CN112501364B - Preparation method of ecological functional leather based on nano material - Google Patents
Preparation method of ecological functional leather based on nano material Download PDFInfo
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
-
- 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
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/32—Material containing basic nitrogen containing amide groups leather skins
- D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a preparation method of ecological functional leather based on a nano material, which comprises a wet dyeing and finishing process and is characterized in that the wet dyeing and finishing process comprises the following process flows: crust leather obtained by tanning with a cationic metal tanning agent → rewet → anionic dyeing 1 → neutralization 1 → anion filling → cation retanning → neutralization 2 → anion filling dyeing → anion fatliquoring → cation fixation 1 → anionic dyeing 2 → cation fixation 2 → cation fatliquoring; the nanometer titanium dioxide modifier is added in at least one of the anion filling procedure and the anion filling dyeing procedure; the application applies the nano titanium dioxide modifier with photocatalysis to the leather-making wet dyeing and finishing section, can remove formaldehyde in leather, can play the role of antibiosis and bacteriostasis, and develops the application of the nano titanium dioxide modifier in the leather wet dyeing and finishing section.
Description
Technical Field
The invention relates to the technical field of leather production, in particular to a preparation method of ecological functional leather based on a nano material.
Background
Nanotechnology is an emerging technology appearing in the 90 s of the 20 th century and is listed as one of the key technologies of the 21 st century by various countries. As a traditional industry, the leather industry faces environmental regulations and pressure of improving the performance requirements of consumers on leather, and green leather and functional leather are the future development directions of the leather industry. As a novel material, the nano material is involved in the research of innovation materials, but the existing nano technology mainly focuses on the modification of nano materials such as montmorillonite, nano zinc oxide, nano silicon dioxide and the like by experimental organic matters to prepare the nano tanning agent, and other aspects are rarely reported.
Disclosure of Invention
The embodiment of the application provides a preparation method of ecological functional leather based on a nano material, and the application uses a nano titanium dioxide modifier with a photocatalytic effect in a leather-making wet dyeing and finishing section, so that formaldehyde in leather can be removed, an antibacterial and bacteriostatic effect can be achieved, and the application of the nano titanium dioxide modifier in the wet dyeing and finishing section is developed.
The embodiment of the application provides a preparation method of ecological functional leather based on a nano material, which comprises a wet dyeing and finishing process, wherein the process flow of the wet dyeing and finishing section is as follows: crust leather obtained by tanning with a cationic metal tanning agent → rewet → anionic dyeing 1 → neutralization 1 → anion filling → cation retanning → neutralization 2 → anion filling dyeing → anion fatliquoring → cation fixation 1 → anionic dyeing 2 → cation fixation 2 → cation fatliquoring;
and a nano titanium dioxide modifier is added in at least one of the anion filling procedure and the anion filling dyeing procedure.
Further, the nano titanium dioxide modifier is a nano titanium dioxide-polyurethane retanning agent.
Further, the preparation method of the nano titanium dioxide-polyurethane retanning agent comprises the following steps:
(1) preparing modified nano titanium dioxide;
(2) dehydrating 1-10 parts of polyol, adding the dehydrated polyol into a reactor, adding 0.2-5 parts of isocyanate, prepolymerizing at 70-100 ℃ for 0.5-4 hours, cooling to 60-70 ℃, adding 0-8 parts of acetone for dilution, and adding 0.05-1 part of a small-molecule chain extender for reacting for 2-6 hours; adding 0.05-1 part of hydrophilic chain extender, reacting for 0.5-4h, cooling to 40-60 ℃, and adding 0.05-1 part of organic acid or organic base for 10-100 min; controlling the temperature to be 25-45 ℃, adding 0.1-2 parts of modified nano titanium dioxide and 0.01-1 part of graphene oxide, and stirring at a high speed for reaction for 10-120 min; controlling the temperature to be 25-45 ℃, adding 2-80 parts of water while stirring at a high speed, and emulsifying and dispersing for 0.5-4 h; adding 0.01-1 part of polyamine compound, controlling the temperature to be 25-45 ℃, stirring and reacting for 10-120min, and removing acetone in the emulsion to obtain the nano titanium dioxide-polyurethane retanning agent;
the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and toluene diisocyanate;
the polyalcohol is one or more of polypropylene glycol, polyethylene glycol, polytetrahydrofuran ether, polybutylene adipate dihydric alcohol and polycaprolactone diol;
the micromolecular chain extender is one or more of ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol;
the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, citric acid, 2, 4-diaminobenzene sulfonic acid, ethylene diamine ethyl sodium sulfonate, carboxyl-containing half ester dihydric alcohol, N-methyldiethanolamine and triethylamine;
the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
Further, the preparation method of the modified nano titanium dioxide comprises the following steps:
adding 1-10 parts of nano titanium dioxide into a reaction container, adding 0.01-1 part of aminosilane coupling agent, 0.01-1 part of epoxy silane coupling agent, 10-100 parts of water and 20-200 parts of ethanol, stirring and dispersing, adjusting the pH to 4-12, then performing ultrasonic dispersion for 3-30min, reacting at the temperature of 20-60 ℃ for 1-10h, filtering, washing and drying to obtain the modified nano titanium dioxide.
