international application publication nos. W091/07375 and W091/13058. Phosphate salts (phosphates) have been proposed as stabilizers for peracid solutions in U.S. Pat. nos. 2,347,434 and 2,590,856. European patent No. 0563584 teaches that stannates can be used to stabilize the peracid solution, provided that the stannate is added to the peracid solution during or after manufacture, or added to the reaction mixture immediately before the reaction begins. Stannates can be used in peracid solutions with a separate addition of co-stabilizer; and only dipicolinic acid and l-hydroxyethane-1, 1-diphosphonic acid are exemplified, although a number of potential co-stabilizers are contemplated, including polyphosphoric acid (polyphosphoric acid) and pyrophosphoric acid and their salts.

While some stabilizer systems for peracid solutions are known, it is still desirable to identify additional or further systems.

Disclosure of Invention

According to one aspect of the present invention there is provided an aqueous solution of a peroxyacid comprising: a peroxy acid; and one or more polymeric stabilizers (polymeric stabilizers) selected from the group consisting of:

a) a phosphino polycarboxylic acid (or salt thereof) having a molecular weight of from 1500 to 10,000 g/mol; and

b) polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromAnd optionally presentA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

The present invention provides stabilized peroxyacid solutions having improved stability against trace metal attack and decomposition. The stabilized peroxyacid solutions are suitable for food applications as well as providing anti-fouling properties to enable their use in oil field applications where metals and anti-fouling are required. The stabilized peroxyacid solution may be used at higher levels of typical stabilizers (phosphates, stannates, dipicolinic acids, chelating agents, etc.) or in the case of removal of the chelating agent when it is not acceptable.

In another aspect, there is provided a method of stabilizing an aqueous solution of peroxyacids by adding an effective amount of one or more polymeric stabilizers as described herein.

According to another aspect of the present invention there is provided a method for sterilising a packaging material comprising contacting said packaging material with an aqueous solution of a peroxyacid according to the present invention.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

To enumerate the numerical ranges herein, each intervening number between them with the same degree of accuracy is explicitly contemplated. For example, for the range 6-9, the numbers 7 and 8 are considered in addition to 6 and 9; and for the range 6.0-7.0, the numbers 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9 and 7.0 are explicitly considered.

The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes at least the degree of error associated with measurement of the particular quantity). The modifier "about" should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression "about 2 to about 4" also discloses the range "2 to 4". The term "about" may refer to plus or minus 10% of the number indicated. For example, "about 10%" may mean a range of 9% to 11%, and "about 1" may mean 0.9-1.1. Other meanings of "about" may be apparent from the context, e.g., rounding off, so, for example, "about 1" may also mean 0.5 to 1.4.

The terms "peroxyacid" and "peracid" are used interchangeably herein.

Unless specifically stated otherwise, for any component,% and ppm herein are by weight based on the total weight of the composition.

Peroxy acids which may be stabilised in solution include those derived from inorganic acids, for example peroxymonosulphuric acid (Caro's acid). Preferred, however, are percarboxylic acids, wherein the pKa of the percarboxylic acid group in aqueous solution is between 6 and 9. Examples of such peracids include low molecular weight aliphatic peroxyacids containing up to 6 carbon atoms, with particularly preferred examples including peracetic acid and perpropionic acid. Other examples include performic acid, perbutyric acid, dipersuccinic acid, diperslutaric acid and dipersoadipic acid. The alkyl portion of the chain may be optionally substituted with one or more substituents selected from halo-, nitro-, amido-, hydroxy-, carboxy-, sulfo-, or phosphono-groups. Contemplated from such groups are monochloroperacetic acid, dichloroperacetic acid, trichloroperacetic acid and trifluoroperacetic acid. Further examples include: mono-peracids of dicarboxylic acids, such as monopersucciic acid (monopersucciic acid), monoperplutaric acid (monoperglucuric acid), monopersadic acid (monopersadic acid); and percitric acid (percitric acid) and pertartaric acid (pertartaric acid). In addition, the substituents may be further derivatized to give groups such as esters or ethers. Examples of these are monoester peracids of the formula:

wherein R represents an alkyl group having 1 to 4 carbons, and x is 1 to 4.

