CN100560071C - Bactericidal composition - Google Patents
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- CN100560071C CN100560071C CNB038239450A CN03823945A CN100560071C CN 100560071 C CN100560071 C CN 100560071C CN B038239450 A CNB038239450 A CN B038239450A CN 03823945 A CN03823945 A CN 03823945A CN 100560071 C CN100560071 C CN 100560071C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention provides a kind of bactericidal composition, comprise a kind of mixture of antimicrobial effective amount (as anticorrosion, sterilization and/or antifungal effective dose), described mixture comprises at least two kinds and is selected from following component: (a) Indian oil of verbena; (b) cinnamic aldehyde, Oleum Cinnamomi, Chinese cinnamon, Cortex Cinnamomi extract, Cortex Cinnamomi leaf oil, 3,4-dihydroxycinnamic acid or its salt, or their mixture; (c) sorbic acid, or its salt; (d) arabo-ascorbic acid, or its salt; (e) benzoic acid, or its salt; (f) arabinogalactan, gala arabinan, or their mixture; (g) six hydrogen-different-alpha-acid, tetrahydrochysene-different-alpha-acid, or their mixture; (h) fragrant milfoil oil, Oleum Santali albi, Forssk oil, cotton Essential lavender oil; (i) gluconic acid Δ lactone.The present invention also provides the cinnamic aldehyde that comprises preservative effective amount or the product (the preferably product except that food, medicine or cosmetics) of cinnamic aldehyde and one or more alkanol-dialkylhydantoin.
Description
The application requires the U.S. Provisional Application 60/403,004 of submission on August 12nd, 2002 and 60/403,169 priority, and two provisional application are in full with reference to being incorporated into this.
Invention field
The present invention relates to (1) bactericidal composition, the method for growth of microorganism is killed and/or suppressed in (2), the method that (3) preserve product with bactericidal composition, and (4) strengthen the method for bactericidal composition.
Background of invention
Though natural prodcuts safety is general expensive, broad-spectrum biological body such as Gram-negative and gram-positive bacterium and fungus there is not biocidal effect.Most of natural prodcuts are only effective to gram-positive bacterium under relative high concentration, and invalid to gram negative bacteria or fungus.
Cinnamic aldehyde is a kind of natural prodcuts, and as (1) correctives, (2) are used for preservative system always, numerous group of (3) control insecticide and Aranea.Referring to United States Patent (USP) 4,525,480,5,306,707,5,536,501,5,676,958 and 5,839,224.
Therefore, still need effectively low-cost and safe preservative system to broad-spectrum micro-organisms.
Summary of the invention
The invention provides a kind of bactericidal composition, comprise the mixture of antimicrobial effective amount (as anticorrosion, sterilization and/or antifungal effective dose), this mixture comprises at least two kinds and is selected from following component:
(a) Indian oil of verbena
(b) cinnamic aldehyde, Oleum Cinnamomi, Chinese cinnamon, Cortex Cinnamomi extract, Cortex Cinnamomi leaf oil, 3,4-dihydroxycinnamic acid or its salt, or their mixture;
(c) sorbic acid, or its salt,
(d) arabo-ascorbic acid, or its salt,
(e) benzoic acid, or its salt,
(f) arabinogalactan, gala arabinan (galactoarabinan), or their mixture,
(g) six hydrogen-different-alpha-acid, tetrahydrochysene-different-alpha-acid, or their mixture,
(h) fragrant achillea millefolium (Achillea fragrantissima) oil, Lignum Santali Albi (Santolina fragrantissima) oil, Forssk oil, cotton Essential lavender oil;
(i) gluconic acid Δ lactone.
The said components of that mixture of the present invention comprises is antibiotic (as anticorrosion, sterilization and/or antifungal) cooperative effective quantity is better.
Those that preferred mixture of the present invention includes but not limited to list in following table.
| Mixture | Component (a) | Component (b) | Component (c) |
| 1 | Cinnamic aldehyde, Indian oil of verbena, arabinogalactan, gala arabinan, or their mixture | Sorbic acid or its salt | - |
| 2 | Cinnamic aldehyde | Milfoil oil (achillea oil), arabinogalactan, gala arabinan, or their mixture | - |
| 3 | Cinnamic aldehyde | Arabinogalactan, gala arabinan, or their mixture | Sorbic acid or its salt |
| 4 | Cinnamic aldehyde | Sorbic acid or its salt | - |
| 5 | Cinnamic aldehyde | Arabo-ascorbic acid or its salt | - |
| 6 | Benzoic acid or its salt (as sodium benzoate) | Arabo-ascorbic acid or its salt | - |
| 7 | Sorbic acid or its salt | Arabo-ascorbic acid or its salt | - |
| 8 | Cinnamic aldehyde, benzoic acid or its salt (as sodium benzoate), or sorbic acid or its salt | Gluconic acid Δ lactone | - |
In all above-mentioned mixture that comprise arabo-ascorbic acid (or its salt) or gluconic acid Δ lactone, arabo-ascorbic acid (or its salt) or gluconic acid Δ lactone strengthen the antibacterial effect of antiseptic (as sorbic acid or benzoic acid) in the mixture.
Another embodiment is by using the bactericidal composition of the present invention of effective dose on substrate or product, kills and/or suppress microorganism in the substrate or the method for growing in product.
Another embodiment is the method that strengthens the bactericidal composition antibacterial effect comprise sorbic acid, benzoic acid or its salt, by in bactericidal composition, adding or comprise arabo-ascorbic acid or its salt, or gluconic acid Δ lactone.
Be a kind of product in another embodiment, comprise the bactericidal composition of the present invention of antibiotic, anticorrosion, sterilization and/or antifungal effective dose.Product can be solid or liquid.Bactericidal composition of the present invention is effective especially as personal care product's antiseptic.
Another embodiment is the method for preserving product (as the personal care product), by add the bactericidal composition of the present invention of anticorrosion effective dose in this product.
Another embodiment is to kill and/or suppress the method for tree or the last other plant fungus of plant (as tree), by use the bactericidal composition of the present invention of effective dose in plant and/or plant surrounding soil.
