1. A preparation process of green environment-friendly fluorine-free bio-based space synthetic leather is characterized by comprising the step of preparing synthetic leather by coating resin, wherein the coating resin comprises at least one of first polyester-polyether blend resin and second polyester-polyether blend resin, and the first polyester-polyether blend resin is prepared from the following components in parts by weight:

bio-based polyether polyol 11-13

Bio-based polyester polyol 7-9

4-6 small molecular chain extender

Isocyanate 9-11

60-66 parts of solvent;

the second polyester-polyether blended resin is prepared from the following components in parts by weight:

biobased polyether polyols 12-14

Bio-based polyester polyol 5-7

4-6 small molecular chain extender

Isocyanate 10-12

60-66 parts of solvent.

2. The process for preparing green environmental protection fluorine-free bio-based space synthetic leather according to claim 1, wherein the coating resin comprises a first polyester polyether blend resin and a second polyester polyether blend resin, wherein the first polyester polyether blend resin and the second polyester polyether blend resin are formulated according to the weight parts of (4-6) to (4-6).

3. The preparation process of green environment-friendly fluorine-free bio-based space synthetic leather according to any one of claims 1-2, which comprises the preparation of coating material, wherein the coating material comprises coating resin.

4. The preparation process of the green environment-friendly fluorine-free bio-based space synthetic leather according to claim 3, wherein the coating material comprises the following components: coating resin, dimethyl formamide, a non-ionic active agent, a fluorine-free hydrolysis-resistant auxiliary agent and a fluorine-free filling material, wherein the components are added in parts by weight of (95-105), (55-65), (1-2), (0.1-1) and (1.5-2.5) in sequence.

5. The preparation process of the green environment-friendly fluorine-free bio-based space synthetic leather according to claim 3, wherein the synthetic leather is prepared by the following steps:

step 1, impregnating the non-woven fabric in an impregnation tank added with an impregnating material, and controlling the pressure of an oil-impregnated press roller to be 5-5.5Kg and the speed to be 9 m/min;

step 2, after impregnation, the non-woven fabric passes through a pre-coagulation tank added with pre-coagulation solid liquid, the pre-coagulation sugar degree is 35-38%, and the pressure of a pre-coagulation oil pressing rod is controlled at 5-5.5 Kg;

step 3, after the treatment of the pre-coagulation tank, ironing the non-woven fabric by an ironing device, wherein the ironing temperature is controlled to be 45-50 ℃;

step 4, after ironing, the non-woven fabric passes through a coating table device provided with a coating knife, and the prepared coating material is coated on the non-woven fabric along a scraper;

step 5, conveying the non-woven fabric subjected to blade coating into a solidification tank with the length of 30 meters for solidification, wherein the solidification sugar degree is 16-18%, and the temperature is 28-32 ℃;

step 6, feeding the non-woven fabric solidified by the solidification tank into a washing tank for washing;

step 7, pre-ironing the non-woven fabric after the non-woven fabric is discharged from the water washing tank by an ironing roller at the temperature of 100-; and drying the pre-ironed non-woven fabric by using drying ovens, wherein the temperature of the drying ovens in the first group is 150 ℃, the temperature of the drying ovens in the second to fourth groups is 160 ℃, and the temperature of the drying ovens in the fifth group is 140 ℃, so that the production of the synthetic leather is finished.

6. The preparation process of the green environment-friendly fluorine-free bio-based space synthetic leather according to claim 5, wherein 15 groups of rinsing baths are arranged in the step 6, the rinsing sugar degrees of the first six groups are controlled to be 20-10%, the rinsing sugar degrees of the middle six groups are controlled to be 10-0%, and the rinsing sugar degrees of the last three groups are 0%; the water washing temperature of the last three groups is controlled at 65-75 ℃.

7. The preparation process of the green and environment-friendly fluorine-free bio-based space synthetic leather according to claim 5, wherein the impregnating resin comprises at least one of a hydrolysis-resistant bio-based impregnating resin I and a hydrolysis-resistant bio-based impregnating resin II, wherein the hydrolysis-resistant bio-based impregnating resin I is prepared from the following components in parts by weight:

biobased polyether polyol 9-11

Bio-based polyester polyol 6-8

3-5 parts of micromolecular chain extender

Isocyanate 8-10

68-72 parts of solvent;

the hydrolysis-resistant bio-based impregnating resin II is prepared from the following components in parts by weight:

bio-based polyether polyol 11-13

Biobased polyester polyol 4-6

3-5 parts of micromolecular chain extender

Isocyanate 7-9

68-72 parts of solvent.

