CN111657291A - Leather mildew preventive and preparation method thereof - Google Patents

Leather mildew preventive and preparation method thereof Download PDF

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Publication number
CN111657291A
CN111657291A CN202010474996.5A CN202010474996A CN111657291A CN 111657291 A CN111657291 A CN 111657291A CN 202010474996 A CN202010474996 A CN 202010474996A CN 111657291 A CN111657291 A CN 111657291A
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leather
mildew
mildew preventive
thiabendazole
octyl
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黄炎洪
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Guangzhou Nuoopu Chemical Technology Co ltd
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Guangzhou Nuoopu Chemical Technology Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/781,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00Surface finishing of leather

Abstract

The invention discloses a leather mildew preventive and a preparation method thereof. The leather mildew preventive disclosed by the invention comprises the following components in percentage by mass: thiabendazole: 1% -5%; and (2) bloom: 5% -15%; 2-n-octyl-4-isothiazolin-3-one: 5% -20%; emulsifier: 8 to 30 percent; cosolvent: 10% -30%; water: and (4) the balance. The leather mildew preventive is simple in preparation method and can be prepared by uniformly mixing the components in batches. According to the invention, the thiabendazole, the dazomet and the 2-n-octyl-4-isothiazolin-3-one which are low in toxicity are compounded, and the three active ingredients have synergistic effect, so that the obtained leather mildew preventive is wide in bacteriostatic spectrum and not easy to generate drug resistance, and the dazomet can kill worm eggs and mites, so that large-area mildew growth of wet blue leather in a storage process can be effectively avoided, the mildew-proof process cost of a tanning enterprise is reduced, and the leather mildew preventive is suitable for being used in a large-dosage tanning industry.

Description

Leather mildew preventive and preparation method thereof
Technical Field
The invention relates to a leather mildew preventive and a preparation method thereof, belonging to the technical field of mildew preventive and bactericide.
Background
The leather product is visible everywhere in daily life of people, is deeply loved by wide consumers, and promotes the rapid development of leather-making enterprises. However, leather mildew growth has been a troublesome problem for leather manufacturers, and many methods for preventing leather mildew exist, and the most effective and commonly used method is to use a leather mildew inhibitor. In recent years, under the influence of environmental protection factors, a plurality of traditional leather mildew preventives (such as halogenated phenol mildew preventives, aldehyde mildew preventives and the like) are forbidden to be used, while the emerging inorganic nano mildew preventives have good mildew-proof effect, but have high use cost and are not suitable for being used in the tanning industry with large use amount.
At present, the mildew preventive commonly used in the industry is 2-thiocyanomethyl-thiobenzothiazole (TCMTB), which is a high-efficiency environment-friendly mildew preventive, but because the mildew preventive is used in the industry for a long time, the drug resistance of fungi is stronger and stronger, the mildew preventive effect of the mildew preventive is greatly reduced, and the actual requirements are difficult to meet again. The high-efficiency low-toxicity mildew inhibitor is the mainstream direction of the current international sterilization and mildew-proof research, the heterocyclic compound mildew inhibitor has low toxicity and good mildew-proof effect, and is widely applied in recent years, but the mildew-proof effect of the mildew inhibitor on partial mildew is not ideal enough, and the actual requirement is difficult to meet.
Therefore, there is a need to develop a leather mildew inhibitor with low toxicity, broad antibacterial spectrum and low drug resistance.
Disclosure of Invention
The invention aims to provide a leather mildew preventive and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a leather mildew preventive comprises the following components in percentage by mass:
thiabendazole: 1% -5%;
and (2) bloom: 5% -15%;
2-n-octyl-4-isothiazolin-3-one: 5% -20%;
emulsifier: 8 to 30 percent;
cosolvent: 10% -30%;
water: and (4) the balance.
