阅读说明：本技术 一种防霉剂及其制备方法与应用 (Mildew preventive, preparation method and application thereof ) 是由 马贺伟 于 2019-09-25 设计创作，主要内容包括：本发明公开了一种防霉剂及其制备方法与应用,涉及杀菌防霉技术领域。所述防霉剂是由苯噻氰、多菌灵、非离子聚醚改性有机硅表面活性剂、三苯乙烯基苯酚聚氧乙烯醚、季铵盐改性的有机膨润土和丙二醇甲醚按照一定顺序混合、高速剪切乳化后复配加工而成。因该防霉剂所用助剂不含有当前国内外法规和标准所规定的禁限用物质,而且气味低,具有生态环保的特点；并且防霉剂中成份互补增效、抗霉菌性能优良,适合用于生皮的铬鞣加工过程中,可赋予蓝湿革良好的防霉性能。(The invention discloses a mildew preventive, a preparation method and application thereof, and relates to the technical field of sterilization and mildew prevention. The mildew preventive is prepared by mixing benzothiophene, carbendazim, a nonionic polyether modified organic silicon surfactant, tristyrylphenol polyoxyethylene ether, quaternary ammonium salt modified organic bentonite and propylene glycol methyl ether in a certain sequence, shearing at a high speed, emulsifying and compounding. The mildew preventive contains no forbidden substances specified by the current domestic and foreign laws and standards, has low smell and is ecological and environment-friendly; and the components in the mildew preventive have complementary synergism and excellent mildew resistance, and the mildew preventive is suitable for being used in the chrome tanning processing process of raw leather and can endow the wet blue leather with good mildew resistance.)

1. The mildew preventive is characterized by being prepared from the following raw materials in parts by mass: 5-30 parts of benzothiophene, 1-10 parts of carbendazim, 10-30 parts of tristyrylphenol polyoxyethylene ether, 0.5-5 parts of nonionic polyether modified organic silicon surfactant, 1-10 parts of quaternary ammonium salt modified organic bentonite, 30-55 parts of propylene glycol methyl ether and 1-10 parts of water.

2. The mildew preventive according to claim 1, wherein the mildew preventive is prepared from the following raw materials in parts by mass: 19-22 parts of benzothiophene, 4-7 parts of carbendazim, 16-19 parts of tristyrylphenol polyoxyethylene ether, 1-3 parts of nonionic polyether modified silicone surfactant, 2.5-4.5 parts of quaternary ammonium salt modified organic bentonite, 44-48 parts of propylene glycol methyl ether and 4-6 parts of water.

3. The method for preparing a mildewcide according to claim 1, comprising the steps of:

(1) preparation of mixture a: sequentially adding the nonionic polyether modified organic silicon surfactant, the quaternary ammonium salt modified organic bentonite and the carbendazim in formula amount into propylene glycol methyl ether I, stirring, shearing and emulsifying to obtain a mixture A-a solution containing the carbendazim;

(2) preparation of mixture B: sequentially adding tristyrylphenol polyoxyethylene ether and benzothiophene in a formula amount into propylene glycol methyl ether II, and stirring to obtain a mixture B-a solution containing benzothiophene;

(3) preparation of the product: and (3) adding the mixture B obtained in the step (2) into the mixture A obtained in the step (1), stirring, shearing and emulsifying, adding propylene glycol monomethyl ether III and water, stirring, and filtering to obtain the mildew preventive product.

4. The method for preparing the mildewcide according to claim 3, wherein the preparation process of the mixture A disclosed in the step (1) is as follows:

41) adding the nonionic polyether modified organosilicon surfactant with the formula amount into propylene glycol methyl ether I, and stirring to obtain a mixture I;

42) starting shearing and emulsifying equipment, sequentially adding the quaternary ammonium salt modified organic bentonite and the carbendazim in the formula amount into the mixture I, shearing and emulsifying, and cooling to room temperature to obtain a mixture A.