Another embodiment is a kind of product (the better product except that food, medicine or cosmetics), comprises cinnamic aldehyde or arabo-ascorbic acid or its salt (as sodium erythorbate) of anticorrosion effective dose.Product is substantially free of to contain and does not contain p-Hydroxybenzoate (as methyl parahydroxybenzoate, ethylparaben and propyl p-hydroxybenzoate) fully.Product can be for example domestic (as personal nursing), industry or corporations' product.The personal care product includes but not limited to shampoo preferably, lotion (as refreshing body water), conditioner and soap.Suitable household products includes but not limited to fabric softener, washing scale remover and hard surface cleaner.According to an embodiment, in the product gross weight is 100%, and product contains the p-Hydroxybenzoate less than about 1,0.5,0.4,0.3,0.25,0.2,0.15,0.1,0.09,0.08,0.07,0.06,0.05,0.04,0.03,0.02 or 0.01 weight %.According to an embodiment preferred, product contains the cinnamic aldehyde less than the olfactory sensation effective dose.Product better contains the cinnamic aldehyde greater than 0.01,0.03,0.05,0.07,0.09 or 0.1 weight %.Product better is substantially free of or does not contain Oleum Cinnamomi fully.According to an embodiment, product does not contain the cinnamic aldehyde of anticorrosion effective dose or the antiseptic outside arabo-ascorbic acid or its salt.According to another embodiment, only antiseptic is cinnamic aldehyde or arabo-ascorbic acid or its salt in the product.
Another embodiment is to kill and/or suppress the method for the growth of microorganism in the product (as removing food, other products beyond medicine or the cosmetics), comprises cinnamic aldehyde from effective dose to product that use.Product better is substantially free of or does not contain p-Hydroxybenzoate fully.
Another embodiment is to preserve product (the better product except that food, medicine or cosmetics), comprises cinnamic aldehyde from effective dose to product that use.Product is substantially free of or does not contain p-Hydroxybenzoate fully.
Another embodiment is to kill and/or suppress the method for the growth of microorganism in the product (as (i) product except that food, or (ii) removing food, the product beyond medicine or the cosmetics), comprises arabo-ascorbic acid from effective dose to product or its salt of using.
Another embodiment is the method for preserving product (better (i) product except that food, or (ii) except that food, medicine or cosmetics product in addition), comprises arabo-ascorbic acid from effective dose to product or its salt of using.Product is substantially free of or does not contain p-Hydroxybenzoate fully.
It is to kill and/or suppress the method for the growth of microorganism on the substrate that an embodiment is arranged again, by cinnamic aldehyde or arabo-ascorbic acid or its salt of using antimicrobial effective amount or anticorrosion effective dose.(better not using any hydroxybenzoate).
Another embodiment is a preservative, comprises a kind of antibiotic Synergistic mixtures, comprises cinnamic aldehyde and at least a conventional personal nursing antiseptic, and as isothiazolone, benzothiazolinone and/or formaldehyde donor are as the dialkylhydantoin of alkanol replacement.The dialkylhydantoin that alkanol replaces is that the chemical compound of formula V down is better:
Wherein, R
1And R
2Be hydrogen or (CH independently of one another
2) OH, condition is R
1And R
2When being not hydrogen, R
3And R
4Be methyl, ethyl, propyl group or aryl independently of one another.The dialkylhydantoin that preferred alkanol replaces includes but not limited to 1,3-dihydroxymethyl-5,5-dimethyl hydantoin (DMDMH) and monomethylol dimethyl hydantoin (MMDMH).It is better that preservative comprises the Synergistic mixtures of anticorrosion effective dose.According to an embodiment, preservative comprises the Synergistic mixtures of sterilization and/or antifungal effective dose.Preservative comprises the cinnamic aldehyde less than the olfactory sensation effective dose.Preferably, preservative is substantially free of or does not contain p-Hydroxybenzoate fully, and preservative can be added in a kind of product, so those that discuss in the application.
Another embodiment is to kill and/or suppress the method for the growth of microorganism in the product (as removing food, the product beyond medicine or the cosmetics), comprises above-mentioned preservative from effective dose to product that use.According to an embodiment, product is substantially free of or does not contain p-Hydroxybenzoate fully.
Another embodiment of the present invention is to kill and/or suppress the method for the growth of microorganism on the base material, by using the preservative of the present invention of antimicrobial effective amount or anticorrosion effective dose.
It is to kill and/or suppress the method for the conk on the base material that an embodiment is arranged again, comprises above-mentioned preservative from effective dose to product that use.According to an embodiment, product is substantially free of or does not contain p-Hydroxybenzoate fully.
The pH of preparation of the present invention and product should be less than 10,9,8.5 or 8.
The accompanying drawing summary
Fig. 1 is (a) not antiseptical shampoo, (b) contain the shampoo of 0.5 weight % Indian oil of verbena, (c) contain the shampoo of 1.2 weight % potassium sorbate and (d) contain the rectangular histogram of 0.5 weight % Indian oil of verbena and the stability (according to count of bacteria) of 0.3 weight % potassium sorbate after 21 days.
Fig. 2 is (a) not antiseptical shampoo, (b) contain the shampoo of 0.05 weight % cinnamic aldehyde, (c) contain the shampoo of 1.2 weight % potassium sorbate and (d) contain the rectangular histogram of the stability (according to count of bacteria) of shampoo after 21 days of 0.05 weight % cinnamic aldehyde and 0.5 weight % potassium sorbate.
Fig. 3 is (a) not antiseptical shampoo, (b) contain the shampoo of 0.05 weight % cinnamic aldehyde, (c) contain the shampoo of 1.0 weight % milfoil oils and (d) contain the rectangular histogram of the stability (according to count of bacteria) of shampoo after 21 days of 0.05 weight % cinnamic aldehyde and 0.75 weight % milfoil oil.
Fig. 4 is (a) not antiseptical shampoo, (b) contains the shampoo of 0.1 weight % cinnamic aldehyde, (c) contains 1.0 weight %Hexahop Gold
TMShampoo and (d) contain 0.1 weight % cinnamic aldehyde and 0.4 weight %HexahopGold
TMThe rectangular histogram of the stability of shampoo after 7 days (according to the fungus counting).
Fig. 5 is (a) not antiseptical shampoo, (b) contains 1.0 weight %Larex
TMThe shampoo of (arabinogalactan) (c) contains the shampoo of 0.6 weight % potassium sorbate and (d) contains 0.5 weight %Larex
TMRectangular histogram with the shampoo of the 0.5 weight % potassium sorbate stability (according to the fungus counting) after 14 days.
