CN109628654B - Manufacturing process of waterproof chromium-free tanned leather - Google Patents
Manufacturing process of waterproof chromium-free tanned leather Download PDFInfo
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- 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
- C14B1/02—Fleshing, unhairing, samming, stretching-out, setting-out, shaving, splitting, or skiving skins, hides, or leather
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- 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
- C14B1/40—Softening or making skins or leather supple, e.g. by staking, boarding, or crippling machines, by dry mills
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- 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
- C14B1/58—Drying
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- 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
- C14C3/08—Chemical tanning by organic agents
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—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
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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
Abstract
The invention relates to the technical field of leather manufacturing processes, and provides a manufacturing process of waterproof chromium-free tanned leather, which comprises the steps of firstly carrying out pickling-free chromium-free combined tanning by adopting organic silicon modified polyurethane resin, an organic synthetic tanning agent and a multi-metal complex tanning agent, then carrying out chromium-free retanning and fixing by utilizing the multi-metal complex tanning agent, and filling and fatliquoring by using a waterproof polymer and a waterproof fatliquoring agent, wherein the obtained chromium-free tanned leather has excellent waterproofness and simultaneously has good physical and chemical properties and subsequent processing properties; the process adopts clean production technologies such as ammonia-free deliming softening one-bath, pickling-free and chrome-free combined tanning, chrome-free retanning, chrome-free fixing and the like in the implementation process, the prepared waterproof chrome-free leather is green, ecological and environment-friendly, excellent in waterproof performance, simple in process flow and strong in practicability, and pollution of heavy metal chrome is eliminated from the source, so that the process is suitable for industrial application.
Description
Technical Field
The invention relates to the technical field of leather-making chemistry and engineering, in particular to a manufacturing process of waterproof chrome-free tanned leather.
Background
In the past, chrome tanning is mainly adopted in leather manufacturing at home and abroad, and the chromium pollution caused by the chromium-containing waste water, the chromium-containing solid waste, the chromium-containing waste leather products and the like brings serious pollution to the environment, so that the problem becomes a technical bottleneck restricting the continuous development of the leather industry. Therefore, the development of the chromium-free ecological leather manufacturing technology is taken as the most important development direction of the leather industry in many developed countries in the world, and the chromium-free leather manufacturing technology is also listed as a key technology of 'Chinese manufacture 2025' in China. Through the continuous exploration of vast tanners for many years, various chrome-free tanning technologies such as organic tanning, vegetable tanning, non-chrome metal tanning and the like have been developed, but leather obtained by each tanning method has defects, such as poor heat resistance and poor washing resistance of organic tanning, hardness and softness of vegetable tanning and zirconium tanning plates and the like. Therefore, the development of a combined chrome-free tanning technology and the preparation of novel chrome-free tanned leather have important practical significance.
Besides chrome-free tanned leathers, functional leathers are another hot spot of current leather industry research. As the name implies, functional leather is leather having a certain characteristic function or performance on the basis of satisfying the conventional performance, including waterproof leather. At present, the research on waterproof leather is more, but the waterproof leather is basically based on chrome tanned wet blue leather, the subsequent wet dyeing and finishing is endowed with waterproofness, and the waterproof leather is fixed by a chrome tanning agent or a chrome-containing material, but the problem is still not well solved because the addition of the waterproof material brings negative effects on the physical and mechanical properties and the sensory properties of the leather. Therefore, the development of the chrome-free tanned leather with excellent waterproofness has good application prospect.
Disclosure of Invention
Therefore, aiming at the problems, the invention provides a manufacturing process of waterproof chrome-free tanned leather, which comprises the steps of firstly carrying out chrome-free combination tanning by adopting organic silicon modified polyurethane resin, organic synthetic tanning agent and multi-metal matched tanning agent, then carrying out chrome-free retanning and fixing by utilizing the multi-metal matched tanning agent, selecting waterproof polymer and waterproof fatliquoring agent with waterproof function for filling and fatliquoring, carrying out waterproof matching design and adjustment on tanning and wet dyeing and finishing, and finally preparing the chrome-free tanned leather with excellent waterproof performance, and simultaneously having good physical and chemical properties and subsequent processing performance; in addition, the process adopts clean production technologies such as ammonia-free deliming softening one-bath, pickling-free and chrome-free combined tanning, chrome-free retanning, chrome-free fixing and the like in the implementation process, the prepared waterproof chrome-free leather is green, ecological and environment-friendly, excellent in waterproof performance, simple in process flow and strong in practicability, and pollution of heavy metal chrome is eliminated from the source, so that the process is suitable for industrial application.
