CN111700080B

CN111700080B - Antibacterial antiviral agent, antibacterial mildew-proof antiviral leather, and preparation method and application thereof

Info

Publication number: CN111700080B
Application number: CN202010574583.4A
Authority: CN
Inventors: 陈广川; 于红光; 吴新磊
Original assignee: Tongxi Group Co ltd
Current assignee: Nanjing Tongxi Dasheng Environmental Protection Technology Co ltd
Priority date: 2020-06-22
Filing date: 2020-06-22
Publication date: 2021-11-09
Anticipated expiration: 2040-06-22
Also published as: CN111700080A

Abstract

The invention provides an antibacterial antiviral agent, antibacterial mildew-proof antiviral leather, and a preparation method and application thereof. The preparation raw materials of the antibacterial and antiviral agent comprise: silver-doped nano bismuth tungstate, silver-doped nano titanium dioxide, erbium-doped nano titanium dioxide, chitosan and plant extract. The leather is prepared from the following raw materials: animal skin, leather degreasing agent, acid, tanning agent and antibacterial antiviral agent. The antibacterial and antiviral agent achieves efficient antibacterial and antiviral effects by utilizing the synergistic cooperation of the metal ions, the photocatalyst and the natural plant extract, and the prepared antibacterial, antifungal and antiviral leather can achieve the broad-spectrum long-acting antibacterial, antifungal and antiviral performance of the leather, so that microorganisms such as bacteria and mold attached to the surface of the leather are difficult to propagate and kill, and efficient virus inactivation is achieved.

Description

Antibacterial antiviral agent, antibacterial mildew-proof antiviral leather, and preparation method and application thereof

Technical Field

The invention belongs to the technical field of leather preparation, and particularly relates to an antibacterial antiviral agent, antibacterial mildew-proof antiviral leather, and a preparation method and application thereof.

Background

The leather is animal skin which is obtained by physical and chemical processing such as unhairing, tanning and the like and is denatured and non-perishable. The leather is formed by tightly weaving natural protein fibers in a three-dimensional space, and the surface of the leather is provided with a special grain layer which has natural grains and luster and comfortable hand feeling. The leather mainly comprises pig leather, cow leather, sheep leather, horse leather, donkey leather, kangaroo leather and the like, and the cow leather and the sheep leather have flat and thin surfaces, small hair holes, compact and compact internal structures, good plumpness and elasticity of leather bodies and good physical properties. Therefore, the superior cattle and sheep leathers are generally used as leather for high-grade products, and the price of the superior cattle and sheep leathers is higher in the bulk leathers. After the leather is used for manufacturing the sports ball, microorganisms can be attached to the surface of the leather in the using process and breed on the surface of the leather, the leather becomes a good living body for the survival and the breeding of the microorganisms and is harmful to the health of a human body all the time, and therefore the research and the development of the antibacterial and antiviral leather become very important. At present, the mainstream antibacterial technology applied to antibacterial leather in the market is to prepare the antibacterial leather by sterilizing nano silver and an organic antibacterial agent, but the antibacterial leather prepared by the antibacterial agent has poor antibacterial persistence and single function and cannot simultaneously achieve consistent effects on various bacteria and viruses.

CN107354251A discloses a preparation method of long-acting antibacterial leather, which is characterized in that after tanning and before washing, a gallic acid modified nano-silver solution is added, the addition amount is 50-120% of the weight of animal fur.

CN106148579A discloses a wet rubbing resistant antibacterial leather and a manufacturing process thereof, the wet rubbing resistant antibacterial leather is prepared by soaking a leather blank in an antibacterial solution after a fatting process, drying and then coating a layer of protective film on the surface, wherein the antibacterial solution comprises: the raw materials comprise the following components in parts by weight: 35-50 parts of honeysuckle, 20-30 parts of glabrous greenbrier rhizome, 3-8 parts of chamomile, 2-7 parts of lavender and 10-20 parts of medical alcohol; the protective film includes: the raw materials comprise the following components in parts by weight: 6-15 parts of beeswax, 25-40 parts of chloroprene rubber, 1-4 parts of rosin, 12-20 parts of ethyl acetate, 0.5-1 part of nano zinc oxide, 1-3 parts of lecithin and 0.5-2 parts of prochloraz. According to the invention, the leather is wet-rubbing resistant and antibacterial by soaking the leather blank in the antibacterial liquid and coating a layer of protective film after the greasing process, but the antibacterial leather prepared by the method has poor antibacterial durability and poor virus inactivation capability.

Therefore, it is necessary to develop leather with broad-spectrum, long-acting, antibacterial, mildewproof and antiviral properties.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an antibacterial antiviral agent, antibacterial mildew-proof antiviral leather, and a preparation method and application thereof. The antibacterial, mildewproof and antiviral leather prepared by the antibacterial, mildewproof and antiviral agent utilizes the synergistic antibacterial and antiviral effects of the metal ions, the photocatalyst and the natural plant extract, can realize the broad-spectrum long-acting antibacterial, mildewproof and antiviral performance of the leather, enables the microorganisms such as bacteria, mildew and the like attached to the surface of the leather to be difficult to propagate and kill, and is efficient in virus inactivation.

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

in a first aspect, the present invention provides an antibacterial and antiviral agent, which is prepared from the following raw materials: silver-doped nano bismuth tungstate, silver-doped nano titanium dioxide, erbium-doped nano titanium dioxide, chitosan and plant extract.

In the invention, the three silver-doped nano bismuth tungstate, silver-doped nano titanium dioxide and erbium-doped nano titanium dioxide belong to metal ion-doped photocatalyst with bacteriostatic activity, and are matched with each other to realize synergistic interaction, so that the broad-spectrum long-acting antibacterial, mildewproof and antiviral properties of leather can be enhanced. Wherein, the metal ions with bacteriostatic activity and the photocatalyst nano-particle carrier have a synergistic antibacterial effect. The photocatalyst nano-particle carrier has a narrow forbidden band width, and under the irradiation of visible light, the photocatalyst nano-particle carrier reduces oxygen molecules to form O free radicals with strong oxidizing property. Meanwhile, the valence band hole and water molecules are subjected to oxidation reaction to form strong-oxidizing-property OH free radicals, the two strong-oxidizing-property free radicals are in contact with viruses and bacteria to generate oxidation-reduction reaction, so that the viruses and the bacteria are inactivated, and the strong-oxidizing-property O free radicals and the strong-oxidizing-property OH free radicals can further oxidize metal ions doped in photocatalyst nano-particle lattices to form high-valence metal ions with stronger sterilizing capability, so that the antibacterial effect of the metal ions is synergistically enhanced.

