CN114921597B - Production method of wear-resistant scratch-resistant chromium-free tanning sofa leather - Google Patents
Production method of wear-resistant scratch-resistant chromium-free tanning sofa leather 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
- C14C13/00—Manufacture of special kinds or leather, e.g. vellum
- C14C13/02—Manufacture of technical leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
- C14C1/065—Enzymatic unhairing
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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
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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
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention relates to the field of industrial leather manufacturing, and discloses a production method of wear-resistant scratch-resistant chrome-free tanning sofa leather, which comprises the following production steps: and (3) ash leaching: carrying out liming by adopting an auxiliary agent with strong dispersed collagen fibers and liming enzyme to cooperate with the dispersed fibers; softening: deeply softening the skin fiber by adopting low-temperature softening enzyme; tanning: tanning the leather blank by adopting zeolite tanning agent; retanning: retanning filling is carried out by adopting an acrylic acid-polyphenol polymer retanning agent; and (3) coating: coating with silica composite bi-component aqueous polyurethane. Compared with the existing processing technology of the wear-resistant leather, the processing of the leather is reinforced from the source (liming and softening), and the optimal chemical materials are preferably selected for combination, so that the leather base material has good compactness and low extensibility, and the coating has excellent wear resistance and scratch resistance. The production process can completely adopt the existing equipment and facilities for mass production, and the process is easy to control and has strong feasibility.
Description
Technical Field
The invention relates to the field of industrial leather manufacturing, in particular to a production method of wear-resistant scratch-resistant chrome-free tanning sofa leather.
Background
Leather is a common fabric for high-grade sofas. Because sofas are large pieces of furniture, which are typically used for years, their durability is increasingly receiving consumer attention. In the use process of the sofa, leather fabrics contacted with the outside are often subjected to friction and scraping effects, particularly the protruding parts of the edges of the suture lines are easy to damage due to friction and scraping, and quality problems such as cracking, coating falling and the like are caused. Friction and scratch thus constitute two independent quality indicators of leather. Meanwhile, along with the progress of society, consumers also put higher and higher requirements on the ecological environment-friendly performance of leather, wherein chrome-free tanning of leather has become a necessary trend of social development. Therefore, the development of the wear-resistant scratch-resistant chrome-free tanning sofa leather has obvious economic value and good social value.
The leather with high wear resistance and scratch resistance is prepared, and the key procedures of liming, softening, tanning, retanning, finishing and the like in the conventional production process are required to be systematically optimized, and particularly, chemical materials are strictly screened. As the properties of the finished leather are determined primarily by the chemical materials. Methods for producing abrasion resistant leather have been described in the prior art. The prior patent document CN103525957A increases the wear resistance by increasing the density of the leather, but the leather prepared by the method has high hardness and poor hand feeling, and loses the natural texture of the leather; the patent document CN109536647A is based on tanned leather, adopts chromium retanning, nano silver, nano titanium dioxide and other materials for treatment, adopts low-temperature (-40 ℃) freeze drying, and the leather prepared by the technology has no ecological and environmental protection property due to chromium, and has low-temperature freeze drying which cannot be matched with the existing leather making technology and equipment, thus the feasibility is not strong. Therefore, a set of production technology of chrome-free tanning sofa leather which is matched with the existing tanning technology and equipment and has high feasibility and excellent wear resistance and scratch resistance is required to be developed.
Disclosure of Invention
The invention provides a production method of wear-resistant scratch-resistant chrome-free tanning sofa leather aiming at the defects in the prior art.
