CN112593020A - Preparation method of antibacterial, mildewproof and antiviral leather, leather and belt - Google Patents
Preparation method of antibacterial, mildewproof and antiviral leather, leather and belt Download PDFInfo
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- CN112593020A CN112593020A CN202011311370.9A CN202011311370A CN112593020A CN 112593020 A CN112593020 A CN 112593020A CN 202011311370 A CN202011311370 A CN 202011311370A CN 112593020 A CN112593020 A CN 112593020A
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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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
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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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
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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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
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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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/04—Fixing tanning agents in the leather
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- General Chemical & Material Sciences (AREA)
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a preparation method of antibacterial, mildewproof and antiviral leather, leather and a belt. The preparation method of the antibacterial, mildewproof and antiviral leather comprises the following steps: (1) tanning: putting leather into tanning liquid containing an antibacterial agent for tanning treatment; (2) retanning: putting the tanned leather into retanning liquid containing an antibacterial agent for retanning treatment; (3) dyeing: and (3) placing the retanned leather in a dye solution containing an antibacterial agent for dyeing treatment to obtain the antibacterial, mildewproof and antiviral leather. In the long-term use process of the belt processed from the leather provided by the invention, antibacterial ions can be slowly released from the inside of the belt, so that the belt achieves the long-term antibacterial, mildewproof and antiviral effects.
Description
Technical field
The invention belongs to the technical field of leather preparation, and particularly relates to a preparation method of leather, leather and a belt, and in particular relates to a preparation method of antibacterial, mildewproof and antiviral leather, leather and a belt.
Background
The main component of leather is the protein structure. Due to the characteristics of the organization structure, a large amount of sweat stains are easily generated on a human body in a humid environment, particularly in summer, and a large amount of sweat on the part covered by the belt cannot be evaporated, so that a large amount of bacteria are particularly easy to breed. If the belt cannot be cleaned in time, mildew is easily generated on the surface of the belt, so that the attractiveness of the belt is seriously influenced, the service life of the belt is seriously shortened, and various skin diseases are easily caused to a human body. Therefore, the antibacterial, mildewproof and antiviral treatment of the belt is vital to the improvement of the quality and the human health of the belt
CN206079163U discloses a utility model patent of antibiotic belt of chloranthus glaber. The main technology of this patent mainly sets up first layer leather, supporting layer and second floor leather, and is connected with the flax fiber layer of at least three-layer between supporting layer and second floor leather, through gluing the sarcandra glabra fibrous layer that can effectively be antibacterial between adjacent flax fiber layer to give the belt antibacterial performance. However, the utility model discloses a mainly place the antibacterial layer inside the belt to can not carry out antibiotic mould proof antiviral function to the belt skin effectively and handle.
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.
CN111700080A discloses an antibacterial antiviral agent, antibacterial mildew-proof antiviral leather, a preparation method and an application thereof, wherein the preparation raw materials of the antibacterial 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 can make the microorganisms such as bacteria and mould attached to the surface of leather difficult to propagate and kill the microorganisms, and can realize high-efficiency inactivation of viruses. However, the antibacterial and antiviral agent needs to be compounded with a plurality of antibacterial agents to achieve efficient virus inactivation, and the antibacterial agent has a complex formula and expensive raw materials, so that the antibacterial and antiviral agent is not suitable for industrial production.
Therefore, the development of a processing method for providing a long-term antibacterial, antifungal and antiviral effect to a belt is a major issue in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of antibacterial, mildewproof and antiviral leather, leather and a belt. The preparation method well solves the problem that the antibacterial layer is arranged inside the belt in the existing antibacterial belt, and the antibacterial, antiviral and mildewproof effects on the surface layer of the belt are difficult to achieve.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of antibacterial, mildewproof and antiviral leather, which comprises the following steps:
(1) tanning: putting leather into tanning liquid containing an antibacterial agent for tanning treatment;
(2) retanning: putting the tanned leather into retanning liquid containing an antibacterial agent for retanning treatment;
(3) dyeing: and (3) placing the retanned leather in a dye solution containing an antibacterial agent for dyeing treatment to obtain the antibacterial, mildewproof and antiviral leather.
