WO1992019212A2 - Glycine anhydride dimethylol as a biocide and preservative - Google Patents

Glycine anhydride dimethylol as a biocide and preservative Download PDF

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Publication number
WO1992019212A2
WO1992019212A2 PCT/US1992/003442 US9203442W WO9219212A2 WO 1992019212 A2 WO1992019212 A2 WO 1992019212A2 US 9203442 W US9203442 W US 9203442W WO 9219212 A2 WO9219212 A2 WO 9219212A2
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WO
WIPO (PCT)
Prior art keywords
substance
glycine anhydride
product
anhydride dimethylol
dimethylol
Prior art date
Application number
PCT/US1992/003442
Other languages
French (fr)
Other versions
WO1992019212A3 (en
Inventor
Phillip A. Berke
William E. Rosen
Original Assignee
Isp Chemicals Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Isp Chemicals Inc. filed Critical Isp Chemicals Inc.
Priority to CS932301A priority Critical patent/CZ230193A3/en
Priority to AU19169/92A priority patent/AU654192B2/en
Priority to JP4511432A priority patent/JPH06507403A/en
Priority to BR9205953A priority patent/BR9205953A/en
Publication of WO1992019212A2 publication Critical patent/WO1992019212A2/en
Publication of WO1992019212A3 publication Critical patent/WO1992019212A3/en
Priority to NO1993933894A priority patent/NO933894D0/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3544—Organic compounds containing hetero rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives

Definitions

  • This invention relates to the use of giycine anhydride dimethylol, as a biocide and an antimicrobial agent to kill microorganisms present in or on substances and to preserve a variety of substances susceptible to microbial contamination.
  • Glycine anhydride dimethylol also known as 1
  • -bis(hydroxymethyl ⁇ - 2,5-piperazinedione is a known chemical compound prepared by reacting glycine anhydride, also referred to as 2,5-piperazinedione with formaldehyde according to the following formula:
  • This invention is based upon the discovery that glycine anhydride dimethylol, also known as 1 , 4-bis(hydroxymethyl.-2,5-piperazinedione, represented by the formula:
  • This compound exhibits biocidal activity against a wide range of microorganisms, including bacteria, yeast and mold.
  • This compound therefore, is an effective biocidal agent which kills microorganisms present in or on a host substance and inhibits microbial growth in or on a variety of substances and products, whether they be solid, liquid or emulsion form.
  • Such products include, but are not limited to, cosmetics, foodstuffs, pharmaceuticals, paints, cutting oils or fluids, agricultural products, oil drilling fluids, lubricants, paper industry products, embalming solutions, cold steriiized medical and dental equipment, cooling towers, fabric impregnation, latexes, swimming pools, inks, household disinfectants, waxes and polishes, toilet bowi cleaners, bathroom cleaners, laundry detergents, soaps, wood preservatives, hospital and medical antiseptic and adhesives.
  • pro ⁇ ucts foo ⁇ stuffs
  • pharmaceuticals, cosmetic and personal hygiene products such as shampoos are of particular interest.
  • Other uses of glycine anhydride dimethylol according to the invention include industrial uses where the compound is used to control microbial growth, such as for slime control in the effluent of paper mills.
  • glycine anhydride dimethylol can be used to kill microorganisms which have contaminated a host substance or as a preservative to inhibit and prevent growth of microorganisms in substances susceptible to microbial growth.
  • the compound is also effective in disinfecting and/or sterilizing surfaces prone to contamination by microorganisms.
  • the effective amount of glycine anhydride dimethylol required will, of course, vary depending upon the mode of use, e.g., as a biocidal agent to kill an established colony of microorganism or as a preservative to inhibit growth of microorganisms, to which it is directed. Those of skill in the art will have no difficulty in determining the requisite effective amounts for particular uses.
  • the glycine anhydride dimethylol When treating a host substance, the glycine anhydride dimethylol can be administered thereto as a solid powder, in aqueous solution or in an emulsion alone or with other ingredients, including other biocides and/or medicaments.