In order to solve the technical problems, the invention is solved by the following technical scheme:
the production method of the wear-resistant scratch-resistant chromium-free tanning sofa leather comprises the following production steps of:
a) And (3) ash leaching: carrying out liming by adopting an auxiliary agent with strong dispersed collagen fibers and liming enzyme to cooperate with the dispersed fibers; adopting an auxiliary agent with strong collagen fiber dispersing capability and liming enzyme, wherein the two materials are used for fully dispersing dehaired peltry fibers in a synergistic way so as to promote the subsequent softening and tanning effects;
b) Softening: the leather fiber is deeply softened by adopting low-temperature softening enzyme, so that the penetration and combination of materials in the retanning process are ensured, the elongation of the finished leather is reduced, and a foundation is laid for the wear resistance and scratch resistance of the finished leather;
c) Tanning: the zeolite tanning agent is adopted to tan the leather blank, so that the traditional tanning with chromium powder is completely abandoned, the finished leather is ensured to have no heavy metal chromium, and the ecological characteristics of the product are outstanding. Meanwhile, the waste liquid discharged after tanning and the waste liquid in the subsequent working procedure are chromium-free, and the comprehensive waste water and the comprehensive sludge are easy to dispose;
d) Retanning: retanning filling is carried out by adopting an acrylic acid-polyphenol polymer retanning agent, and after the material enters the leather fiber, the intermolecular polymerization can be carried out, so that the compactness of leather is effectively improved, and the extensibility is reduced;
e) And (3) coating: coating with silica composite bi-component water-based polyurethane, wherein the component A is isocyanate prepolymer, the component B is polyhydroxy alcohol substance, the component C is water-dispersible silica sol, mixing the three components, rapidly and uniformly mixing, immediately conveying to a roll coater for roll coating, and endowing the leather coating with excellent toughness, wear resistance and scratch resistance.
Preferably, before the ash dipping process of the step a), batch, water dipping, meat removal and dehairing are further required, wherein the dehairing process comprises: adding 90-110 parts of water, SINTERAL DH-280.9-1.1 parts of dehairing auxiliary agent, 0.9-1.1 parts of dehairing protease DOWELLZYM (TM), rotating for 1h, adding 1.4-1.6 parts of lime and 1.4-1.6 parts of sodium sulfide, rotating for 1.8-2.2h until all hair falls off, and filtering hair.
Preferably, the ash dipping step of the step a) specifically includes: adding 180-220 parts of water, 0.9-1.1 parts of lime, 1.0-1.5 parts of liming enzyme DOWELLZYM LM, 1.0-2.0 parts of liming auxiliary SINTERAL B65 (organic acid sodium salt), 0.9-1.1 parts of degreasing agent Supralan, rotating for 18-22 minutes, then rotating for 4.5-5.5 minutes, stopping for 55-65 minutes, and lasting for 8-9 hours; draining, washing with water, and discharging from the drum.
Preferably, in the softening process of the step b), the weight of the trimmed skin blanks is calculated by 100 parts, 180-220 parts of water is added, the water temperature is 30-32 ℃, 1.8-2.2 parts of a deliming agent is added, the rotation is carried out for 8-12 minutes, 0.4-0.6 part of hydrochloric acid is added, the rotation is carried out for 35-45 minutes, the skin blank notch is checked (a phenolphthalein solution is used as an indicator, the skin center is in a first line red color), 1.8-2.2 parts of a softening enzyme DOWELLZYM CBK is added, the rotation is carried out for 90-120 minutes, and liquid is discharged.
Preferably, before the softening step of step b), the method comprises the steps of sheet ash skin trimming; after the softening process of step (b), a pickling step is included.
Preferably, in the tanning process of step c), 6.0 parts of ZLR100 reagent is added in the pickling solution, and rotated for 3.5-4.5 hours, 1.8-2.2 parts of baking soda is added (added in 4 times) until the pH=4.0-4.2; adding 30L of mildew preventive in 0.4-0.6 part, and rotating for 50-70 minutes; discharging liquid, discharging drum, lapping, draining, squeezing water, stretching, shaving, trimming and grading.