Mixtures of peracids, in particular mixtures of mono-and di-persuccinic, perglutaric and peradipic acids, can be used if desired. Particularly suitable are the monoester peracids given above and more particularly mixtures of these acids comprising x ═ 2,3 and 4. The composition may alternatively or additionally include aromatic and substituted aromatic peroxyacids, such as monoperphthalic acid or salts thereof, sulfoperbenzoic acid or salts thereof, chloroperbenzoic acid, and toluene perbenzoic acid.

In addition, one or more higher molecular weight aliphatic peroxyacids having from 6 to 18 carbon atoms may be used in combination with the low molecular weight aliphatic peracids given above, although it is recognized that these higher molecular weight aliphatic peroxyacids may not be completely soluble in the stabilized solution. Particularly suitable higher molecular weight acids are linear aliphatic monoperoxy-fatty acids, or monoperoxy-or diperoxy-dicarboxylic acids. Examples thereof are peroxooctanoic acid, peroxodecanoic acid, monoperoxy-or diperoxyazelaic acid and monoperoxy-or diperoxydodecanedioic acid.

The peracid (which may actually be a mixture of peracids) may be present in a wide range of concentrations, for example not higher than 40%, often not higher than 15% and more often not higher than 10%. The lower limit of the peracid concentration is determined by the user, but is usually not less than 0.001%. The invention is particularly applicable to ready-to-use compositions containing low concentrations of peracid, including for example compositions intended for cleaning and/or disinfecting hard surfaces, particularly non-horizontal surfaces. Such diluted compositions typically contain not less than 0.05%, often not less than 0.1% and more often not less than 0.5%. For example, in many practical embodiments, the peracid content is from 0.2% to often 0.5% to 1.5%. In some embodiments, the peroxyacid content is less than about 35%. In some embodiments, the peroxyacid content is about 1 to 25% by weight, i.e., about 1,2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% by weight. In some embodiments, the peroxyacid is present at about 20-25 wt.%, 21-23 wt.%, 12-18 wt.%, 14-16 wt.%, 2-14 wt.%, 3-12 wt.%, 4-11 wt.%, 5-9 wt.%, about 6-8 wt.%. In some embodiments, the peroxyacid is present at about 22% by weight. In some embodiments, the peroxyacid is present at about 15% by weight. In some embodiments, the peroxyacid is present at about 5% by weight. It is recognized that such compositions may contain significant concentrations of hydrogen peroxide, which may, for example, comprise 1-15% and in many embodiments 3-10% of the composition.

In various embodiments, the hydrogen peroxide is present from about 10% to about 50% by weight of the composition. In some embodiments (e.g., after equilibration and peracetic acid formation), hydrogen peroxide is present at about 10-40 wt.%, 15-35 wt.%, 18-30 wt.%, or about 20-26 wt.% of the composition. In some embodiments, the hydrogen peroxide is present at about 16 wt%, 18 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 34 wt%, or about 36 wt%. In some embodiments, the hydrogen peroxide is about 35% by weight in water, present in about 18% to about 32% by weight of the composition. In some embodiments, the hydrogen peroxide is about 35% by weight in the water, present at about 28% by weight of the composition. In some embodiments, the hydrogen peroxide is about 35% by weight in water, present in about 20% to about 26% by weight of the composition.

The peracid compositions suitable for stabilization according to the invention, and in particular those containing aliphatic peracids, are often conveniently obtained by oxidation of the corresponding aliphatic carboxylic acids with aqueous hydrogen peroxide, optionally in the presence of a strong acid catalyst, and often contain residual amounts of said carboxylic acids and hydrogen peroxide.

In one aspect of the invention, the solution to be stabilized comprises: so-called equilibrium peroxycarboxylic acids, such as peracetic acid, having a peracetic acid content of 0.05 to 40%, preferably 4 to 20%; 5-40% acetic acid; 1-30% of hydrogen peroxide and the balance of water. Optionally, the solution contains sufficient mineral acid (e.g., sulfuric acid) to accelerate the equilibrium.

Such compositions in many cases comprise not more than 40% of the corresponding carboxylic acid and not more than 30% of hydrogen peroxide, the minimum water content being generally 20%. However, in dilute peracid solutions, the concentrations of carboxylic acid and hydrogen peroxide each tend to be selected in the range of 0.1% to 12%. The total concentration of carboxylic acid plus percarboxylic acid is generally between 0.1 and 50%. It is often convenient to limit the concentration of hydrogen peroxide to no more than 7%.