8. The preparation process of the green environmental-friendly fluorine-free bio-based space synthetic leather as claimed in claim 7, wherein the impregnating resin comprises a hydrolysis-resistant bio-based impregnating resin I and a hydrolysis-resistant bio-based impregnating resin II, wherein the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II are prepared from (2-3) to (7-8) by weight.

9. The process for preparing green environment-friendly fluorine-free bio-based synthetic leather according to any one of claims 7 to 8, wherein the impregnation material comprises the following components: the impregnating resin, the dimethyl formamide and the fluorine-free hydrolysis-resistant auxiliary agent are added according to the weight parts of (95-105): (345) -355): 1-2.

10. The process for preparing green environmental-friendly fluorine-free bio-based space synthetic leather according to claim 5, wherein the non-woven fabric is bio-based non-woven fabric.

Background

The bio-based product mainly refers to wood cellulose agricultural wastes such as straws and the like except grains, and is an environment-friendly chemical product and green energy source produced by raw materials. The problems of bio-based products and green energy have become the leading edge of world science and technology, and are the necessary way for human beings to realize sustainable development.

At present, the process of applying the bio-based technology to the production of synthetic leather in the market of sports shoes is less, petroleum-based materials are mostly used for conventional synthetic leather, but the synthetic leather produced by adopting the petroleum-based technology is not green enough, the recycling rate is low, the biodegradability is poor, and fluorine is additionally added, so that the environmental pollution is easily caused.

The invention patent with publication number CN102359023B discloses a microfiber environmental protection flame retardant synthetic leather, which comprises a non-woven fabric, a bottom layer covered on the non-woven fabric, and a surface layer covered on the bottom layer, wherein the surface layer comprises: the adhesive layer covers the bottom layer, and slurry of the adhesive layer comprises the following raw materials in parts by weight: 80-100 parts of first polyurethane resin, 35-50 parts of solvent, 3-7 parts of flame retardant, 10-20 parts of environment-friendly color piece, 2-4 parts of curing agent and 0.5-1.5 parts of catalyst; the middle layer is covered on the bonding layer, and the slurry of the middle layer comprises the following raw materials in parts by weight: 80-100 parts of second polyurethane resin, 40-60 parts of solvent, 3-7 parts of flame retardant and 10-20 parts of environment-friendly color chips; the surface layer is covered on the middle layer, and the slurry of the surface layer comprises the following raw materials in parts by weight; 80-100 parts of third polyurethane resin, 60-80 parts of solvent, 3-7 parts of flame retardant and 10-20 parts of environment-friendly color chips; wherein the first polyurethane resin has a modulus of 25 to 35kg/cm²Molecular weight of 0.6X 10⁵-0.8×10⁵The polyurethane resin of (4); the second polyurethane resin has a modulus of 55-65kg/cm²A polyurethane resin having a molecular weight of 0.8X 105 to 1.0X 105; the third polyurethane resin has a modulus of 65-75kg/cm²Molecular weight 1X 10⁵-1.2×10⁵The polyurethane resin of (1).

Patent publication No. CN203229816U discloses an environment-friendly heat preservation polyurethane synthetic leather, which comprises a mesh non-woven fabric layer, wherein a fluff layer is woven on one surface of the mesh non-woven fabric layer, a resin layer is coated on the other surface of the mesh non-woven fabric layer, and the resin layer sequentially comprises an aqueous polyurethane adhesive layer, a polyurethane foaming layer and an aqueous polyurethane resin layer from bottom to top.

Both the two patents relate to environment-friendly synthetic leather, and the two are mainly used for the production process of the synthetic leather without adding chemicals, so that the produced synthetic leather does not contain excessive chemicals harmful to the environment, thereby reducing the environmental pollution and having certain environmental protection effect, but the environmental protection effect is limited, and higher environmental protection requirements cannot be met.

