Preservation without microbicide
阅读说明：本技术 无杀微生物剂的保存 (Preservation without microbicide ) 是由 J·格劳比茨 K·萨特林 于 2018-05-15 设计创作，主要内容包括：本发明涉及一种抗微生物组合物,其包含与至少一种水溶性或水分散性的锂离子源和任选地至少一种水溶性或水分散性的镁离子源和/或至少一种水溶性或水分散性的钠离子源组合的至少一种水溶性或水分散性的锌离子源,本发明还涉及水性制剂、保存水性制剂以抵抗微生物的方法以及抗微生物组合物用于保存水性制剂以抵抗微生物的用途。(The present invention relates to an antimicrobial composition comprising at least one water-soluble or water-dispersible zinc ion source in combination with at least one water-soluble or water-dispersible lithium ion source and optionally at least one water-soluble or water-dispersible magnesium ion source and/or at least one water-soluble or water-dispersible sodium ion source, to an aqueous formulation, to a method of preserving an aqueous formulation against microorganisms and to the use of an antimicrobial composition for preserving an aqueous formulation against microorganisms.)
1. An antimicrobial composition comprising at least one water soluble or water dispersible zinc ion source in combination with at least one water soluble or water dispersible lithium ion source and optionally at least one water soluble or water dispersible magnesium ion source and/or at least one water soluble or water dispersible sodium ion source.
2. The antimicrobial composition according to claim 1, wherein the antimicrobial composition comprises water, preferably at least one water-soluble or water-dispersible zinc ion source and at least one water-soluble or water-dispersible lithium ion source and optionally at least one water-soluble or water-dispersible magnesium ion source and/or at least one water-soluble or water-dispersible sodium ion source, each present in the composition in an amount of at least 100ppm, such as from 100ppm to 27000ppm, preferably at least 250ppm, such as from 250ppm to 25000ppm, more preferably at least 500ppm, such as from 500ppm to 20000ppm, more preferably at least 600ppm, such as from 600ppm to 15000ppm, even more preferably at least 750ppm, such as from 750ppm to 10000ppm, and most preferably from 750ppm to 5000ppm, calculated to the weight of water.
3. The antimicrobial composition according to claim 1 or 2, wherein the at least one water soluble or water dispersible source of lithium ions is at least one lithium salt, preferably the at least one lithium salt is selected from lithium carbonate, lithium chloride, lithium hydroxide, lithium phosphate, lithium citrate, lithium maleate, lithium acetate and lithium lactate; lithium polymer salts, preferably selected from the group consisting of lithium salts of acrylic acid homopolymers, acrylic acid copolymers such as copolymers of acrylic acid and maleic acid and/or acrylamide, polyphosphoric acid and mixtures thereof, and mixtures thereofMore preferably Li2Na2Polyphosphate, sodium lithium hexamethylphosphate or lithium polyacrylate.
4. The antimicrobial composition according to any one of claims 1 to 3, wherein said at least one water soluble or water dispersible source of magnesium ions is at least one magnesium salt, preferably said at least one magnesium salt is selected from the group consisting of magnesium carbonate, magnesium chloride, magnesium oxide, magnesium hydroxide, magnesium phosphate, magnesium citrate, magnesium maleate, magnesium acetate and magnesium lactate; polymeric salts of magnesium and mixtures thereof, preferably selected from the group consisting of magnesium salts of acrylic acid homopolymers, acrylic acid copolymers such as copolymers of acrylic acid and maleic acid and/or acrylamide, polyphosphoric acid and mixtures thereof.
5. The antimicrobial composition according to any one of claims 1 to 4, wherein the at least one water soluble or water dispersible zinc ion source is at least one zinc salt, preferably the at least one zinc salt is selected from the group consisting of zinc carbonate, zinc oxide, zinc chloride, zinc hydroxide, zinc phosphate, zinc citrate, zinc maleate, zinc acetate and zinc lactate; polymeric salts of zinc and mixtures thereof, preferably selected from zinc salts of acrylic acid homopolymers, acrylic acid copolymers such as copolymers of acrylic acid and maleic acid and/or acrylamide, polyphosphoric acid and mixtures thereof.
6. The antimicrobial composition of any one of claims 1 to 5, wherein the at least one water soluble or water dispersible source of sodium ions is at least one sodium salt, preferably the at least one sodium salt is selected from sodium carbonate, sodium chloride, sodium hydroxide, sodium phosphate, sodium citrate, sodium maleate, sodium acetate and sodium lactate; sodium polymer salts and mixtures thereof, preferably selected from sodium salts of acrylic acid homopolymers, acrylic acid copolymers such as copolymers of acrylic acid and maleic acid and/or acrylamide, polyphosphoric acid and mixtures thereof.