In order to realize the technical problem, the solution scheme adopted by the invention is as follows: a manufacturing process of waterproof chrome-free tanned leather sequentially comprises the following process steps: removing meat from grey pelts, splitting skins, weighing → deliming → softening → chrome-free tanning → standing, wringing, shaving, weighing → rewetting → chrome-free retanning → neutralization → filling → dyeing → fatliquoring → chrome-free fixing → after finishing; wherein, the deashing and softening process adopts a one-bath process, and an ammonia-free deashing agent and an ammonia-free softening enzyme are added in the deashing and softening one-bath process for deashing and softening;
the chrome-free tanning process adopts a pickling-free chrome-free combined tanning process, and organosilicon modified polyurethane resin, an organic synthetic tanning agent and a multi-metal matched tanning agent are added in the pickling-free chrome-free combined tanning process to carry out chrome-free combined tanning;
in the chrome-free retanning procedure, a multi-metal complex tanning agent, a glutaraldehyde tanning agent, an amphoteric amino resin tanning agent and the like are added for carrying out chrome-free retanning;
the filling, dyeing and fat-liquoring process adopts a one-bath process, and an acrylic resin tanning agent, a waterproof polymer, a plant tannin extract, an amino resin tanning agent, a dye and a waterproof fat-liquoring agent are added in the one-bath process for filling, dyeing and fat-liquoring;
in the chromium-free fixing procedure, an aluminum tanning agent and a multi-metal complex tanning agent are added for chromium-free fixing.
Further, the dosage of the reagent is calculated by the weight percentage of the grey naked skin at the back head layer of the split skin, and the deashing and softening one-bath process comprises the following steps: adding water 50-100% at 28-30 deg.C and ammonia-free deashing agent 1-3% into the rotary drum, rotating for 60-90min, adding ammonia-free softening enzyme 0.1-0.5%, rotating for 30-60min, checking whether the buttock incision is uniform and colorless with phenolphthalein, discharging liquid, and washing with water, wherein the final bath lotion has pH of 7.5-8.5.
Further, the non-pickling chromium-free combined tanning process comprises the following steps of (1) measuring the dosage of a reagent by weight percentage of the first grey naked hide after the split skin: adding water 20-50% at 25-30 deg.C and anti-twisting agent 0.1-0.2% into the rotary drum, and rotating for 10 min; adding 1-2% organosilicon modified polyurethane resin, and rotating for 60 min; adding 3-6% organic synthetic tanning agent, and rotating for 120 min; adding 5-15% multi-metal compound tanning agent, rotating for 180min, then rotating for 5min, stopping for 55min, repeating for 5-8 times; adding 0.1-0.5% of automatic alkali-extracting agent, rotating for 180min, and adjusting pH of bath liquid to 3.8-4.2; adding 150% hot water 100 and 100 times, adjusting the temperature of the bath liquid to 40-42 deg.C, rotating for 120min, discharging liquid, and taking out.
Wherein the organic synthetic tanning agent is Granofin Easy F-90, and the multi-metal complex tanning agent is at least one of a zirconium-aluminum-titanium complex tanning agent, an iron-zirconium-aluminum complex tanning agent and a zirconium-aluminum-silicon complex tanning agent.
Furthermore, the dosage of the reagent is calculated by the weight percentage of the evenly shaved chrome-free tanned wet white leather, and the chrome-free retanning process comprises the following steps: adding water 50-100% at 25-30 deg.C into the rotary drum, adding 0.5-1% formic acid, rotating for 30min, and adjusting pH of the bath liquid to 3.0-3.2; adding 1-2% glutaraldehyde tanning agent, and rotating for 30 min; adding 5-10% of multi-metal compound tanning agent, and rotating for 120 min; adding 1-2% sodium formate, and rotating for 60 min; adding 0.5-1.0% sodium bicarbonate for three times, each time at intervals of 30min, and adjusting bath liquid pH to 3.8-4.2; adding 1-3% amphoteric amino resin tanning agent, rotating for 60min, draining, and washing with water.
Furthermore, the dosage of the reagent is calculated by the weight percentage of the even white wet leather without chrome tanning, and the one-bath process of filling, dyeing and greasing comprises the following steps: adding water 30-50% at 25-30 deg.C into the rotary drum, adding waterproof polymer 3-6% and acrylic resin tanning agent 2-4%, and rotating for 60 min; adding 1-3% of waterproof fatting agent, and rotating for 40 min; adding 4-8% amino resin tanning agent, 2-6% plant tannin extract, 2-4% amphoteric acrylic polymer tanning agent, and 1-3% dye, rotating for 120min, and detecting full penetration of buttock incision dye; adding 1-2% of silane cross-linking agent and 6-10% of waterproof fatting agent, and rotating for 90 min; adding 100-150% of hot water at 50-60 deg.C, and rotating for 60 min; adding 1.5-3% formic acid for 4 times, each time at intervals of 20-30min, adjusting bath liquid pH to 3.5-3.7, draining, and washing with water.