Preferably, after the tanning step of step c), further comprising 1) rewetting: adding the skin blank after being cut into a rotary drum, wherein the weight of the skin blank is calculated by 100 parts, water is 140-160 parts, a wetting agent ProSoak is added by 0.4-0.6 part, the water temperature is 22-25 ℃, and the skin blank is rotated for 25-35 minutes and drained; 2) And (3) neutralization: adding 90-110 parts of water, the water temperature is 30-35 ℃, adding 1.8-2.2 parts of neutralized tannin JNG, rotating for 18-22 minutes, adding 0.4-0.6 part of baking soda (added for 3 times), rotating for 35-45 minutes after finishing, and draining.
Preferably, in the retanning step of step d), 45-55 parts of water is added based on 100 parts of the weight of the skin blank, 3.8-4.2 parts of retanning agent Rheoskin 2000 (acrylic acid-polyphenol polymer) is added, and the retanning step is rotated for 18-22 minutes; adding 0.9-1.1 parts of Tara extract Tara, rotating for 18-22 minutes, heating the system to 40-45 ℃, adding 1.8-2.2 parts of acrylic retanning agent R83, and rotating for 35-45 minutes.
Preferably, after the retanning step of step d), the method further comprises the steps of:
and (3) adding grease: carrying out the retanning in the same bath, adding 2.8-3.2 parts of a fatting agent TRUPON SWS, rotating for 18-22 minutes, adding 1.8-2.2 parts of a fatting agent BAPROVOL BA, 0.14-0.16 part of an antioxidant 1010, and rotating for 35-45 minutes;
dyeing: the method is carried out in the same bath as retanning and fatliquoring, and for the conventional operation, the dye dosage is determined by the final color of the product, and the adopted dye is an environment-friendly dye;
fixing: adding 1.4-1.6 parts of zeolite tanning agent ZLR into the bath liquid, rotating for 25-35 minutes, and draining;
washing: 140-160 parts of water is added into the rotary drum, the rotary drum rotates for 13-17 minutes, liquid is discharged, and the liquid is discharged from the drum;
vacuum drying: vacuum temperature is 55-60 ℃, and vacuum time is 220-260 seconds;
and (3) drying the stretched plate, hanging and airing, buffing, conditioning, vibrating and softening and repairing the wound.
Preferably, in the coating step of step e), spraying, rolling, and spraying are combined, wherein: (1) 1 st spraying: 90-110 parts of deionized water, 45-55 parts of cationic waterborne polyurethane, 25-35 parts of waterborne pigment paste and 15-30g/m of spraying amount 2 Then drying at 100-130 ℃ for 1.8-2.2 minutes; (2) roller coating: 28-32 parts of deionized water, 28-32 parts of component A (isocyanate prepolymer), 18-22 parts of component B (polyhydric alcohol substance) and 18-22 parts of component C (water-dispersible silica sol), after being mixed, rapidly stirring and uniformly mixing for 1.8-2.2 minutes, immediately conveying to a roll coater for roll coating, wherein the roll coating quantity is 22-28g/m 2 Then drying at 100-130 ℃ for 1.8-2.2 minutes; (3) spraying for the 2 nd time: 90-110 parts of deionized water, 18-22 parts of light water-based polyurethane, 8-12 parts of cross-linking agent, 4-6 parts of handfeel agent and 8-12g/m of spraying amount 2 Then drying at 100-130 ℃ for 0.8-1.2 min, hanging and drying 22-And 26 hours.