One way to define such a system is by an equilibrium constant K. This can be conveniently expressed for the current system as follows:

for this purpose:

peracetic acid is generally used herein as a representative of peracids for which the corresponding equation is valid.

It will be appreciated that if two initially identical non-equilibrium compositions have different equilibrium constants at the end of the storage period during which equilibrium occurs, then the composition with the higher equilibrium constant will have a higher peracetic acid content.

In another aspect of the invention, the solution to be stabilized is a non-equilibrium solution of a percarboxylic acid (e.g., peracetic acid). Examples are those derived from the distillation of peracetic acid solutions and usually contain only small amounts of acetic acid or hydrogen peroxide. It will be appreciated that the use of such compositions is desirable and often necessary where, for example, acetic acid may cause unwanted side reactions. Further removal downstream in the process is often desirable for environmental and economic reasons, and also serves to slow the growth of microorganisms that may contaminate the pipeline. For the reasons mentioned above, the use of such non-equilibrium solutions may be particularly useful in applications such as pulp delignification, and also in disinfection, particularly in the horticultural industry as well as in hard surface cleaners.

However, because they are non-equilibrium solutions, once formed, they will quickly begin to revert to an equilibrium composition. The stabilization of these non-equilibrium peracids clearly means that the rate of re-equilibration is reduced and therefore the rate of reduction of the concentration of peracetic acid is reduced. Although the process cannot be stopped completely, certain factors such as low temperature are known to slow it down. Such compositions typically contain: not more than 55% of peracetic acid, a small amount of hydrogen peroxide and acetic acid, and the balance of water. In many other embodiments, the peracetic acid solution is further diluted with water to obtain a solution containing 20 to 40% peracetic acid.

In a further aspect, the solutions to be stabilized are those non-equilibrium solutions in which the peracid is present in an amount in excess of the amount present at equilibrium. These solutions may include so-called in-use compositions in which an equilibrium or non-equilibrium solution as described in the previous aspect of the invention is diluted with one or more non-peracid components, most typically with water. Such compositions typically have a peracid concentration of no more than 2%, although the concentration is typically from about 0.001% to about 1%, preferably from about 0.002% to about 0.75%. These solutions may also include compositions that have been cooled for a period of time prior to use, such as during shipping or on-site storage. Because the equilibrium constant of a peracetic acid solution is inversely proportional to temperature, the cooled composition has a higher peracetic acid content than a warmer composition, the extent of which depends on the progression of the composition toward a new equilibrium.

In some embodiments, the one or more polymeric stabilizers are selected from a phosphonopolycarboxylic acid or salt thereof. In some embodiments, the phosphonopolycarboxylic acid has the formula (I)

Wherein R is²Is composed ofR³Is composed ofR⁴Independently at each occurrence is hydrogen or C_1-4An alkyl group; and m and n are each independently an integer, wherein m + n is an integer from 30 to 60. In some embodiments, R⁴Is hydrogen. In some embodiments, the phosphonopolycarboxylic acid has a molecular weight of 3300-3900 g/mol.

In some embodiments, the one or more polymeric stabilizers are selected from polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromA plurality of monomer units of each of (a). In some embodiments, the polymer is derived from A plurality of monomer units of each of (a). The polymeric stabilizer is preferably composed of the specified monomer units.

In some embodiments, the one or more polymeric stabilizers are selected from polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived from A plurality of monomer units of each of (a). In some embodiments, the polymer is derived fromA plurality of monomer units of each of (a). The polymeric stabilizer is preferably composed of the specified monomer units.

In some embodiments, the peroxide solution is stabilized with 0.1 to 1500ppm of one or more polymeric stabilizers.

In some embodiments, the peroxyacid solution is stabilized with 0.1 to 60ppm, 0.1 to 50ppm, 0.1 to 40ppm, 0.1 to 30ppm, 0.1 to 20ppm, 0.1 to 10ppm, 10 to 20ppm, 20 to 30ppm, 30 to 40ppm, 40 to 50ppm, or 50 to 60ppm of one or more polymeric stabilizers. In other embodiments, higher concentrations of one or more polymeric stabilizers are used to stabilize the peroxyacid solution. In some embodiments, the one or more polymer stabilizers are added in an amount of 100ppm or more, 200ppm or more, 300ppm or more, 500ppm or more, 750ppm or more, 1000ppm or more, 1500ppm or more, or 2000ppm or more.