Wherein the waterproof polymer is at least one of waterproof organic silicon polymer and waterproof acrylic polymer; the amino resin tanning agent is at least one of urea-formaldehyde resin, melamine resin and dicyandiamide resin; the plant tannin extract is at least one of chestnut tannin extract and tara tannin extract; the waterproof fatting agent is at least one of a silicon-containing waterproof fatting agent, a synthetic waterproof fatting agent and a wax-containing waterproof fatting agent.
Furthermore, the amount of the reagent is calculated by the weight percentage of the even-shaved chrome-free tanned wet-white leather, and the chrome-free fixing process comprises the following steps: adding water 200-250% at 35-40 deg.C into the rotary drum, adding aluminum tanning agent 1-2%, and rotating for 30 min; adding 1-2% waterproof fatting agent, and rotating for 30 min; adding 3-6% of multi-metal compound tanning agent, and rotating for 90 min; adding 0.5-1% of waterproof fatting agent, rotating for 20min, discharging liquid, washing for 2 times, and taking out.
Further, the post-finishing process comprises the steps of setting aside, squeezing and stretching, vacuum drying, hanging and drying, and vibrating and softening, wherein the moisture of the crust leather after vacuum drying is controlled to be 20-30%, and the moisture of the crust leather after hanging and drying is controlled to be 8-12%.
By adopting the technical scheme, the invention has the beneficial effects that: according to the manufacturing process of the waterproof chromium-free tanned leather, firstly, organic silicon modified polyurethane resin, an organic synthetic tanning agent and a multi-metal complex tanning agent are adopted for carrying out chromium-free combination tanning, then chromium-free retanning and fixing are carried out by utilizing the multi-metal complex tanning agent, and a waterproof polymer and a waterproof fatting agent are used for filling and fatting, so that the obtained chromium-free tanned leather has excellent waterproofness and simultaneously has good physical and chemical properties and subsequent processing properties;
the manufacturing process of the waterproof chromium-free tanned leather adopts ammonia-free deliming softening one-bath, pickling-free chromium-free combined tanning, chromium-free retanning, filling dyeing fatting one-bath and chromium-free fixing and cleaning production technologies in the implementation process, thereby omitting pickling operation, eliminating pollution of heavy metal chromium from the source, greatly reducing ammonia nitrogen and chloride ion pollution, reducing and simplifying process flow, shortening production period and reducing pollution treatment cost, and having remarkable economic benefit and environmental protection benefit.
In conclusion, the waterproof chromium-free leather prepared by the preparation process of the waterproof chromium-free tanned leather is green, ecological and environment-friendly, excellent in waterproof performance, simple in preparation process flow, simple and convenient to operate, strong in practicability and suitable for industrial production and application, and sensory performance and physical and mechanical performance meet requirements of industrial standards.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, so that how to apply technical means to solve technical problems and achieve technical effects can be fully understood and implemented, and it should be noted that the embodiments are only used for further description of the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adjustments according to the above disclosure.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. Various procedures and methods not described in detail are conventional methods well known in the art, and the source, trade name, and if necessary, the constituents of the reagents used are indicated at the first appearance.
A manufacturing process of waterproof chrome-free tanned leather comprises the following process steps:
step 1, soaking, liming, fleshing and flaking cattle hide to prepare softened pelts, and weighing the first layer of the flaked pelts;
step 2, deliming and softening one-bath (the dosage of the reagent is calculated by the weight percentage of the first layer ash pelts weighed in the step 1): adding water 80% at 30 deg.C and ammonia-free deliming agent 2% (DLY from Tsingtaki Kaisha new materials Co.), rotating for 60min, adding ammonia-free softening enzyme 0.3% (U5 from Deshel chemical Co.), rotating for 40min, checking whether the buttock incision is uniform and colorless with phenolphthalein, adjusting the pH of the final bath lotion to 8.0, and discharging.
Step 3, performing chromium-free tanning (the dosage of the reagent is calculated according to the weight percentage of the first layer gray bare leather weighed in the step 1): adding water of 25 deg.C 30% and anti-twisting agent (TJ-A9626 from Tnjiang New Material Co.) 0.1% into the rotary drum, and rotating for 10 min; adding 1.5% organosilicon modified polyurethane resin (KT 4031 of Kate New Material Co.), and rotating for 60 min; adding 4% organic synthetic tanning agent (F-90 of Stahl chemical Co., Ltd.), and rotating for 120 min; adding 12% multi-metal compound tanning agent (zirconium-aluminum-titanium compound tanning agent of Jinkun chemical company), rotating for 180min, then rotating for 5min, stopping for 55min, and repeating for 6 times; adding 0.4% automatic alkali-extracting agent (BTB-08 of Baochar chemical company), rotating for 180min, and adjusting pH of the bath solution to 3.9; adding 120% hot water twice, adjusting bath temperature to 40 deg.C, rotating for 120min, discharging liquid, and taking out.