Disclosure of Invention

The method aims to solve the problems that in the prior art, the process of applying the bio-based technology to the production of synthetic leather is less, petroleum-based materials are mostly used, but the synthetic leather produced by adopting the petroleum-based technology is not green enough and environment-friendly, the recycling rate is low, the biodegradability is poor, and the environment is easily polluted by adding more fluorine. The invention provides a preparation process of green and environment-friendly fluorine-free bio-based space synthetic leather, which adopts bio-based materials to prepare the synthetic leather, does not contain fluorine, can repeatedly and circularly utilize the produced synthetic leather, has excellent biological degradability and has the characteristic of green and environment protection. The specific technical scheme is as follows:

a preparation process of green environment-friendly fluorine-free bio-based space synthetic leather comprises the steps of preparing synthetic leather by coating resin, wherein the coating resin comprises at least one of a first polyester-polyether blended resin and a second polyester-polyether blended resin, and the first polyester-polyether blended resin is prepared from the following components in parts by weight:

the second polyester-polyether blended resin is prepared from the following components in parts by weight:

compared with common resin, the coating resin is mainly prepared from renewable bio-based raw materials, can replace the original petroleum-based raw materials, can be recycled, has more excellent biodegradable performance, and is more environment-friendly for synthetic leather made of the raw materials.

Preferably, the coating resin comprises a first polyester-polyether blend resin and a second polyester-polyether blend resin, wherein the first polyester-polyether blend resin and the second polyester-polyether blend resin are prepared according to the weight parts of (4-6) to (4-6).

Preferably, the method comprises preparing a coating material, wherein the coating material comprises a coating resin.

Preferably, the coating comprises the following components: coating resin, dimethyl formamide, a nonionic activator, a fluorine-free hydrolysis-resistant auxiliary agent and a fluorine-free filling material, wherein the components are added in parts by weight of (95-105), (55-65), (1-2), (0.1-1) and (1.5-2.5) in sequence.

The fluorine-free filler is added in the coating resin, so that the fullness of the slurry can be improved; the nonionic surfactant is added, so that the stripping effect of the PU layer can be improved, the solidification speed of the coating material can be increased, and the production efficiency can be improved.

Preferably, the coating resin is stirred at the stirring speed of 1000-1500r/min at normal temperature for 30-35min until the coating resin, the dimethyl formamide, the nonionic activator, the fluorine-free hydrolysis-resistant auxiliary agent and the fluorine-free filler are completely dissolved, the stirring speed is reduced to 300 +/-50 r/min after the slurry is stirred uniformly, vacuum defoaming is carried out for 90min at the temperature of 28-32 ℃, and the viscosity is controlled to be 14000-15000 cps.

Preferably, the synthetic leather is manufactured by the following steps:

step 1, impregnating the non-woven fabric in an impregnation tank added with an impregnating material, and controlling the pressure of an oil-impregnated press roller to be 5-5.5Kg and the speed to be 9 m/min;

step 2, after impregnation, the non-woven fabric passes through a pre-coagulation tank added with pre-coagulation solid liquid, the pre-coagulation sugar degree is 35-38%, and the pressure of a pre-coagulation oil pressing rod is controlled at 5-5.5 Kg;

step 3, after the treatment of the pre-coagulation tank, ironing the non-woven fabric by an ironing device, wherein the ironing temperature is controlled to be 45-50 ℃;

step 4, after ironing, the non-woven fabric passes through a coating table device provided with a coating knife, and the prepared coating material is coated on the non-woven fabric along a scraper;

step 5, conveying the non-woven fabric subjected to blade coating into a solidification tank with the length of 30 meters for solidification, wherein the solidification sugar degree is 16-18%, and the temperature is 28-32 ℃;

step 6, feeding the non-woven fabric solidified by the solidification tank into a washing tank for washing;

step 7, pre-ironing the non-woven fabric after the non-woven fabric is discharged from the water washing tank by an ironing roller at the temperature of 100-; and drying the pre-ironed non-woven fabric by using an oven, wherein the temperature of the oven in the first group is 150 ℃, the temperature of the oven in the second group to the oven in the fourth group is 160 ℃, and the temperature of the oven in the fifth group is 140 ℃, so that the production of the synthetic leather is finished.