Preferably, the leather mildew preventive comprises the following components in percentage by mass:
thiabendazole: 1% -3%;
and (2) bloom: 8% -10%;
2-n-octyl-4-isothiazolin-3-one: 5% -15%;
emulsifier: 10% -25%;
cosolvent: 10% -30%;
water: and (4) the balance.
Preferably, the emulsifier is at least one of fatty alcohol-polyoxyethylene ether, fatty acid-polyoxyethylene ether, polyoxyethylene-polyoxypropylene block copolymer, fatty alcohol-polyoxyethylene ether phosphate and polyoxyethylene sorbitan monostearate.
Further preferably, the emulsifier is prepared from fatty alcohol-polyoxyethylene ether and tween-60 according to a mass ratio of 1: (0.2-2).
Preferably, the cosolvent is at least one of an alcohol solvent and an alcohol ether solvent.
More preferably, the cosolvent is at least one of dipropylene glycol, tripropylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether.
Still more preferably, the co-solvent is dipropylene glycol.
The preparation method of the leather mildew preventive comprises the following steps:
1) adding the dazomet, the thiabendazole, the cosolvent and the water into a stirrer, and stirring;
2) adding 2-n-octyl-4-isothiazolin-3-one and an emulsifier into a stirrer, and stirring;
3) and transferring the materials in the stirrer into a shearing emulsifying machine, and shearing and emulsifying to obtain the leather mildew preventive.
Preferably, the rotating speed of the stirrer during stirring in the step 1) is 2000-3000 r/min, and the stirring time is 5-10 min.
Preferably, the rotating speed of the stirrer during stirring in the step 2) is 2000-3000 r/min, and the stirring time is 8-10 min.
Preferably, the rotating speed of the shearing emulsifying machine in the shearing emulsification in the step 3) is 8000-9000 r/min, and the time is 20-30 min.
The invention has the beneficial effects that: according to the invention, the thiabendazole, the dazomet and the 2-n-octyl-4-isothiazolin-3-one which are low in toxicity are compounded, and the three active ingredients have synergistic effect, so that the obtained leather mildew preventive is wide in bacteriostatic spectrum and not easy to generate drug resistance, and the dazomet can kill worm eggs and mites, so that large-area mildew growth of wet blue leather in a storage process can be effectively avoided, the mildew-proof process cost of a tanning enterprise is reduced, and the leather mildew preventive is suitable for being used in a large-dosage tanning industry.
Drawings
FIG. 1 is a photograph showing the mildewproof effect of the leather mildewcide according to examples 1 to 3 and comparative examples 1 to 4.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Examples 1 to 3 and comparative examples 1 to 4:
the compositions of the leather mildewcide of examples 1 to 3 and comparative examples 1 to 4 are shown in the following table:
TABLE 1 composition Table of leather mildewcide for examples 1 to 3 and comparative examples 1 to 4
Figure BDA0002515554930000031
Note:
BIOBANTM890: the main active component of the mildew preventive special for leather of the Dow company is 2-n-octyl-4-isothiazoline-3-ketone.
The preparation method of the leather mildewcide of the embodiments 1 to 3 comprises the following steps: 1) adding the dazomet, the thiabendazole, the dipropylene glycol and the deionized water into a stirrer, adjusting the rotating speed of the stirrer to 2500r/min, and stirring for 8 min; 2) adding 2-n-octyl-4-isothiazoline-3-ketone, fatty alcohol-polyoxyethylene ether and tween-60 into a stirrer, adjusting the rotating speed of the stirrer to 2500r/min, and stirring for 8 min; 3) transferring the materials in the stirrer into a shearing emulsifying machine, adjusting the rotating speed of the shearing emulsifying machine to 8000r/min, and stirring for 25 min.
The preparation method of the leather mildewcide of the comparative examples 1 to 3 comprises the following steps: adding the components into a stirrer, and regulating the rotation speed of the stirrer to 2000r/min for 8 min.
