CN117701787B - Manufacturing method of antibacterial and bacteriostatic sofa leather - Google Patents
Manufacturing method of antibacterial and bacteriostatic sofa leather Download PDFInfo
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- CN117701787B CN117701787B CN202410145523.9A CN202410145523A CN117701787B CN 117701787 B CN117701787 B CN 117701787B CN 202410145523 A CN202410145523 A CN 202410145523A CN 117701787 B CN117701787 B CN 117701787B
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- leather
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- solution
- rotary drum
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- 239000010985 leather Substances 0.000 title claims abstract description 234
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 230000003385 bacteriostatic effect Effects 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 61
- 238000000576 coating method Methods 0.000 claims abstract description 61
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005498 polishing Methods 0.000 claims abstract description 54
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical class NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- 238000005238 degreasing Methods 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005554 pickling Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 239000000243 solution Substances 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 238000011282 treatment Methods 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 102000004190 Enzymes Human genes 0.000 claims description 15
- 108090000790 Enzymes Proteins 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 239000005028 tinplate Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000005018 casein Substances 0.000 claims description 13
- 235000021240 caseins Nutrition 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003242 anti bacterial agent Substances 0.000 claims description 12
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000008213 purified water Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- 102000004142 Trypsin Human genes 0.000 claims description 6
- 108090000631 Trypsin Proteins 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 claims description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 6
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- 239000012588 trypsin Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000004367 Lipase Substances 0.000 claims description 5
- 102000004882 Lipase Human genes 0.000 claims description 5
- 108090001060 Lipase Proteins 0.000 claims description 5
- 108091005804 Peptidases Proteins 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000004203 carnauba wax Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000019421 lipase Nutrition 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 150000003457 sulfones Chemical class 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000004365 Protease Substances 0.000 claims description 2
- 235000013869 carnauba wax Nutrition 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims 1
- 239000011527 polyurethane coating Substances 0.000 abstract description 10
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000006124 Pilkington process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 241000588724 Escherichia coli Species 0.000 description 10
- 241000191967 Staphylococcus aureus Species 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- 102000035195 Peptidases Human genes 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 235000019833 protease Nutrition 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
- C14C13/00—Manufacture of special kinds or leather, e.g. vellum
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/44—Mechanical treatment of leather surfaces
- C14B1/50—Glazing
-
- 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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to the technical field of leather, in particular to a manufacturing method of antibacterial and bacteriostatic sofa leather. The manufacturing method of the antibacterial and bacteriostatic sofa leather comprises the following steps: treating leather; coating the modified casein solution on the degreasing leather; pickling and softening leather; tanning leather; preparing an antibacterial coating material; polishing and grinding the coating by a float process; and (5) secondary polishing. According to the invention, the nano silver solution is diluted by acetone and compounded into the polyurethane coating prepared by the PU prepolymer, the nano silver has good antibacterial performance, the modified aqueous polyurethane solution obtained by compounding the nano silver solution and the polyurethane solution has good antibacterial and bacteriostatic capabilities, the polyurethane coating has good wear resistance, a layer of antibacterial coating is coated on the leather in the leather soaking process, and a layer of polyurethane coating is coated on the leather surface for improving the wear resistance, so that the polyurethane coating can better protect the antibacterial coating and improve the antibacterial performance of sofa leather.
Description
Technical Field
The invention relates to the technical field of leather, in particular to a manufacturing method of antibacterial and bacteriostatic sofa leather.
Background
The leather is a main raw material for manufacturing leather sofa, and is used for manufacturing the surface of the sofa, and the leather is mainly made of cowhide, PU leather, PVC vamp leather and the like, and has the advantages of being firm and durable, being well cleaned while being luxurious and being in the atmosphere, and being popular among the public. However, leather is obtained by a series of treatments with animal fur, and thus if the treatments are insufficient in the early stage of producing the leather or the washing is not frequent in the later stage, a skin odor is easily generated.
The odor of the leather sofa is mainly caused by the fact that bacteria on the surface layer of the sofa gather and multiply under the condition that the leather sofa is used for a long time and cleaning is not noticed, so that bad odor is generated, the odor is stopped, the cleaning frequency is required to be noticed, or the preparation method of the antibacterial and bacteriostatic sofa leather is provided, and the prior art problems of the leather sofa are solved.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a manufacturing method of antibacterial and bacteriostatic sofa leather.