The main preparation process of the invention is that in the tanning and retanning processes of leather, a proper amount of antibacterial component is added into tanning agent, so that part of antibacterial ions permeate between connected collagen molecules in the connection process of leather fiber collagen, and the leather is firstly endowed with antibacterial, mildewproof and antiviral treatment from the inside. The process of antibacterial treatment of leather surface layer includes adding antibacterial component into coloring agent, and heating under negative pressure to make the antibacterial ion loaded in the color layer and permeate into leather. In the long-term use process of the belt processed by the leather, the antibacterial ions can be slowly released from the inside of the belt, so that the long-term antibacterial, mildewproof and antiviral effects of the belt are achieved.
Preferably, in steps (1), (2) and (3), the antibacterial agent is each independently selected from silver salts and/or zinc salts.
Because the belt is closely contacted with the skin of a human body, the preparation method of the invention only needs to add silver salt and/or zinc salt to enable the belt to achieve the long-term antibacterial, mildewproof and antiviral effects during the selection process of the antibacterial agent components, thereby avoiding toxic inorganic antibacterial components such as copper, nickel, chromium, cadmium, mercury and the like, and toxic organic antibacterial agents such as guanidine salt, quaternary ammonium salt and the like.
Preferably, the silver salt is selected from silver acetate and/or silver nitrate.
Preferably, the zinc salt is selected from any one of zinc acetate, zinc nitrate or zinc sulfate or a combination of at least two thereof.
Preferably, in the step (1), the tanning liquid containing the antibacterial agent comprises the following components in parts by weight: 0.5-10 parts of antibacterial agent, 1-5 parts of chrome tanning agent, 0.1-0.5 part of acid and 80-120 parts of water.
In the present invention, the amount of the antibacterial agent added to the antibacterial agent-containing tanning liquid may be, for example, 0.5 to 10 parts, and may be, for example, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.
In the present invention, the amount of the chrome tanning agent added to the antimicrobial-containing tanning liquor is 1 to 5 parts, and may be, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.
In the present invention, the amount of the acid added to the antimicrobial agent-containing tanning liquid is 0.1 to 0.5 parts, and may be, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, or the like.
In the present invention, the amount of water added to the antimicrobial agent-containing tanning liquor is 80 to 120 parts, and may be, for example, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, etc.
Preferably, the acid is formic acid and/or acetic acid;
preferably, the pH of the antiseptic containing tanning liquor is 3.5-4.5, and 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, and the like.
Preferably, in the step (1), the mass ratio of the leather to the tanning liquor containing the antibacterial agent is 1 (1-10), and can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 and the like.
Preferably, in step (1), the tanning treatment temperature is 38-45 ℃, for example 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 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 (2), the retanning liquid of the antibacterial agent comprises the following components in parts by weight: 0.5-10 parts of antibacterial agent, 1-5 parts of retanning agent and 80-120 parts of water.
In the present invention, the amount of the antibacterial agent added to the retanning liquor containing an antibacterial agent is 0.5 to 10 parts, and may be, for example, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like.
In the present invention, the amount of the retanning agent added to the retanning liquor containing an antibacterial agent is 1 to 5 parts, and may be, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or the like.
In the present invention, the amount of water added to the retanning liquor containing an antibacterial agent is 80 to 120 parts, and may be, for example, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, and the like.
Preferably, the retanning agent is selected from any one of or a combination of at least two of a melamine retanning agent, a dihydroamine retanning agent, an acrylic resin retanning agent or a multi-metal retanning agent.
Preferably, in the step (2), the mass ratio of the tanned leather to the retanning liquor containing the antibacterial agent is 1 (1-3), and can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3 and the like.
Preferably, in the step (2), the temperature of the retanning treatment is 30-35 ℃, for example, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃ and the like, and the time of the retanning treatment is 8-10h, for example, 8h, 8.5h, 9h, 9.5h, 10h and the like.
