CN114031995B - Anti-mite composition and preparation method and application thereof - Google Patents
Anti-mite composition and preparation method and application thereof Download PDFInfo
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- CN114031995B CN114031995B CN202111373807.6A CN202111373807A CN114031995B CN 114031995 B CN114031995 B CN 114031995B CN 202111373807 A CN202111373807 A CN 202111373807A CN 114031995 B CN114031995 B CN 114031995B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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Abstract
The invention belongs to the technical field of leather auxiliaries, and discloses an anti-mite composition as well as a preparation method and application thereof. The anti-mite composition comprises the following raw materials in parts by weight: 40-50 parts of water, 0.5-4 parts of nitroimidazole substances, 0.2-1.2 parts of zinc salt and 15-20 parts of polyacrylate resin. The zinc ions form coordination connection between the nitroimidazole substances and the polyacrylate resin, so that the compatibility of the nitroimidazole substances and the polyacrylate resin is enhanced, the nitroimidazole substances have better adhesive force in a coating and are not easy to fall off, and the coated leather has a more lasting anti-mite effect in the using process. Compared with the existing finishing agent, the anti-mite composition disclosed by the invention can be used for pertinently protecting leather from being invaded by mites, endowing the leather with better quality and health, and greatly improving the additional value of the finishing agent and the leather product.
Description
Technical Field
The invention belongs to the technical field of leather auxiliaries, and particularly relates to an anti-mite composition as well as a preparation method and application thereof.
Background
Mites belong to a class of small animals in the class of the subclass Guangdong-web of the class Arathropoda of the phylum Arthropoda, and can parasitize in leather, not only can sting the leather to form disability, but also can generate worm eggs and secretion to form worm spots, thus seriously affecting the quality of the leather. In addition, the mites are closely related to human health, almost all the mites can damage the skin of a human body, diseases such as acne rosacea or demodex and the like are caused, and the human health is seriously harmed. Therefore, leather anti-mite is of great importance to improve the quality and health of leather.
During the processing of leather, bactericides and mildewcides are usually added to prevent the leather from rotting and deteriorating, forming mildew stains and the like during the processing, storage and use. However, the active ingredients of the bactericide and the mildewcide mainly act on bacteria and molds, and have little control effect on mites. It can be considered that the leather products prepared by the prior art do not have special anti-mite function. Therefore, special anti-mite agents are introduced, and the anti-mite leather is expected to be obtained in a targeted mode.
Nitroimidazoles are compounds having a nitroimidazole ring structure, and are generally used as drugs because of their strong anti-anaerobic, anti-tumor, and anti-viral effects. In addition, the nitroimidazoles can prevent the oxidation-reduction reaction of mites and the DNA synthesis of the mites, so that the nitrogen chains of the mites are damaged, and the effect of killing the bodies of the mites is realized. Thus, nitroimidazoles are a commonly used anti-mite material. Considering that the surface of the leather is most likely to breed mites, the nitroimidazole substance is introduced into the coating of the leather to form a protective layer on the surface of the leather, so that the growth of the mites is hopeful to be prevented. However, the compatibility of the nitroimidazole substance with the existing leather finishing material is poor, and the nitroimidazole substance is easy to fall off due to the bending and friction of the coating in the using process, so that the anti-mite effect of the leather is greatly reduced, and the leather is difficult to continuously prevent mites. Therefore, how to improve the compatibility of the nitroimidazole substances and the coating and enable the leather to continuously exert the anti-mite effect becomes a problem to be solved urgently for the popularization and application of the functional leather.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to overcome the defects that nitroimidazole substances have poor compatibility with coatings and leather has poor continuous anti-mite effect in the prior art, the invention aims to provide the anti-mite composition which has good compatibility with coatings.
A second object of the present invention is to provide a process for the preparation of an anti-mite composition.
The third purpose of the invention is to provide an application scheme of the anti-mite composition, which can continuously prevent mites after being used for leather finishing.