5. The preparation method of the mildew preventive according to claim 4, wherein in the step 42), the shearing and emulsifying time after adding the quaternary ammonium salt modified organic bentonite is 10-15 min, and the shearing and emulsifying time after adding the carbendazim is 40-60 min.

6. The method for preparing the mildew preventive according to the claim 3, wherein the preparation process of the product disclosed in the step (3) is as follows:

61) adding the mixture B into the mixture A, stirring, shearing and emulsifying to obtain a system I;

62) mixing propylene glycol methyl ether III with water, adding the mixture into the system I, stirring, shearing, emulsifying, standing, and finally filtering to obtain the product, namely the mildew preventive.

7. The method for preparing the mildewcide according to claim 6, wherein the stirring and shearing emulsification time in the step 61) is 10-20 min, and the stirring and shearing emulsification time in the step 62) is 30-60 min.

8. Use of a fungicide as disclosed in claim 1 or prepared by the method disclosed in claim 3 in the process of tanning hides.

9. The use of the mildew preventive according to claim 8, wherein the amount of the mildew preventive is 0.15-0.25% of the weight of the leather blank in the process of tanning the leather blank.

Technical Field

The invention relates to the technical field of sterilization and mildew prevention, in particular to a preparation method of a mildew preventive, and more particularly relates to a preparation method of a mildew preventive for wet blue leather. The mildew preventive is used in the process of tanning and processing the hide into wet blue leather under acidic conditions, and can prevent the wet blue leather from being corroded by mildew.

Background

The wet blue leather is an intermediate product in the leather processing process, is a product of leather fibers after being tanned by chromium powder, and has the main component of protein and a small amount of unremoved natural fat. Due to the weak acidity of the wet blue leather (pH is about 4.0) and the high water content (> 40%) in the fiber, when the environmental temperature and humidity in the storage and transportation process are proper (such as sultry summer), the mold spores can rapidly grow and propagate on the surface of the wet blue leather to form mold spots, which brings obvious influence on the dyeing and finishing in the subsequent leather processing process and reduces the quality of finished leather. Due to the characteristics of the leather-making process, the wet blue leather usually undergoes a long storage period (warrior, lyrium, tanning chemistry, light industrial publishing in china, 3 rd edition, 2011), which results in a very high possibility of being corroded by mold, and therefore, a leather-making enterprise must make a mildew-proof measure to prevent the wet blue leather from mildewing.

Among the various approaches to protect wet blue leather from mold attack, the addition of mold inhibitors is the most effective and conventional means. In the mildew preventive used by the tanning enterprises at present, the application of the product taking benzothiophene (also called TCMTB) as the main effective component is the widest. However, actual conditions show that the benzothiophene has weak fungus inhibition effect on trichoderma, so that the complementary mildew inhibitor components are required to be compounded to achieve a synergistic anti-mildew effect.

Therefore, the development of a broad-spectrum and efficient mildew preventive for wet blue leather is a problem to be solved urgently by those skilled in the art.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide the mildew preventive which has the characteristics of broad spectrum and high efficiency and can prevent the blue wet leather from being corroded by mildew in the storage process.

In order to achieve the purpose, the invention adopts the following technical scheme:

the mildew preventive is prepared from the following raw materials in parts by mass: 5-30 parts of benzothiophene, 1-10 parts of carbendazim, 10-30 parts of tristyrylphenol polyoxyethylene ether, 0.5-5 parts of nonionic polyether modified organic silicon surfactant, 1-10 parts of quaternary ammonium salt modified organic bentonite, 30-55 parts of propylene glycol methyl ether and 1-10 parts of water.

Preferably, the mildew preventive is prepared from the following raw materials in percentage by mass: 19-22 parts of benzothiophene, 4-7 parts of carbendazim, 16-19 parts of tristyrylphenol polyoxyethylene ether, 1-3 parts of nonionic polyether modified silicone surfactant, 2.5-4.5 parts of quaternary ammonium salt modified organic bentonite, 44-48 parts of propylene glycol methyl ether and 4-6 parts of water.

