CN101225450A - A kind of chrome-free tanning production process of goat glove leather - Google Patents

Abstract

The invention relates to a leather processing technology, in particular to a chrome-free tanning production technology of goatskin glove leather. The invention aims to solve the problem that the chromium-containing sewage seriously pollutes the environment in the existing chrome tanning technology. The object of the present invention is achieved through the following technical solutions: a chrome-free tanning production process of goatskin glove leather, including the following steps: softening → pickling → organic phosphine tanning → oxidation → standing on horseback → squeezing and stretching → Shave → water washing → degreasing, rinsing → water washing → retanning and fatliquoring → water washing, and then follow the conventional chrome tanning follow-up process. The invention has the advantages that it can overcome the environmental pollution caused by heavy metal chromium and reduce the cost of sewage treatment in enterprises. The formaldehyde content meets the standard of ecological leather, the shrinkage temperature (Ts) is as high as 88°C, and the physical and mechanical properties can fully meet the requirements of conventional chrome tanned leather.

Description

A kind of chrome-free tanning production process of goat glove leather

Technical field:

The invention relates to a leather processing technology, in particular to a chrome-free tanning production technology of goatskin glove leather.

Background technique:

Chrome tanning is the most widely used method in the world and has the best tanning effect. The leather tanned by it has many advantages such as heat and humidity resistance, good stability, soft and plump finished leather, and good formability. For more than one hundred years since the advent of chrome tanning, it has always occupied a dominant position with its superior tanning performance. With the progress of the times and the development of society, the chrome tanning method will also face severe challenges. On the one hand, the reserves of chromium in the world are limited after all, and the resources of chromium in my country are not abundant. It is an unavoidable reality that a large amount of use will be exhausted. Therefore, it is inevitable to study chromium-free tanning; As people pay more and more attention to their own living environment and quality of life, the environmental pollution problem of chrome tanning has become increasingly prominent. Moreover, with the improvement of people's quality of life, people's consumption concepts are also changing. Compared with before, they tend to pursue natural products and advocate the use of green materials to produce leather products. Pure chrome tanning has been difficult to fully meet the needs of consumers. Therefore, Research on chrome-free tanning has its realities. The emergence of green trade barriers and the implementation of sustainable development strategies reflect the enhancement of people's awareness of environmental protection, and also encourage people to seek pollution-free or low-pollution tanning methods that can replace chrome tanning. Friendly leather chemical materials (i.e. green leather materials) and process technology (i.e. clean process technology) are receiving more and more attention and support, and chrome-free tanning in clean process technology is undoubtedly the trend of leather development in the future.

Invention content:

The purpose of the present invention is to provide a non-production process for goat glove leather, so as to solve the problem of serious environmental pollution caused by chromium-containing sewage in the existing chrome tanning technology.

The object of the present invention is achieved through the following technical solutions:

A chrome-free tanning production process of goatskin glove leather, comprising the following steps: softening → pickling → organic phosphine tanning → oxidation → standing on horseback → squeezing and stretching → smoothing → water washing → degreasing, rinsing → water washing →Retanning and fatliquoring→Washing, and then follow the conventional chrome tanning follow-up process. The amount of additives added in each process is based on the quality of gray leather.

Pickling process: the liquid ratio is 80% (normal temperature), the amount of industrial salt is 6% to 8%, rotate for 20 minutes, control the Baume degree to 6.0 to 6.5, and then add 8% to 12 formic acid with a mass concentration greater than or equal to 85%. ‰, add in 2-3 times, rotate for 20 minutes each time, control the pH to 3.4-3.6, and rotate for 40 minutes;

The tanning process: carry out in the pickling solution, add organic phosphine tanning agent, the organic phosphine tanning agent is tetrakis hydroxymethyl phosphine sulfate, its dosage is 1.5% ~ 2.5%, after rotating for 120min, check the organic phosphine tanning agent with selenium indicator Whether the agent has penetrated completely (the incision is light yellow to prove that the penetration is complete), then stop the drum overnight, rotate for 30 minutes the next morning, add alkali in stages to adjust the pH to 5.5-5.7, rotate for 30 minutes each time, and rotate for 60 minutes at the end; then add 1.5%～ 2.5% synthetic tannin, rotate for 60 minutes;

The oxidation process: bleach with 0.5% to 1% oxidant (liquid ratio is 150%), rotate for 60min, remove residual organic phosphine tanning agent, check that the incision is not colored with a selenium indicator, and prove that the oxidation is complete;

The retanning and fatliquoring process: adding different syntans and fatliquors in stages. In this process, several synthetic tanning agents are selected for combined retanning. At the same time, in order to make the fatliquoring agent penetrate and distribute in the leather fiber evenly, several kinds of fatliquoring agents are used for step-by-step fatliquoring. Agent and fatliquoring agent can select known various products for use.