The manufacturing method of the antibacterial and bacteriostatic sofa leather specifically comprises the following steps:
S1: leather treatment
Soaking the peltry in enough purified water capable of immersing the leather to obtain presoaked leather, putting the presoaked leather into a rotary drum for treatment, spraying enzyme treatment liquid on the surface of the presoaked leather in the rotary working process of the rotary drum, taking out after degreasing, and cleaning with purified water to obtain degreased leather;
S2: coating the modified casein solution on the degreasing leather
Mixing and stirring the nano silver solution and acetone until the nano silver solution is dissolved, performing ultrasonic dispersion to obtain nano silver dispersion, adding casein into a reaction bottle, heating in a water bath at 70-80 ℃, adding borax, stirring until the casein is completely dissolved, adding AEO-9, stirring uniformly, then dropwise adding a mixed initiator into the reaction bottle, performing constant-temperature stirring reaction, mixing the nano silver dispersion and the mixed initiator, dropwise adding the mixture into the reaction bottle, finally performing heat preservation for 2.5-3h to obtain nano Ag/DAAM double-modified casein solution, coating the nano Ag/DAAM double-modified casein solution on the surface of the defatted leather, forming a layer of film on the surface of the defatted leather after the nano Ag/DAAM double-modified casein solution is solidified in an oven, and obtaining leather with a film;
s3: pickling and softening leather
Immersing the leather with the film into the mixed acid solution and cleaning, then adding the leather with the film after pickling into a rotary drum again, adding the mixed acid solution with the same volume to obtain treated leather, and softening the treated leather with trypsin at 30-35 ℃ to obtain softened leather;
S4: tanning leather
Adding softened leather into aqueous solution of sodium chloride, rotating a rotary drum, adding sodium bicarbonate to adjust pH, adding sodium lignin sulfonate into the rotary drum for three times, washing with water, adding aluminum sulfate and sodium citrate into the rotary drum, adjusting with sodium bicarbonate, and finally discharging and drying to obtain tanned leather;
s5: preparation of antibacterial coating material
Adding polytetrahydrofuran ether, a hydrophilic chain extender DMPA, BDO, PDMS and an initiator DBTDL into a reaction box to obtain a PU prepolymer, adding the nano silver dispersion prepared in the step S2 into the reaction box, adding triethylamine to neutralize the nano silver dispersion into salt, stirring the obtained prepolymer at a high speed at normal temperature, decompressing the prepolymer through a decompression valve to evaporate acetone, obtaining modified aqueous polyurethane emulsion in the reaction box, dividing the modified aqueous polyurethane emulsion into two parts with equal volume, heating one part to 80-90 ℃, dropwise adding a reaction mixture, reacting for 2.5-3 hours, adding KPS to react for 10-30 minutes, obtaining a composite antibacterial agent after the reaction is completed, placing tanned leather into the composite antibacterial agent, soaking for 4-6 hours, then vacuum drying, coating the other part of modified aqueous polyurethane emulsion on the surface of tanned leather, and placing the leather at room temperature for 24-48 hours to obtain a coating;
S6: float polishing and grinding coating
Immersing a tin plate and coated leather into the polishing solution, setting the pressure of a grinding head to be 0.3-0.6MPa, enabling the tin plate to coil a main shaft at 100-200r/min, enabling the coated leather to rotate on the tin plate around the main shaft at a rotating speed of 200-300r/min, continuously polishing for 20-30min, and repeatedly polishing for 1-2 times to obtain polished leather;
S7: secondary polishing
And cleaning the surface of the polished leather by using a sponge, uniformly coating a layer of polishing emulsion on the surface of the polished leather, uniformly coating the polished leather by using the sponge, and standing at room temperature for 1-2min to obtain the antibacterial and bacteriostatic sofa leather.
Further, step S2 coats the modified casein solution on the defatted leather, specifically comprising the steps of:
s2.1: 100-120ug/ml nano silver solution is mixed according to the volume ratio of 1: (1-2) mixing and stirring with acetone until the mixture is dissolved, and then performing ultrasonic dispersion for 10-30min to obtain nano silver dispersion;
s2.2: adding 100-120 parts of casein into a reaction bottle, heating in a water bath to 70-80 ℃, adding borax, stirring until the casein is completely dissolved, adding 0.2-0.5 part of AEO-9, uniformly stirring, dissolving 0.5-1 part of mixed initiator into 2-3 parts of deionized water to obtain an initiator aqueous solution, taking one third, dripping into the reaction bottle, and stirring at constant temperature for reaction for 25-30min;
S2.3: mixing the nano silver dispersion liquid with the rest two-thirds initiator aqueous solution, dropwise adding the mixture into a reaction bottle for 30-35min, raising the temperature to 55-60 ℃ during dropwise adding, synchronously evaporating acetone after dropwise adding, raising the temperature to 75-80 ℃, and preserving heat for 2.5-3h to obtain a nano Ag/DAAM double-modified casein solution;
s2.4: coating the nano Ag/DAAM double-modified casein solution on the surface of the degreasing leather, standing for 10-15min, forming a layer of film on the surface of the degreasing leather by the nano Ag/DAAM double-modified casein solution, and then drying in a drying oven at 50-55 ℃ for 5-10min for curing to obtain the leather with the film.
Further, the step S3 of pickling and softening the leather specifically comprises the following steps:
S3.1: cleaning the leather with the film for 1-2 times by purified water, removing surface floating dust, immersing the cleaned leather with the film into mixed acid liquid, wherein the volume ratio of the total volume of the mixed acid liquid to the volume of the degreasing leather is 1: (0.5-0.6);
S3.2: setting the temperature of a rotary drum to be 20-24 ℃, adding the pickled leather with the film into the rotary drum, adding mixed acid liquid with the same volume, setting the rotary drum to rotate for 20-30min, adding 8-10 times of cold water from the shaft hole of the rotary drum to dilute the mixed acid liquid, and keeping the rotary drum to rotate for 120-180min, so that the pH value of the reaction liquid in the rotary strand is adjusted to 3-3.2, and obtaining the treated leather;
s3.3: softening the treated leather with trypsin at 30-35 ℃ and adjusting pH to 7.5-8.5 by NaOH for 6-8h to obtain the softened leather.