It is worth to be noted that the benzothiophene disclosed in the present application is preferably a benzothiophene stock solution with a mass percentage of 80%, and the nonionic polyether modified silicone surfactant is preferably a low molecular weight nonionic polyether modified silicone surfactant.

The mildew inhibitor disclosed by the invention is prepared by mixing benzothiophene, carbendazim, a nonionic polyether modified organic silicon surfactant, tristyrylphenol polyoxyethylene ether, quaternary ammonium salt modified organic bentonite and propylene glycol methyl ether in a certain sequence, shearing at a high speed, emulsifying and compounding. Because the raw materials used by the mildew preventive do not contain forbidden substances specified by the current domestic and foreign laws and standards, the mildew preventive has low smell and the characteristics of ecological environmental protection;

furthermore, the thiabendazole disclosed by the invention is compounded with the thiabendazole, and the thiabendazole has an obvious effect on controlling the propagation of trichoderma fungi, is a common agricultural bactericide, is low in cost and easy to obtain raw materials, so that an efficient and broad-spectrum mildew-proof preparation can be prepared by compounding two mildew-proof agent components of the thiabendazole and the thiabendazole. Subsequent experimental results show that wet blue leather has good anti-mildew effect after the mildew preventive prepared by the invention is used in a chrome tanning process of raw leather (specific experimental data are described below).

The invention also provides a preparation method of the mildew preventive, which comprises the following steps:

(1) preparation of mixture a: sequentially adding the nonionic polyether modified organic silicon surfactant, the quaternary ammonium salt modified organic bentonite and the carbendazim in formula amount into propylene glycol methyl ether I, stirring, shearing and emulsifying to obtain a mixture A-a solution containing the carbendazim;

(2) preparation of mixture B: sequentially adding tristyrylphenol polyoxyethylene ether and benzothiophene in a formula amount into propylene glycol methyl ether II, and stirring to obtain a mixture B-a solution containing benzothiophene;

(3) preparation of the product: and (3) adding the mixture B obtained in the step (2) into the mixture A obtained in the step (1), stirring, shearing and emulsifying, adding propylene glycol monomethyl ether III and water, stirring, and filtering to finally obtain the mildew preventive product.

It should be noted that, in step (3), the qualification performance should be detected before the product is filtered, and the specific implementation method is as follows:

taking a small amount of sample, and dropwise adding 2-3 drops (when the drops are added, the distance between the drops and the water surface is about 2cm) into tap water by using a plastic straw, wherein the sample drops can be uniformly dispersed in the water after being added into the water, and a milky semitransparent solution is formed after slight stirring.

In addition, the sum of the propylene glycol methyl ether I, the propylene glycol methyl ether II and the propylene glycol methyl ether III is the total amount of the propylene glycol methyl ether disclosed by the invention.

Preferably, the preparation process of the mixture A disclosed in the step (1) is as follows:

41) adding the nonionic polyether modified organosilicon surfactant with the formula amount into propylene glycol methyl ether I, and stirring to obtain a mixture I;

42) starting shearing and emulsifying equipment, sequentially adding the quaternary ammonium salt modified organic bentonite and the carbendazim in the formula amount into the mixture I, shearing and emulsifying, and cooling to room temperature to obtain a mixture A.

Preferably, in the step 42), the shearing and emulsifying time after adding the quaternary ammonium salt modified organic bentonite is 10-15 min, and the shearing and emulsifying time after adding the carbendazim is 40-60 min.

Preferably, the preparation process of the product disclosed in the step (3) is as follows:

61) adding the mixture B into the mixture A, stirring, shearing and emulsifying to obtain a system I;

62) mixing propylene glycol methyl ether III with water, adding the mixture into the system I, stirring, shearing, emulsifying, standing, and finally filtering to obtain the product, namely the mildew preventive.