Fig. 6 is (a) not antiseptical shampoo, (b) contain the shampoo of 0.25 weight % Indian oil of verbena, (c) contain the shampoo of 0.6 weight % potassium sorbate and (d) contain the rectangular histogram of the stability (according to fungus counting) of shampoo after 7 days of 0.1 weight % Indian oil of verbena and 0.5 weight % potassium sorbate.
Fig. 7 is (a) not antiseptical shampoo, (b) contains Hexahop Gold
TMShampoo, (c) contain the shampoo of 0.6 weight % potassium sorbate and (d) contain 0.1 weight % cinnamic aldehyde, (e) contain 0.3 weight %HexahopGold
TM, the rectangular histogram of the stability of shampoo after 7 days of 0.1 weight % cinnamic aldehyde and 0.6 weight % potassium sorbate.
Detailed Description Of The Invention
Definition
Term " microorganism " includes but not limited to bacterium, fungi, yeast, algae, insect and insect.
Term " about " or " approximately " refer to the acceptable error range to particular value that determines by those skilled in the art, and the mensuration mode of the value of depending in part on is namely measured the limitation of system. For example, by this area practice, " pact " can refer to 1 or greater than 1 standard deviation in. Perhaps, " pact " can refer at nearly 20% of set-point, better nearly 10%, better nearly 5%, and best 1% scope nearly. Perhaps, to biosystem or method, this term refers in an order of magnitude of a value, more fortunately in 5 times, better in 2 times. When describing occurrence in the application and claims, except as otherwise noted, " pact " refers to should suppose in acceptable error range the particular value term.
Term " personal care product " refers to be intended to be applied to human body, as is applied to the product of skin, hair and nail, includes but not limited to shampoo, conditioner, breast frost, lotion (such as refreshing body water), cosmetics and soap.
Term " sense of smell effective dose " refers to add the reagent of q.s in product, so that product odour to be provided.
Term " enhancing " refers to that compound or composition strengthen or increase the ability of the effect of antimicrobial compound or composition. The effectiveness of combination mixture is better greater than the adjection of composition.
Sorbic acid, arabo-ascorbic acid and benzoic acceptable acid addition salts include but not limited to, alkali metal or alkali salt are such as potassium and sodium.
The component of mixture
The cinnamic acid in any source all can be used for the present invention. For example, cinnamic acid can be from cinnamon bark extract (as from bark and leaf), cinnamon leaves oil, Chinese cinnamon, cinnamon oil, cinnamylidene (cinnamal), cinnamyl alcohol, and their mixture.
Sorbate is sorb potassium preferably.
Erythorbate is sodium isoascorbate preferably.
Benzoate is Sodium Benzoate preferably.
Arabogalactan, the gala araban is set from Larex. Arabogalactan is with Larex UFTMAvailable from Larex Inc.of White Bear Lake, MN.
Preferred six hydrogen-different-alpha-acid and tetrahydrochysene-different-alpha-acid is those that obtain from the hop extraction thing, such as Hezxahop GoldTM(being also referred to as Hexahop at this) can be from John I.Haas, Inc.of Washington, and D.C buys.
Fragrant milfoil oil is Achillea oil preferably.
According to specific embodiments, bactericidal composition comprises at least 0.1% sorbic acid and salt thereof, such as potassium sorbate.
The example of preferred mixture
(i) cinnamic acid and sorbic acid, arabo-ascorbic acid, or their salt
Preferred mixture is cinnamic acid and sorbic acid or its salt, such as potassium sorbate. Another kind of preferred mixture is cinnamic acid and arabo-ascorbic acid or its salt, such as sodium isoascorbate. Cinnamic acid and (i) sorbic acid or its salt, or (ii) weight of arabo-ascorbic acid or its salt is preferably about 10: 1 to about 0.1: 1, more preferably from about 5: 1 to about 0.2: 1.
The concentrate of mixture preferably includes about 2-40 % by weight cinnamic acid and about 10-60 % by weight sorbic acid, arabo-ascorbic acid, or their salt, in water, be with or without hydroxyl cosolvent (such as glycerine or ethanol, they can increase solubility and the stability of cinnamic acid in mixture).
Preferably, comprise (i) cinnamic acid and (ii) sorbic acid, arabo-ascorbic acid, or the pH of the preparation of the mixture of their salt is less than 10,9,8.5 or 8. PH was less than 9 o'clock, and preparation has improved colour stability. According to a preferred embodiment, contain cinnamic acid, sorbic acid, arabo-ascorbic acid, or the preparation of the mixture of their salt, its pH can reduce with hydrochloric acid. Preferably, comprise the hydrochloric acid of q.s in the preparation, to reduce its pH extremely less than 9,8.5 or 8.
Preferred preservative comprises about 5-20 % by weight cinnamic acid, 20-50 % by weight potassium sorbate, second alcohol and water. Better preservative comprises about 15 % by weight cinnamic acids, about 40 % by weight potassium sorbates, 10% ethanol and 35% water.
(ii) arabo-ascorbic acid or its salt, citric acid or its salt, gluconic acid Δ lactone, benzoic acid or its salt, sorbic acid, the combination of EDTA or its salt
Another kind of preferred mixture is (a) arabo-ascorbic acid or its salt (such as sodium isoascorbate) and (b) one or more (i) citric acids or its salt, (ii) gluconic acid Δ lactone, (iii) benzoic acid or its salt (such as Sodium Benzoate), (iv) sorbic acid or its salt, or (v) ethylenediamine tetra-acetic acid (EDTA) or its salt.
Another kind of preferred mixture is (a) benzoic acid or its salt (such as Sodium Benzoate) and (b) one or more (i) citric acids or its salt, (ii) gluconic acid Δ lactone, (iii) sorbic acid or its salt, or (iv) ethylenediamine tetra-acetic acid (EDTA) or its salt.
Arabo-ascorbic acid and its salt usually at preparation as being that color is unsettled in shampoo. Be surprisingly found out that these mixtures are colour stables. Also be surprised to find, arabo-ascorbic acid and its salt and gluconic acid Δ lactone can strengthen the bactericidal effect of citric acid, benzoic acid, EDTA and its salt.
