CN112538551B - Production method of color shoe embryonic leather - Google Patents
Production method of color shoe embryonic leather Download PDFInfo
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- CN112538551B CN112538551B CN202011420364.7A CN202011420364A CN112538551B CN 112538551 B CN112538551 B CN 112538551B CN 202011420364 A CN202011420364 A CN 202011420364A CN 112538551 B CN112538551 B CN 112538551B
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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
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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
- C14C3/04—Mineral tanning
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- 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
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
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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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/653—Nitrogen-free carboxylic acids or their salts
- D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
-
- 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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- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Coloring (AREA)
Abstract
The invention discloses a method for producing color shoe embryonic leather, which comprises the following steps: batching, weighing, neutralizing, retanning and filling → greasing → enriching ammonia → dyeing and fixing the blue wet leather which is subjected to wringing and shaving; the rich ammonia process has been increased between the fatliquoring and dyeing process to this application, and the rich ammonia process is just to add amino in this process, and abundant amino can react with the active carboxyl on the skin collagen fiber on the one hand, increases the content of amino on the collagen fiber, strengthens collagen fiber's positive electrical property, promotes with the ionic action of anionic dye, promotes the absorption and the combination of anionic. The polyammonia material containing benzene ring can promote the pi-pi interaction with anionic dye and promote the adsorption and combination of anionic dye inside collagen fiber.
Description
Technical Field
The invention relates to the technical field of leather making, in particular to a production method of color shoe embryonic leather.
Background
The dilemma which troubles the development of the color upper leather at present is mainly as follows: firstly, color upper leather needs to be subjected to color fixing treatment after retanning and fatliquoring, a chrome tanning agent is usually used for color fixing, the utilization rate of the chrome tanning agent in a fixing stage is low and is only about 70%, and the pressure of sewage treatment and ecological environment is increased by chromium-containing wastewater generated after color fixing; secondly, along with the enhancement of the consciousness of people on product consumption, the requirement on the color accuracy of the color leather is stricter. In the existing process, dyeing is usually carried out at the greasing tail end, and the dyeing process needs to be adjusted for many times, so that the dyeing period is long, and the leather chemical material is seriously wasted.
Disclosure of Invention
The embodiment of the application provides a production method of color shoe embryonic leather, an ammonia-rich process is added between the greasing process and the dyeing process, the ammonia-rich process is to add amino in the process, and on one hand, the rich amino can react with active carboxyl on skin collagen fiber, so that the content of the amino on the collagen fiber is increased, the cation property of collagen fiber is enhanced, the ionic effect with anionic dye is promoted, and the adsorption and combination of anionic dye are promoted.
The embodiment of the application provides a production method of color shoe embryonic leather, which comprises the following procedures: the flushed and smoothed wet blue leather is batched, weighed → neutralized → retanned filled → fatliquoring → rich ammonia → dyeing and color fixing.
Furthermore, in the ammonia-rich process, an amino-containing organic matter and a carboxyl-containing organic matter are added and rotate in a rotary drum for 30-90 minutes.
Furthermore, in the dyeing procedure, amino-containing organic matter and carboxyl-containing organic matter are added, ultrasonic wave is acted for 40-150 minutes, and the temperature is controlled to be 50-90 ℃.
Further, the ammonia-rich process comprises the following specific steps: adding water accounting for 100-300% of the weight of the wet blue leather, then adding amino-containing organic matter accounting for 1-3%, carboxyl-containing organic matter accounting for 0.5-1.5% and acrylic resin accounting for 0-2%, rotating the drum for 10-30 minutes, then adding amino-containing organic matter accounting for 0.5-1.5% and carboxyl-containing organic matter accounting for 0.1-0.5%, rotating the drum for 10-30 minutes, finally adding carboxyl-containing organic matter accounting for 0.1-1.0%, and rotating the drum for 10-30 minutes.
Further, the dyeing and color fixing process comprises the following specific steps: adding water accounting for 100 percent of the weight of wet blue leather, amino-containing organic matter accounting for 0.5 to 1 percent of the weight of wet blue leather, carboxyl-containing organic matter accounting for 1 to 3 percent of the weight of wet blue leather, metal tanning agent accounting for 1 to 2 percent of the weight of wet blue leather and dye accounting for 1 to 3 percent of the weight of wet blue leather, performing ultrasonic action for 30 to 120 minutes at the temperature of between 50 and 90 ℃, then adding cationic oil accounting for 1 to 2 percent of wet blue leather and performing ultrasonic action for 10 to 30 minutes.
Further, the dye is an anionic dye.