The invention has the remarkable technical effects due to the adoption of the technical scheme: compared with the existing processing technology of the wear-resistant leather, the method strengthens the treatment of the leather from the source (liming and softening), and preferably combines the optimal chemical materials, thereby ensuring good compactness and low extensibility of the leather base material and excellent wear resistance and scratch resistance of the coating. The production process can completely adopt the existing equipment and facilities for mass production, and the process is easy to control and has strong feasibility.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The production method of the wear-resistant scratch-resistant chromium-free tanning sofa leather comprises the following production steps of:
a) And (3) ash leaching: carrying out liming by adopting an auxiliary agent with strong dispersed collagen fibers and liming enzyme to cooperate with the dispersed fibers, adding 200 parts of water, 1 part of lime, 1.0 part of liming enzyme DOWELLZYM LM, 2.0 parts of liming auxiliary agent SINTERAL B65 (organic acid sodium salt), 80 parts of degreasing agent Supralan, rotating for 20 minutes, then rotating for 5 minutes, stopping for 60 minutes, and lasting for 8-9 hours; discharging liquid, washing with water and discharging from the drum; adopting an auxiliary agent with strong collagen fiber dispersing capability and liming enzyme, wherein the two materials are used for fully dispersing dehaired peltry fibers in a synergistic way so as to promote the subsequent softening and tanning effects;
b) Softening: the method comprises the steps of deeply softening leather fibers by adopting low-temperature softening enzyme, specifically comprising the steps of adding 200 parts of water, 30-32 ℃ of water temperature, 2 parts of deliming agent, rotating for 10 minutes, 0.5 part of hydrochloric acid, rotating for 40 minutes, checking leather blank cuts (taking phenolphthalein solution as an indicator, and the appearance of first line red at the leather center), adding 2 parts of softening enzyme DOWELLZYM CBK, rotating for 90 minutes, draining liquid, ensuring the penetration and combination of materials in the retanning process, reducing the extensibility of finished leather, and laying a foundation for wear resistance and scratch resistance of the finished leather;
c) Tanning: tanning the leather blank by adopting zeolite tanning agent, adding 6.0 parts of ZLR100 reagent into the pickling solution, rotating for 4 hours, and adding 2 parts of baking soda (added in 4 times) until the pH value is=4.0-4.2; adding 30L of mildew preventive in 0.5 part, and rotating for 60 minutes; discharging liquid, discharging, lapping, draining, squeezing, stretching, shaving, trimming and grading, and completely discarding the traditional tanning of chromium powder, thereby ensuring that the finished leather has no heavy metal chromium and the ecological characteristics of the product are outstanding. Meanwhile, the waste liquid discharged after tanning and the waste liquid in the subsequent working procedure are chromium-free, and the comprehensive waste water and the comprehensive sludge are easy to dispose;
d) Retanning: retanning filling is carried out by adopting an acrylic acid-polyphenol polymer retanning agent, 50 parts of water is added according to 100 parts of the weight of the leather blank, 4 parts of retanning agent Rheoskin 2000 (acrylic acid-polyphenol polymer) is added, and the leather blank is rotated for 20 minutes; adding 1 part of Tara extract, rotating for 20 minutes, heating the system to 40-45 ℃, adding 83 parts of acrylic retanning agent R83 parts, rotating for 40 minutes, and polymerizing the material among molecules after entering leather fibers, so that the compactness of leather is effectively improved, and the extensibility is reduced;
e) And (3) coating: coating with silica composite bi-component water-based polyurethane, wherein the component A is isocyanate prepolymer, the component B is polyhydroxy alcohol substance, the component C is water-dispersible silica sol, mixing the three components, rapidly and uniformly, immediately conveying to a roll coater for roll coating, and the specific coating process comprises a mode of combining spray coating, roll coating and spray coating, wherein: (1) 1 st spraying: 100 parts of deionized water, 50 parts of cationic waterborne polyurethane, 30 parts of waterborne pigment paste and 15g/m of spraying amount 2 Then drying at 110 ℃ for 2 minutes; (2) roller coating: 30 parts of deionized water, 30 parts of component A (isocyanate prepolymer), 20 parts of component B (polyhydric alcohols) and 20 parts of component C (water-dispersible silica sol), and after being mixed, the components are rapidly stirred and evenly mixed for 2 minutes, and then the components are immediately conveyed to a roll coater for roll coating, wherein the roll coating amount is 25g/m 2 Then drying at 110 ℃ for 2 minutes;
(3) Spraying for the 2 nd time: 100 parts of deionized water, 20 parts of light water-based polyurethane, 10 parts of cross-linking agent, 5 parts of handfeel agent and 8-12g/m of spraying amount 2 And then drying for 1 minute at 110 ℃, hanging and airing for 24 hours, so that the leather coating is endowed with excellent toughness, wear resistance and scratch resistance.