After the above-mentioned final water washing step, it also includes a refatting and water washing process. In the refatting process, 150% of water at 40-45°C is added, and then 2.0% of phosphate ester fatliquoring agent, 1.0% of synthetic Fatliquor, 3.0% non-ionic fatliquor, rotate for 60 minutes, then add 1.0% formic acid with a mass concentration greater than or equal to 85%, adjust the pH to 3.3-3.4, and rotate for 30 minutes. Fatliquor can be more evenly penetrated and distributed in the leather fiber.

After the above-mentioned final water washing step, retanning, water washing, neutralization, water washing, dyeing and fatliquoring steps are sequentially included. For high quality dyed leather.

In the above-mentioned tanning process, the alkali can be baking soda, sodium acetate, magnesium oxide or sodium carbonate; in the oxidation process,

The oxidizing agent can be hydrogen peroxide or sodium perborate.

In the above degreasing and rinsing process, 250% to 300% of water at 40 to 45°C is added, and at the same time, 0.45% to 0.5% of degreasing agent, 0.4% to 0.45% of oxalic acid, and 0.15% to 0.2% of polyphosphate , rotate for 60 minutes, and adjust the pH to 5.5-5.7.

Adding 0.1% to 0.5% ethylenediaminetetraacetic acid (E.D.T.A) in the degreasing, rinsing process and retanning and fatliquoring process can improve the whiteness of the white leather of the finished leather and the color brilliance of the dyed leather.

In the above-mentioned retanning and fatliquoring process, 1.5% to 2.5% of zirconium tanning agent or 2% to 4% of aluminum tanning agent can be added. The zirconium tanning agent is zirconium sulfate, and the content of zirconium trioxide is about 28%. ~35% (mass fraction); the aluminum tanning agent is basic aluminum chloride, and the content of aluminum oxide is about 40%-50% (mass fraction). To produce goatskin glove leather with high shrinkage temperature.

The above unexplained procedures are carried out according to the conventional process, and the unexplained leather chemicals are commonly used leather chemicals and are industrial products.

Compared with the prior art, the present invention has the advantages that: the use of organic phosphine tanning agent and the matching chrome-free tanning process to process goatskin glove leather can overcome the pollution of heavy metal chromium to the environment and reduce the cost of sewage treatment in enterprises. The environmentally friendly goat glove leather produced is soft, plump, elastic, elegant, fine-grained, and bright in color. The formaldehyde content of the finished leather meets the standard of ecological leather. The shrinkage temperature (Ts) is as high as 88°C. Meet the requirements of conventional chrome tanned leather.

The chrome-free tanned goatskin glove leather obtained according to the technique of the patent of the present invention is as follows through environmental protection performance test results:

Measurement items Formaldehyde content (mg/kg) Hexavalent chromium content (mg/kg) Pentachlorophenol (mg/kg) Carcinogenic aromatic amines (mg/kg)  Technical indicators of test results 55.32＜150 2.06＜4 Not detected <4 Not detected <28

Detailed ways:

A chrome-free tanning production process for goat glove leather, comprising the following steps in sequence: softening → pickling → organic phosphine tanning → oxidation → standing on horseback → squeezing and stretching → shaving → washing → degreasing, rinsing → washing → relapsing Tanning and fatliquoring→washing→refatting→washing→and then carry out conventional chrome tanning. The follow-up process can include hanging to dry → shoveling → dry cutting → softening → stretching → stretching (the operation of coating the leather is as follows: back cover → spraying surface paste → ironing → spraying the handle) → inspection and grading → measuring ruler storage. The whole process is basically the same as the current chrome tanning production process except for the main processes such as tanning and retanning, and the process can be changed and adjusted according to the existing chrome tanning production process.

The present invention is described in detail below through the examples, wherein only related to the improved process of the present invention, and the unillustrated process is carried out according to the conventional process.