Further, the method also comprises a coating process, wherein the coating process comprises the following specific steps: dried and finished crust leather → spot filling → roller → buffing → bottom coating → roller burnishing → trimming → middle coating → embossing → oil returning → softening → vibration softening → upper coating → roller burnishing → softening → oil returning → vibration softening → vacuum drying → top coating → roller burnishing.
Furthermore, a nano graphene coating agent is added in the upper layer coating process.
Further, the preparation method of the nano graphene finishing agent comprises the following steps:
the method comprises the following steps: preparing carboxylated graphene powder;
step two: preparing a chitosan solution;
step three: taking carboxylated graphene powder, and mixing the carboxylated graphene powder with water to obtain a carboxylated graphene solution;
step four: preparing a nano graphene finishing agent: adding 1-10 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adding 1-5 parts of activating agent, reacting for a period of time, adding 1-5 parts of cross-linking agent, reacting for a period of time, and finally adding 0-3 parts of nano metal material to obtain the nano graphene finishing agent;
the activating agent is selected from at least one of pyruvic acid, beta-hydroxy pyruvic acid, alpha-ketoglutaric acid and 2-carbonyl propionic acid;
the cross-linking agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the nano metal material is selected from at least one of nano titanium dioxide, nano manganese dioxide, nano silicon dioxide, nano zinc oxide, nano iron oxide and nano silver.
Further, the activating agent is selected from at least one of pyruvic acid, beta-hydroxy pyruvic acid, alpha-ketoglutaric acid and 2-carbonyl propionic acid;
the cross-linking agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the nano metal material is selected from at least one of nano titanium dioxide, nano manganese dioxide, nano silicon dioxide, nano zinc oxide, nano iron oxide and nano silver.
Further, the wet dyeing and finishing comprises the following specific steps:
(1) squeezing water, shaving evenly and weighing the crust leather obtained after tanning by using the cationic metal tanning agent, adding the crust leather into a rotary drum, and calculating the using amount of subsequent materials by taking the weighing mass as a reference;
(2) and (3) rewetting: adding 150-400% of water, 0.1-1% of surfactant and 0.1-2% of organic acid into a rotary drum, controlling the temperature to be 25-50 ℃, rotating for 0.5-6h, and draining;
(3) anionic dyeing 1: adding 400% of 150-400% of water into the rotary drum, adding 0.3-2% of anionic dye, controlling the temperature to be 20-40 ℃, rotating for 5-60min, and draining;
(4) and (3) neutralization 1: adding 50-300% of water into the rotary drum, adding 1-5% of neutralizer, controlling the temperature at 20-40 ℃, rotating for 20-180min, adding 0.3-2% of neutralizer and 0-3% of anionic fatting agent, controlling the pH at 4-6, rotating for 20-120min, and draining;
(5) anion filling: adding 10-150% of water into a rotary drum, adding 0-5% of nano titanium dioxide modifier, controlling the temperature to be 20-40 ℃, rotating for 5-60min, adding 2-10% of acrylic resin retanning agent, rotating for 10-120min, adding 0-5% of anionic fatliquoring agent, 2-10% of synthetic tanning agent, 2-10% of amino resin tanning agent and 0-5% of protein filler, rotating for 1-6h, adding 50-200% of water, adding 0.5-1.5% of formic acid, rotating for 10-60min, adding 0.5-1.5% of formic acid, and rotating for 10-60 min;
(6) cation retanning: adding 2-10% of cationic metal tanning agent, 0-5% of protein filler and 0-3% of cationic fatting agent into a rotary drum, controlling the temperature to be 20-40 ℃, rotating for 30-120min, adding 1-4% of neutralizing agent, rotating for 30-120min, and draining;
(7) and (2) neutralization: adding 50-300% of water, 1-4% of neutralizing agent and 0-3% of anionic fatting agent into the rotary drum, controlling the temperature at 20-40 ℃ and the pH at 4-6, rotating for 30-120min, and draining;
(8) anion filling dyeing: adding 10-150% of water into a rotary drum, adding 0.5-10% of polyurethane retanning agent, controlling the temperature to be 20-40 ℃, rotating for 5-60min, adding 2-15% of acrylic resin retanning agent, rotating for 10-120min, adding 2-15% of synthetic tanning agent, 2-15% of amino resin tanning agent, 2-15% of plant tanning agent, 0.5-8% of anionic fatliquoring agent and 1-5% of dye, and rotating for 1-8 h;