Step 4, flatly paving and standing the obtained chrome-free tanned wet-white leather for two days, then squeezing and shaving the leather evenly, weighing the weight of the shaved chrome-free tanned wet-white leather, and determining the weight parts of the reagents used in the subsequent processing steps according to the weight;
and 5, rewetting (the reagent dosage is calculated by the weight percentage of the shaved wet and white leather weighed in the step 4): adding water of 200% at 40 deg.C into a rotary drum, adding 0.6% formic acid (conventional industrial formic acid) and 0.5% fatty aldehyde (PF of BASF chemical), rotating for 60min, and discharging liquid;
step 6, performing chromium-free retanning (the dosage of the reagent is calculated according to the weight percentage of the shaved wet white leather weighed in the step 4): adding water 80% at 30 deg.C and formic acid 0.5% into the rotary drum, rotating for 30min, and adjusting pH of the bath liquid to 3.0; adding 2% glutaraldehyde tanning agent (GT-50 of Pasteur chemical Co.), and rotating for 30 min; adding 5% multi-metal compound tanning agent (zirconium-aluminum-silicon compound tanning agent of Tingjiang new materials Co.), and rotating for 120 min; adding 1% sodium formate (conventional industrial sodium formate), and rotating for 60 min; adding 0.6% sodium bicarbonate (conventional industrial sodium bicarbonate) three times at intervals of 30min, and adjusting bath pH to 4.2; adding 2% amphoteric amino resin tanning agent (MAU of Toepler chemical company), rotating for 60min, draining, and washing with water;
and 7, neutralizing (the dosage of the reagent is calculated by the weight percentage of the shaved wet white leather weighed in the step 4): adding water of 30 deg.C 150%, waterproof neutralizing polymer (A of BASF chemical company) 2%, and sodium formate 1% into the rotary drum, and rotating for 20 min; adding 0.5% sodium bicarbonate, rotating for 60min to obtain final bath solution with pH of 4.8, draining, and washing with water.
And 8, filling, dyeing and fat liquoring one bath (the dosage of the reagent is calculated by the weight percentage of the shaved wet and white leather weighed in the step 4): adding 30% of water with the temperature of 30 ℃ into a rotary drum, adding 2% of waterproof organic silicon polymer (TJ-A9991 of Tingjiang New Material Co.), 3% of waterproof acrylic polymer (SOF of Delui chemical Co.), and 2% of acrylic resin tanning agent (RE of Pasteur chemical Co.), and rotating for 60 min; adding 1.5% silicon-containing waterproof fat-liquoring agent (CD of BASF chemical company) and 1% wax-containing waterproof fat-liquoring agent (HQ of Schill + Seilacher company), and rotating for 40 min; adding 2% melamine resin tanning agent (HB of Toeplier chemical company), 2% dicyandiamide resin tanning agent (DF-585 of Starter chemical company), 2% urea-formaldehyde resin (SK-10 of Securi chemical company), 2% TARA extract (TARA), 3% quebracho extract (KPS), 2% amphoteric acrylic resin tanning agent (TGR of Delry chemical company) and 2% black dye, rotating for 120min, and detecting buttock incision dye penetration; adding 1% silane crosslinking agent (KT 3007 of Kate New Material Co.), 3% silicon-containing waterproof fatting agent, 3% wax-containing waterproof fatting agent, and 2% synthetic waterproof fatting agent (WP of Stmite chemical Co.), and rotating for 90 min; adding 100-150% hot water at 60 deg.C, and rotating for 60 min; adding 3% formic acid for 4 times, each time at intervals of 20min, adjusting bath liquid pH to 3.5-3.7, draining, and washing with water.
Step 9, chromium-free fixation (the reagent dosage is calculated by the weight percentage of the shaved white wet leather weighed in the step 4): adding water of 200% at 35 deg.C into the rotary drum, adding 1.5% aluminum tanning agent (BN of Pasf chemical company), and rotating for 30 min; adding 1% silicon-containing waterproof fatting agent, and rotating for 30 min; adding 5% of multi-metal compound tanning agent, and rotating for 90 min; adding 1% silicon-containing waterproof fatting agent, rotating for 20min, draining, washing for 2 times, and taking out.