7. The antimicrobial composition according to any one of claims 1 to 6, wherein the weight ratio [ Zn/Li ] of the at least one water-soluble or water-dispersible zinc ion source to the at least one water-soluble or water-dispersible lithium ion source is from 100:1 to 1:100, preferably from 10:1 to 1:10, most preferably from 3:1 to 1:3, and/or the weight ratio [ Mg/Zn ] of the at least one water-soluble or water-dispersible magnesium ion source to the at least one water-soluble or water-dispersible zinc ion source is from 100:1 to 1:100, preferably from 10:1 to 1:10, most preferably from 3:1 to 1:3, and/or the weight ratio of the at least one water-soluble or water-dispersible magnesium ion source to the at least one water-soluble or water-dispersible lithium ion source [ Mg/Li ] is from 100:1 to 1:100, preferably 10:1 to 1:10, most preferably 3:1 to 1:3, and/or the weight ratio [ Na/Zn ] of the at least one water-soluble or water-dispersible source of sodium ions to the at least one water-soluble or water-dispersible source of zinc ions is from 100:1 to 1:100, preferably from 10:1 to 1:10, most preferably from 3:1 to 1:3, and/or the weight ratio [ Na/Li ] of the at least one water-soluble or water-dispersible source of sodium ions to the at least one water-soluble or water-dispersible source of lithium ions is from 100:1 to 1:100, preferably from 10:1 to 1:10, most preferably from 3:1 to 1:3, and/or the weight ratio [ Na/Mg ] of the at least one water-soluble or water-dispersible source of sodium ions to the at least one water-soluble or water-dispersible source of magnesium ions is from 100:1 to 1:100, preferably 10:1 to 1:10, most preferably 3:1 to 1: 3.
8. The antimicrobial composition according to any one of claims 1 to 7, wherein the antimicrobial composition is effective against microorganisms, preferably the microorganisms are selected from the group comprising: at least one bacterial strain, at least one fungal strain, mold, yeast, algae, and mixtures thereof.
9. The antimicrobial composition according to claim 8, wherein the at least one bacterial strain is selected from the group comprising species of Pseudomonas (Pseudomonas sp.), such as Pseudomonas aeruginosa (Pseudomonas aeruginosa), Pseudomonas pseudoalcaligenes (Pseudomonas putida), Pseudomonas putida (Pseudomonas putida), Pseudomonas stutzeri (Pseudomonas stutzeri), Pseudomonas mendelia (Pseudomonas mendocina), Pseudomonas oleovorans subspecies (Pseudomonas oleovorans) and mixtures thereof, species of Burkholderia (Burkholderia sp.), such as Burkholderia cepacia (Burkholderia cepacia); various species of the genus Escherichia (Escherichia spp.), such as Escherichia coli (Escherichia coli); alcaligenes sp, such as Alcaligenes faecalis (Alcaligenes faecalis); species of the genus Staphylococcus (Staphylococcus sp), such as Staphylococcus aureus (Staphylococcus aureus); species of the genus Enterococcus (Enterococcus sp.), such as Enterococcus faecalis (Enterococcus faecalis); species of the genus Bacillus (Bacillus sp.), such as Bacillus halophilus (Bacillus halodurans); species of Salmonella (Salmonella sp.); legionella (Legionella), aquatic unicellular (Comomonas aquatica), Brevundimonas intermedia (Brevundimonas intermedia), Rhizobium radiatum (Rhizobium radiobacter), spinobium yanoikuyae, thermomonas species (callimossp.), hydrogenphagemid species (hydrogenhophaga sp.), agricultural isochrysella (Alishewanella agri), arthrobacterium species (arthromobacter sp), chryseobacter amyloliquefaciens (Microbacterium sp.), Microbacterium aurantii (Exiguobacterium aurantiacaum) and mixtures thereof, and/or the at least one fungal strain is selected from the group comprising: saccharomyces cerevisiae (Saccharomyces cerevisiae), Pichia membranaceus (Pichia membranaceus), Rhodotorula mucilaginosa (Rhodotorula Mucor), Fusarium species (Fusarium sp.), Aspergillus species (Aspergillus sp.), such as Aspergillus niger (Aspergillus niger), Aspergillus brasiliensis (Aspergillus brasiliensis) and mixtures thereof, Penicillium species (Penicillium sp.), such as Penicillium pinophilum, Penicillium funiculosum (Penicillium) and mixtures thereof, Brevibacterium sp, Trichoderma species (Aureobasidium pullulans), Trichoderma species (Geiotrichum sp.), Trichoderma species (Acremonium sp.), Streptomyces sp.), Trichoderma species (Aspergillus sp.), Trichoderma sp., Aspergillus sp.), Trichoderma species (Aspergillus sp.), Aspergillus sp., Aspergillus sp., and mixtures thereof, Trichoderma species (Aspergillus sp.), strain, broomcorn sp, Aureobasidium sp, candida sp, Botrytis sp, Stemphylium sp, chachybotrys sp, Chaetomium sp, mycelium sp, Neurospora sp, glochidium sp, leucotrichum sp, Paecilomyces sp, arthrobacter sp, Curvularia sp, and mixtures thereof.