Before the liming step of step a), batch, immersion, fleshing and unhairing are also required, wherein the unhairing step comprises: the weight of the fleshed skin embryo is calculated by 100 parts, 100 parts of water, SINTERAL DH parts of dehairing auxiliary agent, 1 part of dehairing protease DOWELLZYM (TM) and 1 part of dehairing auxiliary agent are added, the mixture is rotated for 1h, then 1.5 parts of lime and 1.5 parts of sodium sulfide are added, and the mixture is rotated for 2h until all hairs are separated, and the hairs are filtered.
Before the softening process of the step b), the method comprises the steps of sheet ash skin trimming; after the softening process of step (b), a pickling step is included.
After the tanning process of step c), further comprising 1) rewetting: adding the skin blank after being cut into a rotary drum, adding 15 parts of water by weight, adding 0.5 part of a wetting agent ProSoak by weight, rotating for 30 minutes at the water temperature of 22-25 ℃, and draining water; 2) And (3) neutralization: 100 parts of water, 30-35 ℃ of water temperature, 2 parts of neutralized tannin JNG and 0.5 part of baking soda (added for 3 times) are added, and after the completion of the addition, the mixture is rotated for 35-45 minutes, and discharged.
After the retanning step of step d), further comprising the steps of:
and (3) adding grease: carrying out the retanning in the same bath, adding 3 parts of a fatting agent TRUPON SWS, rotating for 20 minutes, adding 2 parts of a fatting agent BAPROVOL BA and 0.15 part of an antioxidant 1010, and rotating for 40 minutes;
dyeing: the method is carried out in the same bath as retanning and fatliquoring, and for the conventional operation, the dye dosage is determined by the final color of the product, and the adopted dye is an environment-friendly dye;
fixing: adding 100.5 parts of zeolite tanning agent ZLR into the bath liquid, rotating for 30 minutes, and draining;
washing: 150 parts of water is added into the rotary drum, the rotary drum is rotated for 14 minutes, liquid is discharged, and the rotary drum is discharged;
vacuum drying: vacuum temperature is 55-60 ℃ and vacuum time is 250 seconds;
and (3) drying the stretched plate, hanging and airing, buffing, conditioning, vibrating and softening and repairing the wound.
Example 2
Because the buffalo skin has larger position difference, the skin fibers are thicker and the grain surface is more damaged, the reinforcing fibers are dispersed, and the grain surface coverage is enhanced.
1.5 parts of the use amount of the liming enzyme DOWELLZYM LM in the liming procedure and 2.0 parts of the use amount of the liming auxiliary SINTERAL B65; in the softening process, the softening time is replaced by 120 minutes; in the coating operation, the 1 st spraying is replaced by 30g/m 2 The other operations are the same as in example 1.
Example 3
Brazil cattle hide fiber is knitted similar to U.S. cattle hide, but has more grain surface defects, and grain surface coverage should be enhanced when the Brazil cattle hide fiber is coated.
The spraying amount of the 1 st spraying in the coating procedure is replaced by 30g/m 2 The other operations are the same as in example 1.
TABLE 1 detection results of the main quality index of leather produced by the inventive technique
Using the techniques of the present invention (example 1, example 2, example 3), the primary quality index test results of the leather produced are shown in Table 1. Comparing the content of the current national standard GB/T16799-2018 shows that the measured index completely meets the requirement of the standard, and shows that the technology has applicability to raw leather from different sources.
(1) Influence of liming and softening degree on wear resistance and scratch resistance of product
Comparative example 1 (examination of the degree of fiber dispersion versus abrasion and scratch resistance)
The only difference from example 1 is that: in the liming operation, liming enzyme is not added, and the dosage of liming auxiliary SINTERAL B65 is replaced by 0.5 part; in the softening operation, the rotation time was changed to 30 minutes after adding the softening enzyme DOWELLZYM CBK, and the same procedure was repeated as in example 1.