The use of the polymeric stabilizer system herein does not exclude or limit the presence of other known stabilizers with respect to peroxygen (peroxigen). The stabilized peroxyacid solutions of the invention may comprise further stabilizers and additives, such as phosphates, stannates or chelating agents. The polymeric stabilizer may be used with one or more compounds that may be present at a concentration of 0.001% to 1%. Such compounds are for example: polycarboxylic acids, including, for example, dipicolinic acid, ethylenediaminetetraacetic acid or citric acid; soluble salts in phosphates, which may take the form of simple monomeric species, or condensed linear polyphosphates or cyclic metaphosphates. Other known stabilizers that may be included are organic phosphonates, the molecule of which may additionally contain other functional groups, such as hydroxyl or amino groups. These substances are exemplified by compounds such as l-hydroxyethylidene-1, 1-diphosphonic acid and poly (methyleneamino) -phosphonic acids such as aminotri (methylenephosphonic acid) and diethylenetriamine penta (methylenephosphonic acid).

Useful stannates include alkali metal stannates, particularly sodium stannate (Na)₂(Sn(OH)₆). Stannates further include stannic chloride, stannic oxide, stannic bromide, stannic chromate, stannic iodide, stannic sulfide, tin bis (2, 4-pentanedionate) dichloride, tin dichlorophthalocyanine, stannic acetate, tin tert-butoxide, di-n-butyltin dichloride (IV), stannic methacrylate, stannic fluoride, stannic bromide, stannic phosphate, stannous chloride, stannous fluoride, stannous pyrophosphate, sodium stannate, stannous 2-ethylhexanoate (stannous 2-ethyl hexoate), stannous bromide, stannous chromate, stannous fluoride, stannous methanesulfonate, stannous oxalate, stannous oxide, stannous sulfate, stannous sulfide, barium stannate, calcium stannate, copper (II) stannate, lead stannate dihydrate, zinc stannate, sodium stannate, potassium stannate trihydrate, strontium stannate, cobalt (II) stannate dihydrate, sodium trifluorostannate, ammonium hexachlorostannate, and lithium hexafluorostannate.

Another optional component of the stabilized peroxyacid solution is a soluble salt of a phosphate salt. The phosphate may take the form of a simple monomeric species, or a condensed linear or cyclic polyphosphate (metaphosphate). The monomeric phosphate has the formula M_nH_qPO₄(wherein q is 0, 1 or 2; n is 1,2 or 3; n + q is 3). Here, M may be one or more monovalent cations selected from the group consisting of: li, Na, K, NH₄、NR₄(wherein R represents an alkyl chain comprising 1 to 5C atoms). The polyphosphate has the general formula M_n+2P_nO_3n+lWherein n is 2 to 8, and M may be selected from Li, Na, K, NH₄、NR₄(wherein R represents an alkyl chain comprising 1 to 5C atoms). The cyclic polyphosphate has the general formula M_nP_nO_3nWhere n is 3 to 8 and M may be selected from Li, Na, K, NH₄、NR₄(wherein R represents a linear or branched alkyl group containing 1 to 5C atoms). The above-mentioned substances can optionally be introduced into the stabilizer system in their acid form. Exemplary phosphates include pyrophosphoric acid and metaphosphoric acid (metaphosphoric acid) and their salts (e.g., sodium salts).

Any phosphonic acid based chelating agent may optionally be used, such as aminotrimethylene phosphonic Acid (ATMP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), N-sulfonato aminodimethylene phosphonic acid (SADP), Methylenephosphonic Acid (MADMP), glycine dimethyl phosphonic acid (GDMP), 2-hydroxyphosphonocarboxylic acid (HPAA), polyol phosphates (PAPE), 1-hydroxyethylene-1, 1-diphosphonic acid (HEDP), 1-aminoethane-1, 1-diphosphonic acid, aminotri (methylenephosphonic Acid) (ATMP), ethylene diamine tetra (methylenephosphonic acid), hexamethylenediamine tetra (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid) (DTPMP), diethylenetriamine hexa (methylenephosphonic acid), and 1-aminoalkane-1, 1-diphosphonic acids such as morpholinomethane diphosphonic acid, N-dimethylaminomethyldiphosphonic acid, aminomethyl diphosphonic acid or salts thereof (preferably sodium salts).