(9) anion fatliquoring: adding 70-300% of water into a rotary drum, adding 1-6% of polymer fatting agent, 2-9% of synthetic fatting agent, 0-5% of lanolin fatting agent and 1-6% of phospholipid fatting agent, controlling the temperature to be 40-60 ℃, rotating for 0.5-3h, 0-5% of vegetable oil fatting agent, 0-5% of acrylic resin retanning agent and 1-5% of polycarboxylate, controlling the temperature to be 40-60 ℃, and rotating for 0.5-3 h;
(10) cation fixation 1: adding 0.5-1.5% formic acid into the rotary drum, controlling the temperature at 40-65 deg.C, rotating for 10-60min, adding 0.5-1.5% formic acid, rotating for 10-60min, adding 0.5-4% cationic metal tanning agent, rotating for 10-120min, and draining;
(11) anionic dyeing 2: adding 100-400% of water into the rotary drum, adding 0.5-3% of dye, controlling the temperature to be 45-65 ℃, and rotating for 5-40 min;
(12) cation fixation 2: adding 0.3-2% formic acid into the rotary drum, controlling the temperature at 45-65 deg.C, rotating for 5-40min, adding 0.3-3% cationic metal tanning agent, and rotating for 5-40 min;
(13) cation fatliquoring: adding 0.2-3% of cationic fatting agent and 0-3% of neatsfoot oil fatting agent into the rotary drum, controlling the temperature at 45-65 deg.C, and rotating for 4-30 min;
the neutralizing agent is selected from one of tannin, sodium formate, sodium bicarbonate and formic acid.
Further, the coating agent component of the upper coating comprises: 100-200 parts of water, 100-300 parts of polyurethane copolymer, 20-200 parts of nano graphene finishing agent, 2-20 parts of cross-linking agent, 0-30 parts of flatting agent and 0-20 parts of modified polysiloxane aqueous solution;
the oil return agent in the oil return process comprises the following components: 100 portions of water and 200 portions of synthetic fatting agent.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the nano titanium dioxide modifier is added in the leather retanning filling process, so that free formaldehyde in the leather can be removed for a long time, and the leather can be endowed with antibacterial and bacteriostatic properties; the nano graphene finishing agent is used in a leather finishing working section, can adsorb free formaldehyde in leather, and can improve the physical properties of a leather coating such as wear resistance, dry and wet rub resistance and the like.
2. The wet dyeing and finishing of the leather adopts the alternate negative and positive wet dyeing and finishing, namely, in the wet dyeing and finishing process, a method of alternately adding an anionic material and a cationic material is adopted. The absorption rate of various anionic materials and cationic materials can be improved by a positive and negative alternation method, the combination fastness of various materials in leather is enhanced, the dye uptake and the color fastness of dye are improved, and the using amount of various materials is reduced.
3. The softness of the leather can be improved by a plurality of times of oil return technology in the coating process.
Detailed Description
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to the description and the specific embodiments.
Example 1:
a preparation method of ecological functional leather based on nanometer materials comprises the following steps:
the method comprises the following steps: preparation of nano titanium dioxide-polyurethane retanning agent
(1) Adding 5 parts of nano titanium dioxide into a reaction container, adding 0.4 part of aminosilane coupling agent, 0.1 part of epoxy silane coupling agent, 50 parts of water and 100 parts of ethanol, stirring and dispersing, adjusting the pH value to 10, then carrying out ultrasonic dispersion for 5min, reacting for 5h at the temperature of 30 ℃, filtering, washing and drying to obtain modified nano titanium dioxide;
(2) taking 3 parts of polytetramethylene glycol, dehydrating, adding into a reactor, adding 0.8 part of isophorone diisocyanate, and prepolymerizing for 2 hours at 80 ℃. Cooling to 65 ℃, adding 0.4 part of acetone for dilution, adding 0.3 part of butanediol, and reacting for 4 hours. 0.1 part of dimethylolpropionic acid was added and reacted for 2 hours. The temperature is reduced to 50 ℃, and 0.1 part of triethylamine is added for neutralization for 30 min. Controlling the temperature at 45 ℃, adding 0.2 part of modified nano titanium dioxide and 0.05 part of graphene oxide, and stirring at a high speed for reaction for 60 min. The temperature is controlled to be 40 ℃, 60 parts of water is added while stirring at a high speed, and emulsification and dispersion are carried out for 1 hour. Adding 0.05 part of diethylenetriamine, controlling the temperature to be 30 ℃, stirring and reacting for 30min, and removing acetone in the emulsion to obtain the nano titanium dioxide-polyurethane retanning agent.