Preferably, 15 groups of water washing tanks are arranged in the step 6, the water washing sugar degrees of the first six groups are controlled to be 20-10%, the water washing sugar degrees of the middle six groups are controlled to be 10-0%, and the water washing sugar degrees of the last three groups are 0%; the water washing temperature of the latter three groups is controlled at 65-75 ℃.

Preferably, the method further comprises a step 8 of rolling the product after drying, wherein the rolling thickness is 1.3-1.4mm, and the width is 145-147 cm.

Preferably, in step 4, the coating gap between the scraper and the coating is controlled to be 225 +/-5 filaments, and the coating payment is 1.48 +/-0.05 kg/y.

Preferably, the impregnating compound comprises an impregnating resin, the impregnating resin comprises at least one of a hydrolysis-resistant bio-based impregnating resin I and a hydrolysis-resistant bio-based impregnating resin II, wherein the hydrolysis-resistant bio-based impregnating resin I is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin II is prepared from the following components in parts by weight:

preferably, the impregnating resin comprises a hydrolysis-resistant bio-based impregnating resin I and a hydrolysis-resistant bio-based impregnating resin II, wherein the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II are prepared according to the weight parts of (2-3) to (7-8).

Preferably, the impregnation material comprises the following components: the impregnating resin, the dimethyl formamide and the fluorine-free hydrolysis-resistant auxiliary agent are added according to the weight parts of (95-105): (345) -355): 1-2.

Preferably, the prepared impregnation material is stirred for 15-20 minutes at the stirring speed of 1000-1500r/min at normal temperature until the impregnation resin, the dimethylformamide and the fluorine-free hydrolysis-resistant auxiliary agent are completely dissolved, and the viscosity is controlled at 100-200 cps.

Preferably, the nonwoven fabric is a bio-based nonwoven fabric.

Preferably, the bio-based non-woven fabric adopts the bio-based non-woven fabric with the physical property standard of not less than 18 percent of blasting, not less than 350 percent of 3CM stretching, not less than 30 to 70 percent of elongation and not less than 55 percent of 5CM tearing.

Has the advantages that:

the technical scheme of the invention has the following beneficial effects:

(1) compared with common resin, the first polyester-polyether blended resin and the second polyester-polyether blended resin are all bio-based polyurethane resin mainly prepared from renewable bio-based raw materials, the resin is high in solid content and free of fluorine, the original petroleum-based raw materials are replaced, the resin can be recycled, the biodegradability is excellent, the synthetic leather prepared from the raw materials is more environment-friendly, and the hydrolysis resistance is good. The first hydrolysis-resistant bio-based impregnating resin and the second hydrolysis-resistant bio-based impregnating resin are adopted, the resin has excellent color development, does not contain fluorine, replaces the original petroleum-based raw material, is renewable, can be recycled, has excellent biodegradable performance, and also has the characteristics of environmental protection. The resin is matched with the bio-based non-woven fabric for manufacturing the synthetic leather, the recycling rate of the produced synthetic leather is extremely high, and the pollution to the environment is greatly reduced.

(2) The products produced by the invention are all fluorine-free products, the fluorine-free products can not cause fluorine pollution to the environment and human body, have good environmental protection property, also meet the environmental protection requirement of the times, improve the conditions of fluorine-containing and the like of common synthetic leather, and have better environmental protection property. The product of the invention has high recoverability, all raw materials use bio-based raw materials, the defects of difficult petroleum-based biodegradation and low recovery utilization rate are overcome, and the long-term strategy of sustainable development is realized.

(3) In the prior art, the situation of lowering the physical property of synthetic leather usually occurs when the bio-based technology is adopted for preparing the synthetic leather, the physical property of the product produced by the invention can not be lowered while the product can be recycled, the quality is light, the product is soft and comfortable, the product is suitable for footwear products, particularly sports footwear, but the product can also meet the use physical property requirements of part of clothes.

Detailed Description

The embodiments described in this disclosure are some, but not all embodiments of the inventions. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making an invasive task, are within the scope of the present invention. Thus, the following detailed description of embodiments of the invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.