Further stabilizers to be considered are free radical scavengers. Useful free radical scavengers include pyridine carboxylic acids, such as 2, 6-pyridinedicarboxylic acid and picolinic acid (picolinic acid). The scavenger may be selected from phenols, polyols or thiols. Suitable scavengers are those selected from the group of phenols satisfying the general formula (II)

Wherein R represents at least one substituent selected from the group consisting of alkyl, ether, hydroxyl, carboxylic acid and aliphatic carboxylate groups. Typically, R in (II) represents 1 to 4 substituents. One suitable subset of phenolic scavengers is polyhydroxy benzoic acids or alkyl ester derivatives thereof wherein the benzene nucleus is optionally further substituted with one or more alkyl substituents. Typically, no more than a single carboxylic acid/ester substituent is present. Included in this subclass are dihydroxybenzoic acid, gallic acid, pyrogallic acid, and ester derivatives thereof. Other suitable subclasses include polyhydroxyalkylbenzenes or ether derivatives thereof. Representatives of this subclass include alkylresorcinols and alkylhydroquinones. Other suitable radical scavengers are substituted polyarylates, including those in which one or more aromatic rings are substituted with heteroatoms. A suitable example from this group is 8-hydroxyquinoline.

Also conceivable as phosphorus-containing salts are organic phosphonates which can be introduced in the form of soluble salts or parent acids (parent acids). Compounds which may be considered include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, tert-butylphosphonic acid or phenylphosphonic acid. In addition, the phosphonic acid molecule may contain other functional groups, such as hydroxyl or amino groups. These substances are exemplified by, for example, the following compounds: 1-hydroxyethylidene-1, 1-diphosphonic acid and poly (methyleneamino) phosphonic acids, such as aminotri (methylenephosphonic acid) and diethylenetriamine penta (methylenephosphonic acid).

Other additives that may be considered are sulfuric acid or soluble salts thereof. Organic sulfonic acids (e.g., decyl sulfonic acid, dodecyl sulfonic acid, toluene sulfonic acid, and methyl sulfonic acid) and their salts may also be introduced. The stannate may be used at a concentration of no more than 15%, more preferably 8-12% of the total stabilizer solution.

The other phosphorus-containing additives may be added in a total concentration of not more than 18% relative to the total weight of the stabilizer solution. More preferably, a concentration of 10-14% is used.

It will be appreciated that the compositions of the invention may comprise a mixture of: two or more of one or more polymeric stabilizers, at least one protective colloid, at least one radical scavenger, and at least one phosphonic acid based chelating agent.

Accordingly, in some embodiments of the present invention, there is provided a method of stabilizing an aqueous peroxyacid solution by adding thereto an effective amount of one or more polymeric stabilizers.

The water used to prepare the stabilizer solution may be obtained from a local municipal supply. More preferably, the water is further purified such that its conductivity is reduced to below 1. mu.S/cm. For some applications, ultra-high purity water having a conductivity of less than 0.06. mu.S/cm may be used.

In particular embodiments, the compositions of the present invention may be stable (i.e., have long-term stability) over an extended period of time. The term "long-term stability" refers to a substance that undergoes little or no physical and/or chemical decomposition or degradation over an extended period of time. In a further embodiment, the compositions of the present invention may be stable over extended periods of time such that less than about 5% by weight of each component degrades independently within about one year at about 1atm and about l9 ℃. In another embodiment, the compositions of the present invention may be stable over extended periods of time such that at least about 95% by weight of each component is independently present after about one year at about 1atm and about l9 ℃. Making the composition relatively stable over an extended period of time will enable the composition to maintain its effectiveness over that period of time, thereby ensuring that it remains useful and active for its intended purpose. Conversely, in those compositions that do not maintain their effectiveness over that time, product loss may result, which may be economically expensive.

The compositions of the present invention are useful for effectively reducing the number of microorganisms located on a substrate. In particular embodiments, the compositions are effective to kill and/or inhibit microorganisms (e.g., viruses, fungi, molds, slime bacteria, algae, yeasts, mushrooms, and/or bacteria) and thereby disinfect a substrate.