In the invention, the chitosan can be adsorbed on the surface of the microbial cell to prevent the nutrient substances from being transported to the cell, and the interaction between the positive charge of the chitosan and the negative charge on the surface of the microbial cell membrane changes the permeability of the microbial cell membrane to cause the death of the microbial cell and selectively chelate metal ions which play a key role in the growth of the microbe, thereby inhibiting the growth and the reproduction of the microbe.

In the invention, the plant extract is combined with microbial cells to destroy the integrity of cell membranes and increase the permeability of the membranes, so that intracellular substances of bacteria, mould and other microorganisms are leaked out and are difficult to reproduce and kill, and the metal ion doped photocatalyst with antibacterial activity can be infiltrated into the microbial cells to be combined with DNA to influence the normal function of the DNA, so that the bacteria, mould and other microorganisms attached to the surface of leather are difficult to reproduce and kill, and viruses are inactivated.

The active substances in the raw materials for preparing the antibacterial and antiviral agent are matched with each other and have synergistic interaction, the leather prepared from the antibacterial and antiviral agent has broad-spectrum long-acting antibacterial, mildewproof and antiviral properties, microorganisms such as bacteria, molds and the like attached to the surface of the leather can be difficultly propagated and killed, viruses are inactivated, the sustained-release effect is long in sustainable time, and the long-term stability of the antibacterial property is good.

In the invention, the antibacterial and antiviral agent comprises the following raw materials in parts by weight: 2-6 parts of silver-doped nano bismuth tungstate, 1-4 parts of silver-doped nano titanium dioxide, 1-4 parts of erbium-doped nano titanium dioxide, 3-8 parts of chitosan and 3-8 parts of plant extract.

In the raw materials for preparing the antibacterial and antiviral agent, the silver-doped nano bismuth tungstate is 2-6 parts by weight, such as 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts and the like.

In the raw materials for preparing the antibacterial and antiviral agent, the silver-doped nano titanium dioxide is 1-4 parts by weight, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts and the like.

In the raw materials for preparing the antibacterial and antiviral agent, the erbium-doped nano titanium dioxide is 1-4 parts by weight, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts and the like.

In the raw materials for preparing the antibacterial and antiviral agent, the weight portion of the chitosan is 3-8 parts, and can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts and the like.

In the raw materials for preparing the antibacterial and antiviral agent of the present invention, the weight parts of the plant extract are 3 to 8 parts, and may be, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, and the like.

Preferably, the plant extract comprises: any one or combination of at least two of honeysuckle extract, liquorice extract, glabrous greenbrier rhizome extract or houttuynia cordata extract;

preferably, the raw materials for preparing the antibacterial and antiviral agent further comprise: dispersant A and water;

preferably, the dispersant A comprises any one or combination of at least two of sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate.

Preferably, the preparation raw materials of the antibacterial and antiviral agent comprise the following components in parts by weight: 2-6 parts of silver-doped nano bismuth tungstate, 1-4 parts of silver-doped nano titanium dioxide, 1-4 parts of erbium-doped nano titanium dioxide, 3-8 parts of chitosan, 3-8 parts of plant extract, 0.2-0.8 part of dispersant A and 70-85 parts of water;

in the raw materials for preparing the antibacterial and antiviral agent, the dispersant A is 0.2 to 0.8 part by weight, for example, 0.2 part, 0.4 part, 0.6 part, 0.7 part, 0.8 part and the like.

In the raw materials for preparing the antibacterial and antiviral agent, the weight portion of the water is 70-85 parts, and the water can be 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts and the like.

Preferably, the antibacterial and antiviral agent is prepared by the following method: mixing silver-doped nano bismuth tungstate, silver-doped nano titanium dioxide, erbium-doped nano titanium dioxide, a dispersing agent A and water, heating and ultrasonically treating, and then adding chitosan and plant extract for mixing to obtain the antibacterial and antiviral agent.

Preferably, the temperature of the heating ultrasound is 85-95 ℃, for example, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ and the like, and the time of the heating ultrasound is 20-40min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40 min.

In a second aspect, the invention provides antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: animal skins, leather degreasers, acids, tanning agents and the antibacterial and antiviral agent of the first aspect.

Preferably, the leather is prepared from the following raw materials in parts by weight: 100 parts of animal skin, 0.1-1 part of leather degreasing agent, 1-10 parts of acid, 5-15 parts of tanning agent and 1-10 parts of antibacterial and antiviral agent in the first aspect.

In the raw materials for preparing the leather of the invention, the weight portion of the leather degreasing agent is 0.1-1, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, etc.

In the raw materials for preparing the leather of the present invention, the acid may be 1 to 10 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.

In the raw materials for preparing the leather of the present invention, the tanning agent is 5 to 15 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.

In the raw materials for producing the leather of the present invention, the antibacterial/antiviral agent according to the first aspect may be used in an amount of 1 to 10 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and the like.

Preferably, the animal skin comprises: buffalo leather and/or sheep leather.

Preferably, the leather degreasing agent comprises any one or a combination of at least two of isomeric tridecanol ethers, alkylphenol ethoxylates and octylphenol polyoxyethylene ethers.

Preferably, the acid comprises: formic acid and/or acetic acid.

Preferably, the tanning agent comprises: vegetable tanning agents and/or aldehyde tanning agents.

Preferably, the raw materials for preparing the leather further comprise: an antibacterial and antiviral suspension.

Preferably, the raw materials for preparing the antibacterial and antiviral suspension comprise: nano silver sol, nano zirconium oxide and nano bismuth tungstate.