  • the amount of glycine anhydride dimethylol required to be incorporated into a product for preservation will also vary depending upon the product being protected and the environment of use. Generally, products containing less than about 1 .0% by weight of glycine anhydride dimethylol will be effectively protected from microbial contamination in most environments. Principally for economic reasons, concentrations less than about 0.5% by weight are preferred. Those of skill in the art will have little difficulty in selecting specific amounts required for particular uses based upon the information contained herein, especially in the examples.
  • glycine anhydride dimethylol In addition to glycine anhydride dimethylol, other conventional ingredients may be incorporated into the product requiring preservation, including other antimicrobial agents, suspending agents, wetting agents, anti-scaling agents, corrosion inhibitors and pH control agents. The selection of the particular addition ingredients, if any, will depend upon the particular product requiring preservation.
  • the glycine anhydride dimethylol When blending with the product to be preserved, the glycine anhydride dimethylol may be incorporated as a solid powder or in aqueous solution. The powder is the preferred form since it is easier to handle than a liquid. When the application calls for a liquid formulation, the powder can be readily dissolved in aqueous media.
  • the glycine anhydride dimethylol may be blended into the product as the sole antimicrobial agent or as part of an antimicrobial system with other antimicrobial agents.
  • Such systems are particularly effective when it is necessary to preserve a product against a wide range of microorganisms.
  • antimicrobial agents in the system antimicrobial activity against a particular group of microorganisms can be optimized for a particular product.
  • a common solvent such as propylene glycol, which also exhibits antimicrobial activity and so serves the dual function of solvent and antimicrobial agent.
  • This invention thus provides an effective means for preserving substances susceptible to microbial contamination by inhibiting growth of bacterial, yeast and mold.
  • the compound of the invention is readily incorporated into a variety of forms including liquids, solids and emulsions.
  • the following examples are provided. However, it is to be understood that their purpose is entirely illustrative and in no way intended to limit the scope of the invention. In the examples, all percentages are given by weight unless otherwise noted.
  • MIC Minimum Inhibitory Concentration
  • Aqueous solutions of 1 % glycine anhydride dimethylol were serially diluted with sterile distilled water, and aliquots of different concentrations were mixed with equal volumes of inoculated culture medium.
  • AOAC broth was used for the bacterial culture media
  • Sabourand Liquid Medium was used for the yeast and mold cultures.
  • the mixtures of glycine anhydride dimethylol solution and culture media were incubated at 35 °C for 48 hours for bacteria and yeast, and at 26°C for 7 days for mold. Microbial growth or no growth were determined by visual inspection for cloudiness.
  • the MIC for a given microorganism was the lowest concentration of antimicrobial that remained clear after the incubation period. Results are as follows: Bacteria MIC Gram-Neg. Pseudomonas aeruginosa ATCC 9027 310ppm
  • a typical cosmetic emulsion was prepared for microbiological challenge testing.
  • the emulsion was prepared in four different variations: with no preservative added, with 0.05% glycine anhydride dimethylol, with 0.10% glycine anhydride dimethylol, and with 0.20% glycine anhydride dimethylol.
  • the formulation used for challenge testing was as follows: Phase A %ww
  • Citric Acid (30% Solution) 0.60 0.60 0.60 0.60 0.60
  • a typical shampoo was prepared both with and without glycine anhydride dimethylol, and then challenge tested with several microorganisms.
  • the USP Antimicrobial Preservative Effectiveness Test. (USPXXII Method) was used with minor modifications, with microbial counts made after 24, 48 and 72 hours. The same microorganisms (same ATCC numbers) were used as noted above.
  • the shampoo formulations were as follows:

Abstract

The use of glycine anhydride dimethylol, also known as 1,4-bis(hydroxymethyl)-2,5-piperazinedione, comprising formula (I) to kill microorganisms present in or on a host substance and to preserve products susceptible to contamination by a variety of microorganisms is disclosed.

Description

GLYCINE ANHYDRIDE DIMETHYLOL AS A BIOC1DE AND PRESERVATIVE
BACKGROUND OF THE INVENTION
1. Technical Field of the Invention
This invention relates to the use of giycine anhydride dimethylol, as a biocide and an antimicrobial agent to kill microorganisms present in or on substances and to preserve a variety of substances susceptible to microbial contamination.
2. Description of the Prior art
Glycine anhydride dimethylol, also known as 1 , -bis(hydroxymethyl}- 2,5-piperazinedione is a known chemical compound prepared by reacting glycine anhydride, also referred to as 2,5-piperazinedione with formaldehyde according to the following formula:
CH,OH
Figure imgf000003_0001
SUMMARY OF THE INVENTION
It is an object of the invention to provide a method for killing microorganisms present in or on a host substance by administering to the host an effective biocidal amount of glycine dimethylol anhydride.
It is a further object of the invention to provide a method for preserving products susceptible to contamination by microorganisms by incorporating into the product an antimicrobial effective amount of glycine anhydride dimethylol.
It is a further object of the invention to provide preserved products, that is products which have been protected against contamination by micr oorganisms, containing glycine anhydride dimethylol in an amount which is effective to preserve the product against contamination by microorganisms.
Other objects and advantages of the invention will be evident to those of skill in the art upon review of the detailed description which follows.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention is based upon the discovery that glycine anhydride dimethylol, also known as 1 , 4-bis(hydroxymethyl.-2,5-piperazinedione, represented by the formula:
Figure imgf000004_0001
exhibits biocidal activity against a wide range of microorganisms, including bacteria, yeast and mold. This compound, therefore, is an effective biocidal agent which kills microorganisms present in or on a host substance and inhibits microbial growth in or on a variety of substances and products, whether they be solid, liquid or emulsion form. Such products include, but are not limited to, cosmetics, foodstuffs, pharmaceuticals, paints, cutting oils or fluids, agricultural products, oil drilling fluids, lubricants, paper industry products, embalming solutions, cold steriiized medical and dental equipment, cooling towers, fabric impregnation, latexes, swimming pools, inks, household disinfectants, waxes and polishes, toilet bowi cleaners, bathroom cleaners, laundry detergents, soaps, wood preservatives, hospital and medical antiseptic and adhesives. Of these proαucts, fooαstuffs, pharmaceuticals, cosmetic and personal hygiene products such as shampoos are of particular interest. Other uses of glycine anhydride dimethylol according to the invention include industrial uses where the compound is used to control microbial growth, such as for slime control in the effluent of paper mills.
By virtue of its biocidal activity, glycine anhydride dimethylol can be used to kill microorganisms which have contaminated a host substance or as a preservative to inhibit and prevent growth of microorganisms in substances susceptible to microbial growth. The compound is also effective in disinfecting and/or sterilizing surfaces prone to contamination by microorganisms. The effective amount of glycine anhydride dimethylol required will, of course, vary depending upon the mode of use, e.g., as a biocidal agent to kill an established colony of microorganism or as a preservative to inhibit growth of microorganisms, to which it is directed. Those of skill in the art will have no difficulty in determining the requisite effective amounts for particular uses. When treating a host substance, the glycine anhydride dimethylol can be administered thereto as a solid powder, in aqueous solution or in an emulsion alone or with other ingredients, including other biocides and/or medicaments. The amount of glycine anhydride dimethylol required to be incorporated into a product for preservation will also vary depending upon the product being protected and the environment of use. Generally, products containing less than about 1 .0% by weight of glycine anhydride dimethylol will be effectively protected from microbial contamination in most environments. Principally for economic reasons, concentrations less than about 0.5% by weight are preferred. Those of skill in the art will have little difficulty in selecting specific amounts required for particular uses based upon the information contained herein, especially in the examples.
In addition to glycine anhydride dimethylol, other conventional ingredients may be incorporated into the product requiring preservation, including other antimicrobial agents, suspending agents, wetting agents, anti-scaling agents, corrosion inhibitors and pH control agents. The selection of the particular addition ingredients, if any, will depend upon the particular product requiring preservation. When blending with the product to be preserved, the glycine anhydride dimethylol may be incorporated as a solid powder or in aqueous solution. The powder is the preferred form since it is easier to handle than a liquid. When the application calls for a liquid formulation, the powder can be readily dissolved in aqueous media. The glycine anhydride dimethylol may be blended into the product as the sole antimicrobial agent or as part of an antimicrobial system with other antimicrobial agents. Such systems are particularly effective when it is necessary to preserve a product against a wide range of microorganisms. By careful selection of the antimicrobial agents in the system, antimicrobial activity against a particular group of microorganisms can be optimized for a particular product. When using an antimicrobial system it is further advantageous to incorporate the antimicrobial agents in a common solvent, such as propylene glycol, which also exhibits antimicrobial activity and so serves the dual function of solvent and antimicrobial agent.
