阅读说明：本技术 一种彩色鞋胚革的生产方法 (Production method of color shoe embryonic leather ) 是由 胡杰 陈永榜 姚庆达 李银生 刘伟 但卫华 于 2020-12-08 设计创作，主要内容包括：本发明公开了一种彩色鞋胚革的生产方法,包括如下工序：将经过挤水、削匀的蓝湿革组批、称重→中和→复鞣填充→加脂→富氨→染色固色；本申请在加脂与染色工序之间增加了富氨工序,富氨工序就是在这道工序中加入氨基,丰富的氨基一方面可以与皮胶原纤维上的活性羧基反应,增加胶原纤维上氨基的含量,增强胶原纤维的阳电性,提升与阴离子型染料的离子作用,促进阴离子型的吸附与结合。可以选用含苯环的多氨材料,含苯环的多氨材料可以提升与阴离子型染料的π-π相互作用,进一步促进阴离子型染料在皮胶原纤维内部的吸附与结合。(The invention discloses a method for producing color shoe embryonic leather, which comprises the following steps: batching, weighing → neutralizing → retanning filling → fatliquoring → enriching ammonia → dyeing and fixing the flushed and smoothed wet blue leather; 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.)

1. The production method of the color shoe embryonic leather is characterized by comprising the following steps: the flushed and smoothed wet blue leather is batched, weighed → neutralized → retanned filled → fatliquoring → rich ammonia → dyeing and color fixing.

2. The method for producing colored shoe embryonic leather according to claim 1, wherein the amino-containing organic substance and the carboxyl-containing organic substance are added in the ammonia-rich process, and are rotated in a rotary drum for 30 to 90 minutes.

3. The method for producing colored shoe embryonic leather according to claim 1, wherein the amino-containing organic substance and the carboxyl-containing organic substance are added in the dyeing process, and the ultrasonic wave is applied for 40 to 150 minutes, and the temperature is controlled to be 50 to 90 ℃.

4. The method for producing colored shoe embryonic leather according to claim 1, wherein the ammonia-rich process comprises the following specific steps: adding water in an amount which is 300 percent of the weight of the wet blue leather, then adding 1 to 3 percent of amino-containing organic matter, 0.5 to 1.5 percent of carboxyl-containing organic matter and 0 to 2 percent of acrylic resin, rotating the mixture in a rotary drum for 10 to 30 minutes, then adding 0.5 to 1.5 percent of amino-containing organic matter, 0.1 to 0.5 percent of carboxyl-containing organic matter, rotating the mixture for 10 to 30 minutes, finally adding 0.1 to 1.0 percent of carboxyl-containing organic matter, and rotating the mixture for 10 to 30 minutes.

5. 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 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.

6. The method for producing colored shoe embryonic leather according to claim 5, wherein the dye is an anionic dye.

7. The method for producing color shoe embryonic leather according to claim 5, wherein the metal tanning agent contains at least one metal element selected from zirconium, aluminum, iron, chromium and aluminum.

8. The method for producing colored shoe embryonic leather according to any one of claims 2 to 5, wherein the amino-containing organic substance is at least one of ethylenediamine, triethylamine, 1, 2-dinitrophenylhydrazine, 2, 4-dinitrophenylhydrazine, hydrazine, semicarbazide, and ethyleneurea.

9. The method for producing colored shoe embryonic leather according to any one of claims 2 to 5, wherein the carboxyl group-containing organic substance is at least one of oxalic acid, citric acid, ethylenediaminetetraacetic acid, lactic acid and boric acid.

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, the amino-containing organic matter and the carboxyl-containing organic matter are added in the dyeing procedure, the ultrasonic wave is acted for 40 to 150 minutes, and the temperature is controlled to be 50 to 90 ℃.

Further, the ammonia-rich process comprises the following specific steps: adding water in an amount which is 300 percent of the weight of the wet blue leather, then adding 1 to 3 percent of amino-containing organic matter, 0.5 to 1.5 percent of carboxyl-containing organic matter and 0 to 2 percent of acrylic resin, rotating the mixture in a rotary drum for 10 to 30 minutes, then adding 0.5 to 1.5 percent of amino-containing organic matter, 0.1 to 0.5 percent of carboxyl-containing organic matter, rotating the mixture for 10 to 30 minutes, finally adding 0.1 to 1.0 percent of carboxyl-containing organic matter, and rotating the mixture for 10 to 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 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.

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 fixing color, the multi-ammonia material and the multi-carboxyl material are mutually cooperated to form a stable complex structure with metal ions, so that the absorption of the metal tanning agent is promoted, the color fixing effect is improved, and simultaneously, the total weight metal and COD content in the waste liquid can be reduced by the synergistic effect of the three materials.

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 evenly 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 percent of synthetic grease (BSFR, Sch i l Sei l acher) and 5 percent of phosphate fatliquor (OSL, Toepler chemical) are added, and the mixture is rotated for 120 minutes. Adding 1% formic acid, adding in three times, rotating for 40 minutes, and draining.

4) Rich 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 Material Co., Szechwan) and 1-3% of dye (modern chemical Co., Ltd. in Tai of BG, mountain City of brown dye) into the ultrasonic dyeing instrument, performing ultrasonic wave action for 60 minutes at the temperature of 80 ℃, and then adding 1% of cationic oil (GS, Clariant chemical Co., Ltd.) 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 fatting 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.