Further, step S5 prepares an antibacterial coating material, specifically comprising the steps of:
S5.1: adding 1-2 parts of polytetrahydrofuran ether, 0.5-1 part of hydrophilic chain extender DMPA, 1-1.2 parts of BDO, 1-1.2 parts of PDMS and 0.5-1 part of initiator DBTDL into a reaction box, dropwise adding IPDI at the speed of 1-3 drops/s under the protection of dry nitrogen at the temperature of 80-90 ℃ and keeping the dropwise adding reaction for 4-5 hours to obtain PU prepolymer;
S5.2: adding 1-2 parts of nano silver mixed solution into a reaction box, then cooling the reaction box to 50-60 ℃, adding 3-5 times of acetone solution into the reaction box for dilution, and standing the reaction box until the temperature in the reaction box is reduced to 40-50 ℃;
S5.3: adding triethylamine into a reaction box for neutralization and salifying, finally stirring the obtained prepolymer at a high speed at normal temperature, and reducing pressure through a pressure reducing valve to reduce the boiling point of acetone and remove the acetone by evaporation, thereby obtaining modified aqueous polyurethane emulsion in the reaction box;
s5.4: dividing the modified aqueous polyurethane emulsion into two parts with equal volume, heating one part to 80-90 ℃, dropwise adding a reaction mixture, reacting for 2.5-3h, finally adding KPS, reacting for 10-30min, and obtaining the composite antibacterial agent after the reaction is complete;
S5.5: placing tanned leather in a composite antibacterial agent, wherein the solid-to-liquid ratio is 1: (15-20), soaking for 4-5h, then vacuum drying, coating another part of modified aqueous polyurethane emulsion on the surface of tanned leather, and standing at room temperature for 24-48h to obtain the coated leather.
Further, the mixed initiator of step S2 is DAAM and APS initiator at 1:1-1.2 by volume ratio and is dissolved in deionized water.
Further, the enzyme treatment solution in the step S1 is obtained by mixing 40-50U/g of lipase JZ, 20-40U/g of protease JRH and 4-6U/g of saccharifying enzyme TH.
Further, the mixed acid liquid in the step S3 is prepared by mixing 40-60% of sulfone acid polymer and 0.4-0.6% of formic acid in a ratio of 1: (0.5-0.6) by volume ratio.
Further, the reaction mixture in step S5 is BA with MMA at 1: and (1-2) by mixing.
Further, the polishing liquid in step S6 is an alumina polishing liquid.
Further, the polishing emulsion in step S7 is a carnauba wax emulsion.
The beneficial effects are that: 1. according to the invention, the nano silver solution is diluted by acetone and compounded into the polyurethane coating prepared by the PU prepolymer, the nano silver has good antibacterial performance, the modified aqueous polyurethane solution obtained by compounding the nano silver solution and the polyurethane solution has good antibacterial and bacteriostatic capabilities, the polyurethane coating has good wear resistance, a layer of antibacterial coating is coated on the leather in the leather soaking process, and a layer of polyurethane coating is coated on the leather surface for improving the wear resistance, so that the polyurethane coating can better protect the antibacterial coating and improve the antibacterial performance of sofa leather.
2. According to the invention, the wear-resistant polyurethane coating on the leather surface is polished to be close to an ultra-smooth surface by using the float polishing, so that the coating surface is smoother, dust is prevented from gathering at the more used folds after long-time use, thus bacteria are prevented from gathering, the thickness of the coating polished by the float polishing method is smaller, the precision is higher, and the wear-resistant coating is not polished to expose the antibacterial coating due to excessive polishing, so that the antibacterial effect is achieved.
3. According to the invention, the leather is protected by coating the surface of the leather with a layer of nano Ag/DAAM double-modified casein solution before pickling and tanning, and forming a layer of film on the surface of the leather, so that the surface of the leather is not damaged by acidic substances in the pickling process, the leather surface can be smoother due to the pickling of the leather, the antibacterial coating can be conveniently coated on the leather surface, the film formed by the casein solution also has certain adhesiveness, the adhesion capability of the leather surface and the antibacterial coating can be improved, and the antibacterial coating and the leather are combined more tightly.
Drawings
Fig. 1 is a flowchart of a manufacturing method of an antibacterial and bacteriostatic sofa leather adopted in the embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The manufacturing method of the antibacterial and bacteriostatic sofa leather is shown in fig. 1, and specifically comprises the following steps:
S1: leather treatment
Soaking the peltry in pure water with enough quantity to submerge the leather for 20 hours, taking out the soaked peltry, drying at a low temperature of 60 ℃, dehairing, soaking for 12 hours again to obtain presoaked leather, putting the presoaked leather into a rotary drum for treatment for 90 minutes, setting the temperature of the rotary drum to be 40 ℃, spraying enzyme treatment liquid to the surface of the presoaked leather in the rotary operation of the rotary drum, wherein the enzyme treatment liquid is obtained by mixing lipase JZ with the concentration of 40U/g, proteinase JRH with the concentration of 20U/g and saccharifying enzyme TH with the concentration of 4U/g, and taking out the presoaked leather after degreasing is completed to obtain degreased leather;
S2: coating the modified casein solution on the degreasing leather
100Ug/ml nano silver solution is prepared according to the volume ratio of 1:1, mixing and stirring with acetone until the mixture is dissolved, and then performing ultrasonic dispersion for 10min to obtain nano silver dispersion;
adding 100 parts of casein into a reaction bottle, heating to 80 ℃ in a water bath, adding borax, stirring until the casein is completely dissolved, adding 0.2 part of AEO-9, uniformly stirring, dissolving 0.5 part of mixed initiator into 2 parts of deionized water to obtain an initiator aqueous solution, taking one third of the initiator aqueous solution, dropwise adding into the reaction bottle, and stirring at constant temperature for reaction for 30min;
mixing the nano silver dispersion liquid with the rest two-thirds initiator aqueous solution, dropwise adding the mixture into a reaction bottle for 30min, raising the temperature to 60 ℃ during dropwise adding, synchronously evaporating acetone after dropwise adding, raising the temperature to 80 ℃, and preserving the heat for 3h to obtain a nano Ag/DAAM double-modified casein solution;
coating the nano Ag/DAAM double-modified casein solution on the surface of the degreasing leather, standing for 10min, forming a layer of film on the surface of the degreasing leather by the nano Ag/DAAM double-modified casein solution, and then drying in a 50 ℃ oven for 5min for curing to obtain leather with a film;
s3: pickling and softening leather
Cleaning the leather with the membrane for 2 times by purified water, removing surface floating dust, immersing the cleaned leather with the membrane into mixed acid liquid which is mixed solution of 40 percent of sulfone acid polymer and 0.4 percent of formic acid, and mixing the mixed acid liquid with 1:0.5, and the volume ratio of the total volume of the mixed acid solution to the degreasing leather is 1:0.6;
setting the temperature of a rotary drum to 20 ℃, adding the pickled leather with the film into the rotary drum, adding mixed acid liquid with the same volume, setting the rotary drum to rotate for 30min, adding 10 times of cold water from the shaft hole of the rotary drum to dilute the mixed acid liquid, and keeping the rotary drum to rotate for 120min, so that the pH value of the reaction liquid in the rotary strand is adjusted to 3, and obtaining the treated leather;
the treated leather was softened with trypsin at 30 ℃ and pH was adjusted to 8.5 with NaOH for 8 hours to give a softened leather.