Step 10, after finishing: the method comprises the steps of setting aside, squeezing and stretching → vacuum drying → hanging and drying → shaking and softening, wherein the moisture of the crust leather after vacuum drying is controlled to be 20-30%, and the moisture of the crust leather after hanging and drying is controlled to be 8-12%.
The manufacturing process of the environment-friendly grain-falling leather has the following advantages:
a. in the step 2, deliming and softening are carried out by adopting an ammonia-free deliming agent and ammonia-free softening enzyme in one bath, so that ammonia nitrogen pollution in waste liquid can be effectively reduced, and the characteristics of mild action and deep penetration of the two materials are utilized, so that the deliming and softening process of the pelts is mild, uniform, deep and thorough, and the preparation is prepared for the next chromium-free combination tanning.
b. In the step 3, a pickling-free chromium-free combined tanning process is adopted, firstly, organic silicon modified polyurethane resin KT4031 is adopted for pretreatment, and the KT4031 is cationic polyurethane silica gel which has a good emulsifying and wetting effect on one hand, fully wets intradermal fibers before tanning and further disperses the fibers; on the other hand, the cationic charge of the tanning agent can effectively seal active groups such as carboxyl on the intradermal collagen fiber and ensure the penetration of the subsequent tanning agent, thereby omitting the pickling operation, saving chemical materials, simplifying the process flow and shortening the production period; in addition, KT4031 as polymer polysilicone material, itself has certain waterproof effect, lays the foundation for follow-up improvement leather waterproof nature. After pretreatment, an organic synthetic tanning agent F-90 and a zirconium-aluminum-titanium matched tanning agent are adopted for carrying out chrome-free combined tanning, the organic synthetic tanning agent F-90 and the zirconium-aluminum-titanium matched tanning agent are novel chrome-free tanning agents with high environmental protection performance and good tanning performance, but the novel chrome-free tanning agents have respective defects, F-90 tanned leather is not soft enough and compact and poor in heat resistance, a zirconium-aluminum-titanium tanned leather plate is not hard and soft and good in heat resistance, and the combination tanning of the organic synthetic tanning agent F-90 and the zirconium-aluminum-titanium tanned leather plate can. When in tanning, the characteristics of high pH resistance and good permeability of F-90 are utilized to firstly tan the naked skin, on one hand, the collagen fiber can be slightly shaped, and an active group which can be coordinated with the zirconium-aluminum-titanium complex tanning agent is introduced into the skin, and on the other hand, the pH value of bath liquid can be reduced to about 4-5 after the naked skin is firstly tanned, thereby being beneficial to deeper and more uniform penetration of the zirconium-aluminum-titanium complex tanning agent into the skin and leading the combined tanning to achieve the best synergistic tanning effect. And the liquid replenishing and temperature rising are carried out twice in the later stage of tanning, so that the tanning agent can be penetrated more deeply, the tanning effect is better and uniform, and the chrome-free tanned white wet leather is endowed with good physical and chemical properties. The chromium-free combination tanning eliminates the pollution of heavy metal chromium from the source, and the introduction of metal ions such as zirconium, aluminum, titanium and the like lays a good foundation for the absorption and fixation of subsequent waterproof materials.
c. And (4) flatly laying and standing the obtained chrome-free tanned wet white leather for two days in the step 4, which is favorable for hydrolysis and complexation of free tanning agent molecules among fibers in the leather, promotes the coordination of the tanning agent molecules and active groups on collagen, and enhances the tanning effect.
d. In the rewetting process in the step 5, a degreasing agent is not used, and the fatty aldehyde PF is used for rewetting, so that on one hand, the fatty aldehyde can help to disperse natural grease in the leather and promote the rewetting of the white wet leather, on the other hand, the fatty aldehyde does not influence the waterproof performance of the subsequent waterproof materials, and also helps to uniformly distribute the natural grease in the leather.
e. In the step 6, glutaraldehyde tanning agent GT-50 and zirconium-aluminum-silicon are adopted to carry out chrome-free retanning, the glutaraldehyde tanning agent GT-50 and the zirconium-aluminum-silicon are matched with a tanning agent to carry out chrome-free retanning, the glutaraldehyde tanning agent GT-50 and the zirconium-aluminum-silicon are used for carrying out chrome-free retanning, a more stable cross-linking structure can be formed between collagen molecules in leather, metal ions in the leather are distributed more uniformly, on one hand, a complementary tanning effect is achieved, the leather has good physical and chemical properties, on the other hand, metal ions such as zirconium, aluminum and the like which can be combined with subsequent waterproof materials in the leather. And the addition of the glutaraldehyde tanning agent can also increase the sensory properties of the crust leather, such as softness and the like, and make the subsequent waterproof materials more uniform in penetration. And the amphoteric melamine resin tanning agent is added at the back, so that on one hand, active groups such as carboxyl, amino and the like contained in the tanning agent can be compatible with metal ions such as zirconium, aluminum and the like to play a role in fixing the zirconium-aluminum-silicon compound tanning agent, and on the other hand, the combination and fixation of subsequent waterproof polymers are promoted by using the negative and positive electricity of the tanning agent.