Preferably, the stirring and shearing emulsification time in the step 61) is 10-20 min, and the stirring and shearing emulsification time in the step 62) is 30-60 min.

According to the technical scheme, compared with the prior art, the invention discloses and provides the mildew preventive, and the preparation method and the application thereof, and the mildew preventive has the following excellent effects:

1) the mildew inhibitor disclosed by the invention is a water-based preparation, does not contain volatile organic substances, and the adopted nonionic polyether modified organic silicon surfactant, the triphenylethylene phenol polyoxyethylene ether and the quaternary ammonium salt modified organic bentonite do not contain substances which are forbidden and limited according to the regulations and standards at home and abroad, so that the mildew inhibitor has the characteristic of ecological environmental protection;

2) the mildew preventive disclosed by the invention contains two effective components, namely carbendazim and benzothiophene, and has the characteristics of complementation and synergism, so that the mildew preventive has a broad spectrum;

3) the mildew inhibitor disclosed by the invention needs to be subjected to qualification performance detection before filtration and filling so as to improve the stability and the storage and transportation resistance of a final product.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

FIG. 1 is a flow chart of the preparation process of the mildew preventive disclosed by the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention discloses a broad-spectrum and high-efficiency mildew preventive for wet blue leather, which is prepared from the following raw materials in parts by mass: 5-30 parts of benzothiophene, 1-10 parts of carbendazim, 10-30 parts of tristyrylphenol polyoxyethylene ether, 0.5-5 parts of nonionic polyether modified organic silicon surfactant, 1-10 parts of quaternary ammonium salt modified organic bentonite, 30-55 parts of propylene glycol methyl ether and 1-10 parts of water.

The invention also discloses a preparation method of the mildew preventive, which specifically comprises the following steps of:

1) preparation of mixture a: sequentially adding the nonionic polyether modified organic silicon surfactant, the quaternary ammonium salt modified organic bentonite and the carbendazim in formula amount into propylene glycol methyl ether I, stirring, shearing and emulsifying to obtain a mixture A-a solution containing the carbendazim;

2) preparation of mixture B: sequentially adding tristyrylphenol polyoxyethylene ether and benzothiophene in a formula amount into propylene glycol methyl ether II, and stirring to obtain a mixture B-a solution containing benzothiophene;

3) preparation of the product: and (3) adding the mixture B obtained in the step (2) into the mixture A obtained in the step (1), stirring, shearing and emulsifying, adding propylene glycol monomethyl ether III and water, stirring, and filtering to finally obtain the mildew preventive product.

In order to further optimize the technical scheme, the preparation process of the mixture A disclosed in the step (1) is as follows:

41) adding the nonionic polyether modified organosilicon surfactant with the formula amount into propylene glycol methyl ether I, and stirring to obtain a mixture I;

42) starting shearing and emulsifying equipment, sequentially adding the quaternary ammonium salt modified organic bentonite and the carbendazim in the formula amount into the mixture I, shearing and emulsifying, and cooling to room temperature to obtain a mixture A.

In order to further optimize the technical scheme, in the step 42), the shearing and emulsifying time is 10-15 min after the quaternary ammonium salt modified organic bentonite is added, and the shearing and emulsifying time is 40-60 min after the carbendazim is added.

In order to further optimize the technical scheme, the preparation process of the product disclosed in the step (3) is as follows:

61) adding the mixture B into the mixture A, stirring, shearing and emulsifying to obtain a system I;

62) mixing propylene glycol methyl ether III with water, adding the mixture into the system I, stirring, shearing, emulsifying, standing, and finally filtering to obtain the product, namely the mildew preventive.

In order to further optimize the technical scheme, the stirring and shearing emulsification time in the step 61) is 10-20 min, and the stirring and shearing emulsification time in the step 62) is 30-60 min.

The preparation process and the excellent results of the present invention will be further illustrated with reference to the following examples, but the contents of the present invention are not limited to the following examples.