10. The antimicrobial composition according to any one of claims 1 to 9, wherein the composition is free of microbicide selected from the group comprising: phenol, halophenols, halogen-containing compounds, halogen-releasing compounds, isothiazolinones, aldehyde-containing compounds, aldehyde-releasing compounds, guanidines, sulfones, thiocyanates, pyrithione, antibiotics such as beta-lactam antibiotics, quaternary ammonium salts, peroxides, perchlorates, amides, amines, heavy metals (excluding zinc ions), microbiocidal enzymes, microbiocidal polypeptides, azoles, carbamates, glyphosate, sulfonamides, and mixtures thereof, preferably the composition is free of various microbiocides.
11. An aqueous formulation, preferably a paper making formulation, a paper coating formulation, a fiber formulation, a food formulation, a pharmaceutical formulation, a cosmetic formulation, a plastic formulation, an adhesive formulation, a metal working fluid, a cooling fluid, a primer, a levelling compound and/or a paint formulation, comprising an antimicrobial composition according to any one of claims 1 to 10.
12. The aqueous formulation of claim 11, wherein the aqueous formulation further comprises
(i) At least one inorganic particulate material, preferably said at least one inorganic particulate material is selected from the group comprising: natural ground calcium carbonate, natural and/or synthetic precipitated calcium carbonate, surface modified calcium carbonate, dolomite, kaolin, clay, barite, talc, aluminium hydroxide, aluminium silicate, titanium dioxide, hydromagnesite, perlite, sepiolite, brucite and mixtures thereof, and most preferably the at least one inorganic particulate material comprises natural ground calcium carbonate and/or synthetic precipitated calcium carbonate, and/or
(ii) At least one organic material, preferably said at least one organic material is selected from the group comprising: carbohydrates, such as starch, sugar, cellulose, modified cellulose and cellulose-based pulp, glycerol, hydrocarbons and mixtures thereof.
13. The aqueous formulation of claim 11 or 12, wherein the aqueous formulation has
(i) A pH value of from 2 to 12, preferably from 6 to 12, more preferably from 7 to 10.5, and/or
(ii) A solids content of up to 85.0 wt. -%, preferably of from 10.0 to 82.0 wt. -% and more preferably of from 20.0 to 80.0 wt. -%, based on the total weight of the aqueous formulation.
14. A method for preserving an aqueous formulation against microorganisms, the method comprising the steps of:
a) providing an aqueous formulation, preferably a paper making formulation, a paper coating formulation, a fiber formulation, a food formulation, a pharmaceutical formulation, a cosmetic formulation, a plastic formulation, an adhesive formulation, a metal working fluid, a cooling fluid, a primer, a levelling compound and/or a paint formulation,
b) providing an antimicrobial composition according to any one of claims 1 to 10, and
c) contacting and mixing the aqueous formulation of step a) with the antimicrobial composition of step b) one or more times to obtain a preserved aqueous formulation.
15. Use of an antimicrobial composition according to any one of claims 1 to 10 for preserving an aqueous formulation against microorganisms.
16. The use according to claim 15, wherein the microorganism is selected from the group comprising: at least one bacterial strain, at least one fungal strain, mold, yeast, algae, and mixtures thereof.
17. Use according to claim 15 or 16, wherein the aqueous formulation is a paper making formulation, a paper coating formulation, a fiber formulation, a food formulation, a pharmaceutical formulation, a cosmetic formulation, a plastic formulation, an adhesive formulation, a metal working fluid, a cooling fluid, a primer, a levelling compound and/or a paint formulation.
Examples
Measuring method
The following measurement methods were used to evaluate the parameters given in the specification, examples and claims.
BET specific surface area of the Material
The BET specific surface area is measured according to ISO 9277 by the BET method using nitrogen.