A preparation process of green environment-friendly fluorine-free bio-based space synthetic leather comprises the steps of preparing synthetic leather by coating resin, wherein the coating resin comprises at least one of first polyester-polyether blend resin and second polyester-polyether blend resin, and the first polyester-polyether blend resin is prepared from the following components in parts by weight:

the second polyester-polyether blended resin is prepared from the following components in parts by weight:

compared with common resin, the coating resin is mainly prepared from renewable bio-based raw materials, can replace the original petroleum-based raw materials, can be recycled, has more excellent biodegradable performance, and is more environment-friendly for synthetic leather made of the raw materials.

The solid content of the prepared first polyester-polyether blended resin is 30%, the hundred percent modulus is 60, the tensile strength is more than 45MPa, the elongation is more than or equal to 500, and the viscosity range is 18-25 ten thousand.

The solid content of the prepared second polyester-polyether blended resin is 30%, the hundred percent modulus is 40, the tensile strength is more than 45MPa, the elongation is more than or equal to 500, and the viscosity range is 18-25 ten thousand.

In a preferred embodiment, the solvent in the first polyester-polyether blend resin and the second polyester-polyether blend resin is a solution of DMFA.

As a preferred embodiment, the solvent in the first polyester-polyether blend resin and the second polyester-polyether blend resin comprises a DMFA solution and an MEK solution, wherein the weight part ratio of the DMFA solution to the MEK solution is 65: 5.

As a preferred embodiment, the coating resin comprises a first polyester-polyether blend resin and a second polyester-polyether blend resin, wherein the first polyester-polyether blend resin and the second polyester-polyether blend resin are formulated in the weight ratio of (4-6) to (4-6).

The preparation of the coating material is a preferred embodiment, and the coating material comprises a coating resin.

As a preferred embodiment, the coating comprises the following components: coating resin, dimethyl formamide, a non-ionic active agent, a fluorine-free hydrolysis-resistant auxiliary agent and a fluorine-free filling material, wherein the components are added in parts by weight of (95-105), (55-65), (1-2), (0.1-1) and (1.5-2.5) in sequence.

In a preferred embodiment, the coating resin further contains a color paste, and the weight ratio of the color paste is adjusted according to the material.

The fluorine-free filler is added in the coating resin, so that the fullness of the slurry can be improved; the nonionic surfactant is added, so that the stripping effect of the PU layer can be improved, the solidification speed of the coating material can be increased, and the production efficiency can be improved.

As a preferred embodiment, the coating resin is stirred at the stirring speed of 1000-1500r/min at normal temperature for 30-35min until the coating resin, the dimethyl formamide, the nonionic activator, the fluorine-free hydrolysis-resistant auxiliary agent and the fluorine-free filler are completely dissolved, the stirring speed is reduced to 300 +/-50 r/min after the slurry is stirred uniformly, vacuum deaeration is carried out for 90min, the temperature is 28-32 ℃, and the viscosity is controlled to be 14000-15000 cps.

As a preferred embodiment, the synthetic leather is manufactured by the following steps:

step 1, impregnating the non-woven fabric in an impregnation tank added with an impregnating material, and controlling the pressure of an oil-impregnated press roller to be 5-5.5Kg and the speed to be 9 m/min;

step 2, after impregnation, the non-woven fabric passes through a pre-coagulation tank added with pre-coagulation solid liquid, the pre-coagulation sugar degree is 35-38%, and the pressure of a pre-coagulation oil pressing rod is controlled at 5-5.5 Kg;

step 3, after the treatment of the pre-coagulation tank, ironing the non-woven fabric by an ironing device, wherein the ironing temperature is controlled to be 45-50 ℃;

step 4, after ironing, the non-woven fabric passes through a coating table device provided with a coating knife, and the prepared coating material is coated on the non-woven fabric along a scraper;

step 5, conveying the non-woven fabric subjected to blade coating into a solidification tank with the length of 30 meters for solidification, wherein the solidification sugar degree is 16-18%, and the temperature is 28-32 ℃;

step 6, feeding the non-woven fabric solidified by the solidification tank into a washing tank for washing;

step 7, pre-ironing the non-woven fabric after the non-woven fabric is discharged from the water washing tank by an ironing roller at the temperature of 100-; and drying the pre-ironed non-woven fabric by using an oven, wherein the temperature of the oven in the first group is 150 ℃, the temperature of the oven in the second group to the oven in the fourth group is 160 ℃, and the temperature of the oven in the fifth group is 140 ℃, so that the production of the synthetic leather is finished.