In other embodiments, the composition is effective to sanitize a substrate, thereby simultaneously cleaning and disinfecting the substrate. In other embodiments, the composition can effectively kill or inhibit all forms of life, not just microorganisms, thereby acting as a biocide.

In particular embodiments, the compositions are effective for disinfecting substrates. In a further embodiment, the composition is effective to disinfect a surface of a substrate. In other embodiments, the composition is effective to sterilize a substrate. In a further embodiment, the composition is effective to sterilize the surface of a substrate.

The compositions of the present invention may be formulated for administration according to the preferences of the user and the end use of the composition. For example, the composition can be formulated for use in a sprayable composition, an atomized liquid sprayer, or a liquid applicator. Such formulations (formulations) may include at least one of a spray bottle, an electric sprayer (motorized sprayer), a wipe, a cloth, a sponge, a nonwoven, and a woven fabric. Such formulations may be particularly suitable for applying the composition to the surface of a hospital, physician's office, medical clinic, medical facility, dental office, dental facility, airport, school, pet store, zoo, children day care, senior care home, museum, movie theater, sports facility, sports arena, stadium, lavatory (rest room), bathroom, shopping center, amusement park, church, kosher hall, halal temple, restaurant, food processing facility, food manufacturing facility, pharmaceutical company, hot-water bath (hot-tub), sauna, and/or clean room. Such liquid formulations may be particularly suitable for applying the composition to metal, plastic, natural rubber, synthetic rubber, glass, stone, grout, fiberglass, wood, concrete, construction products and/or building products.

Packaging materials (e.g. for food products) may be sterilised with the stabilised peroxyacid solutions described herein. In some embodiments, the packaging material is made of PET. In some embodiments, the packaging material is contacted with the stabilized peroxyacid solution for a sufficient time to sterilize the packaging material. In some embodiments, the method is washer cold sterilization, which washes the bottle with an aqueous disinfectant solution (upside down) based primarily on peroxy acids (e.g., peracetic acid) as the active chemical. A second washing step with clean water must then be carried out to remove residual disinfectant. The flusher method does not require high temperatures and is also referred to as cold sterilization. The average consumption of peracetic acid is about 0.2 to 0.5ml per unit.

In particular embodiments, the compositions of the present invention may be non-toxic. The term "non-toxic" refers to a substance that has a relatively low degree of damage to living or non-living organisms. Toxicity may refer to an effect on a whole organism, such as an animal, bacterium or plant, and on a substructure of an organism, such as a cell (cytotoxicity) or an organ (organ toxicity), such as the liver (hepatotoxicity). The central concept of toxicology is that the effect is dose-dependent; even water can cause water poisoning when taken in sufficiently large doses, and for very toxic substances such as snake venom, lower doses are present than would be undetectable for their toxic effect. Making the composition relatively non-toxic would enable a wide range of users to safely handle the composition without serious safety problems or risks.

The invention also provides a kit (kit) comprising: (a) a closed container comprising a removable closure; (b) a composition of the invention as described herein, located within the closed container; and (c) printed indicia on the closed container.

In particular embodiments, the closed container may be opaque. In other embodiments, the closed container may be made of High Density Polyethylene (HDPE), thereby providing the desired opacity. Having the closed container made of High Density Polyethylene (HDPE) will reduce the likelihood of the composition degrading and/or decomposing over an extended period of time due to excessive exposure to direct sunlight.

It should be understood that the foregoing detailed description and accompanying examples are exemplary only, and should not be taken as limiting the scope of the invention, which is defined only by the appended claims and equivalents thereof. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications, including but not limited to those relating to the chemical structures, substituents, derivatives, intermediates, syntheses, compositions, formulations, or methods of use of the invention, may be made without departing from the spirit and scope thereof.