In order to achieve the above purpose, the first technical scheme adopted by the invention is as follows:
the anti-mite composition comprises the following raw materials in parts by weight: 40-50 parts of water, 0.5-4 parts of nitroimidazole substances, 0.2-1.2 parts of zinc salt and 15-20 parts of polyacrylate resin.
Further, the nitroimidazole substance is metronidazole and/or ornidazole.
Further, the zinc salt is any one or more of zinc chloride, zinc sulfate and zinc nitrate.
Furthermore, the mite-proof composition also comprises any one or more of 0-10 parts of polyurethane resin, 0-8 parts of nitrocellulose brightener and 0-5 parts of casein.
The second technical scheme adopted by the invention is as follows:
a method of preparing an anti-mite composition comprising the steps of:
mixing water, nitroimidazole substances and zinc salt, and reacting at 60-80 ℃ for 4-6 h to obtain a nitroimidazole zinc complex; and
adding polyacrylate resin, polyurethane resin, nitrocotton brightener and casein into the nitroimidazole zinc complex, and reacting at 25-40 ℃ for 2-4 h.
The third technical scheme adopted by the invention is as follows:
an application of an anti-mite composition in leather finishing.
Further, the specific method applied in leather finishing comprises the following steps:
performing top layer ironing spraying on the leather blank obtained by the conventional bottom layer coating and middle layer coating process for multiple times by using the anti-mite composition, and standing for 2-4 h;
wherein the spraying amount of the anti-mite composition is 2-4 g/sf.
Further, the spraying amount of the anti-mite composition in the multiple top layer ironing spraying is 0.5-1 g/sf per time, the spraying times are 4-8 times, the ironing temperature is 120-140 ℃, and the ironing pressure is 30-40 kg.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the existing finishing agent, the anti-mite finishing agent provided by the invention can protect leather from being invaded by mites in a targeted manner, endows the leather with better quality and health, and greatly improves the additional value of the finishing agent and the leather product.
(2) In the anti-mite composition, zinc ions form coordination connection between the nitroimidazole substance and the polyacrylate resin, so that the compatibility of the nitroimidazole substance and the polyacrylate resin is enhanced, the nitroimidazole substance has better adhesive force in a coating and is not easy to fall off, and the coated leather can continuously prevent mites in the using process, which is an effect difficult to achieve in the prior art.
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FIG. 1 is a graph showing the mite repellency of leathers of example 1 and comparative examples 1 to 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A first embodiment of the present invention provides an anti-mite composition. Comprises the following raw materials in parts by weight: 40-50 parts of water, 0.5-4 parts of nitroimidazole substances, 0.2-1.2 parts of zinc salt and 15-20 parts of polyacrylate resin.
The nitroimidazole substance is a commonly used anti-mite material, and is directly applied to leather coating to achieve poor anti-mite effect, because the nitroimidazole substance is poor in compatibility with the existing leather coating material, the adhesion of the nitroimidazole substance to a leather coating is insufficient, and the coating is easy to fall off due to bending and friction in the using process, so that the anti-mite effect of the leather is greatly reduced, and the continuous anti-mite effect is difficult. In experiments, the applicant finds that the nitroimidazole substance is difficult to dissolve after being directly mixed with the polyacrylate resin, but a complex formed by the nitroimidazole substance and a certain amount of zinc salt has good compatibility with the polyacrylate resin which is a common leather finishing agent, so that the adhesion of the nitroimidazole substance on a coating is obviously improved, and the finished leather still has good anti-mite effect after being bent and rubbed. The principle is as follows: the zinc ions and the hydroxyl of the nitroimidazole substance form coordination bonds to obtain the nitroimidazole zinc complex, the complex further forms coordination with the carboxyl of the polyacrylate resin, so that the zinc ions form coordination connection between the nitroimidazole substance and the polyacrylate resin, the compatibility of the nitroimidazole substance and the leather coating material is enhanced, the nitroimidazole substance has better adhesive force in the using process, and the nitroimidazole substance is not easy to fall off, so that the continuous anti-mite effect is achieved.
