阅读说明：本技术 一种复合型防霉剂及其制备方法与应用 (Composite mildew preventive, and preparation method and application thereof ) 是由 钟晟 马贺伟 邹伟 王荣娅 何若兰 许洁 于 2019-09-25 设计创作，主要内容包括：本发明公开了一种复合型防霉剂及其制备方法与应用,涉及杀菌防霉技术领域。所述复合型防霉剂是由苯噻氰、丙环唑、含氟表面活性剂、乳化剂和溶剂按照一定顺序混合、复配加工而成。因该复合型防霉剂所用原料不含有当前国内外法规和标准所规定的禁限用物质、气味低,具有生态环保的特点；并且所述复合型防霉剂渗透性能好、吸收率高,及防霉剂中有效成份互补增效、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 compound mildew preventive, a preparation method and application thereof, and relates to the technical field of sterilization and mildew prevention. The compound mildew preventive is prepared by mixing benzothiophene, propiconazole, a fluorine-containing surfactant, an emulsifier and a solvent in a certain order and compounding. The raw materials used by the compound mildew preventive do not contain forbidden substances specified by the current domestic and foreign laws and standards, and the compound mildew preventive has the characteristics of low odor and ecological environmental protection; the composite mildew preventive has good permeability and high absorptivity, has excellent complementary and synergistic effect of effective components in the mildew preventive and excellent mildew resistance, is suitable for being used in the chrome tanning processing process of raw leather, and can endow blue wet leather with good mildew resistance.)

1. The compound mildew preventive is characterized by being prepared from the following raw materials in parts by mass: 15-35% of benzothiophene, 2-15% of propiconazole, 0.1-5% of fluorine-containing surfactant, 10-25% of emulsifier and 35-55% of solvent.

2. The compound mildew preventive according to claim 1, which is prepared from the following raw materials in parts by mass: 18-22% of benzothiophene, 8-13% of propiconazole, 0.1-3% of fluorine-containing surfactant, 20-24% of emulsifier and 38-46% of solvent.

3. The compound mildew preventive according to claim 1 or 2, wherein the emulsifier is a mixture of tristyrylphenol polyoxyethylene ether and dodecylbenzene sulfonic acid, and the mass ratio of the tristyrylphenol polyoxyethylene ether to the dodecylbenzene sulfonic acid is (2-8): 1.

4. the compound mildew preventive according to claim 1 or 2, wherein the solvent is a mixture of soybean oil methyl ester and propylene glycol methyl ether, and the mass ratio of the soybean oil methyl ester to the propylene glycol methyl ether is (1-3): 1.

5. the preparation method of the compound mildew preventive according to claim 1, wherein the method specifically comprises the following steps:

(1) adding the emulsifier with the formula amount into the solvent, and stirring to obtain a mixture I;

(2) sequentially adding the fluorine-containing surfactant with the formula amount into the mixture I, and slowly stirring to obtain a mixture II;

(3) adding the benzothioxanil with the formula amount into the mixture II, slowly stirring, and standing to finally obtain a compound mildew preventive product.

6. The preparation method of the compound mildew preventive according to claim 5, wherein the stirring time in the step (1) is 30-50 min, and the stirring time in the step (2) is 30-60 min.

7. The preparation method of the compound mildew preventive according to claim 5, wherein the stirring time in the step (3) is 20-40 min, and the standing time is 1-2 h.

8. Use of the composite type mildewcide as disclosed in claim 1 or prepared by the method of claim 6 in the tanning of hides.

9. The application of the compound mildew preventive according to claim 8, wherein the compound mildew preventive is used in an amount of 0.10-0.20% of the weight of a 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 mildew preventive and a preparation method thereof, and more particularly relates to a composite mildew preventive for wet blue leather and a preparation method thereof.

Background

The wet blue leather is a semi-finished product in the leather processing process, can be stored for a long time, and can be traded and circulated as a commodity, so that the wet blue leather can be subjected to a long storage and transportation period. However, the natural fat remaining in the wet blue leather and the contained protein substances are good nutrient sources for microorganisms, and meanwhile, the weak acidity (pH is about 4.0) of the wet blue leather, sufficient moisture (moisture content is 40-60%) contained in the fibers and storage conditions (usually in a cool and humid environment) provide good growth and propagation conditions for mold, and the factors determine that the wet blue leather in the storage and transportation process is extremely easy to be corroded by the mold. Because the quality of the leather is reduced due to the fact that the blue wet leather has large influence on the quality of the final leather after mildewing (such as uneven dyeing, spots on a coating and the like), the leather-making enterprises must make mildew-proof measures for the blue wet leather to prevent the blue wet 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, the actual situation shows that the inhibition effect of the benzothiophene against part of fungi is not strong, so that the complementary mildew inhibitor component needs to be adopted for compounding to achieve the synergistic anti-mildew effect.

Therefore, the development of a broad-spectrum and high-efficiency composite mildew preventive for blue wet leather is a problem to be solved urgently by the technical personnel in the field.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide the compound 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 compound mildew preventive is prepared from the following raw materials in parts by mass: 15-35% of benzothiophene, 2-15% of propiconazole, 0.1-5% of fluorine-containing surfactant, 10-25% of emulsifier and 35-55% of solvent.

Preferably, the mildew preventive is prepared from the following raw materials in percentage by mass: 18-22% of benzothiophene, 8-13% of propiconazole, 0.1-3% of fluorine-containing surfactant, 20-24% of emulsifier and 38-46% of solvent.