This invention thus provides an effective means for preserving substances susceptible to microbial contamination by inhibiting growth of bacterial, yeast and mold. The compound of the invention is readily incorporated into a variety of forms including liquids, solids and emulsions. To further illustrate the various aspects of the invention, the following examples are provided. However, it is to be understood that their purpose is entirely illustrative and in no way intended to limit the scope of the invention. In the examples, all percentages are given by weight unless otherwise noted.
Example I
Preparation of glycine anhydride dimethyioi.
To a stirred slurry of 1 1 .4 g. (0.1 mole) of glycine anhyαride in 41.0 ml. of water was added 16.2 g. (0.2 mole) of 37% aqueous formaldehyde.
Addition of 0.10 g. of 10% aqueous sodium hydroxide solution caused the suspended solids to dissolve, followed by formation of a heavy white precipitate. The mixture was heated to 70°C, by which time all solids dissolved. On cooling to room temperature, white crystals separated. The crystals were collected, washed with cold water, and dried in vacuum at 100°C for 1 hour. The white crystalline product, glycine anhydride dimethylol weighed 12.6 g. (72.4% yield), m.p. 185-188°C dec. Anal. Calcd. for CβH10N2O4 (174.16): N, 16.09. Anal. Found: N, 16.17.
Example 2 Microbiological Activity
A. Minimum Inhibitory Concentration (MIC)
Aqueous solutions of 1 % glycine anhydride dimethylol were serially diluted with sterile distilled water, and aliquots of different concentrations were mixed with equal volumes of inoculated culture medium. AOAC broth was used for the bacterial culture media, and Sabourand Liquid Medium was used for the yeast and mold cultures. The mixtures of glycine anhydride dimethylol solution and culture media were incubated at 35 °C for 48 hours for bacteria and yeast, and at 26°C for 7 days for mold. Microbial growth or no growth were determined by visual inspection for cloudiness. The MIC for a given microorganism was the lowest concentration of antimicrobial that remained clear after the incubation period. Results are as follows: Bacteria MIC Gram-Neg. Pseudomonas aeruginosa ATCC 9027 310ppm
Gram-Pos. Staphylococcus aureus ATCC 6538 310ppm
Yeast Candida albicans ATCC 10231 310ppm
Mold Aspergillus niger ATCC 16404 2500ppm
B. Challenge tests on a cosmetic emulsion A typical cosmetic emulsion was prepared for microbiological challenge testing. The emulsion was prepared in four different variations: with no preservative added, with 0.05% glycine anhydride dimethylol, with 0.10% glycine anhydride dimethylol, and with 0.20% glycine anhydride dimethylol. The formulation used for challenge testing was as follows: Phase A %ww
Water, Demiπeralized 67.90 67.85 67.80 67.70 Triethanolamine, 99% 1.00 1.00 1.00 1.C0
Phase B
Laneth-5 (and) Ceteth-5 (and) Oleth-5 (and) Steareth-5 Mineral Oil Steanc Acid, XXX Cetyl Alcohol Glycerγl Stearate (and) PEG-100 Stearate
Phase C
Figure imgf000008_0001
Citric Acid (30% Solution) 0.60 0.60 0.60 0.60
Phase D
Water, Demineralized 20.00 20.00 20.00 20.00
Glycine Anhydride Dimethylol (GAD) _____ 0.10 0.20
100.00 100.00 100.00 100.00
Challenge tests were carried out using four different microorganisms, and microbial counts were made after incubating 24, 48, and 72 hours. The USP Antimicrobial Preservative Effectiveness Test (UPS XXII Method) was used with minor modifications.
MICROBIAL COUNTS, 24 HOURS
Figure imgf000008_0002
MICROBIAL COUNTS, 48 HOURS
Figure imgf000008_0003
MICROBIAL COUNTS, 72 HOURS
Figure imgf000009_0001
C. Challenge tests on a shampoo
A typical shampoo was prepared both with and without glycine anhydride dimethylol, and then challenge tested with several microorganisms. The USP Antimicrobial Preservative Effectiveness Test. (USPXXII Method) was used with minor modifications, with microbial counts made after 24, 48 and 72 hours. The same microorganisms (same ATCC numbers) were used as noted above.
The shampoo formulations were as follows:
Phase A %W W
Water, Demineralized Ammonium Lauryl Sulfate 25.00 25.00 Cocamide DEA 6.50 6.50 Cocamideopropyl Botaine 5.00 5.00
Phase B
Citric Acid, 30% Solution
Phase C
Water, Deionized 20.00 20.00
Glycine Anhydride Dimethylol 0.20
100.00 100.00
* qs to pH6 Microbial challenge test results were as follows:
MICROBIAL COUNTS, 24 HOURS
Figure imgf000010_0001
MICROBIAL COUNTS, 48 HOURS
No Preservative 0.2% GAD
P. aeruginosa 1X10* < 10
S. aureus < 10 < 10
C. albicans 2X10* < 10
A. niger 1X105 < 10
MICROBIAL COUNTS, 72 HOURS
Figure imgf000010_0002
D. Preservation of milk
The microbial spoilage of whole milk at room temperature was prevented by the incorporation of 0.16% glycine anhydride dimethylol. The following series of tests were terminated after 59 days.
Figure imgf000011_0001
While the invention has been described in terms of certain preferred embodiments, one skilled in the art will readily appreciate that various modifications, changes, omissions and substitutions may be made without departing from the spirit thereof. It is intended, therefore, that the present invention be limited solely by the scope of the following claims.