Preferably, in the step (3), the dye liquor containing the antibacterial agent comprises the following components in parts by weight: 2-8 parts of an antibacterial agent, 7-12 parts of waterborne acrylic resin, 10-15 parts of waterborne polyurethane resin, 5-8 parts of polyethylene glycol, 3-6 parts of polyethylene wax, 15-25 parts of dye, 2-4 parts of organic silicone oil, 1-3 parts of a surfactant, 15-20 parts of ethylene glycol ethyl ether, 8-24 parts of a cosolvent and 40-50 parts of water.
In the present invention, the amount of the antibacterial agent added to the antibacterial agent-containing dye liquor is 2 to 8 parts, and may be, for example, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, or the like.
In the present invention, the amount of the aqueous acrylic resin added to the antimicrobial-containing dye liquor is 7 to 12 parts, and may be, for example, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, or the like.
In the present invention, the amount of the aqueous polyurethane resin added to the antimicrobial-containing dye solution is 10 to 15 parts, and may be, for example, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, or the like.
In the present invention, the amount of polyethylene glycol added to the antimicrobial-containing dye liquor is 5 to 8 parts, and may be, for example, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, or the like.
In the present invention, the amount of the polyethylene wax added to the antimicrobial-containing dye solution is 3 to 6 parts, and may be, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, or the like.
In the present invention, the amount of the dye added to the antimicrobial agent-containing dye solution is 15 to 25 parts, and may be, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, or the like.
In the present invention, the amount of the silicone oil added to the antimicrobial agent-containing dye liquor is 2 to 4 parts, and may be, for example, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4 parts, or the like.
In the present invention, the amount of the surfactant added to the dye liquor containing an antibacterial agent is 1 to 3 parts, and may be, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, or the like.
In the present invention, the amount of ethylene glycol ethyl ether added to the antimicrobial-containing dye liquor is 15 to 20 parts, and may be, for example, 15 parts, 15.5 parts, 16 parts, 16.5 parts, 17 parts, 17.5 parts, 18 parts, 18.5 parts, 19 parts, 19.5 parts, 20 parts, or the like.
In the present invention, the amount of the cosolvent added to the antibacterial agent-containing dye liquor is 8 to 24 parts, and may be, for example, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, and the like.
In the present invention, the amount of water added to the antimicrobial-containing dye liquor is 40 to 50 parts, and may be, for example, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, and the like.
Preferably, the number average molecular weight of the polyethylene glycol is 200-1000, and may be, for example, 200, 400, 600, 800, 1000, and the like.
Preferably, the dye is selected from any one of azo dyes, arylmethane dyes or phthalocyanine dyes or a combination of at least two thereof.
Preferably, the surfactant is sodium dodecylbenzenesulfonate.
Preferably, the cosolvent is a mixed solution of glycerol, glycol and isopropanol in a mass ratio of (1-3) to (5-8) to (3-8);
wherein "1-3" can be, for example, 1, 1.5, 2, 2.5, 3, etc., and "5-8" can be, for example, 5, 5.5, 6, 6.5, 7, 7.5, 8, etc.; "3-8" can be, for example, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, etc.
Preferably, in the step (3), the dyeing treatment is specifically: and (3) immersing the retanned leather into the dye solution containing the antibacterial agent, performing negative pressure treatment, and then performing negative pressure drying to obtain the antibacterial, mildewproof and antiviral leather.
Preferably, in the step (3), the mass ratio of the retanned leather to the dye liquor containing the antibacterial agent is 1 (1-3), and can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3 and the like.
Preferably, in step (3), the pressure of the negative pressure treatment is 20 to 40kPa, such as 20kPa, 22kPa, 24kPa, 26kPa, 28kPa, 30kPa, 32kPa, 34kPa, 36kPa, 38kPa, 40kPa, etc., the time of the negative pressure treatment is 30 to 60min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc., and the temperature of the negative pressure treatment is 30 to 40 ℃, such as 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, etc.
Preferably, in the step (3), the pressure of the negative pressure drying is 10 to 15kPa, such as 10kPa, 11kPa, 12kPa, 13kPa, 14kPa, 15kPa, etc., the time of the negative pressure drying is 5 to 20min, such as 5min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, etc., and the temperature of the negative pressure drying is 65 to 80 ℃, such as 65 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, etc.