It is worth noting that the benzothia cyanide disclosed in the present application is preferably a benzothia cyanide stock solution with a mass percentage of 80%.

Preferably, the emulsifier is a mixture of tristyrylphenol polyoxyethylene ether and dodecylbenzene sulfonic acid, wherein the mass ratio of the tristyrylphenol polyoxyethylene ether to the dodecylbenzene sulfonic acid is (2-8): 1.

preferably, the mass ratio of the tristyrylphenol polyoxyethylene ether to the dodecylbenzene sulfonic acid is (6-7): 1.

preferably, the solvent is a mixture consisting of soybean oil methyl ester and propylene glycol methyl ether, wherein the mass ratio of the soybean oil methyl ester to the propylene glycol methyl ether is (1-3): 1.

preferably, the mass ratio of the soybean oil methyl ester to the propylene glycol methyl ether is (1-2): 1.

the compound mildew inhibitor disclosed by the invention is prepared by mixing and compounding benzothiophene, propiconazole, a fluorine-containing surfactant, an emulsifier and a solvent in a certain sequence. The raw materials used by the compound mildew preventive do not contain forbidden substances specified by the current domestic and foreign laws and standards, and the compound mildew preventive has the characteristics of low smell and ecological environmental protection;

furthermore, the invention discloses a compounding technology of benzothiophene and propiconazole, wherein propiconazole is a triazole bactericide which has excellent anti-mould performance and inhibits the synthesis of ergosterol in cell membranes by an antibacterial mechanism, so that the prepared compound mould-proof preparation has the characteristics of high efficiency and broad spectrum. And subsequent experimental results show that the wet blue leather has good anti-mildew effect after the compound 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 compound mildew preventive, which comprises the following steps:

(1) adding the emulsifier with the formula amount into the solvent, and stirring to obtain a mixture I;

(2) sequentially adding the fluorine-containing surfactant and the propiconazole in the formula amount into the mixture I, and slowly stirring to obtain a mixture II;

(3) adding the benzothiophene with the formula amount into the mixture II, slowly stirring, standing, filtering and filling to finally obtain the compound 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 of the sample into tap water by using a plastic straw (when the sample is dropwise added, the distance between the drops and the water surface is about 2cm), wherein the sample can be rapidly and uniformly dispersed in the water in a mist form after the drops of the sample are added into the water, and a light blue semitransparent solution is formed after slight stirring.

Preferably, the stirring time in the step (1) is 30-50 min, and the stirring time in the step (2) is 30-60 min.

Preferably, the stirring time in the step (3) is 20-40 min, and the standing time is 1-2 h.

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

1) the composite mildew inhibitor disclosed by the invention is an aqueous preparation, does not contain volatile organic substances, and the adopted fluorine-containing surfactant, emulsifier and thickener do not contain substances for banning specified by current domestic and foreign laws and standards, and has the characteristics of low odor and ecological environmental protection.

2) The compound mildew preventive disclosed by the invention has the characteristics of complementation and synergism due to the fact that the compound mildew preventive contains two effective components of propiconazole and benzothiophene, so that the mildew preventive has a broad spectrum.

3) The fluorine-containing surfactant is adopted in the composite mildew preventive disclosed by the invention, so that the permeability of the effective components of the mildew preventive is improved, the diffusion and absorption of the effective components in leather fibers can be better promoted, and the mildew prevention effect of wet blue leather is enhanced.

4) The composite 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 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 a preparation process of the compound 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 composite mildew preventive for wet blue leather, which is prepared from the following raw materials in percentage by mass: 15-35% of benzothiophene, 2-15% of propiconazole, 0.1-3% of fluorine-containing surfactant, 10-25% of emulsifier and 35-55% of solvent.

In order to further optimize the above technical solution, theThe structural formula of the fluorine-containing surfactant is as follows: r_FCH₂CH₂O(CH₂CH₂O)_nH，R_F＝CF₃CF₂(CF₂CF₂)_m，n＝0～15，m＝1～3。

In order to further optimize the technical scheme, the emulsifier is a mixture consisting of tristyrylphenol polyoxyethylene ether and dodecylbenzene sulfonic acid, wherein the mass ratio of the tristyrylphenol polyoxyethylene ether to the dodecylbenzene sulfonic acid is (2-8): 1.

in order to further optimize the technical scheme, a solvent is a mixture consisting of soybean oil methyl ester and propylene glycol methyl ether, wherein the mass ratio of the soybean oil methyl ester to the propylene glycol methyl ether is (1-3): 1.

with the attached drawing 1, the invention also discloses a preparation method of the compound mildew preventive, which specifically comprises the following steps:

1) adding the emulsifier with the formula amount into the solvent, and stirring to obtain a mixture I;

2) sequentially adding the fluorine-containing surfactant and the propiconazole in the formula amount into the mixture I, and slowly stirring to obtain a mixture II;

3) adding the benzothiophene with the formula amount into the mixture II, slowly stirring, standing, filtering and filling to finally obtain the compound mildew preventive product.

In order to further optimize the technical scheme, the stirring time in the step (1) is 30-50 min, and the stirring time in the step (2) is 30-60 min.

In order to further optimize the technical scheme, the stirring time in the step (3) is 20-40 min, and the standing time is 1-2 h.

The invention also discloses the application of the compound type mildew preventive in the process of tanning the hide.

And in the process of tanning the hide, the using amount of the compound mildew preventive is 0.10-0.20% of the weight of the hide blank.

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.