And (3) performance testing:
1) minimum inhibitory concentration test:
the leather contaminants are mainly trichoderma, aspergillus and penicillium, so trichoderma viride, aspergillus niger, aspergillus terreus, penicillium citrinum and escherichia coli are selected as experimental bacteria to test the minimum inhibitory concentration of thiabendazole, dazomet, 2-n-octyl-4-isothiazolin-3-one and the compound thereof.
The test method is as follows:
a. preparing a spore bacterium suspension: respectively carrying out activated culture on experimental bacteria and preparing spore bacteria suspension, and ensuring the survival rate of spores to be more than 95%;
b. preparing sample solutions with different concentrations: preparing a 3% thiabendazole solution, a 10% dazomet solution, a 15% 2-n-octyl-4-isothiazoline-3-one solution, a 3% thiabendazole + 10% dazomet solution, a 3% thiabendazole + 15% 2-n-octyl-4-isothiazoline-3-one solution, a 10% dazomet + 15% 2-n-octyl-4-isothiazoline-3-one solution, a 3% thiabendazole + 10% dazomet + 15% 2-n-octyl-4-isothiazoline-3-one solution, and a series of sample solutions with different concentrations (for example, 10mg of a 3% thiabendazole solution is added to 1L of deionized water as an initial solution, obtaining a sample solution with the concentration of 10 mg/L);
c. preparing a culture medium plate containing a mildew preventive: firstly sucking 1mL of sample solution, placing the sample solution in a sterilized culture dish, then adding about 20mL of culture medium at about 45 ℃, fully mixing the culture medium and the sample solution, standing and cooling (till methanol is completely volatilized), and meanwhile, setting a culture medium flat plate without the sample solution as a blank control;
d. test bacteria inoculation-0.5 mL (about 1 × 10 bacteria content) was added to each dish6±2×105spores/mL) is uniformly coated by a coating rod, and is cultured in an incubator at 28 ℃ and 90% RH for 4-5 days, and the result is observed;
e. determination of minimum inhibitory concentration: the lowest concentration of the sample solution at which colony growth is completely inhibited is the lowest inhibitory concentration (MIC) of the sample against the test bacteria, and single colony growth is negligible.
The results of the Minimum Inhibitory Concentration (MIC) test of thiabendazole, dazomet and 2-n-octyl-4-isothiazolin-3-one on the experimental bacteria are shown in the following table:
TABLE 2 results of the minimum inhibitory concentration test for the individual components
Figure BDA0002515554930000041
The results of the Minimum Inhibitory Concentration (MIC) test of 2 or 3 combinations of thiabendazole, dazomet and 2-n-octyl-4-isothiazolin-3-one on experimental bacteria are shown in the following table:
table 3 minimum inhibitory concentration test results for the formulations
Figure BDA0002515554930000051
As can be seen from tables 2 and 3: obvious synergistic effect exists among thiabendazole, dazomet and 2-n-octyl-4-isothiazoline-3-ketone.
2) The leather mildew preventive of the embodiment 1-3 and the comparative example 1-4 is subjected to a mildew resistance test, and the test method comprises the following steps: the pickled cowhides are taken and divided into 7 groups in parallel, 2 cowhides in each group are subjected to chrome tanning and bath replacement, the leather mildew preventive in the examples 1 to 3 and the leather mildew preventive in the comparative examples 1 to 4 are respectively added according to 0.15% of the weight of the leather, the mixture is rolled for 10h, taken out and dried for 30min, the dried wet blue hides are respectively cut into squares of 25mm multiplied by 25mm, then the mildew resistance grade is evaluated according to the test method for resisting the growth of mildew of ASTM D4576-2001 blue raw materials (leather), the inoculated mildew is formed by equivalently mixing the mildew such as aspergillus terreus, aspergillus niger, trichoderma viride, penicillium citrinum, aspergillus flavus, penicillium cordyceum, paecilomyces variotii and the like, the results are observed and recorded every 7 days of culture, the test is carried out for 21 days, the mildew resistance test results are shown in the following table, and the mildew resistance effect photograph after 21:
TABLE 4 results of the test of the mildewproof property of the leather mildewcide of examples 1 to 3 and comparative examples 1 to 4
Figure BDA0002515554930000052
As can be seen from table 4 and fig. 1: the leather mildew inhibitor has obvious mildew-proof synergistic effect, can effectively inhibit blue wet leather mildew growth, and has the mildew-proof effect remarkably superior to that of a special mildew inhibitor BIOBAN for commercially available leatherTM890。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A leather mildew preventive is characterized in that: the composite material comprises the following components in percentage by mass:
thiabendazole: 1% -5%;
and (2) bloom: 5% -15%;
2-n-octyl-4-isothiazolin-3-one: 5% -20%;
emulsifier: 8 to 30 percent;
cosolvent: 10% -30%;
water: and (4) the balance.