Preferred mixture includes but not limited to those that following table is listed. Also listed better and better weight ratio in the table.
| Mixture | Component (a) | Component (b) | Better weight ratio | Better weight ratio |
| 1 | Benzoic acid or its salt | Arabo-ascorbic acid or its salt | About 0.1: 1 to about 20: 1 | About 0.2: 1 to about 5: 1 |
| 2 | Sorbic acid or its salt | Arabo-ascorbic acid or its salt | About 0.1: 1 to about 20: 1 | About 0.2: 1 to about 5: 1 |
| 3 | Benzoic acid or its salt | Gluconic acid Δ lactone | About 0.1: 1 to about 20: 1 | About 0.2: 1 to about 5: 1 |
| 4 | Gluconic acid Δ lactone | Arabo-ascorbic acid or its salt | About 0.1: 1 to about 20: 1 | About 0.2: 1 to about 5: 1 |
| 5 | Gluconic acid Δ lactone | Benzoic acid or its salt | About 0.1: 1 to about 20: 1 | About 0.2: 1 to about 5: 1 |
Better mixture includes but not limited to those that following table is listed.
| Mixture | Component (a) | Component (b) | Better weight ratio | Better weight ratio |
| 1 | Sodium Benzoate | Sodium isoascorbate | About 1: 1 to about 5: 1 | About 3: 1 |
| 2 | Potassium sorbate | Sodium isoascorbate | About 1: 1 to about 5: 1 | About 3: 1 |
| 3 | Sodium Benzoate | Gluconic acid Δ lactone | About 1: 1 to about 5: 1 | About 3: 1 |
| 4 | Gluconic acid Δ lactone | Sodium isoascorbate | About 1: 1 to about 5: 1 | About 3: 1 |
| 5 | Gluconic acid Δ lactone | Sodium Benzoate | About 0.1: 1 to about 5: 1 | About 3: 1 |
Bactericidal composition
Bactericidal composition of the present invention can be used as antiseptic, fungicide and bactericide (such as anti-allergen, tree and plant fungi, and the bacterium of plant and tree), be used as the anticorrisive agent of papermaking, weaving, agricultural, coatings industry and personal nursing, family expenses, industry and corporations' product. Bactericidal composition can join on the matrix that is subject to the growth of microorganism impact and preserve. For example, protective system can join the personal care product, such as shampoo, conditioner, breast frost, lotion (such as bath foam), cosmetics or soap; Household products is such as fabric softener, washing scale remover or crust cleaning agent; Or industrial products, such as paint, coating, timber, textile, adhesive, sealant, leather, rope, paper, paper pulp, cardboard, Sheetrock (sheet rock), ceiling ceramic tile, plastics, fuel, oil, oil, rubber hydraulic fluid, working metal liquid, starch (such as pet food starch), or mineral slurry, such as clay slip, calcium carbonate or titanium oxide (TiO2)。
That product generally contains is antibiotic, anticorrosion, kill antibacterial, and/or the bactericidal composition of antifungal effective dose.According to an embodiment, be benchmark in the product gross weight, product contains each component of the 0.1-2.0 weight % bactericidal composition of having an appointment.According to another embodiment, be benchmark in the product gross weight, product contains have an appointment 0.1-1 or 2.0 weight % bactericidal compositions.
The cinnamic aldehyde preservative system
Cinnamic aldehyde and (i) cinnamic aldehyde (ii) at least a mixture in alkanol dialkylhydantoin, isothiazolone (isothiazolone) and the benzisothia oxazolone (benzisothiazolone) (below be called " preservative system ") be used as antibacterial, antifungal and bactericide are (as anti-allergen, the tree fungus, and tree antibacterial), with as the antiseptic in papermaking, fabric, agricultural and the coating, and the antiseptic in personal nursing, domestic, industry and the corporations' product.Preservative system can join on the substrate that is subject to the growth of microorganism influence, to preserve substrate.For example, preservative system can join the personal care product, as shampoo, conditioner, cream, lotion (as refreshing body water), cosmetics or soap; Household products is as fabric softener, washing scale remover or hard surface cleaner; Or industrial products, as paint, coating, timber, textile, binding agent, sealant, leather, rope, paper, paper pulp, cardboard, Sheetrock, ceiling ceramic tile, plastics, fuel, oil, oil, rubber hydraulic fluid, working metal liquid, starch (as pet food starch), or mineral slurry, as clay slip, calcium carbonate or titanium oxide (TiO
3).
Bactericidal composition of the present invention and preservative system general action are rapidly (as reducing microorganism (as antibacterial and/or fungus) counting 95 usually in 1 hour, 99,99.9 or 99.99%), and can be long-time (as at least 7,10,14 or 28 days) remain valid (as keeping) less than 10cfu/g.Term " preservative effective amount " refer to keep microorganism count less than 1000,100 or 10cfu/g reach at least 1,4, the amount of 7,10,14 or 28 days preservative system.
Bactericidal composition and preservative system can comprise solvent Ru Shui and water miscible solvent, include but not limited to alcohols (as methanol, ethanol, propanol, isopropyl alcohol and butanols), glycol (as glycerol, diglycerol, butanediol, fourth oxygen glycol, propylene glycol and dipropylene glycol), esters, ethers, polyethers, and their combination in any.For example, solvent can comprise water and one or more glycol and/or one or more alcohol, as glycerol, phenoxyethanol, benzylalcohol or ethanol.A kind of specific solvent systems comprises water and a kind of alcohol such as ethanol.
Those skilled in the art all know, can comprise other adjuvant in bactericidal composition and preservative system.Suitable adjuvant includes but not limited to antiseptic; Solubilizing agent; Chelating agen such as ethylenediaminetetraacetic acid (EDTA) and salt and zeolite; Surfactant such as cation, anion, nonionic and amphoteric surfactant; Antioxidant such as butylated hydroxyanisol (BHA) and butylated hydroxytoluene (BHT); Amine oxide; Tertiary amine; Zinc compound; Hydrotropic agent; Fluoride; Magnesium salt; Calcium salt; Carboxylic acid; Phosphate; Phosphate ester; Formaldehyde donor; Glycerin polyoxyethylene (7) ether (glycereth-7); Myristic acid Fructus Amomi Rotundus ester; Glutaraldehyde; Biguanide; Natural prodcuts such as geraniol, lichenic acid and tea tree oil; And the combination in any of above-mentioned substance.Suitable antiseptic includes but not limited to, the chlorination quaternary ammonium; The carbonic acid quaternary ammonium; Benzalkonium chloride; Contain iodine compound such as 3-iodo-2-propynyl butyl carbamate (IPBC); Beta-lactam such as dimethyl beta-lactam and halogenation beta-lactam; Isothiazolone; P-Hydroxybenzoate such as methyl parahydroxybenzoate, ethylparaben and propyl p-hydroxybenzoate; Dehydroactic acid and salt thereof; Isoprocil (isocil); Chloroxylenol; Phenyl phenol; Benzylalcohol; Phenethanol; Benzoic acid and salt thereof such as sodium benzoate; Methaform; Sorbic acid and salt thereof; Triclosan; Neko; And the combination in any of above-mentioned substance.