Step two: preparation of nano graphene finishing agent
(1) Preparation of carboxylated graphene powder
Adding 1 part of graphene oxide into 1000 parts of deionized water, performing ultrasonic dispersion for 60 minutes, then adding 10 parts of sodium hydroxide, performing ultrasonic dispersion for 30 minutes, then adding 20 parts of alpha-bromoacetic acid, performing ultrasonic dispersion for 30 minutes, finally adjusting the reaction temperature to 30 ℃, performing reaction for 6 hours to obtain a carboxylated graphene dispersion liquid, alternately washing the obtained product with acetic acid and deionized water for 6 times, finally washing the product with absolute ethyl alcohol for 3 times, and performing vacuum drying on the product to obtain carboxylated graphene powder;
(2) preparation of Chitosan solution
Dissolving 5 parts of acetic acid in 100 parts of deionized water, then adding 2.5 parts of chitosan, and adjusting the pH value of the solution to 3.5 to obtain a chitosan solution;
(3) preparing a carboxylated graphene solution:
adding 2.5 parts of carboxylated graphene powder into 100 parts of deionized water, performing ultrasonic dispersion for 5 minutes, and adjusting the pH value of the solution to 4.5 to obtain a carboxylated graphene solution;
(4) adding 5 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adjusting the pH value of the solution to 3.5, reacting for 3 hours at 30 ℃, then adding 2.5 parts of pyruvic acid, reacting for 3 hours at 35 ℃, then adding 2.5 parts of triethylene tetramine, reacting for 3 hours at 40 ℃, finally adding 1 part of nano titanium dioxide, and reacting for 1 hour at 40 ℃ to obtain the nano graphene coating agent.
Step three: preparation of functional leather
(1) Wet blue leather obtained by chrome tanning of Xingheng leather science and technology limited company is taken, squeezed with water, shaved evenly and weighed (the subsequent material dosage is calculated by taking the weight as the reference) and added into a rotary drum.
(2) And (3) rewetting: adding 300% of water into a rotary drum, adding 0.5% of surfactant SAF (Delhi leather technology Co., Ltd.), 0.3% of oxalic acid, controlling the temperature at 40 ℃, rotating for 2h, and draining.
(3) Anionic dyeing 1: adding 300% of water into the rotary drum, adding 0.8% of anionic dye, controlling the temperature at 30 ℃, rotating for 20min, and draining.
(4) And (3) neutralization 1: adding 150% of water into a rotary drum, adding 1.5% of neutralized tannin PAK (Langshan chemical, China Co., Ltd.), 1.5% of sodium formate, controlling the temperature at 30 deg.C, and rotating for 10 min; adding 1% sodium bicarbonate and 1% anionic fatliquor MIR90 (Yiwen chemical Co., Ltd.), controlling pH to 4.8-5.2, rotating for 50min, and draining.
(5) Anion filling: adding 50% water into rotary drum, adding 1% polyurethane retanning agent CC-01 (Langshan chemical, China, Inc.), controlling temperature at 30 deg.C, and rotating for 10 min. Adding 2% of acrylic resin retanning agent TP340(ALPA leather chemical Co., Ltd.), and 3% of acrylic resin retanning agent CC (Vanmatu chemical materials Co., Ltd.) and rotating for 60 min. 0.5% of anionic fatliquor OSL (Toepler), 2% of synthetic tanning agent F0 (Pasteur Co., Ltd.), 3% of amino resin tanning agent HB (Toepler Co., Ltd.), 2% of protein filler FB (Deshel chemical industry Co., Ltd.) were added thereto, and the mixture was rotated for 90 minutes. Adding 100% water, adding 1% formic acid, controlling temperature at 30 deg.C, rotating for 20min, adding 1% formic acid, and rotating for 20 min.
(6) Cation retanning: adding chrome tanning agent AB (Turkey Rinshan group) 3%, protein filler CCL (Huaka trade Co., Ltd.) 1.5%, and cationic fatting agent GS (Steyr leather chemical Co., Ltd.) 1% into the rotary drum, controlling the temperature at 30 deg.C, and rotating for 60 min. Adding 1% sodium formate and 1% sodium bicarbonate, rotating for 60min, and draining.
(7) And (2) neutralization: adding 150% of water, 1.5% of baking soda and 0.5% of anionic fatliquoring agent MIR90 (Yiwen chemical Co., Ltd.), controlling the temperature at 30 deg.C and pH at 4.8-5, rotating for 60min, and draining.