As the preferable technical scheme of the invention, the leather also needs to be functionalized by using the antibacterial and antiviral suspension, wherein the nano silver sol, the nano zirconium oxide and the nano bismuth tungstate are matched with each other for synergism, so that the antibacterial and antiviral properties of the leather can be further improved. The nano silver sol is attached to the leather, and silver ions with positive charges are released to react with sulfydryl with negative charges in bacterial protease, so that bacteria cannot be split and propagated to be killed. In addition, under the action of light, silver ions can play a catalytic role, activate oxygen in water and air, generate hydroxyl radicals and active oxygen ions, and destroy the proliferation capacity of bacteria in a short time to kill cells. The nano zirconium oxide and the nano bismuth tungstate have strong adsorption effect on bacteria so as to promote full action of nano silver antibacterial particles and the bacteria and strengthen the antibacterial effect.

Preferably, the antibacterial and antiviral suspension is prepared from the following raw materials in parts by weight: 1-6 parts of nano silver sol, 1-4 parts of nano zirconium oxide and 1-6 parts of nano bismuth tungstate.

In the raw materials for preparing the antibacterial and antiviral suspension, the weight portion of the nano silver sol is 1-6 parts, and can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts and the like.

In the raw materials for preparing the antibacterial and antiviral suspension, the weight portion of the nano zirconia is 1-4 parts, such as 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts and the like.

In the raw materials for preparing the antibacterial and antiviral suspension, the parts by weight of the nano bismuth tungstate are 1-6 parts, such as 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts and the like.

Preferably, the raw materials for preparing the antibacterial and antiviral suspension further comprise: dispersant B and water.

Preferably, the dispersant B comprises any one or a combination of at least two of polyacrylamide, methyl amyl alcohol or fatty acid polyglycol ester.

Preferably, the antibacterial and antiviral suspension is prepared from the following raw materials in parts by weight: 1-6 parts of nano silver sol, 1-4 parts of nano zirconium oxide, 1-6 parts of nano bismuth tungstate, 0.2-0.8 part of dispersant B and 62-78 parts of water.

In the raw materials for preparing the antibacterial and antiviral suspension, the dispersant B is 0.2-0.8 part by weight, and can be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part and the like.

In the raw materials for preparing the antibacterial and antiviral suspension, the water is 62-78 parts by weight, such as 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts and the like.

Preferably, the antibacterial and antiviral suspension is prepared by the following method: mixing nano silver sol, nano zirconium oxide, nano bismuth tungstate, a dispersing agent B and water, and heating and ultrasonically treating to obtain the antibacterial and antiviral suspension.

Preferably, the temperature of the heating ultrasound is 85-95 ℃, for example, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ and the like, and the time of the heating ultrasound is 20-40min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min and the like.

Preferably, the raw materials for preparing the antibacterial, mildewproof and antiviral leather further comprise: dyes and levelling agents.

Preferably, the dye comprises: any one of azo dyes, anthraquinone dyes or triphenylmethane dyes or a combination of at least two of the dyes.

Preferably, the leveling agent comprises: any one or the combination of at least two of polyoxyethylene ether, fatty alcohol, alkylphenol or fatty alcohol sulfate.

Preferably, the leather is prepared from the following raw materials in parts by weight: 100 parts of animal skin, 0.1-1 part of leather degreasing agent, 1-10 parts of acid, 5-15 parts of tanning agent, 1-10 parts of antibacterial and antiviral agent of claim 1 or 2, 5-50 parts of antibacterial and antiviral suspension, 0.5-3 parts of dye and 0.1-2 parts of leveling agent.

In the raw materials for preparing the leather of the present invention, the antibacterial and antiviral suspension is 5 to 50 parts by weight, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.

In the raw materials for preparing the leather of the invention, the dye is 0.5 to 3 parts by weight, for example, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts and the like.

In the raw materials for preparing the leather of the present invention, the leveling agent is 0.1 to 2 parts by weight, for example, 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, etc.

In a third aspect, the present invention provides a method for preparing antibacterial, mildewproof and antiviral leather according to the second aspect, wherein the method for preparing the antibacterial, mildewproof and antiviral leather comprises the following steps:

(1) pretreatment: degreasing and washing the animal skin by adopting a leather degreasing agent and acid to obtain a skin blank;

(2) tanning treatment: tanning the leather blank obtained in the step (1) by using a tanning agent;

(3) and (3) antibacterial treatment: and (3) performing antibacterial treatment on the tanned leather blank by adopting an antibacterial antiviral agent to obtain the antibacterial, mildewproof and antiviral leather.

Preferably, the mass ratio of the animal skin, the leather degreasing agent and the acid in the step (1) is 100 (0.1-1) to (0.1-2): wherein "0.1-1" can be 0.1, 0.2, 0.4, 0.6, 0.8, 1, etc.; wherein "0.1-2" may be 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, etc.

Preferably, in the step (1), the degreasing washing specifically comprises the following steps:

(a) first water washing: placing the animal skin in a rotary drum, mixing the animal skin with water, heating in a water bath, adding a leather degreasing agent and acid, rotating, and cleaning with water to obtain degreased animal skin;

(b) and (3) second water washing: placing the degreased animal skin obtained in the step (a) in a rotary drum, adding acid in batches, rotating, and cleaning with water to obtain a skin blank;

preferably, in step (a), the temperature of the water bath heating is 40-45 deg.C, such as 40 deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, etc.

Preferably, in step (a), the rotation time is 50-70min, such as 50min, 52min, 54min, 56min, 58min, 60min, etc.

Preferably, in step (b), the adding acid in batches and rotating is specifically: placing the defatted animal skin obtained in step (a) in a rotating drum, adding 0.1-1 part (such as 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part) of acid, rotating for 10-20min (such as 10min, 12min, 14min, 16min, 18min, 20min, etc.), adding 0.5-2 parts (such as 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, 2 parts, etc.) of acid, rotating for 10-20min (such as 10min, 12min, 14min, 16min, 18min, 20min, etc.), and finally adding 0.5-2 parts (such as 0.5 part, 0.6 part, 0.8 part, 1.6 part, 1.8 min, 10min, 14min, 16min, 18min, 20min, etc.), and rotating for 10-2 min, 20min, etc.).

Preferably, in step (2), the tanning treatment has a pH of 3.5-4.5, which may be, for example, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5 parts, etc.