In a second aspect, the invention provides leather, and the leather is prepared by the preparation method of the antibacterial, mildewproof and antiviral leather.
In a third aspect, the present invention provides a belt manufactured from the leather of the second aspect.
The leather obtained by the preparation method of the invention is continuously subjected to the working procedures of subsequent edging and finishing, greasing, drying, softening, coating, punching and assembling, and finally the finished product of the antibacterial, mildewproof and antiviral belt is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) the main preparation process of the invention is that in the tanning and retanning processes of leather, a proper amount of antibacterial component is added into tanning agent, and firstly, the leather is given antibacterial, mildewproof and antiviral treatment from the inside; then negative pressure treatment is carried out in the dyeing process, so that not only are antibacterial ions loaded on the belt color layer, but also the antibacterial ions permeate into the leather of the belt, and the antibacterial ions can be slowly released from the inside of the belt in the long-term use process of the belt, so that the belt achieves the long-term antibacterial, mildewproof and antiviral effects;
(2) the antibacterial, mildewproof and antiviral belt 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 following preparations and examples have the following sources of the components: chrome tanning agent was purchased from (Chromosal B, alkalinity 33%, Cr2O3Chrome tanning agent with a content of 26%, purchased from langerhans), retanning agent from (manufacturer: shandong Li Ning New materials Co., Ltd, trade name: RVL acrylic resin retanning agent), waterborne acrylic resin purchased from (manufacturer: baiton, mark: BD-8334), aqueous polyurethane resins available from (manufacturer: yongyuxin material and brand number: AJS-6001), polyethylene glycol-400 (manufacturer: sanbang chemical south china limited), polyethylene wax was purchased from (manufacturer: craine, brand: 9615A) Dyes are commercially available from (azo dyes 12225-21-7, manufacturer: shandong Kuoquan Biotech Co., Ltd.), silicone oil was purchased from (amino silicone oil 63148-62-0, manufacturer: ningbo Yongfront chemical Co., Ltd.).
Preparation example 1
The preparation example provides a dye liquor containing an antibacterial agent, and the preparation method of the dye liquor containing the antibacterial agent comprises the following steps:
(1) mixing 6 parts of polyethylene glycol-400, 5 parts of polyethylene wax, 20 parts of dye, 3 parts of organic silicone oil, 2 parts of sodium dodecyl benzene sulfonate, 18 parts of ethylene glycol ethyl ether, 2 parts of glycerol, 6 parts of ethylene glycol and 6 parts of isopropanol, heating to 50 ℃, and adding 9 parts of waterborne acrylic resin and 12 parts of waterborne polyurethane resin to obtain a mixed solution A; mixing 5 parts of silver acetate and 40-50 parts of water to obtain a mixed solution B;
(2) and mixing the mixed solution A and the mixed solution B, and uniformly stirring to obtain the dye solution containing the antibacterial agent.
Preparation example 2
This preparation example provides an antibacterial agent-containing dye solution, which is different from preparation example 1 only in that 5 parts of silver acetate is replaced with 5 parts of zinc acetate, and the contents of other components and preparation method are the same as those of preparation example 1.
Comparative preparation example 1
The comparative preparation example provides a dye solution, and is different from the preparation example 1 only in that silver acetate is not added in the dye solution, and the contents of other components and the preparation method are the same as the preparation example 1.
Comparative preparation example 2
The comparative preparation example provides a dye solution which is different from the preparation example 1 only in that 5 parts of silver acetate is replaced by 5 parts of dimethyldiallylammonium chloride, and the contents of other components and the preparation method are the same as the preparation example 1.