S4: tanning leather
Adding softened leather into 5% sodium chloride water solution, rotating the drum for 60min, and adding sodium bicarbonate to adjust pH to 6;
Firstly adding 2% sodium lignin sulfonate into a rotary drum, rotating the rotary drum for 60min, then adding 4% sodium lignin sulfonate, rotating the rotary drum for 120min, adding 6% sodium lignin sulfonate for the third time, stopping the drum, standing for 24h, rotating for 30min, then washing with water for 2 times, adding 3% aluminum sulfate into the rotary drum, rotating for 120min, adding 3% sodium citrate, rotating for 120min, regulating pH to 6 with sodium bicarbonate, rotating for 120min, discharging the drum, and drying to obtain tanned leather.
S5: preparation of antibacterial coating material
Adding 1 part of polytetrahydrofuran ether, 0.5 part of hydrophilic chain extender DMPA, 1 part of BDO, 1 part of PDMS and 0.5 part of initiator DBTDL into a reaction box, dropwise adding IPDI at a speed of 1 drop/s under the protection of dry nitrogen at a temperature of 80 ℃, and keeping the dropwise adding reaction for 4 hours to obtain a PU prepolymer;
Adding 1 part of nano silver mixed solution into a reaction box, then cooling the reaction box to 50 ℃, adding acetone solution with the volume being 3 times of that of the reaction box for dilution, and standing the reaction box until the temperature in the reaction box is reduced to 40 ℃;
adding triethylamine into a reaction box for neutralization and salifying, finally stirring the obtained prepolymer at a high speed at normal temperature, and reducing pressure through a pressure reducing valve to reduce the boiling point of acetone and remove the acetone by evaporation, thereby obtaining modified aqueous polyurethane emulsion in the reaction box;
Dividing the modified aqueous polyurethane emulsion into two parts with equal volume, heating one part to 80 ℃, and dropwise adding a reaction mixture, wherein the reaction mixture is prepared by mixing BA and MMA according to a ratio of 1:1, reacting for 3 hours, and finally adding KPS to react for 10 minutes, and obtaining the composite antibacterial agent after the reaction is complete;
Placing tanned leather in a composite antibacterial agent, wherein the solid-to-liquid ratio is 1:20, soaking for 4 hours, then vacuum drying, coating another part of modified aqueous polyurethane emulsion on the surface of tanned leather, and standing for 24 hours at room temperature to obtain coated leather.
S6: float polishing and grinding coating
The method comprises the steps of immersing a tin plate and coated leather into polishing liquid, wherein the polishing liquid is alumina polishing liquid, setting the pressure of a grinding head to be 0.3MPa, enabling the tin plate to be coiled around a main shaft to rotate at 100r/min, enabling the coated leather to rotate around a self shaft on the tin plate at a rotating speed of 200r/min, continuously polishing for 20min, and repeatedly polishing for 2 times to obtain polished leather.
S7: secondary polishing
And cleaning the surface of the polished leather by using a sponge, uniformly coating a layer of polishing emulsion on the surface of the polished leather, wherein the polishing emulsion is Brazil wax emulsion, uniformly coating the polishing emulsion by using the sponge, and standing at room temperature for 2min to obtain the antibacterial and bacteriostatic sofa leather.