Particle size distribution (diameter) of particulate material<X mass percent of particles) and weight average diameter (d)50)
The weight-average particle diameter and the particle diameter mass distribution of the particulate material are determined by a sedimentation method, i.e. sedimentation behavior analysis in a gravitational field. The Sedigraph from Micromeritics Instrument Corporation was usedTM5100 measurement is carried out.
The methods and apparatus are known to the skilled person and are generally used to determine the particle size of fillers and pigments. Na was measured at 0.1 wt%4P2O7In an aqueous solution of (a). The samples were dispersed using a high speed stirrer and sonicator.
pH measurement
The pH of the water sample was measured at about 25 ℃ by using a standard pH meter.
Brookfield viscosity
All Brookfield viscosities were measured at 100rpm and at room temperature (20. + -. 3 ℃ C.) using a Brookfield DV-II viscometer equipped with a LV-3 spindle.
Amount of additive
Unless otherwise indicated, all amounts expressed in ppm represent mg per kg of water in the aqueous formulation. The concentration in the aqueous preparation water is further expressed in mmol/kg (millimole/kg) or mol/l (mol/l) according to the international system of units.
Bacterial count
All cited bacteria numbers in the table below are cfu/ml (colony forming units per ml) or cfu/plate (colony forming units per plate), wherein cfu/ml is determined after 2-3 days post inoculation according to the counting method described in "bestimung von aeroben mesophilen Keimen", schweizeris lebensmitetlbuch, chapter 56, section 7.01, 1985 edition, revised 1988 edition. Unless otherwise stated, each tryptic soy agar plate (TSA, prepared using BD 236950) was plated in phosphate buffered saline (PBS; pH 7.4, 137mmol/l NaCl, 2.7mmol/l KCl, 10mmol/l Na2HPO4，1.8mmol/l KH2PO4) 0.1ml of 1:10 dilution. The TSA plates were then incubated at 30 ℃ for 48 hours or 72 hours. Colony forming units (cfu) were then counted and reported as cfu/plate. Counts above 100000cfu/ml are reported as 100000 cfu/ml.
Solids content
The solids content was measured using a Moisture Analyzer from Mettler-Toledo MJ 33. The method and apparatus are known to the skilled person.
Amount of sodium and lithium
All sodium and lithium amounts expressed in ppm correspond to mg values per kg of final product.
Bacteria, yeast and mold for preparation
Species of the genus Pseudomonas (Pseudomonas sp.), such as Pseudomonas aeruginosa (Pseudomonas aeruginosa) DSM-1707 and Pseudomonas putida (Pseudomonas putida) DSM-50906, Pseudomonas pseudoalcaligenes (Pseudomonas pseudoalcaligenes) DSM-50188T, Burkholderia cepacia (Burkholderia pacia), such as Burkholderia cepacia ATCC-21809, Alcaligenes faecalis (Alcaligenes faecalis), such as enterococcus faecalis ATCC-25094, Escherichia coli DSM-1576 and Staphylococcus aureus, such as Staphylococcus aureus (Staphylococcus aureus) strain DSM 346, and fresh yeast cultures of Saccharomyces cerevisiae DSM-1333; pichia membranaceus (Pichia membranaceus) DSM-70179 and Rhodotorula mucilaginosa (Rhodotorula mucor) DSM-18184 were incubated for 16-20 hours at 30 ℃ with stirring at 150 revolutions per minute (rpm) by inoculating 3ml of liquid growth medium (tryptic soy broth, e.g.Fluka, No.22092) from a single colony of the stock culture, resulting in about 1X 109Cell density of individual cells/ml. Overnight cultures of bacteria/yeast and fungi (in tryptic soy broth) were mixed together in equal amounts and 100 μ l of the resulting mixture was added to 50ml of primer (see below).
Primer coating
Table 1 below summarizes the primer formulations used to test for antimicrobial activity.
Table 1:
latex paint
By weight%
[kg]
Tap water
32.4
324.0
Wetting and dispersing agent#1
0.1
1.0
Rheology modifier#2
0.5
5.0
Sodium hydroxide, 10%
0.1
1.0
Defoaming agent#3
0.3
3.0
Wetting and dispersing agent#4
0.3
3.0
Rheology modifier#5
0.4
4.0
White pigment#6
6.0
60.0
Bulking agents#7
13.0
130.0
Increment ofAgent for treating cancer#8
23.0
230.0
Matting agent#9
7.0
70.0
Bulking agents#10
5.0
50.0
Adhesive agent#11
11.5
115.0
Defoaming agent#12
0.4
4.0
Total of
100
1000.0
#1 wetting and dispersing agent relates to sodium polyphosphate, which is commercially available as Calgon N new from BK Giulini Chemie.