f. In the step 7, the waterproof neutralization polymer A and the sodium formate are adopted for neutralization, and the characteristics of mild neutralization performance and good permeability of the polymer A and the sodium formate are utilized, so that the pH of the crust leather is slowly increased firstly, and the slow and uniform neutralization is ensured. Then adding baking soda with stronger neutralization performance, and gradually neutralizing the leather along the neutralization force in the front, wherein the three components are matched to ensure deep and uniform neutralization, and a foundation is laid for the uniform distribution of the subsequent waterproof fatting agent along the cross section of the leather from outside to inside. And the waterproof neutralizing polymer can not only play a role of uniform neutralization, but also initially form a waterproof layer in the leather along with the deepening and the uniformity of the neutralization, so that the leather is endowed with a certain waterproof function.
g. In the step 8, firstly, a waterproof organic silicon polymer TJ-A9991 and a waterproof acrylic polymer SOF which are waterproof and have filling capacity are selected and matched with an acrylic resin tanning agent RE for first-step filling, so that on one hand, the waterproof organic silicon polymer TJ-A9991 and the waterproof acrylic polymer SOF can more quickly and uniformly penetrate deep into leather to establish a waterproof system from the inside, and on the other hand, the polymer and the leather can firstly play a first-step filling role to prepare for subsequent main filling; then selecting a silicon-containing waterproof fatting agent CD and a wax-containing waterproof fatting agent HQ which have good waterproof performance and can endow the crust leather with softness and fullness, on one hand, further strengthening a waterproof system by utilizing the good waterproofness of the two materials, on the other hand, softening the crust leather by utilizing the softness and lubricity of the two materials, lubricating fibers, and utilizing the permeation of subsequent fillers such as tannin extract and the like; selecting amino resin with selective filling property, amphoteric acrylic resin, castanea mollissima extract and tara tannin extract with good permeability and filling property for main filling, so that on one hand, the crust leather is endowed with good skeleton and performance, and on the other hand, the crust leather plays a role in sealing the previously added waterproof polymer and waterproof oil, so that the crust leather forms a good waterproof layer; and then, the waterproof oil is added at low temperature in one bath, so that the absorptivity of the filling material and the waterproof fatting agent can be improved, on the other hand, the waterproof fatting agent added after filling can not only form a waterproof layer on the surface of the filling layer in the leather, but also can be deeply inserted into the filling layer together with part of subsequently penetrated fillers, so that the waterproof fatting agent can be penetrated better and uniformly and deeply, and is matched and combined with metal ions such as zirconium, aluminum and the like uniformly distributed in the leather to construct a better and stable waterproof layer structure. In addition, in the fatting process, a silane crosslinking agent KT 3007 is added, and various waterproof fatting agents can be crosslinked by utilizing the good crosslinking performance of the silane crosslinking agent KT 3007, so that a more stable waterproof structure is formed, and the waterproof performance is improved. And finally, adding formic acid for multiple times, and gradually reducing the pH value of the bath liquid, so that the waterproof fatting agent is uniformly and slowly absorbed and combined, and the crust leather is endowed with better and uniform waterproof performance.
h. In step 12, firstly adding an aluminum tanning agent BN to preliminarily fix the waterproof polymer and the waterproof fatting agent absorbed by the crust leather in the filling and fatting process, and ensuring the combination and fixation of the waterproof material in the crust leather; and then adding a waterproof fatting agent CD for 2 times, and carrying out secondary fixation by adopting a zirconium-aluminum-silicon matched tanning agent, so that on one hand, the fixation of a waterproof material in the leather is enhanced, and on the other hand, the crust leather is endowed with better waterproof and antifouling performances, thereby comprehensively ensuring that the crust leather has good waterproof performance.
The waterproof chromium-free leather prepared by the preparation process of the waterproof chromium-free tanned leather is green, ecological and environment-friendly, has excellent waterproof performance, and has sensory performance and physical and mechanical performance meeting the requirements of industrial standards. The detection shows that the dynamic waterproof frequency of the waterproof chrome-free tanned leather is more than 5 ten thousand times, the static water absorption rate is less than 20 percent, the tearing force is more than 60N, the shrinkage temperature is more than 90 ℃, the hand feeling is soft, full and elastic, and the grain surface is compact, fine and smooth. And the manufacturing process is simple in flow, simple and convenient to operate, high in practicability and suitable for industrial production and application.