TABLE 2 influence of the extent of liming and softening on the elongation, abrasion and scratch resistance of leather
Liming and softening are to disperse and open the fiber bundles of the pelt and release more active groups, thereby facilitating the penetration and combination of tanning agent and retanning agent, and ensuring good compactibility and low elongation of the base material (leather blank). The degree of liming and softening therefore affects the overall properties of the leather (including abrasion and scratch resistance). The elongation, abrasion resistance and scratch resistance of the leather prepared in comparative example 1 and comparative example 1 are compared in Table 2, wherein the elongation (21.3%) of the sample of comparative example 1 is significantly higher than that of example 1 (8.4%), indicating that the substrate (skin blank) prepared in comparative example 1 has a higher elongation and also results in a reduction in the scratch resistance of the sample coating (grade 3 at 20N). This indicates that insufficient graying and softening results in reduced scratch resistance of the leather product coating.
(2) Effect of retanning agent Rheoskin 2000 on abrasion and scratch resistance of products
Comparative example 2
The only difference from example 1 is that: in the retanning operation, the amount of retanning agent Rheoskin 2000 was replaced with 1.0 parts, otherwise as in example 1.
TABLE 3 Effect of retanning agent Rheoskin 2000 on leather elongation, abrasion and scratch resistance
After being combined with the leather fibers, the retanning agent has a fixing effect on the fibers, and macroscopically shows that the leather fibers are firmer and the extensibility is reduced. The ability of different retanning agents to fix the skin fibers is greatly different, and the different amounts of the same retanning agent have a great influence on the fixing degree of the skin fibers. The elongation, abrasion and scratch resistance properties of leather are compared in Table 3 for the retanning agent material Rheoskin 2000 in amounts of 4.0 parts (example 1) and 1.0 part (comparative example 2), respectively. The results show that at lower levels of retanning agent (comparative example 2), the elongation increase is more pronounced (16.4%) while a scratch resistance test is performed, a pressure of 15N already producing a clear scratch line (grade 2). Thus, the proper amount of retanning agent material Rheoskin 2000 should be ensured.
Rheoskin 2000 is a major component of an acrylic acid-polyphenol polymer which imparts good filling properties to leather without significantly degrading the feel of the leather. While the use of the tanning extract Tara or the acrylic retanning agent R83 is increased, although better filling property can be obtained, the hand feeling of leather is reduced. Therefore, based on the judgment of the overall performance of leather, rheoskin 2000 is a key material for preparing high-wear-resistance scratch-resistance chrome-free tanning sofa leather. (3) Influence of silica on abrasion and scratch resistance
Comparative example 3
The only difference from example 1 is that: the roll coating step of the finishing operation was carried out in the same manner as in example 1 except that the component C (water-dispersible silica sol) was not added.
TABLE 4 Effect of silica on leather abrasion and scratch resistance
The two-component polyurethane coating has excellent mechanical properties, and water can be selected as a dispersion in each component, so that the production process is ensured to be clean. Meanwhile, the silicon dioxide contains hydroxyl, so that the silicon dioxide can also be used as a reaction component to be added into the two-component polyurethane to strengthen the crosslinking of the coating. In addition, the unreacted silica is dispersed in the coating, which imparts good abrasion resistance and scratch resistance to the coating. The effect of silica on the abrasion and scratch resistance of the coating is compared in table 4, and the results show that the abrasion resistance of the leather is significantly better than that of the coating without silica (comparative example 3) and that the scratch resistance of the coating without silica (comparative example 3) is also poorer when silica is incorporated in the coating (example 1). The use of silica in the finishing process thus ensures excellent abrasion and scratch resistance of the coating.