Example 1
The embodiment provides a preparation method of antibacterial, mildewproof and antiviral leather, which comprises the following steps:
(1) tanning: putting 100 parts of leather into a rotary drum, soaking the leather into 200 parts of tanning liquid containing an antibacterial agent, and tanning for 9 hours at 40 ℃, wherein the tanning liquid containing the antibacterial agent comprises the following components in parts by weight: 2 parts of silver acetate, 3 parts of chrome tanning agent, 0.2 part of formic acid and 100 parts of water, wherein the pH value is 4.0;
(2) retanning: putting tanned leather into a rotary drum, immersing the leather into 200 parts of retanning liquid containing an antibacterial agent, and performing retanning treatment for 9 hours at 32 ℃, wherein the retanning liquid containing the antibacterial agent comprises the following components in parts by weight: 2 parts of silver acetate, 1 part of zinc acetate, 2 parts of retanning agent and 100 parts of water;
(3) dyeing: and (2) immersing the retanned leather into the dye solution containing the antibacterial agent, performing negative pressure treatment for 40min at 35 ℃ under 30kPa, and then performing negative pressure drying at 75 ℃ under 12kPa to obtain the antibacterial, mildewproof and antiviral leather, wherein the dye solution containing the antibacterial agent is the dye solution containing the antibacterial agent provided in preparation example 1.
Example 2
The embodiment provides a preparation method of antibacterial, mildewproof and antiviral leather, which comprises the following steps:
(1) tanning: putting 100 parts of leather into a rotary drum, soaking the leather into 300 parts of tanning liquid containing an antibacterial agent, and tanning for 9 hours at 40 ℃, wherein the tanning liquid containing the antibacterial agent comprises the following components in parts by weight: 3 parts of zinc acetate, 2 parts of chrome tanning agent, 0.2 part of formic acid and 100 parts of water, wherein the pH value is 4.0;
(2) retanning: putting tanned leather into a rotary drum, immersing the leather into 200 parts of retanning liquid containing an antibacterial agent, and performing retanning treatment for 9 hours at 32 ℃, wherein the retanning liquid containing the antibacterial agent comprises the following components in parts by weight: 1 part of silver acetate, 1 part of zinc acetate, 3 parts of retanning agent and 100 parts of water;
(3) dyeing: and (2) immersing the retanned leather into the dye solution containing the antibacterial agent, performing negative pressure treatment for 50min at the temperature of 30 ℃ under the condition of 25kPa, and then performing negative pressure drying at the temperature of 70 ℃ under the condition of 14kPa to obtain the antibacterial, mildewproof and antiviral leather, wherein the dye solution containing the antibacterial agent is the dye solution containing the antibacterial agent provided in preparation example 1.
Example 3
This example provides a method for producing antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial agent-containing dye liquor provided in preparation example 1 in step (3) is replaced with the antibacterial agent-containing dye liquor provided in preparation example 2, and the other preparation steps are the same as example 1.
Example 4
This example provides a method for preparing antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the pressure of the negative pressure treatment in step (3) is 20kPa, the time of the negative pressure treatment is 60min, the temperature of the negative pressure treatment is 30 ℃, and other preparation steps are the same as example 1.
Example 5
The present embodiment provides a method for preparing antibacterial, mildewproof and antiviral leather, which is different from embodiment 1 only in that the pressure of the negative pressure treatment in step (3) is 40kPa, the time of the negative pressure treatment is 30min, the temperature of the negative pressure treatment is 40 ℃, and other preparation steps are the same as embodiment 1.
Example 6
The present example provides a method for preparing antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the pressure of the negative pressure treatment in step (3) is 15kPa, the time of the negative pressure treatment is 80min, and other preparation steps are the same as example 1.
Example 7
The embodiment provides a preparation method of antibacterial, mildewproof and antiviral leather, which is different from the embodiment 1 only in that the pressure of the negative pressure drying in the step (3) is 10kPa, the time of the negative pressure drying is 20min, the temperature of the negative pressure drying is 65 ℃, and other preparation steps are the same as the embodiment 1.
Example 8
The embodiment provides a preparation method of antibacterial, mildewproof and antiviral leather, which is different from the embodiment 1 only in that the pressure of the negative pressure drying in the step (3) is 15kPa, the time of the negative pressure drying is 5min, the temperature of the negative pressure drying is 80 ℃, and other preparation steps are the same as the embodiment 1.
Example 9
The present embodiment provides a method for preparing antibacterial, mildewproof and antiviral leather, which is different from embodiment 1 only in that the pressure of the negative pressure drying in step (3) is 5kPa, the time of the negative pressure drying is 30min, and other preparation steps are the same as embodiment 1.