Preferably, in step (2), the tanning treatment temperature is 38-45 ℃, for example 38 ℃, 40 ℃, 42 ℃, 44 ℃, 45 ℃ and the like, and the tanning treatment time is 8-10h, for example 8h, 8.5h, 9h, 9.5h, 10h and the like.

Preferably, in the step (3), the antibacterial treatment is specifically: placing the tanned skin embryo in a rotary drum, adding water and antibacterial antiviral agent, rotating for 20-40min (such as 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, etc.), adding acid, and rotating for 20-30min (such as 20min, 22min, 24min, 26min, 28min, 30min, etc.).

Preferably, the mass ratio of the water, the antibacterial and antiviral agent and the acid is (80-100): (4-10): (0.5-2).

Wherein "80-100" can be 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, etc.; "4-10" can be 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, etc.; "0.5-2" can be 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, etc.

Preferably, the step (3) further comprises, after the antibacterial treatment: and (4) dyeing treatment: and (3) placing the leather after the antibacterial treatment in a mixed solution of a dye solution and an antibacterial and antiviral suspension for soaking, adding acid, soaking and washing.

Preferably, in step (4), the dye solution comprises: dyes, levelling agents and water.

Preferably, in the step (4), the mass ratio of the dye to the leveling agent to the water is (0.5-5): (0.1-2): 100;

wherein "0.5-5" can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.; "0.1-2" can be 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, etc.

In step (4), the time for soaking in the mixed solution is preferably 45 to 60min, and may be, for example, 45min, 50min, 55min, 60min, or the like.

In step (4), the mass of the acid is preferably 1 to 2% of the mass of the mixed solution, and may be, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, or the like.

Preferably, in the step (4), the time for soaking after adding the acid is 50-70min, such as 50min, 55min, 60min, 65min, 70min, etc.

Preferably, the dyeing treatment in step (4) further comprises: and (5) drying treatment: and standing the dyed leather and drying.

Preferably, in the step (5), the standing time is 12-24h, such as 12h, 14h, 16h, 18h, 20h, 22h, 24h and the like.

Preferably, in the step (5), the drying temperature is 60-120 ℃, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ and the like can be used.

Preferably, the preparation method of the antibacterial, mildewproof and antiviral leather comprises the following steps:

(1) pretreatment: placing animal skin in a rotary drum, mixing with water, heating in water bath at 40-45 deg.C, adding leather degreasing agent and acid, rotating for 50-70min, and cleaning with water to obtain degreased animal skin; placing the degreased animal skin into a rotary drum, adding 0.1-1 part of acid, rotating for 10-20min, adding 0.5-2 parts of acid, rotating for 10-20min, finally adding 0.5-2 parts of acid, rotating for 10-20min, and cleaning with water to obtain a skin blank;

(2) tanning treatment: tanning the leather embryo obtained in the step (1) by using a tanning agent for 8-10h at the pH value of 3.5-4.5 and the temperature of 38-45 ℃;

(3) and (3) antibacterial treatment: placing the tanned skin embryo in a rotary drum, adding water and antibacterial antiviral agent, rotating for 20-40min, adding acid, and rotating for 20-30 min;

(4) dyeing treatment: soaking the leather after the antibacterial treatment in a mixed solution of a dye solution and an antibacterial and antiviral suspension for 45-60min, adding acid, soaking for 50-70min, and washing with water;

(5) and (3) drying treatment: standing the dyed leather for 12-24h, and drying at 60-120 ℃ to obtain the antibacterial, mildewproof and antiviral leather.

The invention realizes the broad-spectrum long-acting antibacterial, mildewproof and antiviral performance of the leather by adding the antibacterial and antiviral finishing procedure after tanning and performing functional treatment on the leather in the dyeing procedure, so that microorganisms such as bacteria, mold and the like attached to the surface of the leather are difficult to propagate and are killed.

In a third aspect, the present invention provides the use of an antibacterial and antiviral leather according to the first aspect in the manufacture of a hand-touch sports ball;

preferably, the sports ball comprises any one of a football, a basketball, an american football, a volleyball or a handball.

Compared with the prior art, the invention has the following beneficial effects:

(1) the antibacterial and antiviral agent disclosed by the invention utilizes the synergistic effect of the metal ions, the photocatalyst and the plant extract to improve the antibacterial, mildewproof and antiviral effects, and the leather prepared by the antibacterial and antiviral agent realizes the broad-spectrum long-acting antibacterial, mildewproof and antiviral properties, so that microorganisms such as bacteria, molds and the like attached to the surface of the leather are difficult to propagate and kill, and viruses are inactivated;

(2) the antibacterial, mildewproof and antiviral leather has the antibacterial rate of over 99 percent on bacteria such as large intestine, aureococcus and the like, the antiviral activity rate of over 99 percent on viruses such as H1N1, H3N2 and the like, and the mildewproof grade is 0.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The sources of the components in the following examples are as follows: yellow cattle leather (manufacturer: He Xin leather Co., Ltd., Dongguan), sheep leather (manufacturer: He Xin leather Co., Ltd., Dongguan), leather degreasing agent (manufacturer: Sangda chemical engineering (Nantong) Co., Ltd., type: E-1310), vegetable tanning agent (manufacturer: Zhengzhou Jishui chemical engineering Co., Ltd.), aldehyde tanning agent (manufacturer: Tazhou Korea Biotech Co., Ltd., type: MF), dye (manufacturer: Suzhou Huimei dye Co., Ltd., type: MF), dye (manufacturer: Suzhou Vietui dye Co., Ltd., type)Number: r-122), leveling agent (manufacturer: the types of the Haian petrochemical plant in Jiangsu province are as follows: o-25); silver-doped nano bismuth tungstate (self-made reference: preparation characterization of doped bismuth tungstate and research on degradation of dye wastewater, prepared by hydrothermal method), silver-doped nano titanium dioxide (self-made reference: preparation of silver-doped nano titanium dioxide and photocatalytic performance thereof, prepared by sol-gel method), and erbium-doped nano titanium dioxide (self-made reference: erbium-doped nano TiO₂Microstructure and photocatalytic performance, prepared by a sol-gel method), dispersant a (manufacturer: shandong Yushuo chemical Co., Ltd, model number: SHMP), chitosan (manufacturer: shanghai yi run bioengineering ltd), flos Lonicerae extract (manufacturer: guangzhou American-exemplary biotechnology limited), licorice extract (manufacturer: guangzhou American-exemplary biotechnology limited), rhizoma smilacis glabrae extract (manufacturer: american biotechnology limited, guangzhou); nano silver sol (manufacturer: Hangzhou Hengnan New Material Co., Ltd., model: HN-TA33Ag), nano zirconia (manufacturer: Suzhou Kangshuo chemical Co., Ltd., model: TBD-5YZ30), and dispersant B (manufacturer: Suzhou, Japanese chemical engineering technology Co., Ltd., model: PAM).