(4) Influence of the two-component polyurethane on the abrasion resistance and scratch resistance
Comparative example 4
The only difference from example 1 is that: in the roll coating step of the finishing operation, 50 parts of aqueous polyurethane RODA Pur 64/N was used in place of the A component and the B component, and the same procedure as in example 1 was followed.
TABLE 5 influence of polyurethane types on the abrasion and scratch resistance of leather
The polyurethane type has a significant impact on the properties of the coating. In the experiment, equal parts of conventional aqueous polyurethane are adopted to replace double-component polyurethane, and the double-component polyurethane is compounded with silicon dioxide and then roll-coated. The results show that the coating obtained by the coating method has obviously poorer abrasion resistance and scratch resistance (see table 5). The reason is that under this condition, silica does not react sufficiently with polyurethane, resulting in a large amount of silica particles being embedded in the coating layer only in physical form, but rather causing damage to the properties of the coating layer.
Thus, based on the results of tables 4 and 5, it can be seen that: the component A (isocyanate prepolymer), the component B (polyhydric alcohol substance) and the component C (water-dispersible silica sol) adopted in the invention have good cooperativity, and can endow the coating with excellent wear resistance and scratch resistance under reasonable compounding.
Claims (10)
1. A production method of wear-resistant scratch-resistant chrome-free tanning sofa leather is characterized by comprising the following steps of: the production steps comprise:
a) And (3) ash leaching: carrying out liming by adopting an auxiliary agent with strong dispersed collagen fibers and liming enzyme to cooperate with the dispersed fibers;
b) Softening: deeply softening the skin fiber by adopting low-temperature softening enzyme;
c) Tanning: tanning the leather blank by adopting zeolite tanning agent;
d) Retanning: retanning filling is carried out by adopting an acrylic acid-polyphenol polymer retanning agent;
e) And (3) coating: coating with silica composite bi-component water polyurethane, wherein the component A is isocyanate prepolymer, the component B is polyhydroxy alcohol substance, the component C is water-dispersible silica sol, mixing, rapidly mixing, immediately conveying to a roll coater for roll coating, and drying at 100-130 ℃.
2. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: before the liming step of step a), batch, immersion, fleshing and unhairing are also required, wherein the unhairing step comprises: the weight of the fleshed skin embryo is calculated by 100 parts, 90-110 parts of water, 0.9-1.1 parts of dehairing auxiliary agent, 0.9-1.1 parts of dehairing protease are added, the mixture is rotated for 1h, then 1.4-1.6 parts of lime and 1.4-1.6 parts of sodium sulfide are added, and the mixture is rotated for 1.8-2.2h until all hair falls off, and the hair is filtered.
3. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: the ash dipping procedure of the step a) specifically comprises the following steps: adding 180-220 parts of water, 0.9-1.1 parts of lime, 1.0-1.5 parts of liming enzyme, 1.0-2.0 parts of liming auxiliary agent, 0.9-1.1 parts of degreasing agent, rotating for 18-22 minutes, then rotating for 4.5-5.5 minutes, stopping for 55-65 minutes, and lasting for 8-9 hours, wherein the weight of the fleshed skin embryo is calculated by 100 parts; draining, washing with water, and discharging from the drum.
4. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: in the softening process of the step b), the weight of the trimmed skin blanks is calculated by 100 parts, 180-220 parts of water is added, the water temperature is 30-32 ℃, 1.8-2.2 parts of a deliming agent is added, the rotation is carried out for 8-12 minutes, 0.4-0.6 part of hydrochloric acid is added, the rotation is carried out for 35-45 minutes, the cut of the skin blanks is inspected, 1.8-2.2 parts of softening enzyme is added, the rotation is carried out for 90-120 minutes, and liquid is discharged.
5. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: before the softening process of the step b), the method comprises the steps of sheet ash skin trimming; after the softening process of step (b), a pickling step is included.
6. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: in the tanning procedure of the step c), 6.0 parts of ZLR100 reagent is added in the pickling liquid, the rotary motion is carried out for 3.5 to 4.5 hours, and 1.8 to 2.2 parts of baking soda is added until the pH=4.0 to 4.2; adding 0.4-0.6 part of mildew inhibitor, and rotating for 50-70 minutes; discharging liquid, discharging drum, lapping, draining, squeezing water, stretching, shaving, trimming and grading.
7. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: after the tanning process of step c), further comprising 1) rewetting: adding the skin blank after being cut into a rotary drum, adding 140-160 parts of water by weight of 100 parts, adding 0.4-0.6 part of wetting agent by weight of 100 parts, rotating for 25-35 minutes at the water temperature of 22-25 ℃, and draining water; 2) And (3) neutralization: adding 90-110 parts of water, the water temperature is 30-35 ℃, adding 1.8-2.2 parts of neutral tannin, rotating for 18-22 minutes, adding 0.4-0.6 part of baking soda, rotating for 35-45 minutes after finishing, and draining.
8. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: in the retanning procedure of the step d), 45-55 parts of water is added according to 100 parts of the weight of the leather embryo, 3.8-4.2 parts of retanning agent Rheoskin is added, and the leather embryo is rotated for 18-22 minutes; adding 0.9-1.1 parts of tara tannin extract, rotating for 18-22 minutes, heating the system to 40-45 ℃, adding 1.8-2.2 parts of acrylic retanning agent, and rotating for 35-45 minutes.
9. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: after the retanning step of step d), further comprising the steps of:
and (3) adding grease: carrying out the retanning in the same bath, adding 2.8-3.2 parts of fatliquoring agent, rotating for 18-22 minutes, adding 1.8-2.2 parts of fatliquoring agent, 0.14-0.16 part of antioxidant and rotating for 35-45 minutes;
dyeing: the method is carried out in the same bath as retanning and fatliquoring, and for the conventional operation, the dye dosage is determined by the final color of the product, and the adopted dye is an environment-friendly dye;
fixing: adding 1.4-1.6 parts of zeolite tanning agent into the bath liquid, rotating for 25-35 minutes, and draining;
washing: 140-160 parts of water is added into the rotary drum, the rotary drum rotates for 13-17 minutes, liquid is discharged, and the liquid is discharged from the drum;
vacuum drying: vacuum temperature is 55-60 ℃, and vacuum time is 220-260 seconds;
and (3) drying the stretched plate, hanging and airing, buffing, conditioning, vibrating and softening and repairing the wound.
10. The method for producing the wear-resistant scratch-resistant chrome-free tanning sofa leather according to claim 1, which is characterized in that: in the coating process of the step e), a mode of combining spraying, rolling coating and spraying is adopted, wherein: (1) 1 st spraying: 90-110 parts of deionized water, 45-55 parts of cationic waterborne polyurethane, 25-35 parts of waterborne pigment paste and 15-30g/m of spraying amount 2 Then drying at 100-130 ℃ for 1.8-2.2 minutes; (2) roller coating: 28-32 parts of deionized water, 28-32 parts of isocyanate prepolymer, 18-22 parts of polyhydroxy alcohols and 18-22 parts of water-dispersible silica sol, and after mixing, rapidly stirring and uniformly mixing for 1.8-2.2 minutes, immediately conveying to a roll coater for roll coating, wherein the roll coating amount is 22-28g/m 2 Then drying at 100-130 ℃ for 1.8-2.2 minutes; (3) spraying for the 2 nd time: 90-110 parts of deionized water, 18-22 parts of light water-based polyurethane, 8-12 parts of cross-linking agent, 4-6 parts of handfeel agent and 8-12g/m of spraying amount 2 Then drying at 100-130 deg.C for 0.8-1.2 min, hanging and drying for 22-26 hr.
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| CN117305523B (en) * | 2023-10-08 | 2024-06-25 | 兄弟科技股份有限公司 | Method for improving retanning filling chromium-free tanning effect of leather scraps |
| CN117701787B (en) * | 2024-02-02 | 2024-05-03 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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