Example 10
The embodiment provides a preparation method of antibacterial, mildewproof and antiviral leather, which comprises the following steps:
(1) tanning: putting 100 parts of leather into a rotary drum, soaking the leather into 200 parts of tanning liquid containing an antibacterial agent, and tanning for 9 hours at 40 ℃, wherein the tanning liquid containing the antibacterial agent comprises the following components in parts by weight: 2 parts of silver acetate, 3 parts of chrome tanning agent, 0.2 part of formic acid and 100 parts of water, wherein the pH value is 4.0;
(2) retanning: putting tanned leather into a rotary drum, immersing the leather into 200 parts of retanning liquid containing an antibacterial agent, and performing retanning treatment for 9 hours at 32 ℃, wherein the retanning liquid containing the antibacterial agent comprises the following components in parts by weight: 3 parts of silver acetate, 2 parts of retanning agent and 100 parts of water;
(3) dyeing: and (2) immersing the retanned leather into the dye solution containing the antibacterial agent, soaking for 60min at 35 ℃ under normal pressure, and drying at 75 ℃ under normal pressure to obtain the antibacterial, mildewproof and antiviral leather, wherein the dye solution containing the antibacterial agent is the dye solution containing the antibacterial agent provided in preparation example 1.
Comparative example 1
The present comparative example provides a method for preparing antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial agent-containing dye liquor provided in preparation example 1 in step (3) is replaced with the antibacterial agent-containing dye liquor provided in comparative preparation example 1 in equal mass, and the other preparation steps are the same as example 1.
Comparative example 2
The present comparative example provides a method for preparing antibacterial, antifungal and antiviral leather, which is different from example 1 only in that the antibacterial agent-containing dye liquor provided in preparation example 1 in step (3) is replaced with the antibacterial agent-containing dye liquor provided in comparative preparation example 1 in equal mass, and the other preparation steps are the same as example 1.
Comparative example 3
The comparative example provides a preparation method of antibacterial, mildewproof and antiviral leather, and the difference from the example 1 is that in the step (1) tanning, silver acetate is not added in the tanning solution, and other preparation steps are the same as the example 1.
Comparative example 4
The comparative example provides a preparation method of antibacterial, mildewproof and antiviral leather, which is different from the preparation method of the example 1 only in that in the step (2), silver acetate and zinc acetate are not added into the retanning liquid any more, and other preparation steps are the same as the preparation method of the example 1.
Application example 1
This application example provides a belt prepared from the leather provided in example 1 by the following process:
(a) edging and finishing: adopting an edge grinding machine to carry out edge grinding and finishing on the leather provided by the embodiment 1;
(b) fat liquoring: weighing 100g of the leather obtained in the step (a), adding 100g of water, adding 4g of phospholipid fatting agent and 1g of formic acid, and rotating at the speed of 10 revolutions per minute for 60min at 50 ℃ in a rotating drum;
(c) and (3) drying: discharging and stacking, and controlling water at 25 ℃ for 24 hours;
(d) softening: sheathing the dried leather with a protective bag, and then putting the leather into a milling drum to mill for 3 hours at 12 revolutions per minute;
(e) coating: ironing, finishing and coating the softened belt;
(f) punching: carrying out macropore on the belt obtained by coating;
(g) assembling: and (4) selecting a belt buckle for assembling to obtain the finished antibacterial, mildewproof and antiviral belt.
Application examples 2 to 10
The application examples 2 to 10 differ from the application example 1 only in that the leathers provided in example 1 were replaced with the leathers provided in the corresponding examples 2 to 10, respectively.
Application comparative examples 1 to 4
Application examples comparative examples 1 to 4 differ from application example 1 only in that the leathers provided in example 1 were replaced with the leathers provided in corresponding comparative examples 1 to 4, respectively.