Bactericidal composition and preservative system can join water base or oil based system or emulsion in.To the suitable solvent of oil based system is phenyl phenol and/or benzylalcohol.
Bactericidal composition can be a liquid or solid.
When Synergistic blend only contains two kinds when being selected from above-mentioned component, the weight ratio of first component and second component is usually about 0.01: 100 to about 100: 0.01 scope, and better about 0.1: 20 to about 20: 0.1, better about 0.1: 10 to about 10: 1.When Synergistic blend contained three kinds of components, the 3rd component can be any amount, but the weight ratio of common the 3rd component and first or second component is about 0.01: 100 to about 100: 0.01.
For preparation contains the preparation of product of the present invention, generally at first prepare the concentrated solution of bactericidal composition and preservative system.In the concentrate gross weight is 100%, and concentrated solution comprises bactericidal composition and the preservative system of about 0.01-100 weight %, better comprises bactericidal composition and the preservative system of about 5-80 weight %.To the bactericidal composition of two components, concentrated solution comprises about 0.01-99.9 weight % first component and about 99.99-0.01 weight % second component (is benchmark in concentrated solution gross weight 100%).When preservative system is cinnamic aldehyde, be benchmark in concentrated solution gross weight %, concentrated solution can comprise about 0.01-100 weight % cinnamic aldehyde, better comprises about 5-80 weight % cinnamic aldehyde.Table A is listed the component in the typical concentrated solution of the dialkylhydantoin mixture that cinnamic aldehyde/alkanol replaces and the scope (is benchmark in concentrated solution gross weight 100%) of component.
Table A
| Scope | Cinnamic aldehyde | Dialkylhydantoin, isothiazolone, benzisothia oxazolone that alkanol replaces |
| Wide region | About 0.01-99.9% | About 99.99-0.01% |
| Better | About 5-95% | About 95-5% |
Before the use, the better same solvent dilution that concentrated solution is used in the more handy and concentrated solution, and/or join in a kind of product.Use the diluent of compositions to comprise antibiotic, anticorrosion, antifungal usually or kill the bactericidal composition or the preservative system of antibacterial effective dose.
The diluent that uses generally contains 0.0001 weight % or the 0.01 weight % concentrated solution to about 2 weight % of having an appointment.According to an embodiment preferably, the diluent of use comprises the concentrated solution of about 0.1 weight %.In the better implement scheme, the diluent of use contains the concentrated solution of 0.2,0.25 or 0.30 weight %.Be benchmark in the diluent gross weight of using 100%, the diluent of use generally contains each antibacterial component of the 0.01-2.0 weight % that has an appointment.According to embodiment preferably, bactericidal composition contains the 0.001-10 weight % that has an appointment, better about 0.01-1 weight %, each antibacterial component (as cinnamic aldehyde) of better about 0.05-0.5 weight %.When preservative system is cinnamic aldehyde, be benchmark in the diluent gross weight of using, the diluent of use contains has an appointment 0.001,0.005,0.01,0.02,0.03,0.04,0.05,0.06,0.07 0.08,0.09 or 0.1 weight % is to about 1,0.5,0.4,0.3,0.25,0.2,0.15,0.1,0.09,0.08,0.07,0.06,0.05,0.04,0.03,0.02 or 0.01 weight % cinnamic aldehyde.Table B is listed in component and the content range (the diluent gross weight of using 100% is the benchmark meter) thereof in the diluent of use.
Table B
| Scope | Cinnamic aldehyde | Dialkylhydantoin, isothiazolone, benzisothia oxazolone that alkanol replaces |
| Wide region | About 0.001-10 weight % | About 0.001-10 weight % |
| Better | About 0.01-1 weight % | About 0.01-1 weight % |
| Better | About 0.05-0.5 weight % | About 0.05-0.5 weight % |
According to another embodiment, in a product, add the foregoing preservatives system, its concentration is for to count about 0.1-1 weight % or 2 weight % by product gross weight 100% for benchmark.
Another embodiment of the invention is to suppress microorganism, antibacterial (as staphylococcus aureus (S.aureus) (ATCC#6538), bacillus pyocyaneus (P.aeruginosa) (ATCC#9027) and escherichia coli (E.coli) (ATCC#8739)) and/or fungus (comprise plant epiphyte and tree fungus) (as Candida albicans, aspergillus niger and La Muluo vaccine (Phytophthora ramrum)) method of growing on substrate specifically is to use antibiotic, anticorrosion, as to kill antibacterial or antifungal effective dose bactericidal composition or preservative system on substrate.Bactericidal composition or antiseptic can be used by any method known in the art, include but not limited to brushing, dip-coating, immersion, vacuum impregnation and pressurized treatments.A specific embodiment is a kind of method that suppresses to set fungus La Muluo epidemic disease bacteria growing, for use the bactericidal composition of the present invention or the preservative system of antifungal effective dose on the substrate (as tree) of tree mildew bacterium or tree mildew bacteria growing.The La Muluo vaccine can cause Oak Tree sudden death (Sudden OkaDeath).
Bactericidal composition of the present invention can also prepare by mixing antibacterial component and optional solvent and adjuvant.Mixture can heat and/or stir and quicken to mix.
Embodiment
The following examples explanation the present invention, but be not construed as limiting.Unless point out in addition, all part and percentage number averages provide by weight.
Embodiment 1
According to each the anion shampoo sample among the following described test pattern 1-3.According to following step preparation standard mixed cell solution.With three golden black staphylococcuses (ATCC#6538), the agar stab of bacillus pyocyaneus (ATCC#9027) and escherichia coli (ATCC#8739) was cultivated about 24 hours at about 35 ℃ respectively.Then, each puncture is washed with 3mL 0.85% sterile saline solution.The washing liquid of three punctures is concentrated in together formation organism mixture.By adding saline this organism mixture is adjusted to about 1.00 at the absorbance of 530nm.With saline blank correction spectrogrph.The separatory such as 5mL of this organism mixture are mixed, make standardization mixed cell solution.Then, inoculation 0.2mL standardization mixed cell solution and mixing in 40 gram samples of each shampoo.Getting 1 this mixture of gram is added in 20 * 150mm nut test tube of sterilization.