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 (9)
1. A manufacturing process of waterproof chromium-free tanned leather sequentially comprises the following procedures of unhairing grey bare leather, splitting leather, weighing → deliming, softening → chromium-free tanning → standing, wringing, shaving, weighing → rewetting → chromium-free retanning → neutralization → filling, dyeing, fatliquoring → chromium-free fixing → after finishing, and is characterized in that:
the deashing and softening process adopts a one-bath process, and an ammonia-free deashing agent and an ammonia-free softening enzyme are added in the deashing and softening one-bath process for deashing and softening;
the chrome-free tanning process adopts a pickling-free chrome-free combined tanning process, and organosilicon modified polyurethane resin, an organic synthetic tanning agent and a multi-metal matched tanning agent are added in the pickling-free chrome-free combined tanning process to carry out chrome-free combined tanning;
in the chrome-free retanning procedure, a multi-metal complex tanning agent, a glutaraldehyde tanning agent and an amphoteric amino resin tanning agent are added for carrying out chrome-free retanning;
the filling, dyeing and fat-liquoring process adopts a one-bath process, and an acrylic resin tanning agent, a waterproof polymer, a plant tannin extract, an amino resin tanning agent, a dye and a waterproof fat-liquoring agent are added in the one-bath process for filling, dyeing and fat-liquoring;
in the chromium-free fixing procedure, an aluminum tanning agent and a multi-metal complex tanning agent are added for chromium-free fixing.
2. The manufacturing process of the waterproof chrome-free tanned leather according to claim 1, characterized in that: the reagent dosage is calculated by the weight percentage of the grey naked skin of the back head layer of the split skin, and the deashing and softening one-bath process comprises the following steps: adding water 50-100% at 28-30 deg.C and ammonia-free deashing agent 1-3% into the rotary drum, rotating for 60-90min, adding ammonia-free softening enzyme 0.1-0.5%, rotating for 30-60min, checking whether the buttock incision is uniform and colorless with phenolphthalein, discharging liquid, and washing with water, wherein the final bath lotion has pH of 7.5-8.5.
3. The manufacturing process of the waterproof chrome-free tanned leather according to claim 1, characterized in that: the agent dosage is calculated by the weight percentage of the grey naked leather of the back head layer of the sheet leather, and the pickling-free chromium-free combination tanning process comprises the following steps: adding water 20-50% at 25-30 deg.C and anti-twisting agent 0.1-0.2% into the rotary drum, and rotating for 10 min; adding 1-2% organosilicon modified polyurethane resin, and rotating for 60 min; adding 3-6% organic synthetic tanning agent, and rotating for 120 min; adding 5-15% multi-metal compound tanning agent, rotating for 180min, then rotating for 5min, stopping for 55min, repeating for 5-8 times; adding 0.1-0.5% of automatic alkali-extracting agent, rotating for 180min, and adjusting pH of bath liquid to 3.8-4.2; adding 150% hot water 100 and 100 times, adjusting the temperature of the bath liquid to 40-42 deg.C, rotating for 120min, discharging liquid, and taking out.
4. The process for manufacturing the waterproof chrome-free tanned leather according to claim 1 or 3, characterized in that: the organic synthetic tanning agent is Granofin Easy F-90; the multi-metal complex tanning agent is at least one of a zirconium-aluminum-titanium complex tanning agent, an iron-zirconium-aluminum complex tanning agent and a zirconium-aluminum-silicon complex tanning agent.
5. The manufacturing process of the waterproof chrome-free tanned leather according to claim 1, characterized in that: the agent dosage is calculated by the weight percentage of the white wet leather which is evenly shaved and tanned without chrome, and the chrome-free retanning process comprises the following steps: adding water 50-100% at 25-30 deg.C into the rotary drum, adding 0.5-1% formic acid, rotating for 30min, and adjusting pH of the bath liquid to 3.0-3.2; adding 1-2% glutaraldehyde tanning agent, and rotating for 30 min; adding 5-10% of multi-metal compound tanning agent, and rotating for 120 min; adding 1-2% sodium formate, and rotating for 60 min; adding 0.5-1.0% sodium bicarbonate for three times, each time at intervals of 30min, and adjusting bath liquid pH to 3.8-4.2; adding 1-3% amphoteric amino resin tanning agent, rotating for 60min, draining, and washing with water.