And (3) performance testing:
the belts provided in the application examples 1-10 and the belts provided in the application comparative examples 1-4 are respectively tested for the antibacterial rate, the mildew-proof grade and the antiviral property of escherichia coli and staphylococcus aureus before and after 3 months of use, 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 1:
TABLE 1
As can be seen from the test data in Table 1, the antibacterial, mildewproof and antiviral belt has the antibacterial rate of over 99 percent for bacteria such as large intestine, staphylococcus aureus and the like, the antiviral activity rate of over 99 percent for viruses such as H1N1, H3N2 and the like, and the mildewproof grade is 0. The main preparation process is that in the tanning and retanning process of leather, proper amount of antibacterial component is added into the chrome tanning agent to make part of antibacterial ions permeate between connected collagen molecules in the connection process of leather fiber collagen, and the leather is firstly given with antibacterial, mildewproof and antiviral treatment from the inside. The antibacterial treatment process for the leather surface layer comprises the steps of adding an antibacterial component into a coloring agent, then loading antibacterial ions on a belt color layer under the condition of negative pressure heating, enabling the antibacterial ions to permeate into the leather of the belt, and slowly releasing the antibacterial ions from the inside of the belt in the long-term use process of the belt, so that the belt achieves the long-term antibacterial, mildewproof and antiviral effects.
As is clear from comparison between application example 1 and application example 6, it is difficult to improve the antibacterial effect even if the pressure of the negative pressure treatment is too low or the time is prolonged. As can be seen from comparison between application example 1 and application example 9, it is difficult to improve the antibacterial effect even if the negative pressure drying pressure is too low or the time is prolonged. As can be seen from a comparison between application examples 1 and 10, the antibacterial agent and the leather can be more firmly bonded by performing the negative pressure treatment and the negative pressure drying, and the antibacterial, antifungal and antiviral effects can be further improved.
As can be seen from the comparison between application example 1 and application comparative examples 1, 3 and 4, the leather treated without adding an antibacterial agent in any one step of dyeing, tanning or retanning has poor antibacterial effect and does not have lasting antibacterial, mildewproof and antiviral effects. As can be seen from the comparison between the application example 1 and the application comparative example 2, the silver antibacterial agent is replaced by the quaternary ammonium salt antibacterial agent during dyeing, although the antibacterial effect of the leather treated without the antibacterial agent is obviously improved, the lasting antibacterial, mildewproof and antiviral effects are still poor.
The applicant states that the invention is described in the above examples to illustrate the preparation method of antibacterial, mildewproof and antiviral leather, leather and belt, but the invention is not limited to the above examples, i.e. the invention is not limited to 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 (10)
1. The preparation method of the antibacterial, mildewproof and antiviral leather is characterized by comprising the following steps:
(1) tanning: putting leather into tanning liquid containing an antibacterial agent for tanning treatment;
(2) retanning: putting the tanned leather into retanning liquid containing an antibacterial agent for retanning treatment;
(3) dyeing: and (3) placing the retanned leather in a dye solution containing an antibacterial agent for dyeing treatment to obtain the antibacterial, mildewproof and antiviral leather.
2. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 1, wherein in the steps (1), (2) and (3), the antibacterial agents are respectively and independently selected from silver salt and/or zinc salt;
preferably, the silver salt is selected from silver acetate and/or silver nitrate;
preferably, the zinc salt is selected from any one of zinc acetate, zinc nitrate or zinc sulfate or a combination of at least two thereof.
3. The method for preparing antibacterial, mildewproof and antiviral leather according to claim 1 or 2, wherein in the step (1), the tanning liquid containing the antibacterial agent comprises the following components in parts by weight: 0.5-10 parts of antibacterial agent, 1-5 parts of chrome tanning agent, 0.1-0.5 part of acid and 80-120 parts of water;
preferably, the acid is formic acid and/or acetic acid;
preferably, the pH of the antiseptic containing tanning liquor is between 3.5 and 4.5.
4. The method for preparing the antibacterial, mildewproof and antiviral leather according to any one of claims 1 to 3, wherein in the step (1), the leather and the tanning liquid containing the antibacterial agent are in a mass ratio of 1 (1-10);
preferably, in the step (1), the temperature of the tanning treatment is 38-45 ℃, and the time of the tanning treatment is 8-10 h.