In this test tube, add 9mL sterilization D/E nertralizer meat soup, mix forming 10
-1Dilution.Water with phosphate-buffered is diluted to 10
-6, make serial dilutions.Serial dilutions is placed on the tryptic soy agar, cultivated 2 days at about 35 ℃.After 21 days, carry out count of bacteria.
Anionic Protein matter shampoo Compositions comprises the sodium lauryl tri(oxyethyl) sulfate of 35 weight %; 25 weight % dodecyltriethanolamine sulfates; 3 weight % coconut diethanolamide (cocamide DEA); 1 weight % hydrolytic collagen can Polypro 5000
TMFrom Hormel Foods ofAustin, MN buys; With 36 weight % deionized waters.
Mix an amount of antibacterial component and above-mentioned Anionic Protein matter shampoo Compositions, and with extremely about 50 ℃ of this mixture heated, about 15 minutes, preparation contained the bactericidal composition of sample.
The results are shown in Fig. 1-3.
Embodiment 2
According to each the anion shampoo sample among the following described test pattern 4-7.According to following step preparation standard mixed cell solution.Two Candida albicans agar stabs and four aspergillus niger agar slants were cultivated about 48 hours and 7 days at about 25 ℃ respectively.Then, each puncture is collected the back and is macerated in tissue grinder with the flushing of 3mL 0.85% sterile saline solution.0.85% saline solution that adds q.s in each puncture is at microscopically each inoculum with Neubauer Hemocytometer naked eyes counting Candida albicans and aspergillus niger.Each standardization inoculum equal-volume of Candida albicans and aspergillus niger is mixed, form standardization mixed fungus solution.
Inoculation 0.4mL standardization mixed fungus solution and mixing in 40 gram samples of each shampoo.Getting 1 this mixture of gram is added in 20 * 150mm nut test tube of sterilization.
In this test tube, add 9mL sterilization D/E nertralizer meat soup, mix forming 10
-1Dilution.Water with phosphate-buffered is diluted to 10
-6, make serial dilutions.Serial dilutions is placed on the Sabouraud's dextrose agar, cultivated 5 days at about 25 ℃.After 0,7 and/or 14 day, carry out the fungus counting.
Anionic Protein matter shampoo Compositions is described in the embodiment 1.Mix an amount of antibacterial component and Anionic Protein matter shampoo Compositions, and with extremely about 50 ℃ of this mixture heated, about 15 minutes, preparation shampoo sample.
The results are shown in Fig. 4-7.
Embodiment 3
Repeat embodiment 1 described method with the preservative of listing in the following table 1.With shampoo pH regulator to 6.5.The result also lists in table 1.
Table 1
| |
0 day cfu/g | 7 days cfu/g | 14 days cfu/g | 28 days cfu/g |
| 0.3 weight % mixture contains 75% potassium sorbate and 25% sodium erythorbate | 1-3×10 6 | ＜10 | ＜10 | ＜10 |
| 0.3 weight % mixture contains 75% sodium benzoate and 25% sodium erythorbate | 1-3×10 6 | ＜10 | ＜10 | ＜10 |
| 0.45 weight % sodium erythorbate | 1-3×10 6 | ＞3×10 6 | ＞3×10 6 | ＞3×10 6 |
| 0.45 weight % sodium benzoate | 1-3×10 6 | 1×10 5 | 7×10 5 | ＜10 |
| 0.45 weight % potassium sorbate | 1-3×10 6 | 1×10 5 | 6×10 4 | Do not measure |
| Antiseptical shampoo not | 1-3×10 6 | ＞3×10 6 | ＞3×10 6 | ＞3×10 6 |
" mixture of quaternary ammonium compound and long-chain fatty acid is as antifungal (Mixtures of Quaternary Ammonium Compounds and Long chain Fatty Acids asAntifungal Agents) " of employing C.E.Kull etc., Applied Microbiology, method described in the 9:538-541 (1961) is calculated the synergism of 0.3% diluent of 3% diluent of (1) potassium sorbate (75%) and sodium erythorbate (25%) and (2) sodium benzoate (75%) and sodium erythorbate (25%) to mixed cell in the shampoo by table 1.Measure collaborative value (Q
A/ Q
a+ Q
B/ Q
b).Q
ABe the concentration (weight %) of potassium sorbate or sodium benzoate in the mixture, produce 100% bacteriostatic after 7 days, be i.e. plate counting＜10cfu/g early.Q
aBe that only potassium sorbate or sodium benzoate produce the required concentration of 100% bacteriostatic (weight %).Q
BBe arabo-ascorbic acid na concn (weight %) in the mixture, produce 100% bacteriostatic.Q
bBe that only sodium erythorbate produces the required concentration of 100% bacteriostatic (weight %).
As (Q
A/ Q
a+ Q
B/ Q
b) value less than 1 o'clock, this mixture is a synergism.(Q
A/ Q
a+ Q
B/ Q
b) value be 1 and when bigger, represent adjection and antagonism respectively.The results are shown in following table 2.
Table 2
| Preservative blends | Q A | Q a | Q B | Q b | Q A/Q a+ Q B/Q b |
| 75% potassium sorbate and 25% sodium erythorbate | 0.225％ | 0.075％ | 0.45％ | 0.45％ | 0.67(＜1) |
| 75% sodium benzoate and 25% sodium erythorbate | 0.225％ | 0.075％ | 0.45％ | 0.45％ | 0.67 |
Embodiment 4
According to each the anion shampoo sample in the following described test chart 3.Mixed cell solution according to following step preparation standardization.With three staphylococcus aureuses (ATCC#6538), the agar stab of bacillus pyocyaneus (ATCC#9027) and escherichia coli (ATCC#8739) was cultivated about 24 hours at about 35 ℃ respectively.Then, each puncture is washed with 3mL 0.85% sterile saline solution.The washing liquid of three punctures is concentrated in together formation organism mixture.By adding saline this organism mixture is adjusted to about 1.00 at the absorbance of 530nm.With saline blank correction spectrogrph.The separatory such as 5mL of this organism mixture are mixed, make standardization mixed cell solution.Then, inoculation 0.2mL standardization mixed cell solution and mixing in 40 gram samples of each shampoo.Getting 1 this mixture of gram is added in 20 * 150mm nut test tube of sterilization.