#2 rheology modifier relates to methyl ethyl hydroxyethyl cellulose, commercially available from Akzo Nobel Corp. as Bermocoll Prime 3500.
#3 antifoam relates to mineral oil based antifoam commercially available from Byk Chemie as BYK 038.
#4 wetting and dispersing agent relates to the sodium salt of an acrylic polymer, which is commercially available as ECODIS P50 from Coatex SA.
#5 rheology modifier relates to a polyurethane, which is commercially available from Coatex SA as Coapur 2025.
#6 white pigment relates to titanium dioxide, which is commercially available as Tiona 595 from Millenium Inorganic Chemicals.
#7 extender relates to dry ground calcium carbonate (Italian marble) having a median diameter (d)50) 0.8 μm, and the maximum cut length (d)98) At 5 μm, commercially available as Omyacarb Extra-CL from Omya International AG.
#8 extender relates to dry ground calcium carbonate (Italian marble) having a median diameter (d)50) 4.5-6.5 μm, less than or equal to 30ppm of screen residue>100 mu m, and less than or equal to 0.1 percent of screen residue>45 μm (ISO 787/7), commercially available from Omya International AG in the form of Omyacarb 5-GU.
#9 matting agent relates to dry ground calcium carbonate (Italian marble) having a median diameter (d)50) 20 μm, less than or equal to 0.8 percent of screen residue>60 mu m, and less than or equal to 2 percent of screen residue>45 μm (ISO 787/7), commercially available from Omya International AG in the form of Omya calcium AV.
#10 extender relates to dry ground calcium carbonate (Italian marble) having a median diameter (d)50) 6 μm, and the maximum cut length (d)98) 19 μm, commercially available from Mondo Minerals as FINNTALC M20 SL-AW.
The #11 adhesive relates to a non-plasticized aqueous polymer dispersion based on styrene and acrylate (53% dispersion) commercially available from Clariant as Mowilith LDM 187153%.
#12 antifoam relates to polymer-based, VOC-and silicone-free antifoam agents commercially available from BYK Chemie as BYK 012.
Antimicrobial activity testing in primers
As shown in Table 2, samples of the primer formulation were mixed with varying amounts of ZnO, MgCO3、Li2CO3And/or Na2CO3And (4) mixing.
Table 2:
amount refers to the amount of the corresponding ion relative to the weight of water in the primer.
A primer formulation E1-E9 containing the antimicrobial composition according to table 2 was prepared, a 50ml aliquot of the primer formulation was mixed with a 800 μ l (Mix-all) aliquot, mixed well and incubated in the dark at room temperature for one week. One week later, 100. mu.l of PBS buffer (phosphate buffered saline 10mM, pH 7.4, 137mmol/l NaCl, 2.7mmol/l KCl, 10mmol/l Na) diluted 1:10 was added2HPO4，1.8mmol/l KH2PO4) Plated (100 colony forming units (cfu) per ml of coating) on standard TSA (tryptic Soy agar) plates and incubated at 30 ℃ in a Binder 3.1 incubator. Samples were analyzed after 48 hours for bacterial growth and after 72 hours for yeast/fungus/mold growth.
Bacterial/yeast and mold counts for antimicrobial activity testing of treated primers
Unless otherwise indicated, the recited bacterial/yeast and fungal counts are given in cfu/plate. In table 3 below, the antimicrobial activity of the primer formulations prepared according to table 2 is shown. Antimicrobial activity was tested weekly for 10 weeks (w0 to w10) according to the microbial activity test in the primer described above. This means that aliquots of the primer formulation were taken over 10 weeks and tested weekly with the above described fresh bacteria/yeast and mold mixture to evaluate the long term effect of antimicrobial activity of the added antimicrobial composition in the primer formulation.
Table 3:
as can be seen from the data in table 3, the composition comprising at least one water soluble or water dispersible zinc ion source in combination with at least one water soluble or water dispersible lithium ion source (E3) showed antimicrobial efficacy for at least two weeks, while the composition lacking at least one water soluble or water dispersible zinc ion source (E5) or at least one water soluble or water dispersible lithium ion source (E4) showed no antimicrobial efficacy. It can further be concluded that the antimicrobial efficacy of the composition can be further improved if the composition further comprises at least one water-soluble or water-dispersible source of magnesium ions and/or at least one water-soluble or water-dispersible source of sodium ions.
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