5. The method for preparing antibacterial, mildewproof and antiviral leather according to any one of claims 1 to 4, wherein in the step (2), the retanning liquid of the antibacterial agent comprises the following components in parts by weight: 0.5-10 parts of antibacterial agent, 1-5 parts of retanning agent and 80-120 parts of water;
preferably, the retanning agent is selected from any one of or a combination of at least two of a melamine retanning agent, a dihydroamine retanning agent, an acrylic resin retanning agent or a multi-metal retanning agent.
6. The method for preparing antibacterial, mildewproof and antiviral leather according to any one of claims 1 to 5, wherein in the step (2), the mass ratio of the tanned leather to the retanning liquid containing the antibacterial agent is 1 (1-3);
preferably, in the step (2), the temperature of the retanning treatment is 30-35 ℃, and the time of the retanning treatment is 8-10 h.
7. The method for preparing antibacterial, mildewproof and antiviral leather according to any one of claims 1 to 6, wherein in the step (3), the dye liquor containing the antibacterial agent comprises the following components in parts by weight: 2-8 parts of an antibacterial agent, 7-12 parts of waterborne acrylic resin, 10-15 parts of waterborne polyurethane resin, 5-8 parts of polyethylene glycol, 3-6 parts of polyethylene wax, 15-25 parts of dye, 2-4 parts of organic silicone oil, 1-3 parts of a surfactant, 15-20 parts of ethylene glycol ethyl ether, 8-24 parts of a cosolvent and 40-50 parts of water;
preferably, the number average molecular weight of the polyethylene glycol is 200-1000;
preferably, the dye is selected from any one of azo dyes, arylmethane dyes or phthalocyanine dyes or a combination of at least two of the dyes;
preferably, the surfactant is sodium dodecylbenzenesulfonate;
preferably, the cosolvent is a mixed solution of glycerol, glycol and isopropanol in a mass ratio of (1-3) to (5-8) to (3-8).
8. The method for preparing antibacterial, mildewproof and antiviral leather according to any one of claims 1 to 7, wherein in the step (3), the dyeing treatment is specifically as follows: immersing the retanned leather into the dye solution containing the antibacterial agent, performing negative pressure treatment, and then performing negative pressure drying to obtain the antibacterial, mildewproof and antiviral leather;
preferably, in the step (3), the mass ratio of the retanned leather to the dye liquor containing the antibacterial agent is 1 (1-3);
preferably, in the step (3), the pressure of the negative pressure treatment is 20-40kPa, the time of the negative pressure treatment is 30-60min, and the temperature of the negative pressure treatment is 30-40 ℃;
preferably, in the step (3), the pressure of the negative pressure drying is 10-15kPa, the time of the negative pressure drying is 5-20min, and the temperature of the negative pressure drying is 65-80 ℃.
9. Leather produced by the method for producing antibacterial, mildewproof and antiviral leather according to any one of claims 1 to 8.
10. A belt, characterized in that it is manufactured from the leather according to claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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| CN106222328A (en) * | 2016-08-31 | 2016-12-14 | 四川大学 | A kind of manufacture method of durable antibiotic antibacterial type leather |
| CN107312895A (en) * | 2017-08-04 | 2017-11-03 | 海宁森德皮革有限公司 | A kind of production method of negative oxygen ion multi-purpose vehicle(MPV) interior trim leather |
| CN107354245A (en) * | 2017-08-15 | 2017-11-17 | 宁夏成丰农业科技开发股份有限公司 | A kind of improved tibet lamp cleanly production technique |
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|---|---|---|---|---|
| CN106222328A (en) * | 2016-08-31 | 2016-12-14 | 四川大学 | A kind of manufacture method of durable antibiotic antibacterial type leather |
| CN107312895A (en) * | 2017-08-04 | 2017-11-03 | 海宁森德皮革有限公司 | A kind of production method of negative oxygen ion multi-purpose vehicle(MPV) interior trim leather |
| CN107354245A (en) * | 2017-08-15 | 2017-11-17 | 宁夏成丰农业科技开发股份有限公司 | A kind of improved tibet lamp cleanly production technique |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
| CN117701787B (en) * | 2024-02-02 | 2024-05-03 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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Application publication date: 20210402 |