In this test tube, add 9mL sterilization D/E nertralizer meat soup, mix forming 10
-1Dilution.Water with phosphate-buffered is diluted to 10
-6, make serial dilutions.Serial dilutions is placed on the tryptic soy agar, cultivated 2 days at about 35 ℃.After 0,7 and 14 day, carry out count of bacteria.The results are shown in table 1.
Anionic Protein matter shampoo Compositions comprises the sodium lauryl tri(oxyethyl) sulfate of 35 weight %; 25 weight % dodecyltriethanolamine sulfates; 3 weight % coconut diethanolamide (cocamide DEA); 1 weight % hydrolytic collagen can Polypro 5000
TMFrom Hormel Foods ofAustin, MN buys; With 36 weight % deionized waters.
Preparation contains the sample of cinnamic aldehyde and other antiseptic, and method is to mix an amount of antiseptic and above-mentioned Anionic Protein matter shampoo Compositions, and with extremely about 50 ℃ of this mixture heated, about 15 minutes.
Table 3
*-LiquaPar Optima be phenyl phenol (with) methyl parahydroxybenzoate (with) p-Hydroxybenzoic acid isopropyl ester (with) p-Hydroxybenzoic acid isobutyl ester (with) butyl p-hydroxybenzoate, can be from ISP Labs of Wayne, NJ buys.
All percents in the table 3 are to be 100% weight % in the shampoo gross weight.
Embodiment 5
According to each the anion shampoo sample in the following described test following table 4.Mixed cell solution according to following step preparation standardization.Two Candida albicans and four aspergillus niger agar slants were cultivated about 48 hours and 7 days at about 25 ℃ respectively.Then, each inclined-plane is also macerated in tissue grinder with 3mL 0.85% sterile saline solution washing, collection.0.85% saline solution that adds q.s on each inclined-plane is at microscopically each inoculum with Neubauer Hemocytometer naked eyes counting Candida albicans and aspergillus niger.Each standardization inoculum equal volume amounts of Candida albicans and aspergillus niger is mixed, form standardization mixed fungus solution.
Inoculation 0.4mL standardization mixed fungus solution and mixing in 40 gram samples of each shampoo.Getting 1 this mixture of gram is added in 20 * 150mm nut test tube of sterilization.
In this test tube, add 9mL sterilization D/E nertralizer meat soup, mix forming 10
-1Dilution.Water with phosphate-buffered is diluted to 10
-6, make serial dilutions.Serial dilutions is placed on the Sabouraud's dextrose agar, cultivated 5 days at about 25 ℃.After 0 and 14 day, carry out the fungus counting.The results are shown in table 9.
Anionic Protein matter shampoo Compositions is described in the embodiment 4.Mix an amount of antibacterial component and Anionic Protein matter shampoo Compositions, and with extremely about 50 ℃ of this mixture heated, about 15 minutes, preparation shampoo sample.
Table 4
Embodiment 6
According to each the cream sample in the embodiment 1 described method test following table 5.Glyceryl monostearate (GMS) cream of listing according to following described preparation table 3.Mixed polyoxyethylene glyceryl monostearate, glyceryl monostearate, 16/octadecanol (cearyl alcohol) and propanoic acid Fructus Amomi Rotundus ester in first container, and be heated to 60 ℃.In second container, mix the deionized water of glycerol and sterilization and be heated to 60 ℃.Pour the solution in first container into second container.Second container kept 10 minutes at 60 ℃.Cool off the solution in second container.With sodium hydroxide this pH value of solution is adjusted to 7, makes the GMS cream.
Table 5
The cream sample that Zb following table 6 is listed, method are to mix an amount of antiseptic and GMS, and with extremely about 50 ℃ of this mixture heated, 10-15 minute.The results are shown in following table 6.
Table 6
Being prepared as of the cream sample that following table 7 is listed mixed an amount of antiseptic and GMS, and with extremely about 50 ℃ of this mixture heated, 10-15 minute.The results are shown in following table 7.
Table 7
Embodiment 7
With the shampoo sample of listing in the following table 8, repeat embodiment 4 described methods.The results are shown in Table 8.
Table 8
*-Glydant 2000
TM Be 70% solution of hydantoins material, comprise about 36% dihydroxymethyl dimethyl hydantoin (DMDMH), about 29% monomethylol dimethyl hydantoin (MMDMH) and about 5% dimethyl hydantoin (DMH); With 30% water.Can be from Lonza Inc.of Fair Lawn, NJ buys.
" mixture of quaternary ammonium compound and long-chain fatty acid is as antifungal " of employing C.E.Kull etc., Applied Microbiology, the method described in the 9:538-541 (1961), cinnamic aldehyde/Glydant 2000 in the computer chart 8
TMSolution is to staphylococcus aureus, bacillus pyocyaneus and colibacillary synergism.Measure the synergism value (Q in the table 7
A/ Q
a+ Q
B/ Q
b).Q
ABe the concentration (weight %) of cinnamic aldehyde in the mixture, produce 100% bacteriostatic after 14 days, i.e. plate count＜10cfu/g.Q
aBe that only cinnamic aldehyde reaches the required concentration of 100% bacteriostatic (weight %).Q
BBe Glydant 2000 in the mixture
TMConcentration (weight %) produces 100% bacteriostatic.Q
bBe Glydant 2000 only
TMProduce the required concentration of 100% bacteriostatic (weight %).
As (Q
A/ Q
a+ Q
B/ Q
b) value less than 1 o'clock, this mixture has synergism.(Q
A/ Q
a+ Q
B/ Q
b) value be 1 and greater than 1 o'clock, represent adjection and antagonism respectively.The results are shown in following table 9 and 10.