Example 2
The manufacturing method of the antibacterial and bacteriostatic sofa leather is shown in fig. 1, and specifically comprises the following steps:
S1: leather treatment
Soaking the peltry in pure water with enough quantity to submerge the leather for 20 hours, taking out the soaked peltry, drying at a low temperature of 60 ℃, dehairing, soaking for 12 hours again to obtain presoaked leather, putting the presoaked leather into a rotary drum for treatment for 90 minutes, setting the temperature of the rotary drum to be 40 ℃, spraying enzyme treatment liquid to the surface of the presoaked leather in the rotary operation of the rotary drum, wherein the enzyme treatment liquid is obtained by mixing lipase JZ with the concentration of 40U/g, proteinase JRH with the concentration of 20U/g and saccharifying enzyme TH with the concentration of 4U/g, and taking out the presoaked leather after degreasing is completed to obtain degreased leather;
S2: coating the modified casein solution on the degreasing leather
120Ug/ml nano silver solution is prepared according to the volume ratio of 1:2, mixing and stirring with acetone until the mixture is dissolved, and then performing ultrasonic dispersion for 30min to obtain nano silver dispersion;
120 parts of casein is added into a reaction bottle, heated to 80 ℃ in a water bath, borax is added and stirred until the casein is completely dissolved, 0.5 part of AEO-9 is added and stirred uniformly, 1 part of mixed initiator is dissolved into 3 parts of deionized water to obtain an initiator aqueous solution, one third of the initiator aqueous solution is taken, the solution is dropwise added into the reaction bottle, and the reaction is carried out for 30min under constant temperature stirring;
mixing the nano silver dispersion liquid with the rest two-thirds initiator aqueous solution, dropwise adding the mixture into a reaction bottle for 30min, raising the temperature to 60 ℃ during dropwise adding, synchronously evaporating acetone after dropwise adding, raising the temperature to 80 ℃, and preserving the heat for 3h to obtain a nano Ag/DAAM double-modified casein solution;
Coating the nano Ag/DAAM double-modified casein solution on the surface of the degreasing leather, standing for 10min, forming a layer of film on the surface of the degreasing leather after the nano Ag/DAAM double-modified casein solution is dried in a baking oven at 50 ℃ for 5min for curing, and obtaining the leather with the film
S3: pickling and softening leather
Cleaning the degreasing leather with purified water for 2 times to remove surface floating dust, immersing the cleaned leather with the membrane into mixed acid liquid which is mixed solution of 60% of sulfone acid polymer and 0.6% of formic acid, and mixing the mixed acid liquid with 1:0.6, and the volume ratio of the total volume of the mixed acid solution to the degreasing leather is 1:0.5;
setting the temperature of a rotary drum to 20 ℃, adding the pickled leather with the film into the rotary drum, adding mixed acid liquid with the same volume, setting the rotary drum to rotate for 30min, adding 8 times of cold water from the shaft hole of the rotary drum to dilute the mixed acid liquid, and keeping the rotary drum to rotate for 120min, so that the pH value of the reaction liquid in the rotary strand is adjusted to 3.2, and obtaining the treated leather;
the treated leather was softened with trypsin at 30 ℃ and pH was adjusted to 8.5 with NaOH for 8 hours to give a softened leather.
S4: tanning leather
Adding softened leather into 5% sodium chloride water solution, rotating the drum for 60min, and adding sodium bicarbonate to adjust pH to 6;
Firstly adding 2% sodium lignin sulfonate into a rotary drum, rotating the rotary drum for 60min, then adding 4% sodium lignin sulfonate, rotating the rotary drum for 120min, adding 6% sodium lignin sulfonate for the third time, stopping the drum, standing for 24h, rotating for 30min, then washing with water for 2 times, adding 3% aluminum sulfate into the rotary drum, rotating for 120min, adding 3% sodium citrate, rotating for 120min, regulating pH to 6 with sodium bicarbonate, rotating for 120min, discharging the drum, and drying to obtain tanned leather.
S5: preparation of antibacterial coating material
Adding 2 parts of polytetrahydrofuran ether, 1 part of hydrophilic chain extender DMPA, 1.2 parts of BDO, 1.2 parts of PDMS and 1 part of initiator DBTDL into a reaction box, dropwise adding IPDI at a speed of 1 drop/s under the protection of dry nitrogen at a temperature of 80 ℃, and keeping the dropwise adding reaction for 4 hours to obtain a PU prepolymer;
adding 2 parts of nano silver mixed solution into a reaction box, then cooling the reaction box to 50 ℃, adding acetone solution with the volume being 5 times of that of the reaction box for dilution, and standing the reaction box until the temperature in the reaction box is reduced to 40 ℃;
adding triethylamine into a reaction box for neutralization and salifying, finally stirring the obtained prepolymer at a high speed at normal temperature, and reducing pressure through a pressure reducing valve to reduce the boiling point of acetone and remove the acetone by evaporation, thereby obtaining modified aqueous polyurethane emulsion in the reaction box;
Dividing the modified aqueous polyurethane emulsion into two parts with equal volume, heating one part to 80 ℃, and dropwise adding a reaction mixture, wherein the reaction mixture is prepared by mixing BA and MMA according to a ratio of 1:1.2, reacting for 3 hours, and finally adding KPS to react for 10 minutes, and obtaining the composite antibacterial agent after the reaction is complete;
placing tanned leather in a composite antibacterial agent, wherein the solid-to-liquid ratio is 1:15, soaking for 4 hours, then vacuum drying, coating another part of modified aqueous polyurethane emulsion on the surface of tanned leather, standing for 24 hours at room temperature to obtain coated leather.
S6: float polishing and grinding coating
The method comprises the steps of immersing a tin plate and coated leather into polishing liquid, wherein the polishing liquid is alumina polishing liquid, setting the pressure of a grinding head to be 0.3MPa, enabling the tin plate to be coiled around a main shaft to rotate at 100r/min, enabling the coated leather to rotate around a self shaft on the tin plate at a rotating speed of 200r/min, continuously polishing for 20min, and repeatedly polishing for 2 times to obtain polished leather.
S7: secondary polishing
And cleaning the surface of the polished leather by using a sponge, uniformly coating a layer of polishing emulsion on the surface of the polished leather, wherein the polishing emulsion is Brazil wax emulsion, uniformly coating the polishing emulsion by using the sponge, and standing at room temperature for 2min to obtain the antibacterial and bacteriostatic sofa leather.