In some embodiments, the nitroimidazole compound is metronidazole and/or ornidazole, that is, the nitroimidazole compound may be metronidazole, ornidazole, or a mixture of metronidazole and ornidazole.
In some embodiments, the zinc salt is any one or more of zinc chloride, zinc sulfate, and zinc nitrate.
In order to improve the film-forming property, the anti-mite composition can also comprise any one or more of 0-10 parts of polyurethane resin, 0-8 parts of nitrocotton brightener and 0-5 parts of casein.
A second embodiment of the present invention provides a method of preparing an anti-mite composition comprising the steps of: mixing water, nitroimidazole substances and zinc salt, and reacting at 60-80 ℃ for 4-6 h to obtain a nitroimidazole zinc complex; and adding polyacrylate resin, polyurethane resin, nitrocotton brightener and casein into the nitroimidazole zinc complex, and reacting for 2-4 h at 25-40 ℃.
The preparation method comprises the following steps of preparing the anti-mite composition, wherein the first step is to enable zinc ions to fully react with nitroimidazole substances to form nitroimidazole zinc complexes, and the second step is to enable polyacrylate resins to further participate in coordination with the zinc ions, so that the effect of bridging between the nitroimidazole substances and the polyacrylate resins by the zinc ions is achieved, and the compatibility of the nitroimidazole substances and the polyacrylate resins is enhanced. If only one-step reaction is adopted, the coordination reaction of the nitroimidazole substance and the polyacrylate resin with zinc ions has a competitive relationship, and the polyacrylate resin is more easily coordinated with the zinc ions, so that the nitroimidazole substance is difficult to coordinate with the zinc ions, and the technical effect of enhancing the compatibility of the nitroimidazole substance and the polyacrylate resin which is expected to be achieved by the invention is difficult to achieve.
A third embodiment of the invention provides the use of an anti-mite composition, i.e. in leather finishing.
When the anti-mite composition is applied to leather coating, the compatibility of nitroimidazole substances and leather coating materials can be obviously enhanced, the adhesion force of the anti-mite composition on leather is obviously improved, and the anti-mite composition is not easy to fall off in the using process, so that the continuous anti-mite effect is achieved.
In some embodiments, the specific method of application in leather finishing comprises: performing top layer ironing spraying on the leather blank obtained by the conventional bottom layer coating and middle layer coating process for multiple times by using the anti-mite composition, and standing for 2-4 h; wherein the spraying amount of the anti-mite composition is 2-4 g/sf.
The spraying amount of the anti-mite composition in the multiple top layer ironing spraying is 0.5-1 g/sf per time, the spraying times are 4-8 times, the ironing temperature is 120-140 ℃, and the ironing pressure is 30-40 kg.
The leather blanks obtained by the conventional base coating and intermediate coating processes are finished semi-finished products obtained by treating leather with base coating and intermediate coating agents and coating processes well known to those skilled in the art.
The ironing spraying refers to that after a certain amount of finishing agent is sprayed, the coating is ironed, so that the coating is smooth and a shaping effect is generated.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the anti-mite composition, the preparation method and the application, and the performance test, which are provided by applying the above embodiments of the invention.
In the following specific examples and comparative examples, the method for measuring the anti-mite rate of leather before and after rubbing and bending is as follows:
the leather samples were equilibrated for 48 h at a temperature of 20. + -. 2 ℃ and a relative humidity of 65. + -. 5%. Then, the leather sample is bent 1000 times by adopting a folding resistance tester according to a method of QB/T2714 standard 2005 & ltdetermination of folding resistance fastness of leather physical and mechanical tests & gt. The skin sample is taken out, and the skin sample is rubbed for 200 times by adopting a reciprocating friction tester by further referring to a method of light industry standard QB/T2537 and 2001 reciprocating friction color fastness of leather color fastness test. And taking out the leather sample, and further testing the mite avoidance rate of the leather by referring to a method of national standard GB/T24253-. The higher the aversion rate of the leather to mites, the better the mite-proof effect of the leather is.