(8) Anion filling dyeing: adding 50% of water into a rotating drum, adding 4% of nano titanium dioxide-polyurethane retanning agent, controlling the temperature to be 30 ℃, rotating for 20min, adding 3% of acrylic resin retanning agent TP340(ALPA leather chemical company), 3% of acrylic resin retanning agent 1084 (Langsheng chemical Chinese Co., Ltd.), rotating for 40min, adding 1% of synthetic tanning agent T-M (Basofu corporation), 2% of synthetic tanning agent OS (Langsheng chemical Chinese Co., Ltd.), 3% of amino resin tanning agent HB (Toepller company), 2% of amino resin tanning agent DCT (Steckel leather chemical Co., Ltd.), 3% of vegetable tanning agent ME (Jinfeng leather chemical Co., Ltd.), 1% of anion fatliquoring agent EY (Stema chemical Co., Ltd.), 2% of dye, and rotating for 2 h.
(9) Anionic fatliquor: adding 70-300% of water into a rotary drum, adding 3% of polymer fatliquor GS-606 (Schmidt leather chemical Co., Ltd.), 3% of synthetic fatliquor SU (Wantongli chemical materials Co., Ltd., Xiamen), 1.5% of lanolin fatliquor ZBN (Biokimica), 2% of phospholipid fatliquor BA (Stemao chemical Co., Ltd.), 0-2% of vegetable oil fatliquor BCA (Vid leather chemical Co., Ltd.), controlling the temperature to be 50 ℃, rotating for 30min, adding 1% of acrylic resin retanning agent R83 (Toeplier Co., Ltd.), 2% of polycarboxylate (MAP chemical Co., Ltd.), controlling the temperature to be 40-60 ℃, and rotating for 40 min.
(10) Cation fixation 1: adding 1% formic acid into the rotary drum, controlling the temperature at 50 deg.C, rotating for 10min, adding 1% formic acid, rotating for 40min, adding 1% chrome tanning agent AB (Turkey Jinshan group), rotating for 30min, and draining.
(11) Anionic dyeing 2: adding 300% of water into the rotary drum, adding 1% of dye, controlling the temperature to be 55 ℃, and rotating for 15 min.
(12) Cation fixation 2: adding 0.6% formic acid into the rotary drum, controlling the temperature at 55 deg.C, rotating for 15min, adding 1% aluminum tannin AL (Sichuan Desaier chemical industry Co., Ltd.), and rotating for 10 min.
(13) Cation fatliquoring: adding 0.5% cationic fatting agent GS (Steyr leather chemical Co., Ltd.) and 0.5% neatsfoot oil fatting agent OPE (Shanghai Feng Zheng Wanwei leather chemical Co., Ltd.) into the rotary drum, controlling the temperature at 55 deg.C, rotating for 15min, and draining.
(14) Washing out the drum with water, and standing by setting aside (8 h).
(15) Squeezing water, stretching, vacuum drying (38 deg.C, 4min), hanging and air drying (24h), drying in drying tunnel (4h), returning water, standing (8h), and softening by shaking (5-grade).
(16) Point supplement: 100 parts of mending paste 8182 (Miji chemical Co., Ltd.) is taken and mending is performed on the defective part of crust leather.
(17) Knurling roller (100 ℃, 50kg), and buffing;
(18) bottom layer coating: preparing a bottom layer coating agent, and spraying for 3 times;
the bottom coating formula comprises: 200 parts of water, 20 parts of a polyurethane finishing agent RU3904 (Steyr leather chemical Co., Ltd.), 100 parts of a polyurethane finishing agent RU3989 (Steyr leather chemical Co., Ltd.), and 40 parts of a surfactant PT4235 (Steyr leather chemical Co., Ltd.);
(19) performing roller burnishing (at 130 ℃, 30-40kg), and trimming;
(20) coating the middle layer: preparing a middle layer coating agent, and spraying for 3 times;
the formula of the middle layer coating agent is as follows: 300 parts of water, 200 parts of polyurethane finishing agent RU3904 (Steyr leather chemical Co., Ltd.), 150 parts of acrylic resin finishing agent RA-2 (Steyr leather chemical Co., Ltd.), 100 parts of acrylic resin finishing agent SB-300 (Langshan chemical Chinese Co., Ltd.), 60 parts of filler S-C01 (Langshan chemical Chinese Co., Ltd.), 40 parts of casein 688/B (Delui leather science Co., Ltd.), and 120 parts of coating;
(21) embossing (100 ℃, 3 seconds);
(22) oil return: preparing an oil return agent, and returning oil from the back;
the formula of the oil return agent is as follows: 100 parts of water and 5 parts of synthetic fat liquor 94S (sima chemical industry Co., Ltd.).