Example 1:

process Amount/% Materials Temperature/℃ time/min pH Remark pickling 80 water room temperature 7.0 table salt 20 Measure Baume 6~6.5 1.0 Formic acid 2×20+40 3.4～3.6 tanned 2 Organic Phosphine Tanning Agent (Granofin FCC) 120 Overnight turn 30min the next day 0.4 baking soda 5×30+60 5.5～5.7 2.0 Synthetic Tannin (Tanicor KW) 60 Liquid control oxidation 150 water room temperature 0.7 Sodium perborate 60 Check for oxidation Washed 200 water room temperature 10 Take a horse test Ts ≥ 85 ℃ degreasing, rinsing 300 water 40 0.5 Degreaser (Tergolix SL-01) The amount of degreasing agent is based on 0.4 Oxalic acid Circumstances are adjusted appropriately 0.2 Polyphosphate (Feliderm MPP) 0.1 E.D.T.A. 60 5.5～5.7 Liquid control Washed 200 water 35 10 Liquid control Retanning, 100 water 35

Fatliquor 0.1 E.D.T.A. 60 2.0 Synthetic fatliquor (Derminol CST) 60℃ for fatliquor 2.0 Phosphate fatliquor (Derminol SF) Add after hot water emulsification 2.0 Styrene-maleic anhydride retanning agent (Tergotan TSP) 4.0 Resin retanning agent (Tergotan RFC) 40 6.0 Sulfone alternative synthetic tanning agent (TergotanS) 60 100 Water (55°C) 45 5 3.0 Sulfated natural oil (Derminol RA) 60℃ for fatliquor 3.0 Phosphate fatliquor (Derminol SF) 60 Add after hot water emulsification 1.0 Formic acid 10 1.0 Formic acid 45 3.5～3.6 Liquid control Washed 300 water 45 10 Liquid control Refat 150 water 45 2.0 Phosphate fatliquor (Derminol SF) Hot water for fatliquor 1.0 Synthetic fatliquor (Derminol CST) Add after emulsification 3.0 Non-ionic fatliquor (DermafinishLB) 60 1.0 Formic acid 30 3.3～3.4 Liquid control Washed 300 water 20 10 Liquid control

Note: English product codes are examples of products, all of which are products of Clariant, Switzerland.

Example 2:

process Amount/% Materials Temperature/℃ time/min pH Remark pickling 80 water room temperature 7.0 table salt 20 Measure Baume 6~6.5 1.0 Formic acid

0.3 Sulfuric acid (mass fraction 98%) 2×20+40 2.5～2.8 3 Zirconium tanning agent or aluminum tanning agent 60 0.5 baking soda 40 3.4～3.6 Tanning 2.5 Organophosphine tanning agent (Granofin FCC) 120 Overnight turn 30min the next day 1.0 Aromatic organic acid neutral salt (FelidermDP) 1.0 Cationic fatliquor (Catalix L) 60 0.3 Sodium Carbonate 5×30+60 5.5～5.7 2.0 Synthetic Tannin (Tanicor KW) 60 Liquid control oxidation 150 water room temperature 0.7 hydrogen peroxide 60 Check for oxidation Washed 200 water room temperature 10 Take a horse test Ts ≥ 85 ℃ Degreasing/rinsing 250 water 45 0.45 Degreaser (Tergolix SL-01) The amount of degreasing agent is based on 0.45 Oxalic acid Circumstances are adjusted appropriately 0.15 Polyphosphate (Feliderm MPP) 0.15 E.D.T.A. 60 5.5～5.7 Liquid control Washed 200 water 35 10 Liquid control Retanning, fatliquoring 100 water 35 4.0 Synthetic fatliquor (Derminol CST) 60℃ for fatliquor 3.0 Sulfated natural oil (Derminol RA) Add after hot water emulsification 2.0 Styrene-maleic anhydride copolymer (Tergotan TSP) 4.0 Resin retanning agent (Tergotan RFC) 60

5.0 Sulfone alternative synthetic tanning agent (TergotanS) 30 3.0 Aromatic Syntans (SyncotanMRL) 30 1.5 Dye (Derma Brown DR) 30 5.0 Tannin extract (Granifin AL) 60 100 water 45 5 5.0 Sulfated natural oil (Derminol RA) Add the fatliquor after emulsifying with hot water at 60°C 3.0 Phosphorylated fatliquor (Derminol SF) 60 1.0 Formic acid 10 1.0 Formic acid 45 3.5～3.6 Liquid control Washed 300 water 20 10 Liquid control

Note: English product codes are examples of products, all of which are products of Clariant, Switzerland.