Some of the material information used in the embodiments of the present invention may be as follows:
polyacrylate resin: DESORAY DA3130 Soft acrylic resin available from Sichuan Deshel New materials science and technology Ltd, Dawilik RA1150 Soft acrylic resin available from Sichuan Dawei science and technology Ltd, TJ-C2083 acrylic resin available from Sichuan Tejiang New materials Ltd, RA-18 Water-based acrylic resin available from Stall Fine coating (Suzhou) Ltd, Melio available from Clarian chemical industries (China) Ltd®Resin Resina-820 acrylic resin and AQUADERM manufactured by Langsheng chemical (China) Co., Ltd®X-Shield L2 aqueous fluorinated acrylate.
Polyurethane resin: dawiuyou NU2581 nonionic polyurethane resin produced by Dawawei science and technology Co., Ltd, RU-73-961 Unires aqueous polyurethane resin produced by Stahl Fine coating (Suzhou) Co., Ltd, and AQUADER produced by Langsheng chemical (China) Co., Ltd®Finish HAT polyurethane resin.
Nitrocotton brightener: TJ-C6337 nitro-cotton gloss oil produced by Sichuan Tingjiang New materials Co., Ltd, and ISODERM produced by Langsheng chemical (China) Co., Ltd®LA 300-N EXP 2200 nitrocotton brightener and LW-77-268 aqueous transparent nitrocotton gloss oil manufactured by Stahl Fine coatings (Suzhou) Co.
Casein: b1-1 water-soluble protein adhesive manufactured by Sttalr Fine paint (Suzhou) Co., Ltd., Melio manufactured by Craiden chemical industry (China) Co., Ltd®Top 288 protein adhesive and BAYSIN produced by Langsheng chemical (China) Co., Ltd®X-tra Luster P21 casein.
Example 1
Preparation of an anti-mite composition:
(1) putting 45 parts of water, 2 parts of metronidazole and 0.7 part of zinc chloride in parts by weight into a reactor, and stirring at 70 ℃ for 6 hours to obtain a metronidazole zinc complex;
(2) and (2) adding 17.5 parts of DESORAY DA3130 soft acrylic resin into the metronidazole zinc complex in the step (1), and stirring for 3 hours at the temperature of 25 ℃ to obtain the high-compatibility, durable and anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top ironing spraying on the leather blanks obtained by the conventional bottom coating process and middle coating process for 4 times by using the anti-mite composition, wherein the spraying amount is 0.75 g/sf each time, the total spraying amount is 3 g/sf, the ironing temperature is 140 ℃, the pressure is 30 kg, and standing for 2 hours to obtain the anti-mite leather.
The repelling rate of the leather prepared just in this example to mites was determined to be 96%, and the repelling rate to mites after rubbing and bending was determined to be 95%, and the results are shown in fig. 1.
Example 2
Preparation of an anti-mite composition:
(1) putting 40 parts of water, 0.5 part of ornidazole and 0.2 part of zinc sulfate in parts by weight into a reactor, and stirring for 5 hours at the temperature of 80 ℃ to obtain an ornidazole zinc complex;
(2) and (2) adding 20 parts of soft acrylic resin in Dawilik RA1150 and 5 parts of RU-73-961 Unires aqueous polyurethane resin into the ornidazole zinc complex in the step (1), and stirring for 2 hours at the temperature of 32 ℃ to obtain the high-compatibility durable anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top ironing spraying on the leather blanks obtained by the conventional bottom coating process and middle coating process for 4 times by using the anti-mite composition, wherein the spraying amount is 1 g/sf each time, the total spraying amount is 4 g/sf, the ironing temperature is 130 ℃, the pressure is 35 kg, and standing for 3 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have a mite avoidance rate of 90% and a mite avoidance rate of 88% after rubbing and bending.