Example 3
The manufacturing method of the antibacterial and bacteriostatic sofa leather is shown in fig. 1, and specifically comprises the following steps:
S1: leather treatment
Soaking the peltry in pure water with enough quantity to submerge the leather for 20 hours, taking out the soaked peltry, drying at a low temperature of 60 ℃, dehairing, soaking for 12 hours again to obtain presoaked leather, putting the presoaked leather into a rotary drum for treatment for 90 minutes, setting the temperature of the rotary drum to be 40 ℃, spraying enzyme treatment liquid to the surface of the presoaked leather in the rotary operation of the rotary drum, wherein the enzyme treatment liquid is obtained by mixing lipase JZ with the concentration of 40U/g, proteinase JRH with the concentration of 20U/g and saccharifying enzyme TH with the concentration of 4U/g, and taking out the presoaked leather after degreasing is completed to obtain degreased leather;
S2: coating the modified casein solution on the degreasing leather
100Ug/ml nano silver solution is prepared according to the volume ratio of 1:1, mixing and stirring with acetone until the mixture is dissolved, and then performing ultrasonic dispersion for 30min to obtain nano silver dispersion;
Adding 100 parts of casein into a reaction bottle, heating to 70 ℃ in a water bath, adding borax, stirring until the casein is completely dissolved, adding 0.2 part of AEO-9, uniformly stirring, dissolving 0.5 part of mixed initiator into 2 parts of deionized water to obtain an initiator aqueous solution, taking one third of the initiator aqueous solution, dropwise adding into the reaction bottle, and stirring at constant temperature for reacting for 25min;
Mixing the nano silver dispersion liquid with the rest two-thirds initiator aqueous solution, dropwise adding the mixture into a reaction bottle, finishing the dropwise adding for 35min, raising the temperature to 55 ℃ during the dropwise adding, synchronously evaporating acetone when the dropwise adding is finished, raising the temperature to 75 ℃, and preserving the heat for 2.5h to obtain a nano Ag/DAAM double-modified casein solution;
coating the nano Ag/DAAM double-modified casein solution on the surface of the degreasing leather, standing for 15min, forming a layer of film on the surface of the degreasing leather after the nano Ag/DAAM double-modified casein solution is dried in a baking oven at 55 ℃ for 10min, and curing to obtain the leather with the film
S3: pickling and softening leather
Cleaning the degreasing leather with purified water for 2 times to remove surface floating dust, immersing the cleaned leather with the membrane into mixed acid liquid which is mixed solution of 40% of sulfone acid polymer and 0.4% of formic acid, and mixing the mixed acid liquid with 1:0.5, and the volume ratio of the total volume of the mixed acid solution to the degreasing leather is 1:0.6;
Setting the temperature of a rotary drum at 24 ℃, adding the pickled leather with the film into the rotary drum, adding mixed acid liquid with the same volume, setting the rotary drum to rotate for 20min, adding 10 times of cold water from the shaft hole of the rotary drum to dilute the mixed acid liquid, and keeping the rotary drum to rotate for 180min, so that the pH value of the reaction liquid in the rotary strand is adjusted to 3, and obtaining the treated leather;
The treated leather was softened with trypsin at 35 ℃ and pH was adjusted to 8.5 with NaOH for 6 hours to give a softened leather.
S4: tanning leather
Adding softened leather into 5% sodium chloride water solution, rotating the drum for 60min, and adding sodium bicarbonate to adjust pH to 6;
Firstly adding 2% sodium lignin sulfonate into a rotary drum, rotating the rotary drum for 60min, then adding 4% sodium lignin sulfonate, rotating the rotary drum for 120min, adding 6% sodium lignin sulfonate for the third time, stopping the drum, standing for 24h, rotating for 30min, then washing with water for 2 times, adding 3% aluminum sulfate into the rotary drum, rotating for 120min, adding 3% sodium citrate, rotating for 120min, regulating pH to 6 with sodium bicarbonate, rotating for 120min, discharging the drum, and drying to obtain tanned leather.
S5: preparation of antibacterial coating material
Adding 1 part of polytetrahydrofuran ether, 0.5 part of hydrophilic chain extender DMPA, 1 part of BDO, 1 part of PDMS and 0.5 part of initiator DBTDL into a reaction box, dropwise adding IPDI at a speed of 1 drop/s under the protection of dry nitrogen at a temperature of 90 ℃, and keeping the dropwise adding reaction for 5 hours to obtain a PU prepolymer;
Adding 1 part of nano silver mixed solution into a reaction box, then cooling the reaction box to 60 ℃, adding acetone solution with the volume being 3 times of that of the reaction box for dilution, and standing the reaction box until the temperature in the reaction box is reduced to 50 ℃;
adding triethylamine into a reaction box for neutralization and salifying, finally stirring the obtained prepolymer at a high speed at normal temperature, and reducing pressure through a pressure reducing valve to reduce the boiling point of acetone and remove the acetone by evaporation, thereby obtaining modified aqueous polyurethane emulsion in the reaction box;
Dividing the modified aqueous polyurethane emulsion into two parts with equal volume, heating one part to 90 ℃, and dropwise adding a reaction mixture of BA and MMA according to a ratio of 1:1, reacting for 2.5 hours, and finally adding KPS to react for 30 minutes, and obtaining the composite antibacterial agent after the reaction is complete;
Placing tanned leather in a composite antibacterial agent, wherein the solid-to-liquid ratio is 1:20, soaking for 5 hours, then vacuum drying, coating another part of modified aqueous polyurethane emulsion on the surface of tanned leather, and standing for 28 hours at room temperature to obtain coated leather.