Preparation examples 1 to 3 and comparative preparation examples 1 to 5

The formula of each preparation example is shown in the following table 1 (as indicated by '4' in table 1 to represent that the content of the corresponding component is 4 parts by weight):

TABLE 1

The antibacterial antiviral agent is prepared by the following preparation method: mixing silver-doped nano bismuth tungstate, silver-doped nano titanium dioxide, erbium-doped nano titanium dioxide, a dispersing agent A and water, heating to 90 ℃, performing ultrasonic treatment for 30min, adding chitosan and a plant extracting solution, and mixing to obtain the antibacterial and antiviral agent.

Preparation examples 9 to 14

Preparation examples 9 to 14 provided antibacterial and antiviral suspensions, and the formulations of the respective preparation examples in parts by weight are shown in the following table 2 (in table 1, "4" represents the content of the corresponding component as 4 parts by weight):

TABLE 2

	Nano silver sol	Nano zirconium oxide	Nano bismuth tungstate	Dispersant B	Water (W)
						Preparation example 4	4	2	2	0.4	72
Preparation example 5	2	2	4	0.5	62
						Preparation example 6	6	1	1	0.6	78
Preparation example 7	0	4	4	0.4	72
						Preparation example 8	5	0	3	0.4	72
Preparation example 9	5	3	0	0.4	72

The antibacterial and antiviral suspension is prepared by the following preparation method: mixing nano silver sol, nano zirconium oxide, nano bismuth tungstate, a dispersing agent B and water, heating to 90 ℃, and carrying out ultrasound for 30min to obtain the antibacterial and antiviral suspension.

Example 1

The embodiment provides an antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: 100 parts of yellow cattle leather, 0.5 part of leather degreasing agent, 5.5 parts of formic acid, 2 parts of vegetable tanning agent, 5 parts of antibacterial and antiviral agent provided by preparation example 1, 1 part of dye, 0.5 part of leveling agent and 20 parts of antibacterial and antiviral suspension provided by preparation example 4.

The preparation method of the antibacterial, mildewproof and antiviral leather provided by the embodiment comprises the following steps:

(1) pretreatment: placing 100 parts of buffalo leather into a rotary drum, mixing with 100 parts of water, heating in water bath at 40 ℃, adding 0.5 part of leather degreasing agent and 1 part of formic acid, rotating for 60min, and cleaning with water to obtain degreased animal skin; placing the degreased animal skin in a rotary drum, adding 0.5 part of formic acid, rotating for 15min, adding 1 part of formic acid, rotating for 15min, finally adding 1 part of formic acid, rotating for 15min, and cleaning with water to obtain a skin blank;

(2) tanning treatment: putting the leather blank obtained in the step (1) into a rotary drum, mixing the leather blank with 100 parts of water, adding 2 parts of plant tanning agent, and tanning for 9 hours at 40 ℃ when the pH value is 4;

(3) and (3) antibacterial treatment: placing the tanned leather embryo into a rotary drum, adding 100 parts of water and 5 parts of antibacterial and antiviral agent, rotating for 30min, adding 1 part of formic acid, and rotating for 25 min;

(4) dyeing treatment: placing the leather after the antibacterial treatment in a mixed solution of a dye solution (the dye solution comprises 1 part of dye, 0.5 part of leveling agent and 100 parts of water) and 20 parts of antibacterial and antiviral suspension for soaking for 50min, adding 1 part of formic acid, soaking for 60min, and washing the leather embryo with water;

(5) and (3) drying treatment: and standing the dyed leather blank for 12 hours, and drying at 80 ℃ to obtain the antibacterial, mildewproof and antiviral leather.

Example 2

The embodiment provides an antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: 100 parts of sheep leather, 0.6 part of leather degreasing agent, 5.5 parts of formic acid, 1 part of vegetable tanning agent, 6 parts of antibacterial and antiviral agent provided by preparation example 2, 2 parts of dye, 0.5 part of leveling agent and 25 parts of antibacterial and antiviral suspension provided by preparation example 5.

(1) pretreatment: placing 100 parts of sheep leather into a rotary drum, mixing with 100 parts of water, heating in water bath at 40 ℃, adding 0.6 part of leather degreasing agent and 1 part of formic acid, rotating for 60min, and cleaning with water to obtain degreased animal leather; placing the degreased animal skin in a rotary drum, adding 0.5 part of formic acid, rotating for 15min, adding 1 part of formic acid, rotating for 15min, finally adding 1 part of formic acid, rotating for 15min, and cleaning with water to obtain a skin blank;

(2) tanning treatment: putting the leather blank obtained in the step (1) into a rotary drum, mixing the leather blank with 100 parts of water, adding 1 part of plant tanning agent, and tanning for 9 hours at 40 ℃ when the pH value is 4.5;

(3) and (3) antibacterial treatment: placing the tanned leather embryo into a rotary drum, adding 100 parts of water and 6 parts of antibacterial and antiviral agent, rotating for 30min, adding 1 part of formic acid, and rotating for 25 min;

(4) dyeing treatment: placing the leather after the antibacterial treatment in a mixed solution of a dye solution (the dye solution comprises 2 parts of dye, 0.5 part of leveling agent and 100 parts of water) and 25 parts of antibacterial and antiviral suspension for soaking for 50min, adding 1 part of formic acid, soaking for 60min, and washing the leather embryo with water;

(5) and (3) drying treatment: and standing the dyed leather blank for 18h, and drying at 60 ℃ to obtain the antibacterial and antiviral leather.