(23) Softening (1h), vibrating and softening (6-grade);
(24) coating the upper layer: preparing an upper coating agent and spraying once;
the upper layer coating agent formula comprises: 120 parts of water, 160 parts of polyurethane finishing agent LN.A (St. leather chemical Co., Ltd.), 50 parts of polyurethane finishing agent 1418 (Delry. leather science Co., Ltd.), 100 parts of nano-graphene finishing agent, 5 parts of cross-linking agent and 5 parts of modified polysiloxane aqueous solution;
(25) tumbling (130 ℃, 30-40kg) and milling (1 h);
(26) oil return: 100 parts of water and 5 parts of synthetic fat liquor 94S (sima chemical Co., Ltd.);
(27) shaking for softening (grade 6), and vacuum drying (70 deg.C, 20 s);
(28) coating the top layer: preparing top coating agent, and spraying for 1 time
The top layer coating agent formula comprises: 100 parts of water, 5 parts of modified polysiloxane solution 5230 (Steyr leather chemical Co., Ltd.) and 5 parts of hand feeling agent MA330 (Jinjiang Sanxing Tai trade Co., Ltd.);
(29) tumbling (100 ℃, 20-30 kg).
Example 2
A preparation method of ecological functional leather based on nanometer materials comprises the following steps:
the method of example 2 is the same as example 1, except that the anion filling step and the anion filling dyeing step are as follows:
(5) anion filling: adding 50% of water into the rotary drum, adding 3% of nano titanium dioxide-polyurethane retanning agent, controlling the temperature at 30 ℃, and rotating for 10 min. Adding 2% of acrylic resin retanning agent TP340(ALPA leather chemical Co., Ltd.), and 3% of acrylic resin retanning agent CC (Vanmatu chemical materials Co., Ltd.) and rotating for 60 min. 0.5% of anionic fatliquor OSL (Toepler), 2% of synthetic tanning agent F0 (Pasteur Co., Ltd.), 3% of amino resin tanning agent HB (Toepler Co., Ltd.), 2% of protein filler FB (Deshel chemical industry Co., Ltd.) were added thereto, and the mixture was rotated for 90 minutes. Adding 100% water, adding 1% formic acid, controlling temperature at 30 deg.C, rotating for 20min, adding 1% formic acid, and rotating for 20 min.
(8) Anion filling dyeing: adding 50% of water into a rotating drum, adding 1% of a polyurethane retanning agent CC-01 (Langshan chemical Chinese Co., Ltd.), controlling the temperature at 30 ℃, rotating for 20min, adding 3% of an acrylic resin retanning agent TP340(ALPA leather chemical Co., Ltd.), 3% of an acrylic resin retanning agent 1084 (Langshan chemical Chinese Co., Ltd.), rotating for 40min, adding 1% of a syntan T-M (Pasteur corporation), 2% of a syntan OS (Langshan chemical Chinese Co., Ltd.), 3% of an amino resin tanning agent HB (Toepler Co., Ltd.), 2% of an amino resin tanning agent DCT (Steal leather chemical Co., Ltd.), 3% of a vegetable tanning agent ME (Jinfeng leather chemical Co., Ltd.), 1% of an anionic fatliquor EY (Simma chemical Co., Ltd.), 2% of a dye, and rotating for 2 h.
Example 3
A preparation method of ecological functional leather based on nanometer materials comprises the following steps:
the method of example 3 is the same as example 1, except that the anion filling step and the anion filling dyeing step are as follows:
(5) anion filling: adding 50% of water into the rotary drum, adding 2% of nano titanium dioxide-polyurethane retanning agent, controlling the temperature at 30 ℃, and rotating for 10 min. Adding 2% of acrylic resin retanning agent TP340(ALPA leather chemical Co., Ltd.), and 3% of acrylic resin retanning agent CC (Vanmatu chemical materials Co., Ltd.) and rotating for 60 min. 0.5% of anionic fatliquor OSL (Toepler), 2% of synthetic tanning agent F0 (Pasteur Co., Ltd.), 3% of amino resin tanning agent HB (Toepler Co., Ltd.), 2% of protein filler FB (Deshel chemical industry Co., Ltd.) were added thereto, and the mixture was rotated for 90 minutes. Adding 100% water, adding 1% formic acid, controlling temperature at 30 deg.C, rotating for 20min, adding 1% formic acid, and rotating for 20 min.