Example 3
Preparation of an anti-mite composition:
(1) putting 50 parts of water, 4 parts of metronidazole and 1.2 parts of zinc nitrate into a reactor, and stirring for 4 hours at the temperature of 60 ℃ to obtain a metronidazole zinc complex;
(2) and (2) adding 15 parts of TJ-C2083 acrylic resin and 4 parts of LW-77-268 water-based transparent nitrocellulose gloss oil into the metronidazole zinc complex in the step (1), and stirring for 4 hours at the temperature of 40 ℃ to obtain the high-compatibility, durable and anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top ironing spraying on the leather blanks obtained by the conventional bottom coating process and middle coating process for 4 times by using the anti-mite composition, wherein the spraying amount is 0.5 g/sf each time, the total spraying amount is 2 g/sf, the ironing temperature is 120 ℃, the pressure is 40 kg, and standing for 4 hours to obtain the anti-mite leather.
The leather prepared just in this example was determined to have a mite avoidance rate of 98%, and the mite avoidance rate after rubbing and bending was determined to be 98%.
Example 4
Preparation of an anti-mite composition:
(1) putting 40 parts of water, 0.5 part of ornidazole, 0.35 part of zinc chloride and 0.35 part of zinc sulfate in parts by weight into a reactor, and stirring for 4 hours at the temperature of 60 ℃ to obtain an ornidazole zinc complex;
(2) and (2) adding 15 parts of RA-18 water-based acrylic resin, 8 parts of TJ-C6337 nitrocotton gloss oil and 2.5 parts of B1-1 water-soluble protein adhesive into the ornidazole zinc complex obtained in the step (1), and stirring for 3 hours at the temperature of 25 ℃ to obtain the high-compatibility, durable and anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top-layer ironing spraying on the leather blanks obtained by the conventional bottom-layer coating process and middle-layer coating process for 3 times by using the anti-mite composition, wherein the spraying amount is 1 g/sf each time, the total spraying amount is 3 g/sf, the ironing temperature is 130 ℃, the pressure is 30 kg, and standing for 3 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have a mite avoidance rate of 87% and a mite avoidance rate of 86% after rubbing and bending.
Example 5
Preparation of an anti-mite composition:
(1) putting 50 parts of water, 1 part of metronidazole, 1 part of ornidazole, 0.6 part of zinc chloride and 0.6 part of zinc nitrate into a reactor, and stirring at the temperature of 80 ℃ for 5 hours to obtain a nitroimidazole zinc complex;
(2) and (2) adding 17.5 parts of MelioResinA-820 acrylic resin and 5 parts of MelioTop 288 protein adhesive into the nitroimidazole zinc complex obtained in the step (1), and stirring at the temperature of 32 ℃ for 2 hours to obtain the high-compatibility durable anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top ironing spraying on the leather blanks obtained by the conventional bottom coating process and middle coating process for 4 times by using the anti-mite composition, wherein the spraying amount is 0.5 g/sf each time, the total spraying amount is 2 g/sf, the ironing temperature is 120 ℃, the pressure is 35 kg, and standing for 4 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have a mite avoidance rate of 94% and a mite avoidance rate of 93% after rubbing and bending.