Example 3

The embodiment provides an antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: 100 parts of yellow cattle leather, 0.4 part of leather degreasing agent, 5.5 parts of formic acid, 1 part of aldehyde tanning agent, 8 parts of antibacterial and antiviral agent provided by preparation example 3, 1 part of dye, 0.5 part of leveling agent and 30 parts of antibacterial and antiviral suspension provided by preparation example 6.

(1) pretreatment: placing 100 parts of buffalo leather into a rotary drum, mixing with 100 parts of water, heating in water bath at 40 ℃, adding 0.4 part of leather degreasing agent and 1 part of formic acid, rotating for 60min, and cleaning with water to obtain degreased animal skin; placing the degreased animal skin in a rotary drum, adding 0.5 part of formic acid, rotating for 15min, adding 1 part of formic acid, rotating for 15min, finally adding 1 part of formic acid, rotating for 15min, and cleaning with water to obtain a skin blank;

(2) tanning treatment: putting the leather blank obtained in the step (1) into a rotary drum, mixing the leather blank with 100 parts of water, adding 1 part of aldehyde tanning agent, and tanning for 9 hours at 40 ℃ when the pH value is 4;

(3) and (3) antibacterial treatment: placing the tanned leather embryo into a rotary drum, adding 100 parts of water and 8 parts of antibacterial and antiviral agent, rotating for 30min, adding 1 part of formic acid, and rotating for 25 min;

(4) dyeing treatment: placing the leather after the antibacterial treatment in a mixed solution of a dye solution (the dye solution comprises 1 part of dye, 0.5 part of leveling agent and 100 parts of water) and 30 parts of antibacterial and antiviral suspension for soaking for 50min, adding 1 part of formic acid, soaking for 60min, and washing the leather embryo with water;

Example 4

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral suspension provided in preparation example 4 is replaced with the antibacterial and antiviral suspension provided in preparation example 7, and the contents of other components and the preparation method are the same as those of example 1.

Example 5

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral suspension provided in preparation example 4 is replaced with the antibacterial and antiviral suspension provided in preparation example 8, and the contents of other components and the preparation method are the same as those of example 1.

Example 6

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral suspension provided in preparation example 4 is replaced with the antibacterial and antiviral suspension provided in preparation example 9, and the contents of other components and the preparation method are the same as those of example 1.

Example 7

The embodiment provides an antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: 100 parts of cattle leather, 0.5 part of leather degreasing agent, 5.5 parts of formic acid, 2 parts of vegetable tanning agent, 25 parts of antibacterial and antiviral agent provided in preparation example 1, 1 part of dye and 0.5 part of leveling agent.

(3) and (3) antibacterial treatment: placing the tanned leather embryo into a rotary drum, adding 100 parts of water and 25 parts of antibacterial and antiviral agent, rotating for 30min, adding 1 part of formic acid, and rotating for 25 min;

(4) dyeing treatment: soaking the leather subjected to antibacterial treatment in a dye solution (the dye solution comprises 1 part of dye, 0.5 part of leveling agent and 100 parts of water) for 50min, adding 1 part of formic acid, soaking for 60min, and washing the leather blank with water;

Comparative example 1

The embodiment provides an antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: 100 parts of cattle leather, 0.5 part of leather degreasing agent, 5.5 parts of formic acid, 2 parts of vegetable tanning agent, 1 part of dye, 0.5 part of leveling agent and 20 parts of antibacterial and antiviral suspension provided by preparation example 9.

(3) dyeing treatment: soaking the tanned leather in a mixed solution of a dye solution (the dye solution comprises 1 part of dye, 0.5 part of leveling agent and 100 parts of water) and 20 parts of antibacterial and antiviral suspension for 50min, adding 1 part of formic acid, soaking for 60min, and washing the leather blank with water;

(4) and (3) drying treatment: and standing the dyed leather blank for 12 hours, and drying at 80 ℃ to obtain the antibacterial, mildewproof and antiviral leather.

Comparative example 2

The embodiment provides an antibacterial, mildewproof and antiviral leather, which is prepared from the following raw materials: 100 parts of yellow cattle leather, 0.5 part of leather degreasing agent, 5.5 parts of formic acid, 2 parts of dye, 1 part of dye, 0.5 part of leveling agent and 30 parts of antibacterial and antiviral suspension provided in preparation example 9.

(2) tanning treatment: putting the leather blank obtained in the step (1) into a rotary drum, mixing the leather blank with 100 parts of water, and adding 2 parts of tanning agent for 9 hours at the temperature of 40 ℃ when the pH value is 4;

(3) and (3) antibacterial treatment: placing the tanned leather embryo into a rotary drum, adding 100 parts of water and 15 parts of antibacterial and antiviral suspension, rotating for 30min, adding 1 part of formic acid, and rotating for 25 min;

(4) dyeing treatment: placing the leather after the antibacterial treatment in a mixed solution of a dye solution (the dye solution comprises 1 part of dye, 0.5 part of leveling agent and 100 parts of water) and 15 parts of antibacterial and antiviral suspension for soaking for 50min, adding 1 part of formic acid, soaking for 60min, and washing the leather embryo with water;

Comparative example 3

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral agent provided in preparation example 1 is replaced with the antibacterial and antiviral agent provided in comparative preparation example 1, and the contents of other components and the preparation method are the same as those of example 1.

Comparative example 4

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral agent provided in preparation example 1 is replaced with the antibacterial and antiviral agent provided in comparative preparation example 2, and the contents of other components and the preparation method are the same as those of example 1.

Comparative example 5

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral agent provided in preparation example 1 is replaced with the antibacterial and antiviral agent provided in comparative preparation example 3, and the contents of other components and the preparation method are the same as those of example 1.

Comparative example 6

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral agent provided in preparation example 1 is replaced with the antibacterial and antiviral agent provided in comparative preparation example 4, and the contents of other components and the preparation method are the same as those of example 1.

Comparative example 7

This example provides an antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial and antiviral agent provided in preparation example 1 is replaced with the antibacterial and antiviral agent provided in comparative preparation example 5, and the contents of other components and the preparation method are the same as those of example 1.