(8) Anion filling dyeing: adding 50% of water into a rotating drum, adding 3% of nano titanium dioxide-polyurethane retanning agent, controlling the temperature to be 30 ℃, rotating for 20min, adding 3% of acrylic resin retanning agent TP340(ALPA leather chemical company), 3% of acrylic resin retanning agent 1084 (Langsheng chemical Chinese Co., Ltd.), rotating for 40min, adding 1% of synthetic tanning agent T-M (Basofu corporation), 2% of synthetic tanning agent 0S (Langsheng chemical Chinese Co., Ltd.), 3% of amino resin tanning agent HB (Toeplier Co., Ltd.), 2% of amino resin tanning agent DCT (Stetall leather chemical Co., Ltd.), 3% of vegetable tanning agent ME (Jinfeng leather chemical Co., Ltd.), 1% of anionic fatliquor EY (Stema chemical company Co., Ltd.), 2% of dye, and rotating for 2 h.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (6)
1. The preparation method of the ecological functional leather based on the nano material comprises a wet dyeing and finishing process and is characterized in that the wet dyeing and finishing process comprises the following process flows: crust leather obtained by tanning with cationic metal tanning agent → rewet → anionic dyeing 1 → neutralization 1 → anion filling → cation retanning → neutralization 2 → anion filling dyeing → anion fatliquoring → cation fixing 1 → anionic dyeing 2 → cation fixing 2 → cation fatliquoring;
a nanometer titanium dioxide modifier is added in at least one of the anion filling procedure and the anion filling dyeing procedure;
the nano titanium dioxide modifier is a nano titanium dioxide-polyurethane retanning agent;
the preparation method of the nano titanium dioxide-polyurethane retanning agent comprises the following steps:
(1) preparing modified nano titanium dioxide: adding 1-10 parts of nano titanium dioxide into a reaction container, adding 0.01-1 part of aminosilane coupling agent, 0.01-1 part of epoxy silane coupling agent, 10-100 parts of water and 20-200 parts of ethanol, stirring and dispersing, adjusting the pH to 4-12, then performing ultrasonic dispersion for 3-30min, reacting at the temperature of 20-60 ℃ for 1-10h, filtering, washing and drying to obtain modified nano titanium dioxide;
(2) dehydrating 1-10 parts of polyol, adding the dehydrated polyol into a reactor, adding 0.2-5 parts of isocyanate, prepolymerizing at 70-100 ℃ for 0.5-4h, cooling to 60-70 ℃, adding 0-8 parts of acetone for dilution, and adding 0.05-1 part of a small-molecule chain extender for reacting for 2-6 h; adding 0.05-1 part of hydrophilic chain extender, reacting for 0.5-4h, cooling to 40-60 ℃, and adding 0.05-1 part of organic acid or organic base for 10-100 min; controlling the temperature to be 25-45 ℃, adding 0.1-2 parts of modified nano titanium dioxide and 0.01-1 part of graphene oxide, and stirring at a high speed for reaction for 10-120 min; controlling the temperature to be 25-45 ℃, adding 2-80 parts of water while stirring at a high speed, and emulsifying and dispersing for 0.5-4 h; adding 0.01-1 part of polyamine compound, controlling the temperature to be 25-45 ℃, stirring and reacting for 10-120min, and removing acetone in the emulsion to obtain the nano titanium dioxide-polyurethane retanning agent;
the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and toluene diisocyanate;
the polyalcohol is one or more of polypropylene glycol, polyethylene glycol, polytetrahydrofuran ether, polybutylene adipate dihydric alcohol and polycaprolactone diol;
the micromolecular chain extender is one or more of ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol;
the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, citric acid, 2, 4-diaminobenzene sulfonic acid, ethylene diamine ethyl sodium sulfonate, carboxyl-containing half ester dihydric alcohol, N-methyldiethanolamine and triethylamine;
the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
2. The method for preparing ecological functional leather based on nanometer materials as claimed in claim 1, further comprising a finishing process, wherein the finishing process comprises the following specific steps: dried and finished crust leather → spot filling → roller → buffing → bottom coating → roller burnishing → trimming → middle coating → embossing → oil returning → softening → vibration softening → upper coating → roller burnishing → softening → oil returning → vibration softening → vacuum drying → top coating → roller burnishing.
3. The method for preparing ecological functional leather based on nanometer materials as claimed in claim 2, wherein nanometer graphene finishing agent is added in the upper layer finishing process.
4. The method for preparing the ecological functional leather based on the nano-material according to claim 3, wherein the method for preparing the nano-graphene finishing agent comprises the following steps:
the method comprises the following steps: preparing carboxylated graphene powder;
step two: preparing a chitosan solution;
step three: taking carboxylated graphene powder, and mixing the carboxylated graphene powder with water to obtain a carboxylated graphene solution;
step four: preparing a nano graphene finishing agent: adding 1-10 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adding 1-5 parts of activating agent, reacting for a period of time, adding 1-5 parts of cross-linking agent, reacting for a period of time, and finally adding 0-3 parts of nano metal material to obtain a nano graphene finishing agent;
the activating agent is selected from at least one of pyruvic acid, beta-hydroxy pyruvic acid, alpha-ketoglutaric acid and 2-carbonyl propionic acid;
the cross-linking agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine;
the nano metal material is selected from at least one of nano titanium dioxide, nano manganese dioxide, nano silicon dioxide, nano zinc oxide, nano iron oxide and nano silver.