S6: float polishing and grinding coating
The method comprises the steps of immersing a tin plate and coated leather into polishing liquid, wherein the polishing liquid is alumina polishing liquid, setting the pressure of a grinding head to be 0.3MPa, enabling the tin plate to be coiled around a main shaft to rotate at 100r/min, enabling the coated leather to rotate around a self shaft on the tin plate at a rotating speed of 200r/min, continuously polishing for 20min, and repeatedly polishing for 2 times to obtain polished leather.
S7: secondary polishing
And cleaning the surface of the polished leather by using a sponge, uniformly coating a layer of polishing emulsion on the surface of the polished leather, wherein the polishing emulsion is Brazil wax emulsion, uniformly coating the polishing emulsion by using the sponge, and standing at room temperature for 2min to obtain the antibacterial and bacteriostatic sofa leather.
Comparative example 1
Compared with the examples, the commercial cowhide leather used in this comparative example, specifically, the imported cowhide layer sold by Yi Si leather Co., dongguan, was recorded as comparative example 1, and the growth of bacteria when they were co-cultured with the composite coated leather was tested using E.coli and Staphylococcus aureus as experimental strains, respectively, and the absorbance (OD 600) of the solution at 600nm at different time points was recorded to determine the order of magnitude of E.coli and Staphylococcus aureus, and was tabulated as shown in Table 1:
It can be seen that the OD 600 values of the example 1, the example 2 and the example 3 after 4-24 hours are smaller than those of the comparative example 1, and the antibacterial effect is better as shown by the fact that the numbers of the escherichia coli and the staphylococcus aureus in the culture dishes of the example 1, the example 2 and the example 3 are smaller.
Comparative example 2
In this comparative example, compared with example 1, the mixed solution of nano silver was not added in steps S2 and S5, but acetone was directly added, and the other steps were unchanged, and the resulting sofa leather was designated as comparative example 2.
The bacteria growth conditions of the bacteria when the escherichia coli and the staphylococcus aureus are used as experimental strains and are respectively tested when the escherichia coli and the staphylococcus aureus are co-cultured with the composite coating leather, the light absorption value (OD 600) of the solution at 600nm at different time points is recorded to judge the order of magnitude of the escherichia coli and the staphylococcus aureus, and the order of magnitude is arranged into a table, as shown in Table 2:
It can be seen that the OD 600 value of example 1 after 4-24 hours is smaller than that of comparative example 2, and the fact that the number of escherichia coli and staphylococcus aureus in the culture dish of example 1 is smaller is proved, the antibacterial effect is better, and the addition of nano silver is proved to improve the antibacterial capability of sofa leather.
Comparative example 3
In this comparative example, the procedure of "coating modified aqueous polyurethane emulsion on the surface of tanned leather" in step S5.5 was not performed, and the modified aqueous polyurethane emulsion was left at room temperature for 24 to 48 hours ", and the other steps were not changed, and the obtained sofa leather was designated as comparative example 3.
The method is characterized in that escherichia coli and staphylococcus aureus are used as experimental strains, the growth conditions of bacteria when the escherichia coli and the staphylococcus aureus are co-cultured with the composite coating leather are respectively tested, and the light absorption values (OD 600) of solutions at different time points at 600nm are recorded to judge the orders of magnitude of the escherichia coli and the staphylococcus aureus.
After being arranged into tables, the tables are shown in Table 3:
It can be seen that the OD 600 value of the embodiment 1 after 4-24 hours is smaller than that of the comparative example 3, the antibacterial coating has certain antibacterial property, and the water-based polyurethane coating improves the wear resistance, protects the antibacterial coating and improves the antibacterial and bacteriostatic capacities of the sofa leather.
Comparative example 4
In this comparative example, step S2 was not performed, after obtaining a defatted leather, the defatted leather was directly subjected to pickling in step S3 and softening of the leather, then subjected to tanning in step S4 and preparation of an antibacterial coating material in step S5, the obtained sofa leather was designated as comparative example 4, the coated leather obtained after the end of step S5 in example 1 was designated as example 1, the test was performed by the paint film adhesion measuring method prescribed in GB/T1720-1989 in comparative example 4 and example 1, and the test results were collated into a table by repeating three experiments, as shown in table 4:
It can be seen that the leather coating of example 1 has a better adhesion rating, i.e. better adhesion.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (5)
1. The manufacturing method of the antibacterial and bacteriostatic sofa leather is characterized by comprising the following steps of:
S1: treating leather:
Soaking the peltry in enough purified water capable of immersing the leather to obtain presoaked leather, putting the presoaked leather into a rotary drum for treatment, spraying enzyme treatment liquid on the surface of the presoaked leather in the rotary working process of the rotary drum, taking out after degreasing, and cleaning with purified water to obtain degreased leather;
S2: coating the modified casein solution on the degreasing leather, and specifically comprises the following steps:
S2.1: 100-120 mug/ml nano silver solution is mixed according to the volume ratio of 1: (1-2) mixing and stirring with acetone until the mixture is dissolved, and then performing ultrasonic dispersion for 10-30min to obtain nano silver dispersion;