And (3) performance testing:

the antibacterial and antiviral leathers provided by the above examples 1-8 and the antibacterial and antiviral leathers provided by the comparative examples 1-7 are tested for the antibacterial rate and the mildew-proof grade of Escherichia coli and Staphylococcus aureus, wherein the antibacterial rate is tested by GB/T31402-2015; the test method of the mildew-proof grade is GB/T24128-2009; the antiviral test method is ISO 21702-2019.

The specific test results are shown in table 3:

TABLE 3

The test data in table 3 show that the antibacterial, mildewproof and antiviral leather has the antibacterial rate of over 99% for bacteria such as large intestine, staphylococcus aureus and the like, the antiviral activity rate of over 99% for viruses such as H1N1, H3N2 and the like, and the mildew-proof grade is 0, so that the leather prepared by the invention has the antibacterial, mildewproof and antiviral properties with broad-spectrum and long-acting effects, can make microorganisms such as bacteria, mildew and the like attached to the surface of the leather difficult to reproduce and kill, can inactivate viruses, has long lasting time and good long-term stability of the antibacterial properties.

As can be seen from the comparison between the example 1 and the examples 4 to 6, the nano silver sol, the nano zirconium oxide and the nano bismuth tungstate in the antibacterial and antiviral suspension have a synergistic interaction effect, so that the antibacterial and antiviral performance of leather can be further improved, and when any one of the components is lacked, the antibacterial and antiviral effects are reduced. As is clear from the comparison between example 1 and example 7, the antibacterial and antiviral effects are reduced unless the functionalization treatment of the antibacterial and antiviral suspension is performed in the dyeing treatment step.

Comparative example 1 the leather was not treated with the antibacterial before dyeing, and even though the functionalization treatment of the antibacterial and antiviral suspension was carried out in the post dyeing treatment step, the reduction of the antibacterial and antiviral effects of the leather was very significant. Comparative example 2 the leather was treated with an antibacterial treatment before dyeing, but the antibacterial and antiviral agents provided by the present invention were not used, and the prepared leather, although improved compared to comparative example 1, still had much lower antibacterial and antiviral effects and poor broad-spectrum antibacterial activity compared to example 1.

As can be seen from the comparison between example 1 and comparative examples 3 to 7, the active substances in the raw materials for preparing the antibacterial and antiviral agent provided by the present invention cooperate with each other, so that a synergistic effect exists, microorganisms such as bacteria and molds attached to the surface of leather are difficult to propagate and killed, viruses are inactivated, the sustained release effect is long in lasting time, the antibacterial property is good in long-term stability, and the antibacterial and antiviral effect is significantly reduced due to the absence of any active ingredient in the antibacterial and antiviral agent.

The applicant states that the invention is illustrated by the above examples to show the antibacterial and antiviral agent, the antibacterial and antifungal and antiviral leather, and the preparation method and application thereof, but the invention is not limited to the above examples, that is, the invention is not meant to be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The antibacterial and antiviral agent is characterized by comprising the following raw materials in parts by weight: 2-6 parts of silver-doped nano bismuth tungstate, 1-4 parts of silver-doped nano titanium dioxide, 1-4 parts of erbium-doped nano titanium dioxide, 3-8 parts of chitosan, 3-8 parts of plant extract, 0.2-0.8 part of dispersant A and 70-85 parts of water;

the plant extract comprises: any one or combination of at least two of honeysuckle extract, liquorice extract, glabrous greenbrier rhizome extract or houttuynia cordata extract.

2. The antibacterial and antiviral agent according to claim 1, wherein said dispersing agent a comprises any one or a combination of at least two of sodium tripolyphosphate, sodium hexametaphosphate, or sodium pyrophosphate.

3. The antibacterial and antiviral agent according to claim 1, wherein said antibacterial and antiviral agent is prepared by the following method: mixing silver-doped nano bismuth tungstate, silver-doped nano titanium dioxide, erbium-doped nano titanium dioxide, a dispersing agent A and water, heating and ultrasonically treating, and then adding chitosan and plant extract for mixing to obtain the antibacterial and antiviral agent.

4. The antibacterial and antiviral agent according to claim 3, wherein the temperature of said heat sonication is 85-95 ℃ and the time of said heat sonication is 20-40 min.

5. The antibacterial, mildewproof and antiviral leather is characterized by comprising the following raw materials: an animal skin, a leather degreaser, an acid, a tanning agent and the antibacterial antiviral agent of any of claims 1-4.

6. The antibacterial, mildewproof and antiviral leather as claimed in claim 5, wherein the leather is prepared from the following raw materials in parts by weight: 100 parts of animal skin, 0.1-1 part of leather degreasing agent, 1-10 parts of acid, 5-15 parts of tanning agent and 1-10 parts of antibacterial and antiviral agent according to claim 1 or 2.

7. The antibacterial, mildewproof and antiviral leather according to claim 5, wherein the animal skin comprises: buffalo leather and/or sheep leather.

8. The antibacterial, mildewproof and antiviral leather as claimed in claim 5, wherein the leather degreasing agent comprises any one or a combination of at least two of isomeric tridecanol ethers, alkylphenol ethoxylates and octylphenol ethoxylates.

9. The antibacterial, mildewproof and antiviral leather according to claim 5, wherein the acid comprises: formic acid and/or acetic acid.

10. The antibacterial, mildewproof and antiviral leather according to claim 5, wherein the tanning agent comprises: vegetable tanning agents and/or aldehyde tanning agents.

11. The antibacterial, mildewproof and antiviral leather as claimed in claim 5, wherein the leather is prepared from the following raw materials: an antibacterial and antiviral suspension.

12. The antibacterial, mildewproof and antiviral leather as claimed in claim 11, wherein the antibacterial and antiviral suspension is prepared from the following raw materials: nano silver sol, nano zirconium oxide and nano bismuth tungstate.

13. The antibacterial, mildewproof and antiviral leather as claimed in claim 12, wherein the antibacterial and antiviral suspension is prepared from the following raw materials in parts by weight: 1-6 parts of nano silver sol, 1-4 parts of nano zirconium oxide and 1-6 parts of nano bismuth tungstate.