Embodiment 3 (adopt this scheme when goatskin glove leather needs shrinkage temperature higher than 100 ℃):

process Amount/% Materials Temperature/℃ time/min pH Remark Before this treatment process is with embodiment 2. Retanning, fatliquoring 100 water 35 3.0 Phosphorylated Fatliquor (Derminol SF) 10 6.0 Tannin extract (Granofin TA) 40 1.5 Dye 20 3.0 Styrene-maleic anhydride copolymer (Tergotan TSP) 2.0 Sulfitated fatliquor (DerminolSJB) 60 1.0 Formic acid 30 3.5 1.0 Leveling agent (Dermagen PC) 40 Liquid control

Washed 300 water 5 Liquid control Retanning 100 water 35 2.0 Cationic oil (Catalix CX) 3.0 Zirconium tanning agent 60 1.0 Sodium formate 30 0.5 baking soda 30 4.2 Liquid control Washed 300 water 5 Liquid control neutralize 100 water 35 1.5 Sodium formate 20 1.0 ammonium bicarbonate 40 5.5 Liquid control Washed 300 water 5 Liquid control Dyeing, fatliquoring 100 water 45 1.0 Dye 20 4.0 Phosphorylated Fatliquor (DerminolSU-10) 3.0 Phosphorylated Fatliquor (Derminol SF) 4.0 Sulfitated fatliquor (DerminolSJB) 3.0 Sulfated natural oil (Derminol RA) 60 1.0 Formic acid 10 1.0 Formic acid 40 3.3 Liquid control Washed 300 water 10 Liquid control

Claims (7)

1. the chrome-free tanning production technique of goat skin gloves leather, include following step: softening → pickling → organic phosphine tanning → oxidation → as to take horse to leave standstill → water squeezing stretching, extension → shaving → washing → degreasing, rinsing → washing → retanning stuffing → washing, chrome tanning subsequent technique routinely carries out then, the addition of additive is a benchmark with the graywall quality in each operation

Pickling procedure: liquor ratio is 80% (normal temperature), the Industrial Salt consumption is 6%～8%, rotate 20min, the control degree Beaume is 6.0～6.5, add mass concentration then more than or equal to 85% formic acid 8%～12 ‰, divide 2-3 adding, rotate 20min at every turn, control pH is 3.4～3.6, rotates 40min again;

Described tanning operation: in pickling liquid, carry out, add the organic phosphine tanning agent, the organic phosphine tanning agent is a sulfuric acid tetra methylol phosphine, its consumption is 1.5%～2.5%, checks whether the organic phosphine tanning agent permeates fully (otch shows light yellow proof infiltration fully) with the selenium indicator behind the rotation 120min, stops then to rouse and spends the night, rotate 30min morning next day, it is 5.5～5.7 that gradation adds alkali adjusting pH, rotates 30min at every turn, rotates 60min at last; Add 1.5%～2.5% syntannin then, rotate 60min;

Described oxidation operation: the oxygenant with 0.5%～1% (liquor ratio is 150%) bleaching, rotate 60min, remove residual organic phosphine tanning agent, check that with the selenium indicator otch does not develop the color, prove that oxidation is complete;

Described retanning stuffing operation: carry out gradation with different synthetic tanning agentes and fatting agent and add.

2. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 1, it is characterized in that: also comprise stuffing again and washing step behind the described last water-washing step, be added with 150% 40～45 ℃ water in the stuffing operation again, 2.0% phosphate fat-liquoring agent, 1.0% synthetic fat liquor, 3.0% nonionic fatting agent are added in gradation then, rotate 60min, adding 1.0% mass concentration again, to regulate pH more than or equal to 85% formic acid be 3.3～3.4, rotates 30min.

3. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 1 is characterized in that: also include retanning again behind the described last water-washing step successively, washing, neutralization, washing, dyeing, stuffing operation.

4. as the chrome-free tanning production technique of claim 2 or 3 described a kind of goat skin gloves leather, it is characterized in that: in the described tanning operation, alkali is sodium bicarbonate, sodium-acetate, magnesium oxide or yellow soda ash; In the oxidation operation, oxygenant is hydrogen peroxide or Sodium peroxoborate.

5. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 4, it is characterized in that: in described degreasing, the rinsing process, be added with 250%～300% 40～45 ℃ water, add 0.45%～0.5% grease-removing agent simultaneously, 0.4%～0.45% oxalic acid, 0.15%～0.2% poly phosphate, rotate 60min, regulating pH is 5.5～5.7.

6. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 5 is characterized in that: add 0.1%～0.5% ethylenediamine tetraacetic acid (EDTA) (E.D.T.A) in described degreasing, rinsing process and the retanning stuffing operation.

7. the chrome-free tanning production technique of a kind of goat skin gloves leather as claimed in claim 6, it is characterized in that: in described retanning, the stuffing operation, add 1.5%～2.5% zirconium tanning agent again or add 2%～4% aluminum tanning agent, described zirconium tanning agent is a zirconium sulfate, about 28%～35% (massfraction) of zirconium sesquioxide content; Aluminum tanning agent is an aluminium chlorohydroxide, about 40%～50% (massfraction) of aluminium sesquioxide content.