2. The leather mildewcide of claim 1, wherein: the composite material comprises the following components in percentage by mass:
thiabendazole: 1% -3%;
and (2) bloom: 8% -10%;
2-n-octyl-4-isothiazolin-3-one: 5% -15%;
emulsifier: 10% -25%;
cosolvent: 10% -30%;
water: and (4) the balance.
3. The leather mildewcide according to claim 1 or 2, wherein: the emulsifier is at least one of fatty alcohol-polyoxyethylene ether, fatty acid-polyoxyethylene ether, polyoxyethylene-polyoxypropylene block copolymer, fatty alcohol-polyoxyethylene ether phosphate and polyoxyethylene sorbitan monostearate.
4. The leather mildewcide according to claim 3, wherein: the emulsifier is prepared from fatty alcohol-polyoxyethylene ether and tween-60 in a mass ratio of 1: (0.2-2).
5. The leather mildewcide according to claim 1 or 2, wherein: the cosolvent is at least one of alcohol solvents and alcohol ether solvents.
6. The leather mildewcide according to claim 5, wherein: the cosolvent is at least one of dipropylene glycol, tripropylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether.
7. A method for preparing a leather mildewcide according to any one of claims 1 to 6, wherein the steps of: the method comprises the following steps:
1) adding the dazomet, the thiabendazole, the cosolvent and the water into a stirrer, and stirring;
2) adding 2-n-octyl-4-isothiazolin-3-one and an emulsifier into a stirrer, and stirring;
3) and transferring the materials in the stirrer into a shearing emulsifying machine, and shearing and emulsifying to obtain the leather mildew preventive.
8. The method of claim 7, wherein: the rotating speed of the stirrer during stirring in the step 1) is 2000-3000 r/min, and the stirring time is 5-10 min.
9. The production method according to claim 7 or 8, characterized in that: the rotating speed of the stirrer during stirring in the step 2) is 2000-3000 r/min, and the stirring time is 8-10 min.
10. The production method according to claim 7 or 8, characterized in that: the rotating speed of the shearing emulsifying machine in the shearing emulsifying in the step 3) is 8000-9000 r/min, and the time is 20-30 min.
CN202010474996.5A 2020-05-29 2020-05-29 Leather mildew preventive and preparation method thereof Pending CN111657291A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101779641A (en) * 2009-12-21 2010-07-21 许庆华 Alcohol-group leather sterilization mildewcide
CN102318624A (en) * 2011-06-07 2012-01-18 深圳市北岳海威化工有限公司 Antifungal and antibacterial agent for waterproof leather product and preparation method of antifungal and antibacterial agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101779641A (en) * 2009-12-21 2010-07-21 许庆华 Alcohol-group leather sterilization mildewcide
CN102318624A (en) * 2011-06-07 2012-01-18 深圳市北岳海威化工有限公司 Antifungal and antibacterial agent for waterproof leather product and preparation method of antifungal and antibacterial agent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
夏金兰等: ""羧甲基壳聚糖银噻苯咪唑的制备及其抑菌性能"", 《中南大学学报》 *
陈仪本等: "《工业杀菌剂》", 31 May 2001, 化学工业出版社 *
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