14. The antibacterial, mildewproof and antiviral leather as claimed in claim 11, wherein the antibacterial and antiviral suspension is prepared from the following raw materials: dispersant B and water.

15. The antibacterial, mildewproof and antiviral leather as claimed in claim 14, wherein the dispersant B comprises any one or a combination of at least two of polyacrylamide, methyl amyl alcohol or fatty acid polyglycol ester.

16. The antibacterial, mildewproof and antiviral leather as claimed in claim 12, wherein the antibacterial and antiviral suspension is prepared from the following raw materials in parts by weight: 1-6 parts of nano silver sol, 1-4 parts of nano zirconium oxide, 1-6 parts of nano bismuth tungstate, 0.2-0.8 part of dispersant B and 62-78 parts of water.

17. The antibacterial, mildewproof and antiviral leather according to claim 12, wherein the antibacterial and antiviral suspension is prepared by the following method: mixing nano silver sol, nano zirconium oxide, nano bismuth tungstate, a dispersing agent B and water, and heating and ultrasonically treating to obtain the antibacterial and antiviral suspension.

18. The antibacterial, mildewproof and antiviral leather as claimed in claim 17, wherein the temperature of the heating ultrasound is 85-95 ℃, and the time of the heating ultrasound is 20-40 min.

19. The antibacterial, mildewproof and antiviral leather according to claim 5, wherein the antibacterial, mildewproof and antiviral leather is prepared from the following raw materials: dyes and levelling agents.

20. The antibacterial, mildewproof and antiviral leather according to claim 19, wherein the dye comprises: any one of azo dyes, arylmethane dyes or phthalocyanine dyes or a combination of at least two of them.

21. The antibacterial, mildewproof and antiviral leather according to claim 19, wherein the leveling agent comprises: any one or the combination of at least two of polyoxyethylene ether, fatty alcohol, alkylphenol or fatty alcohol sulfate.

22. The antibacterial, mildewproof and antiviral leather as claimed in claim 5, wherein the leather is prepared from the following raw materials in parts by weight: 100 parts of animal skin, 0.1-1 part of leather degreasing agent, 1-10 parts of acid, 5-15 parts of tanning agent, 1-10 parts of antibacterial and antiviral agent of claim 1 or 2, 5-50 parts of antibacterial and antiviral suspension, 0.5-3 parts of dye and 0.1-2 parts of leveling agent.

23. The method for preparing antibacterial, mildewproof and antiviral leather according to any one of claims 5 to 22, wherein the method for preparing antibacterial, mildewproof and antiviral leather comprises the following steps:

24. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, wherein the mass ratio of the animal skin, the leather degreasing agent and the acid in the step (1) is 100 (0.1-1) to (0.1-2).

25. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, wherein in the step (1), the degreasing and washing specifically comprises the following steps:

(b) and (3) second water washing: placing the degreased animal skin obtained in the step (a) in a rotary drum, adding acid in batches, rotating, and then washing with water to obtain a skin embryo.

26. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 25, wherein the water bath heating temperature in the step (a) is 40-45 ℃.

27. The method for preparing leather having antibacterial, antifungal and antiviral effects as claimed in claim 25, wherein the rotation time in the step (a) is 50-70 min.

28. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 25, wherein in the step (b), the acid is added in batches and the rotating is carried out by: placing the degreased animal skin obtained in the step (a) into a rotary drum, adding 0.1-1 part of acid, rotating for 10-20min, adding 0.5-2 parts of acid, rotating for 10-20min, and finally adding 0.5-2 parts of acid, and rotating for 10-20 min.

29. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, wherein the tanning treatment has a pH of 3.5 to 4.5 in the step (2).

30. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, wherein in the step (2), the tanning temperature is 38-45 ℃ and the tanning time is 8-10 h.

31. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, wherein in the step (3), the antibacterial treatment is specifically as follows: placing the tanned skin embryo in a rotary drum, adding water and antibacterial antiviral agent, rotating for 20-40min, adding acid, and rotating for 20-30 min.

32. The method for preparing leather having antibacterial, antifungal and antiviral effects as claimed in claim 31, wherein the mass ratio of the water, the antibacterial and antiviral agents and the acid is (80-100): (4-10): (0.5-2).

33. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, wherein the step (3) of antibacterial treatment further comprises the following steps: and (4) dyeing treatment: and (3) placing the leather after the antibacterial treatment in a mixed solution of a dye solution and an antibacterial and antiviral suspension for soaking, adding acid, soaking and washing.

34. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 33, wherein in the step (4), the dyeing solution comprises the following components in parts by weight: dyes, levelling agents and water.

35. The method for preparing leather with antibacterial, mildewproof and antiviral effects as claimed in claim 34, wherein in the step (4), the mass ratio of the dye to the leveling agent to the water is (0.5-5): 0.1-2): 100.

36. The method for preparing antibacterial, antifungal and antiviral leather according to claim 33, wherein the soaking time in the mixed solution in the step (4) is 45-60 min.

37. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 33, wherein in the step (4), the mass of the acid is 1-2% of the mass of the mixed solution.

38. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 33, wherein the soaking time after the acid is added in the step (4) is 50-70 min.

39. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 33, wherein the dyeing treatment in the step (4) further comprises the following steps: and (5) drying treatment: and standing the dyed leather and drying.

40. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 39, wherein the standing time in the step (5) is 12 to 24 hours.

41. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 39, wherein the drying temperature in the step (5) is 60-120 ℃.

42. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 23, comprising the following steps of:

(1) pretreatment: placing animal skin in a rotary drum, mixing with water, heating in water bath at 40-45 deg.C, adding leather degreasing agent and acid, rotating for 50-70min, and cleaning with water to obtain degreased animal skin; placing the degreased animal skin in a rotary drum, adding acid in batches, rotating, and cleaning with water to obtain a skin blank;

43. Use of antibacterial, mildewproof, and antiviral leather according to claims 5 to 22 in the manufacture of a hand-touch sports ball.

44. The use according to claim 43, wherein the hand-contact sport ball comprises any one of a football, a basketball, a soccer ball, a volleyball or a handball.