5. The method for preparing ecological functional leather based on nano-materials according to claim 1, wherein the wet dyeing and finishing process comprises the following specific steps:
(1) squeezing water, shaving evenly and weighing the crust leather obtained after tanning by the cationic metal tanning agent, adding the crust leather into a rotary drum, and calculating the using amount of subsequent materials by taking the weighing mass as a reference;
(2) and (3) rewetting: adding 150-400% of water, 0.1-1% of surfactant and 0.1-2% of organic acid into a rotary drum, controlling the temperature to be 25-50 ℃, rotating for 0.5-6h, and draining;
(3) anionic dyeing 1: adding 400% of 150-400% of water into the rotary drum, adding 0.3-2% of anionic dye, controlling the temperature to be 20-40 ℃, rotating for 5-60min, and draining;
(4) and (3) neutralization 1: adding 50-300% of water into the rotary drum, adding 1-5% of neutralizer, controlling the temperature at 20-40 ℃, rotating for 20-180min, adding 0.3-2% of neutralizer and 0-3% of anionic fatting agent, controlling the pH at 4-6, rotating for 20-120min, and draining;
(5) anion filling: adding 10-150% of water into a rotary drum, adding 0-5% of nano titanium dioxide modifier, controlling the temperature to be 20-40 ℃, rotating for 5-60min, adding 2-10% of acrylic resin retanning agent, rotating for 10-120min, adding 0-5% of anionic fatliquoring agent, 2-10% of synthetic tanning agent, 2-10% of amino resin tanning agent and 0-5% of protein filler, rotating for 1-6h, adding 50-200% of water, adding 0.5-1.5% of formic acid, rotating for 10-60min, adding 0.5-1.5% of formic acid, and rotating for 10-60 min;
(6) cation retanning: adding 2-10% of cationic metal tanning agent, 0-5% of protein filler and 0-3% of cationic fatting agent into a rotary drum, controlling the temperature to be 20-40 ℃, rotating for 30-120min, adding 1-4% of neutralizing agent, rotating for 30-120min, and draining;
(7) and (2) neutralization: adding 50-300% of water, 1-4% of neutralizing agent and 0-3% of anionic fatting agent into the rotary drum, controlling the temperature at 20-40 ℃ and the pH at 4-6, rotating for 30-120min, and draining;
(8) anion filling dyeing: adding 10-150% of water into a rotary drum, adding 0.5-10% of polyurethane retanning agent, controlling the temperature to be 20-40 ℃, rotating for 5-60min, adding 2-15% of acrylic resin retanning agent, rotating for 10-120min, adding 2-15% of synthetic tanning agent, 2-15% of amino resin tanning agent, 2-15% of plant tanning agent, 0.5-8% of anionic fatliquoring agent and 1-5% of dye, and rotating for 1-8 h;
(9) anion fatliquoring: adding 70-300% of water into a rotary drum, adding 1-6% of polymer fatting agent, 2-9% of synthetic fatting agent, 0-5% of lanolin fatting agent and 1-6% of phospholipid fatting agent, controlling the temperature to be 40-60 ℃, rotating for 0.5-3h, 0-5% of vegetable oil fatting agent, 0-5% of acrylic resin retanning agent and 1-5% of polycarboxylate, controlling the temperature to be 40-60 ℃, and rotating for 0.5-3 h;
(10) cation fixation 1: adding 0.5-1.5% formic acid into the rotary drum, controlling the temperature at 40-65 deg.C, rotating for 10-60min, adding 0.5-1.5% formic acid, rotating for 10-60min, adding 0.5-4% cationic metal tanning agent, rotating for 10-120min, and draining;
(11) anionic dyeing 2: adding 400% of 100-400% of water into the rotary drum, adding 0.5-3% of dye, controlling the temperature to be 45-65 ℃, and rotating for 5-40 min;
(12) cation fixation 2: adding 0.3-2% formic acid into the rotary drum, controlling the temperature at 45-65 deg.C, rotating for 5-40min, adding 0.3-3% cationic metal tanning agent, and rotating for 5-40 min;
(13) cation fatliquoring: adding 0.2-3% of cationic fatting agent and 0-3% of neatsfoot oil fatting agent into the rotary drum, controlling the temperature at 45-65 deg.C, and rotating for 4-30 min;
the neutralizing agent is selected from one of tannin, sodium formate, sodium bicarbonate and formic acid.
6. The method for preparing ecological functional leather based on nanometer materials as claimed in claim 2 or 3, wherein the coating agent component of the upper coating comprises: 100-200 parts of water, 100-300 parts of polyurethane copolymer, 20-200 parts of nano graphene finishing agent, 2-20 parts of cross-linking agent, 0-30 parts of flatting agent and 0-20 parts of modified polysiloxane aqueous solution;
the oil return agent in the oil return process comprises the following components: 100 portions of water and 200 portions of synthetic fatting agent.
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