Claims

What is claimed is:
1. A method of killing microorganisms in or on a host substance comprising administering to the substance an effective biocidal amount of glycine anhydride dimethylol of the formula:
Figure imgf000012_0001
2. The method as defined in Claim 1 , wherein the glycine anhydride dimethylol is administered in aqueous solution.
3. The method as defined in Claim 1 , wherein the glycine anhydride dimethylol is administered in an emulsion.
4. The method as defied in Claim 1 , wherein the glycine anhydride dimethylol is administered as a powder.
5. The method as defined by Claim 1 , wherein the glycine anhydride dimethylol is administered in conjunction with another biocidal agent.
6. A method for protecting a substance against contamination by microorganisms comprising incorporating in the substance an effective antimicrobial amount of glycine anhydride dimethylol for the formula:
CH .OH
Figure imgf000012_0002
CH .OH
7. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in an amount less than about 1.0% by weight.
8. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in an amount less than about 0.5% by weight.
9. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in solid form.
10. The method as defined by Claim 6; wherein said glycine anhydride dimethylol is incorporated into said substance in aqueous solution.
11. The method as defined in Claim 6, wherein said substance is a cosmetic product.
12. The method as defined in Claim 6, wherein said substance is a personal hygiene product.
13. The method as defined in Claim 12, wherein said personal hygiene product is a shampoo.
14. The method as defined in Claim 6, wherein said substance is a pharmaceutical product.
15. The method as defined in Claim 6, wherein said substance is a foodstuff.
16. The method as defined in Claim 6, wherein said substance is the effluent from a paper mill.
17. A preserved product comprising a substance susceptible to microbial contamination and an effective microbial growth inhibiting amount of glycine anhydride dimethylol for the formula:
Figure imgf000014_0001
18. The product defined by Claim 17, wherein said glycine anhydride dimethylol is present in an amount less than about 1.0% by weight.
19. The product defined by Claim 18, wherein said glycine anhydride dimethylol is present in an amount less than 0.5% by weight.
20. The product defined by Claim 17, wherein said substance is a cosmetic.
21. The product defined by Claim 17, wherein said substance is a personal hygiene product.
22. The product defined by Claim 21 , wherein said substance is a shampoo.
23. The product defined by Claim 17, wherein said substance is a pharmaceutical product.
24. The product defined by Claim 17, wherein said substance is a foodstuff.
PCT/US1992/003442 1991-05-01 1992-04-30 Glycine anhydride dimethylol as a biocide and preservative WO1992019212A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CS932301A CZ230193A3 (en) 1991-05-01 1992-04-30 Method of killing micro-organisms employing glycine-anhydride dimethylol as a biocide and a preserved product based on said substance
AU19169/92A AU654192B2 (en) 1991-05-01 1992-04-30 Glycine anhydride dimethylol as a biocide and preservative
JP4511432A JPH06507403A (en) 1991-05-01 1992-04-30 Glycine anhydride dimethylol as biocide and preservative
BR9205953A BR9205953A (en) 1991-05-01 1992-04-30 Dimethylol glycine anhydride as a biocide and preservative
NO1993933894A NO933894D0 (en) 1991-05-01 1993-10-28 GLYCINANHYDRIDE DIMETYLOL AS A BIOSIDE AND PRESERVATIVE

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US07/694,252 US5244653A (en) 1991-05-01 1991-05-01 Glycine anhydride dimethylol as a biocide and preservative
US694,252 1991-05-01

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WO1992019212A3 WO1992019212A3 (en) 1993-01-21

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JP (1) JPH06507403A (en)
CN (1) CN1066170A (en)
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BR (1) BR9205953A (en)
CA (1) CA2109418A1 (en)
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MX (1) MX9201988A (en)
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CZ230193A3 (en) 1994-07-13
AU1916992A (en) 1992-12-21
EP0583357A1 (en) 1994-02-23
US5244653A (en) 1993-09-14
WO1992019212A3 (en) 1993-01-21
ZA923063B (en) 1993-04-28
EP0583357A4 (en) 1994-05-18
JPH06507403A (en) 1994-08-25
AU654192B2 (en) 1994-10-27
NO933894L (en) 1993-10-28
MX9201988A (en) 1992-11-01
CA2109418A1 (en) 1992-11-02
NO933894D0 (en) 1993-10-28
BR9205953A (en) 1994-09-27
CN1066170A (en) 1992-11-18
US5593681A (en) 1997-01-14
US5707993A (en) 1998-01-13

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