6. The manufacturing process of the waterproof chrome-free tanned leather according to claim 1, characterized in that: the reagent dosage is calculated by the weight percentage of the white wet leather without chrome tanning after shaving, and the one-bath process of filling, dyeing and greasing comprises the following steps: adding water 30-50% at 25-30 deg.C into the rotary drum, adding waterproof polymer 3-6% and acrylic resin tanning agent 2-4%, and rotating for 60 min; adding 1-3% of waterproof fatting agent, and rotating for 40 min; adding 4-8% amino resin tanning agent, 2-6% plant tannin extract, 2-4% amphoteric acrylic polymer tanning agent, and 1-3% dye, rotating for 120min, and detecting full penetration of buttock incision dye; adding 1-2% of silane cross-linking agent and 6-10% of waterproof fatting agent, and rotating for 90 min; adding 100-150% of hot water at 50-60 deg.C, and rotating for 60 min; adding 1.5-3% formic acid for 4 times, each time at intervals of 20-30min, adjusting bath liquid pH to 3.5-3.7, draining, and washing with water.
7. The process for manufacturing the waterproof chrome-free tanned leather according to claim 1 or 6, characterized in that: the waterproof polymer is at least one of waterproof organic silicon polymer and waterproof acrylic polymer; the plant tannin extract is at least one of chestnut tannin extract and tara tannin extract; the amino resin tanning agent is at least one of urea-formaldehyde resin, melamine resin and dicyandiamide resin; the waterproof fatting agent is at least one of a silicon-containing waterproof fatting agent, a synthetic waterproof fatting agent and a wax-containing waterproof fatting agent.
8. The manufacturing process of the waterproof chrome-free tanned leather according to claim 1, characterized in that: the reagent dosage is calculated by the weight percentage of the even-shaved chrome-free tanned wet-white leather, and the chrome-free fixing process comprises the following steps: adding water 200-250% at 35-40 deg.C into the rotary drum, adding aluminum tanning agent 1-2%, and rotating for 30 min; adding 1-2% waterproof fatting agent, and rotating for 30 min; adding 3-6% of multi-metal compound tanning agent, and rotating for 90 min; adding 0.5-1% of waterproof fatting agent, rotating for 20min, discharging liquid, washing for 2 times, and taking out.
9. The manufacturing process of the waterproof chrome-free tanned leather according to claim 1, characterized in that: the post-finishing process comprises the steps of setting up, standing, squeezing and stretching, vacuum drying, hanging and airing, and vibrating and softening, wherein the moisture of the crust leather after vacuum drying is controlled to be 20-30%, and the moisture of the crust leather after hanging and airing is controlled to be 8-12%.
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| CN111321260B (en) * | 2020-03-31 | 2022-01-28 | 河南中牛实业有限公司 | Environment-friendly chromium-free retanning method for leather |
| CN111893223B (en) * | 2020-08-28 | 2022-04-22 | 焦作隆丰皮草企业有限公司 | Retanning splitting process for environment-friendly vegetable elastic leather product |
| CN112501364B (en) * | 2020-12-08 | 2022-09-20 | 兴业皮革科技股份有限公司 | Preparation method of ecological functional leather based on nano material |
| CN113215332B (en) * | 2021-04-15 | 2022-04-26 | 兴业皮革科技股份有限公司 | Method for improving antibacterial performance of chrome-free tanned white wet leather |
| CN113201605B (en) * | 2021-04-15 | 2022-04-26 | 兴业皮革科技股份有限公司 | Tanning process for multi-component chrome-free combined tanned white wet leather of cattle and application thereof |
| CN113278740B (en) * | 2021-04-26 | 2022-07-26 | 安徽银河皮革有限公司 | Green processing method of ecological leather |
| CN113201606B (en) * | 2021-05-06 | 2022-10-18 | 兴业皮革科技股份有限公司 | Production process of heavy metal-free tanned cow leather |
| CN113462824B (en) * | 2021-06-11 | 2022-03-18 | 中国皮革制鞋研究院有限公司 | Method for improving performance of organic chrome-free tanned leather |
| CN113621741A (en) * | 2021-08-18 | 2021-11-09 | 东莞诺德科技有限公司 | Preparation process of waterproof leather |
| CN114231669B (en) * | 2021-09-28 | 2023-10-24 | 柏德皮革(中国)有限公司 | Compact leather crust leather process |
| CN114941043A (en) * | 2022-06-28 | 2022-08-26 | 河南中牛实业有限公司 | Retanning and dyeing method and application of environment-friendly cattle leather |
| CN115838841A (en) * | 2022-11-28 | 2023-03-24 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Method for preparing waterproof leather by using zeolite tanning agent and application thereof |
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| CN100360686C (en) * | 2005-12-02 | 2008-01-09 | 四川大学 | Clean production method of chromium-free automobile cushion leather |
| CN107641668B (en) * | 2017-09-27 | 2020-07-07 | 兴业皮革科技股份有限公司 | Clean ecological cattle vamp leather water field production process |
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