Examples

Equilibrium peroxyacetic acid was prepared by: 58.5 parts by weight of 50% by weight hydrogen peroxide, 28.4 parts by weight of acetic acid, 12.1 parts by weight of deionized water and 0.9 parts by weight of concentrated sulfuric acid (calculated initial active oxygen content: 13.77% by weight) were mixed, the mixture was divided into five equal samples, stabilizers were added to the different samples in the amounts given in Table 1, and the mixture was allowed to stand at room temperature. HEDP is 1-hydroxyethylidene-1, 1-diphosphonic acid. A4161 is Acumer from Rohm and Haas^TM4161: the acid form of the phosphonopolycarboxylic acid has a pH of from 3.0 to 3.5 and a molecular weight of 3300-3900g/mol, determined by GPC. The stability of the equilibrium peroxyacetic acid was evaluated after 1 month by: the volume of oxygen released by the decomposition of a 100ml sample kept at 60 ℃ after an equilibration time of 45 minutes within 15 minutes was determined by using a gas metering tube. If the volume of oxygen released in this test exceeds 3ml, the equilibrium peroxyacetic acid is not stable enough to be transported. The results are given in table 1.

The samples were analyzed for peracetic acid content and hydrogen peroxide content after 13 weeks and after 20 weeks by: the hydrogen peroxide is redox titrated with cerium (IV) sulfate, followed by addition of iodide and back titration with thiosulfate for determination of the peroxyacid content. Table 2 gives the results of the analysis, the active oxygen content calculated from the analysis and the fraction of active oxygen lost in the 7-week interval between the analyses.

TABLE 1

TABLE 2

For completeness, various aspects of the invention are set forth in the following numbered clauses:

clause 1. an aqueous composition comprising

A peroxy acid; and

one or more polymeric stabilizers selected from the group consisting of:

a) a phosphonopolycarboxylic acid or a salt thereof, the phosphonopolycarboxylic acid having a molecular weight of from 1500 to 10,000 g/mol; and

b) polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromAnd optionally presentA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

Clause 2. the composition of clause 1, wherein the one or more polymeric stabilizers are selected from the group consisting of the phosphonopolycarboxylic acids or salts thereof.

Clause 3. the composition of clause 2, wherein the phosphonopolycarboxylic acid has the formula (I):

wherein

R²Is composed of

R³Is composed of

R⁴Independently at each occurrence is hydrogen or C_1-4An alkyl group; and is

m and n are each independently an integer, wherein m + n is an integer from 30 to 60.

Clause 4. the composition of clause 3, wherein R⁴Is hydrogen.

Clause 5. the composition of clause 3 or 4, wherein the phosphonopolycarboxylic acid has a molecular weight of 3300-3900 g/mol.

Clause 6. the composition of clause 1, wherein the one or more polymeric stabilizers are selected from polymers having a molecular weight of 3000 to 15,000g/mol, or salts thereof, derived fromA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

Clause 7. the composition of clause 6, wherein the polymer is derived from A plurality of monomer units of each of (a).

Clause 8. the composition of clause 1, wherein the one or more polymeric stabilizers is selected from a polymer having a molecular weight of 3000 to 15,000g/mol, or a salt thereof, the polymer being derived fromA plurality of monomer units of each of (1), wherein R¹Is hydrogen or C_1-4Alkyl and L¹Is C_2-6An alkylene group.

Clause 9. the composition of clause 8, wherein the polymer is derived from A plurality of monomer units of each of (a).

Clause 10. the composition of any one of clauses 1-9, comprising 0.1-1500ppm of the one or more polymeric stabilizers.

Clause 11. the composition of any of clauses 1-10, wherein the peroxyacid is one or more of peracetic acid and peroxooctanoic acid.

Clause 12. the composition of any of clauses 1-11, having a peroxyacid concentration of less than about 35 wt.%.

Clause 13. the composition of any of clauses 1-12, comprising 4-20 wt.% peracetic acid, 5-40 wt.% acetic acid, 1-30 wt.% hydrogen peroxide, and water in chemical equilibrium between peracetic acid, acetic acid, hydrogen peroxide, and water.

Clause 14. the composition of any one of clauses 1-13, having ≦ 5ppm of a chelating substance other than the one or more polymeric stabilizers.

Clause 15. a method of aseptically sterilizing or disinfecting a surface, comprising contacting the surface with the composition of any of clauses 1-14.

Clause 16. the method of clause 15, wherein the surface is a surface possessed by a packaging material.

Clause 17. the method of clause 15 or 16, which is washer cold sterilization.

Clause 18. the method of any of clauses 15-17, wherein the surface is contacted with an aqueous solution prepared by diluting the composition of any of clauses 1-14 with water to a peroxyacid content of about 0.001 to about 1 wt.%.