Table 9
To 7 days
| Preservative blends | Q A | Q B | Q a | Q b | Q A/Q a+ Q B/Q b |
| 0.05％Glydant 2000 TM | - | - | 0.05％ | - | - |
| 0.10% cinnamic aldehyde | - | - | - | 0.1％ | - |
| 0.02％Glydant 2000 TMWith 0.025% cinnamic aldehyde | 0.02％ | 0.025％ | - | - | 0.65 |
Table 10
To 14 days
| Preservative blends | Q A | Q B | Q a | Q b | Q A/Q a+ Q B/Q b |
| 0.05％Glydant 2000 TM | - | - | 0.05％ | - | - |
| 0.10% cinnamic aldehyde | - | - | - | 0.05％ | - |
| 0.02％Glydant 2000 TMWith 0.025% cinnamic aldehyde | 0.02％ | 0.025％ | - | - | 0.90 |
Embodiment 8
The minimal inhibitory concentration (MIC) of test preservative blends.MIC is the least concentration that a kind of component suppresses growth of microorganism.This research adopts Hamilton Micro Lab AT Plus Autodilutor Liquid processing system to carry out.The autodilutor program is based on the standard application method SAPM#412-01-1 of Lonza.Use Hamilton Autodilutor,, the initial concentration of antiseptic combination diluted 50% with the nutrient meat soup in the 96 hole titer plate, and in specimen microbe inoculation.
The antiseptic of test is Isocil
TM(mixture of methyl isothiazolone and methyl-chloro-isothiazolone), Benzocil
TM(benzisothia oxazolone) and Lonzagard
TM(benzethonium chloride) is (all available from Lonza Inc.ofFair Lawn, NJ) with the compositions of variable concentrations and cinnamic aldehyde.On each test slab, also comprise matched group.Each preservative blends is to staphylococcus aureus and escherichia coli (ATCC#8739), and each preservative blends doubles to test.
Test slab dilutes by Hamilton Autodilutor, with the test microbionation, obtains about 10 then
6Colony-forming units/gram specimen (cfu/g).Then, dull and stereotyped 32 ℃ of cultivations 72 hours.Determine the result by detecting on every flat board in the specimen growth with control wells (turbidity in the macroscopy hole).MIC shown in the following table 11 does not show the antiseptic of growth or the minimum testing level of preservative blends.
(7.5ppm activity) Benzocil
TMEffectively suppress growth with the mixture of 25ppm cinnamic aldehyde.(0.47ppm activity) Isocil
TMAlso effectively suppress growth with the mixture of 6.3ppm cinnamic aldehyde.
Table 11
| Test substances | MIC to S.Aureus |
| Cinnamic aldehyde | 125ppm |
| Isocil TM(isothiazolone) | (0.585ppm activity) |
| Benzocil TM(benzisothia oxazolone) | (9.375ppm activity) |
Kull above adopting, above described method is calculated Isocil by the MIC value that table 11 is listed
TM/ cinnamic aldehyde and Benzocil
TMThe synergism value of/cinnamic aldehyde compositions is listed in following table 12 and 13.
Table 12
| Preservative blends | Q A | Q B | Q a | Q b | Q A/Q a+ Q B/Q b |
| (0.585ppm activity) Isocil TM | - | - | 0.585 | - | - |
| The 125ppm cinnamic aldehyde | - | - | - | 125 | - |
| (0.47ppm activity) Isocil TMWith the 6.3ppm cinnamic aldehyde | 0.47 | 6.3 | - | - | 0.85 |
Table 13
| Preservative blends | Q A | Q B | Q a | Q b | Q A/Q a+ Q B/Q b |
| (9.375ppm activity) Benzocil TM | - | - | ＞9.375 | - | - |
| The 125ppm cinnamic aldehyde | - | - | - | ＞125 | - |
| (7.5ppm activity) Benzocil TMWith the 25ppm cinnamic aldehyde | 7.5 | 25 | - | - | ＜1.0 |
Embodiment 9
Adopt the Gardner color test, the colour stability of test cinnamic aldehyde/potassium sorbate mixture.Add hydrochloric acid, the pH that regulates preparation is to specified pH.The results are shown in following table.
**************
Above-mentioned all patents, application, article, publication and method of testing are all with reference to being incorporated into this.
Those skilled in the art can propose many changes according to top detailed description.So tangible change is within the four corner of accessory claim book.
Claims (4)
1. antibiotic and anticorrosion concentrated solution, it comprises cinnamic aldehyde and Glydant 2000
TMSynergistic blend, wherein Glydant 2000
TMWith the ratio of cinnamic aldehyde be 0.02%: 0.025%, Glydant 2000
TMBe 70% solution of hydantoins material, comprise 36% dihydroxymethyl dimethyl hydantoin, 29% monomethylol dimethyl hydantoin, 5% dimethyl hydantoin and 30% water.
2. preservative, it contains the described antibiotic and anticorrosion concentrated solution of 0.01～2 weight % claim 1.
3. the application of the non-therapeutic purposes of the described preservative of claim 2 aspect the inhibition growth of microorganism.
4. the described preservative of claim 2 is in the application that suppresses the non-therapeutic purposes aspect the conk on the substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40316902P | 2002-08-12 | 2002-08-12 | |
| US60/403,169 | 2002-08-12 | ||
| US60/403,004 | 2002-08-12 |
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|---|---|---|---|
| CN200910178255A Division CN101703080A (en) | 2002-08-12 | 2003-08-12 | Antimicrobial compositions |
| CN200910178254A Division CN101703047A (en) | 2002-08-12 | 2003-08-12 | antimicrobial compositions |
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| CN100560071C true CN100560071C (en) | 2009-11-18 |
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| EP2486922A4 (en) | 2009-10-08 | 2013-05-29 | Phlora Bio Technology Invest Ltd | Composition comprising benzoic acid in combination with organic acid preservatives as active components and use thereof |
| CN102422847A (en) * | 2011-10-18 | 2012-04-25 | 浙江农林大学 | Weed killer containing plant essential oil, and application thereof |
| CN103040922A (en) * | 2012-12-17 | 2013-04-17 | 青岛研博电子有限公司 | Antimicrobial composition |
| US10271551B2 (en) * | 2016-06-22 | 2019-04-30 | Lonza Inc. | Preservative composition for wet wipes |
| EP3520785A4 (en) * | 2016-10-09 | 2020-05-27 | Shenzhen Eulikan Biotechnology Co., Ltd. | Uses of bacteriostatic agent formula in preparing composition for vaginal use and composition for vaginal use |
| EP3813776A1 (en) * | 2019-05-09 | 2021-05-05 | Codex Beauty LLC | Preservative systems |
| KR102623892B1 (en) * | 2019-09-30 | 2024-01-11 | 주식회사 엘지화학 | Super absorbent polymer and preparation method thereof |
| CN113826623A (en) * | 2020-06-08 | 2021-12-24 | 中国科学院大连化学物理研究所 | Bio-based disinfectant and preparation method |
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