Further, the metal tanning agent contains at least one metal element of zirconium, aluminum, iron, chromium and aluminum.
Further, the amino-containing organic matter is at least one of ethylenediamine, triethylamine, 1, 2-dinitrophenylhydrazine, 2, 4-dinitrophenylhydrazine, hydrazine, semicarbazide and ethyleneurea.
Further, the organic matter containing carboxyl is at least one of oxalic acid, citric acid, ethylene diamine tetraacetic acid, lactic acid and boric acid.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the application has increased rich ammonia process between currying and dyeing process, and rich ammonia process is to add amino in this process, and abundant amino can react with the active carboxyl on the skin collagen fibre on the one hand, increases the content of amino on the collagen fibre, strengthens collagen fibre's cationic nature, promotes with the ionic reaction of anionic dye, promotes anionic absorption and combines. The polyammonia material containing benzene ring can promote the pi-pi interaction with anionic dye and promote the adsorption and combination of anionic dye inside collagen fiber.
The polyamino material is generally strong in alkalinity, in order to reduce hydrolysis of the polyamino to the collagen fiber, a small amount of polycarboxyl material is required to be added for neutralization, on one hand, the polycarboxyl material can react with amino to generate more stable amido bond to reduce alkalinity, and on the other hand, the polycarboxyl material can also cross-link the collagen fiber, the polyamino material and organic synthetic dye.
In the dyeing process, ultrasonic waves are adopted as an auxiliary means to enhance the movement of the high-molecular chain segment and enhance the permeation and combination of the material in the collagen fiber, so that the rapid dyeing is realized. In addition, the ultrasonic waves can also open the entanglement chain segments of the collagen fibers of the leather, further loosen the fibers, and soften crust leather by cooperating with organic amine, thereby improving the softness of the crust leather.
When the color is fixed, the polyamino material and the polycarboxyl material are cooperated with each other to form a stable complex structure with metal ions, so that the absorption of a metal tanning agent is promoted, the color fixing effect is improved, and meanwhile, the total weight metal and COD content in the waste liquid can be reduced due to the cooperation of the polyamino material, the polycarboxyl material and the metal ions.
Compared with the existing dyeing method, the dyeing method adopted by the application can reduce the dyeing time by more than 30%, and the softness of the embryonic leather can be improved by more than 10%.
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 production method of color shoe embryonic leather comprises the following steps:
1) batching and weighing the flushed and shaved wet blue leather
2) Neutralization
Adding water 200% of the weight of wet blue leather and formic acid 0.2% of the weight of wet blue leather into a rotary drum, rotating for 20 minutes, adding modified glutaraldehyde 1.2% (GT-50, Basff chemical Co., Ltd.) and anionic fatty alcohol sulfate 1% (LSW, Baume chemical Co., Ltd.), and rotating for 60 minutes; adding 2% synthetic tannin (FBV, Yixiang chemical company), 1% ammonium bicarbonate and 1% sodium formate, and rotating for 20 minutes; finally, 0.4% ammonium bicarbonate is added, and the mixture is drained after rotating for 40 minutes.
3) Retanning, filling and fatliquoring
The temperature of the rotary drum is controlled to be 35 ℃, zirconium aluminum tanning agent (TWLZ, Tingjiang chemical industry) accounting for 5 percent of the weight of wet blue leather is added into the rotary drum, the rotary drum is rotated for 30 minutes, then 2 percent of phenol synthetic tanning agent (340, Linqian technology), 10 percent of medium molecular acrylic acid (R-28, Linqian technology), 3 percent of macromolecular acrylic acid (RE, Basff chemical industry) are added, the rotary drum is rotated for 60 minutes, and then 2 percent of chestnut tannin extract (KPS, Jinfeng leather chemical industry), 2 percent of protein filler (FB, Desel chemical industry), 4 percent of melamine amino resin (DLF, Pasff chemical industry) are added, and the rotary drum is rotated for 120 minutes. Finally, the temperature is adjusted to 52 ℃, 10% synthetic grease (BSFR, Sch i l Sei l acher) and 5% phosphate fatliquor (OSL, Topule chemical) are added, and the mixture is rotated for 120 minutes. Adding 1% formic acid in three times, rotating for 40 min, and draining.
4) Rich in ammonia
200% water, 1.5% ethylene diamine, 0.5% 2, 4-dinitrophenylhydrazine, 0.5% citric acid, 2% acrylic resin (R83, Toeplier chemical dye (Jiaxing) Co., Ltd.) by weight of wet blue leather were added to the drum, and the drum was rotated for 10 minutes, then 0.5% ethylene diamine, 0.1% citric acid, and rotated for 10 minutes, and finally 0.3% citric acid, 0.5% ethylene diamine tetraacetic acid, and rotated for 10 minutes.