Example 6
Preparation of an anti-mite composition:
(1) putting 45 parts of water, 2 parts of metronidazole, 2 parts of ornidazole, 0.1 part of zinc sulfate and 0.1 part of zinc nitrate into a reactor, and stirring at the temperature of 70 ℃ for 6 hours to obtain a nitroimidazole zinc complex;
(2) adding 20 parts of polyaquadermx-Shield L2 into the nitroimidazole zinc complex in the step (1), and stirring for 4 hours at the temperature of 40 ℃ to obtain the high-compatibility, durable and long-lasting anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top-layer ironing spraying on the leather blanks obtained by the conventional bottom-layer coating process and middle-layer coating process for 5 times by using the anti-mite composition, wherein the spraying amount is 0.8 g/sf each time, the total spraying amount is 4 g/sf, the ironing temperature is 140 ℃, the pressure is 40 kg, and standing for 2 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have a mite avoidance rate of 99% and a mite avoidance rate of 99% after rubbing and bending.
Example 7
Preparation of an anti-mite composition:
(1) putting 50 parts of water, 3 parts of metronidazole, 1 part of ornidazole, 0.2 part of zinc chloride, 0.2 part of zinc sulfate and 0.3 part of zinc nitrate into a reactor, and stirring at the temperature of 80 ℃ for 4 hours to obtain a nitroimidazole zinc complex;
(2) and (2) adding 17.5 parts of soft acrylic resin in Dawilk RA1150 and 10 parts of BAYDERMBottom 10UD polyurethane resin into the nitroimidazole zinc complex in the step (1), and stirring for 3 hours at the temperature of 32 ℃ to obtain the high-compatibility durable anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) ironing and spraying the leather blanks obtained by the conventional bottom layer coating process and middle layer coating process for 6 times by using the anti-mite composition, wherein the spraying amount is 0.5 g/sf each time, the total spraying amount is 3 g/sf, the ironing temperature is 120 ℃, the pressure is 30 kg, and the leather blanks are kept still for 3 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have an aversion rate to mites of 98%, and the aversion rate to mites after rubbing and bending was found to be 98%.
Example 8
Preparation of an anti-mite composition:
(1) putting 45 parts of water, 0.2 part of metronidazole, 0.3 part of ornidazole, 0.3 part of zinc chloride, 0.3 part of zinc sulfate and 0.3 part of zinc nitrate into a reactor, and stirring at the temperature of 60 ℃ for 6 hours to obtain a nitroimidazole zinc complex;
(2) adding 20 parts of MelioResin A-820 acrylic resin, 5 parts of Dawiu NU2581 nonionic polyurethane resin, 4 parts of ISODERMLA 300-N EXP 2200 nitrocellulose brightener and 5 parts of B1-1 water-soluble protein adhesive into the nitroimidazole zinc complex in the step (1), and stirring at the temperature of 40 ℃ for 2 hours to obtain the high-compatibility, durable and anti-mite composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top ironing spraying on the leather blanks obtained by the conventional bottom coating process and middle coating process for 2 times by using the anti-mite composition, wherein the spraying amount is 1 g/sf each time, the total spraying amount is 2 g/sf, the ironing temperature is 130 ℃, the pressure is 40 kg, and standing for 2 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have an aversion rate to mites of 82%, and after rubbing and bending treatment, to have an aversion rate to mites of 81%.
Example 9
Preparation of an anti-mite composition:
(1) putting 40 parts of water, 1 part of metronidazole, 1 part of ornidazole, 0.7 part of zinc chloride, 0.7 part of zinc sulfate and 0.6 part of zinc nitrate into a reactor, and stirring at 70 ℃ for 5 hours to obtain a nitroimidazole zinc complex;
(2) adding 15 parts of AQUADERMX-Shield L2 aqueous fluorinated acrylate and 4 parts of Dawiu NU2581 nonionic polyurethane resin into the nitroimidazole zinc complex in the step (1), and stirring at the temperature of 25 ℃ for 4 h to obtain the high-compatibility durable acarid-preventing composition.
The application of the anti-mite composition in leather finishing comprises the following steps:
and (3) performing top ironing spraying on the leather blanks obtained by the conventional bottom coating process and middle coating process for 5 times by using the anti-mite composition, wherein the spraying amount is 0.8 g/sf each time, the total spraying amount is 4 g/sf, the ironing temperature is 140 ℃, the pressure is 35 kg, and standing for 4 hours to obtain the anti-mite leather.