S2.2: adding 100-120 parts of casein into a reaction bottle, heating in a water bath to 70-80 ℃, adding borax, stirring until the casein is completely dissolved, adding 0.2-0.5 part of AEO-9, uniformly stirring, dissolving 0.5-1 part of mixed initiator into 2-3 parts of deionized water to obtain an initiator aqueous solution, mixing DAAM and APS initiator, dissolving into the deionized water to obtain a mixed initiator, taking one third, dropwise adding into the reaction bottle, and stirring at constant temperature for reaction for 25-30min;
S2.3: mixing the nano silver dispersion liquid with the rest two-thirds initiator aqueous solution, dropwise adding the mixture into a reaction bottle for 30-35min, raising the temperature to 55-60 ℃ during dropwise adding, synchronously evaporating acetone after dropwise adding, raising the temperature to 75-80 ℃, and preserving heat for 2.5-3h to obtain a nano Ag/DAAM double-modified casein solution;
S2.4: coating the nano Ag/DAAM double-modified casein solution on the surface of the degreasing leather, standing for 10-15min, forming a layer of film on the surface of the degreasing leather by the nano Ag/DAAM double-modified casein solution, and then drying in a drying oven at 50-55 ℃ for 5-10min for curing to obtain the leather with the film;
S3: pickling and softening leather, comprising the following steps:
S3.1: cleaning the leather with the film for 1-2 times by purified water, removing surface floating dust, immersing the cleaned leather with the film into mixed acid liquid, wherein the volume ratio of the total volume of the mixed acid liquid to the volume of the degreasing leather is 1: (0.5-0.6);
s3.2: setting the temperature of a rotary drum to be 20-24 ℃, adding the pickled leather with the film into the rotary drum, adding mixed acid liquid with the same volume, setting the rotary drum to rotate for 20-30min, adding 8-10 times of cold water from the shaft hole of the rotary drum to dilute the mixed acid liquid, and keeping the rotary drum to rotate for 120-180min, so that the pH value of the reaction liquid in the rotary drum is adjusted to 3-3.2, and obtaining the treated leather;
S3.3: softening the treated leather with trypsin at 30-35 ℃, regulating pH to 7.5-8.5 by NaOH, and softening for 6-8h to obtain softened leather;
S4: tanning leather:
Adding softened leather into aqueous solution of sodium chloride, rotating a rotary drum, adding sodium bicarbonate to adjust pH, adding sodium lignin sulfonate into the rotary drum for three times, washing with water, adding aluminum sulfate and sodium citrate into the rotary drum, adjusting with sodium bicarbonate, and finally discharging and drying to obtain tanned leather;
S5: the preparation method of the antibacterial coating material specifically comprises the following steps:
S5.1: adding 1-2 parts of polytetrahydrofuran ether, 0.5-1 part of hydrophilic chain extender DMPA, 1-1.2 parts of BDO, 1-1.2 parts of PDMS and 0.5-1 part of initiator DBTDL into a reaction box, dropwise adding IPDI at the speed of 1-3 drops/s under the protection of dry nitrogen at the temperature of 80-90 ℃ and keeping the dropwise adding reaction for 4-5 hours to obtain PU prepolymer;
S5.2: adding 1-2 parts of nano silver mixed solution into a reaction box, then cooling the reaction box to 50-60 ℃, adding 3-5 times of acetone solution into the reaction box for dilution, and standing the reaction box until the temperature in the reaction box is reduced to 40-50 ℃;
S5.3: adding triethylamine into a reaction box for neutralization and salifying, finally stirring the obtained prepolymer at a high speed at normal temperature, and reducing pressure through a pressure reducing valve to reduce the boiling point of acetone and remove the acetone by evaporation, thereby obtaining modified aqueous polyurethane emulsion in the reaction box;
S5.4: dividing the modified aqueous polyurethane emulsion into two parts with equal volume, heating one part to 80-90 ℃, dropwise adding a reaction mixture, wherein the reaction mixture is prepared by mixing BA and MMA in a ratio of 1: mixing the components (1-2) in a volume ratio, reacting for 2.5-3h, and finally adding KPS to react for 10-30min, and obtaining the composite antibacterial agent after the reaction is complete;
S5.5: placing tanned leather in a composite antibacterial agent, wherein the solid-to-liquid ratio is 1: (15-20), soaking for 4-5h, then drying in vacuum, coating another part of modified aqueous polyurethane emulsion on the surface of tanned leather, and standing at room temperature for 24-48h to obtain coated leather;
s6: float polishing and polishing the coating:
immersing a tin plate and coated leather into the polishing solution, setting the pressure of a grinding head to be 0.3-0.6MPa, enabling the tin plate to coil a main shaft at 100-200r/min, enabling the coated leather to rotate on the tin plate around the main shaft at a rotating speed of 200-300r/min, continuously polishing for 20-30min, and repeatedly polishing for 1-2 times to obtain polished leather;
S7: secondary polishing:
And cleaning the surface of the polished leather by using a sponge, uniformly coating a layer of polishing emulsion on the surface of the polished leather, uniformly coating the polished leather by using the sponge, and standing at room temperature for 1-2min to obtain the antibacterial and bacteriostatic sofa leather.
2. The method for producing antibacterial and bacteriostatic sofa leather according to claim 1, characterized in that the enzyme treatment solution in the step S1 is obtained by mixing 40-50U/g lipase JZ, 20-40U/g protease JRH and 4-6U/g saccharifying enzyme TH.
3. The method for producing antibacterial and bacteriostatic sofa leather according to claim 1, characterized in that the mixed acid solution in step S3 is prepared from 40-60% of sulfone acid polymer and 0.4-0.6% of formic acid in a ratio of 1: (0.5-0.6) by volume ratio.
4. The method for producing an antibacterial and bacteriostatic sofa leather according to claim 1, characterized in that the polishing liquid in step S6 is an alumina polishing liquid.
5. The method of producing an antibacterial and bacteriostatic sofa leather according to claim 1, wherein the polishing emulsion in step S7 is a carnauba wax emulsion.
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