5) Dyeing and fixation
Putting the product obtained in the previous procedure into an ultrasonic dyeing instrument, adding 200% of water, 0.5% of ethylenediamine, 1% of citric acid, 1% of zirconium-aluminum tanning agent (TWLZ, New Sichuan Tingjiang Material Co., Ltd.), 1-3% of dye (modern chemical Co., Ltd. in Tai of BG, Mount City) into the ultrasonic dyeing instrument, performing ultrasonic wave action for 60 minutes at the temperature of 80 ℃, and then adding 1% of cationic oil (Craian chemical Co., Ltd. GS) into the ultrasonic dyeing instrument, and performing ultrasonic wave action for 10 minutes.
Comparative example 1
A production method of color shoe embryonic leather comprises the following steps:
comparative example 1 the production process is largely the same as example 1, the dye fixing procedure is different, and comparative example 1 has no ammonia rich procedure.
The dyeing and color fixing process comprises the following specific steps:
taking wet blue as a mass reference, adding 200% of water into a greased rotary drum, controlling the temperature to be 60 ℃, adding 1% of TWLZ, rotating for 30 minutes, adding a dye, rotating for 30 minutes, adding 0.3% of formic acid, rotating for 15 minutes, adding the dye, rotating for 30 minutes, adding 0.3% of formic acid, rotating for 15 minutes, finally adding a cationic greasing agent for 0.5%, and rotating for 15 minutes. For a total of 165 minutes.
The experimental tests of example 1 and comparative example 1 were carried out, and the obtained experimental data are shown in table 1:
TABLE 1
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 (4)
1. The production method of the color shoe embryonic leather is characterized by comprising the following steps: batching, weighing → neutralizing → retanning filling → fatliquoring → enriching ammonia → dyeing and fixing the flushed and smoothed wet blue leather;
the ammonia-rich process comprises the following specific steps: adding water accounting for 100-300% of the weight of the wet blue leather, then adding amino-containing organic matter accounting for 1-3%, carboxyl-containing organic matter accounting for 0.5-1.5% and acrylic resin accounting for 0-2%, rotating in the rotary drum for 10-30 minutes, then adding amino-containing organic matter accounting for 0.5-1.5% and carboxyl-containing organic matter accounting for 0.1-0.5%, rotating for 10-30 minutes, finally adding carboxyl-containing organic matter accounting for 0.1-1.0%, and rotating for 10-30 minutes;
the amino-containing organic matter is at least one of ethylenediamine, triethylamine, 1, 2-dinitrophenylhydrazine, 2, 4-dinitrophenylhydrazine, hydrazine, semicarbazide and ethyleneurea;
the organic matter containing carboxyl is at least one of oxalic acid, citric acid, ethylenediamine tetraacetic acid, lactic acid and boric acid.
2. The method for producing the colored shoe embryonic leather according to the claim 1, wherein the dyeing and color fixing process comprises the following specific steps: adding water accounting for 100-300% of the weight of the wet blue leather, amino-containing organic matter accounting for 0.5-1%, carboxyl-containing organic matter accounting for 1-3%, metal tanning agent accounting for 1-2% and dye accounting for 1-3%, performing ultrasonic action for 30-120 minutes at the temperature of 50-90 ℃, then adding cationic oil accounting for 1-2% and performing ultrasonic action for 10-30 minutes.
3. The method for producing colored shoe embryonic leather according to claim 2, wherein the dye is an anionic dye.
4. The method for producing color shoe embryonic leather according to claim 2, wherein the metal tanning agent contains at least one metal element selected from zirconium, aluminum, iron, chromium and aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011420364.7A CN112538551B (en) | 2020-12-08 | 2020-12-08 | Production method of color shoe embryonic leather |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011420364.7A CN112538551B (en) | 2020-12-08 | 2020-12-08 | Production method of color shoe embryonic leather |
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| CN112538551A CN112538551A (en) | 2021-03-23 |
| CN112538551B true CN112538551B (en) | 2022-09-09 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107881269B (en) * | 2017-11-30 | 2020-12-01 | 兴业皮革科技股份有限公司 | Production method of waterproof flame-retardant upper leather |
| CN109182620B (en) * | 2018-09-07 | 2021-09-21 | 兴业皮革科技股份有限公司 | Leather making method by step greasing |
| CN110628960B (en) * | 2019-09-09 | 2021-06-15 | 兴业皮革科技股份有限公司 | Production process of thick natural pattern-falling high-grade sofa leather |
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