The leather prepared just in this example was found to have a mite avoidance rate of 96%, and the mite avoidance rate after rubbing and bending was found to be 96%.
Comparative example 1
According to the formula of the anti-mite composition in the example 1, various raw materials are directly mixed instead of the method of the two-step reaction in the example 1, and the raw materials are directly mixed and then placed in a reactor and stirred for 3 hours at the temperature of 25 ℃ to obtain the anti-mite composition.
The application of the anti-mite composition in leather finishing was the same as in example 1.
According to the determination, the leather prepared just in the comparative example has the aversion rate of 96% to mites, and the aversion rate to mites after the leather is rubbed and bent is 84%, and the detection result is shown in figure 1.
Comparative example 2
According to the parts by weight, 45 parts of water, 2 parts of metronidazole and 17.5 parts of DESORAY DA3130 soft acrylic resin are placed in a reactor and stirred for 3 hours at the temperature of 25 ℃ to obtain the anti-mite composition.
The application of the anti-mite composition in leather finishing was the same as in example 1.
According to the determination, the leather prepared just in the comparative example has an aversion rate to mites of 95%, and the aversion rate to mites after the leather is rubbed and bent is 66%, and the detection result is shown in fig. 1.
Comparative example 3
According to the parts by weight, 45 parts of water, 2 parts of metronidazole and 0.7 part of zinc chloride are placed in a reactor and stirred for 3 hours at the temperature of 25 ℃ to obtain the anti-mite composition.
The application of the anti-mite composition in leather finishing was the same as in example 1.
According to the determination, the leather prepared just in the comparative example has an aversion rate to mites of 95%, and the aversion rate to mites after the leather is rubbed and bent is 43%, and the detection result is shown in fig. 1.
The mite-repelling ratio of the leathers according to example 1 and comparative examples 1 to 3 can be seen: the composition of comparative example 3, which contains 2 parts of metronidazole and 0.7 part of zinc chloride, although the newly prepared leather has a mite-repelling rate of 95%, is extremely weak against bending and rubbing due to the absence of film-forming substances after being used for leather finishing, and the treated leather has a mite-repelling rate of only 43% and is extremely weak in mite-preventing effect; the composition of comparative example 2 contains 2 parts of metronidazole and 17.5 parts of polyacrylate resin, and although the repelling rate of the freshly prepared leather to mites is 95%, the coating formed is not resistant to bending and friction due to weak compatibility of the metronidazole and the polyacrylate resin, and the repelling rate of the treated leather to mites is also low and is only 66%; the composition of comparative example 1 contains 2 parts of metronidazole, 0.7 part of zinc chloride and 17.5 parts of polyacrylate resin, and although the repelling rate of the freshly prepared leather to mites is 96%, the polyacrylate resin and zinc ions are more easily coordinated, the coordination time is short, the coordination temperature is low, so that the zinc ions cannot be coordinated with the metronidazole, and the connection effect between the metronidazole and the polyacrylate resin cannot be realized, so that the intermiscibility between the metronidazole and the coating is still insufficient, and the repelling rate of the leather subjected to bending and rubbing treatment to mites is reduced to 84%; when 2 parts of metronidazole and 0.7 part of zinc chloride in the composition in the example 1 firstly form a metronidazole zinc complex, then the polyacrylate resin is added, and zinc ions can simultaneously form coordinate bonds with the metronidazole and the polyacrylate resin, namely, the zinc ions and the metronidazole and the polyacrylate resin play a role in connection, so that the compatibility of the metronidazole zinc complex and the polyacrylate resin is improved, the repelling rate of the leather to mites is up to 96% when the composition is applied to coating, the repelling rate of the leather to the mites is also up to 95% after bending and rubbing treatment, and the composition has a strong mite prevention effect.
The analysis of the comparative example and the example shows that only when the nitroimidazole compounds and the zinc ions form the complex and then the polyacrylate resin is added, the zinc ions can form the connection between the nitroimidazole compounds and the acrylic acid, so that the compatibility of the composition is increased, and the composition has stronger wear resistance and bending resistance after being used for leather coating, and realizes the continuous anti-mite effect, which is the effect difficult to achieve by the prior art. Therefore, compared with the prior art, the coordination combination of the nitroimidazole substance, the zinc salt and the polyacrylate resin has remarkable progress, so that the leather can generate a beneficial anti-mite effect.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The anti-mite composition is characterized by comprising the following raw materials in parts by weight: 40-50 parts of water, 0.5-4 parts of nitroimidazole substance, 0.2-1.2 parts of zinc salt and 15-20 parts of carboxyl-containing polyacrylate resin;
wherein the nitroimidazole substance is metronidazole and/or ornidazole;
the anti-mite composition is obtained by reacting water, nitroimidazole substances and zinc salt to form a nitroimidazole zinc complex, and then reacting carboxyl-containing polyacrylate resin with the nitroimidazole zinc complex.
2. The anti-mite composition of claim 1, wherein the zinc salt is any one or more of zinc chloride, zinc sulfate, and zinc nitrate.
3. The anti-mite composition of claim 1 or 2, further comprising any one or more of 0 to 10 parts of a polyurethane resin, 0 to 8 parts of a nitrocellulose brightener, and 0 to 5 parts of casein.
4. A process for preparing an anti-mite composition according to any one of claims 1 to 3, comprising the steps of: mixing water, nitroimidazole substances and zinc salt, and reacting at 60-80 ℃ for 4-6 h to obtain a nitroimidazole zinc complex; and
adding carboxyl-containing polyacrylate resin, polyurethane resin, nitrocotton brightener and casein into the nitroimidazole zinc complex, and reacting at 25-40 deg.C for 2-4 h.
5. An anti-acarid composition prepared by the method of claim 4.
6. Use of an anti-mite composition according to any of claims 1 to 3 or 5 in leather finishing.
7. The use according to claim 6, wherein said specific method of application in leather finishing comprises: performing top layer ironing spraying on the leather blank obtained by the conventional bottom layer coating and middle layer coating process for multiple times by using the anti-mite composition, and standing for 2-4 h;
wherein the spraying amount of the anti-mite composition is 2-4 g/sf.
8. The use of claim 7, wherein the anti-mite composition is applied in an amount of 0.5-1 g/sf per application, the number of applications is 4-8, the ironing temperature is 120-140 ℃, and the ironing pressure is 30-40 kg.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2729853A1 (en) * | 2008-07-02 | 2010-01-07 | Troy Corporation | Synergistic antimicrobial mixtures |
| CN102199389A (en) * | 2011-04-07 | 2011-09-28 | 陕西科技大学 | Self-crosslinking acrylic resin leather finishing agent and preparation method thereof |
| US20170258693A1 (en) * | 2014-12-16 | 2017-09-14 | Colgate-Palmolive Company | Metal Salt Compositions |
| CA2983526A1 (en) * | 2016-10-26 | 2018-04-26 | Covestro Llc | Antimicrobial propprant |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2729853A1 (en) * | 2008-07-02 | 2010-01-07 | Troy Corporation | Synergistic antimicrobial mixtures |
| CN102199389A (en) * | 2011-04-07 | 2011-09-28 | 陕西科技大学 | Self-crosslinking acrylic resin leather finishing agent and preparation method thereof |
| US20170258693A1 (en) * | 2014-12-16 | 2017-09-14 | Colgate-Palmolive Company | Metal Salt Compositions |
| CA2983526A1 (en) * | 2016-10-26 | 2018-04-26 | Covestro Llc | Antimicrobial propprant |
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