As a preferred embodiment, step 6 is provided with 15 groups of rinsing baths, the rinsing sugar degrees of the first six groups are controlled to be 20-10%, the rinsing sugar degrees of the middle six groups are controlled to be 10-0%, and the rinsing sugar degrees of the last three groups are 0%; the water washing temperature of the last three groups is controlled at 65-75 ℃.

In a preferred embodiment, in step 6, the nonwoven fabric is observed to measure the thickness and width after it is coagulated in the coagulation tank and before it is washed in the water tank.

As a preferred implementation mode, the method further comprises a step 8 of rolling the product after drying, wherein the rolling thickness is 1.3-1.4mm, and the width is 145-147 cm.

In a preferred embodiment, in step 4, the coating gap between the scraper and the coating is controlled to be 225 +/-5 filaments, and the coating payment is controlled to be 1.48 +/-0.05 kg/y.

In a preferred embodiment, the impregnating compound comprises an impregnating resin, and the impregnating resin comprises at least one of a hydrolysis-resistant bio-based impregnating resin No. one and a hydrolysis-resistant bio-based impregnating resin No. two, wherein the hydrolysis-resistant bio-based impregnating resin No. one is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin II is prepared from the following components in parts by weight:

the prepared hydrolysis-resistant type I bio-based impregnating resin has the solid content of 30 percent, the hundred percent modulus of 70, the tensile strength of more than 35MPa, the elongation of more than or equal to 400 and the viscosity range of 10-12 ten thousand.

The solid content of the prepared hydrolysis-resistant bio-based impregnating resin II is 30%, the hundred percent modulus is 100, the tensile strength is more than 35MPa, the elongation is more than or equal to 400, and the viscosity range is 15-18 ten thousand.

In a preferred embodiment, the solvent in the hydrolysis-resistant bio-based impregnating resin No. one and the hydrolysis-resistant bio-based impregnating resin No. two is a DMFA solution.

In a preferred embodiment, the solvents in the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II comprise a DMFA solution and an MEK solution, wherein the ratio of the DMFA solution to the MEK solution in parts by weight is 65: 5.

In a preferred embodiment, the impregnating resin comprises a hydrolysis-resistant bio-based impregnating resin I and a hydrolysis-resistant bio-based impregnating resin II, wherein the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II are prepared according to the weight parts of (2-3) to (7-8).

As a preferred embodiment, the impregnation material comprises the following components of impregnation resin, dimethyl formamide and fluorine-free hydrolysis-resistant auxiliary agent which are added according to the weight parts of (95-105), (345) -355) and (1-2).

In a preferred embodiment, the soaking material further comprises color paste, and the weight parts of the color paste are adjusted according to the material.

As a preferable embodiment, the prepared impregnation material is stirred for 15-20 minutes at the stirring speed of 1000-.

In a preferred embodiment, the nonwoven fabric is a bio-based nonwoven fabric.

In a preferred embodiment, the bio-based non-woven fabric has physical property standards of blasting being equal to or more than 18, 3CM stretching being equal to or more than 350, elongation being equal to or more than 30% -70%, and 5CM tearing being equal to or more than 55.

The sugar degree in the invention is the concentration of DMF in DMF water solution, and the data is obtained after measurement by an Abbe refractometer.

Example one

A preparation process of green environment-friendly fluorine-free bio-based space synthetic leather comprises the steps of preparing synthetic leather by coating resin, wherein the coating resin comprises a first polyester-polyether blend resin and a second polyester-polyether blend resin, and the first polyester-polyether blend resin is prepared from the following components in parts by weight:

the second polyester-polyether blended resin is prepared from the following components in parts by weight:

the first polyester-polyether blended resin and the second polyester-polyether blended resin are prepared according to the weight ratio of 5: 5.

Also comprises the preparation of a coating material, wherein the coating material comprises the following components: the coating comprises coating resin, dimethyl formamide, a nonionic active agent, a fluorine-free hydrolysis-resistant auxiliary agent, a fluorine-free filling material and color paste, wherein the components are added in a weight ratio of 100:60:1:0.5:2.2:1 in sequence. The coating resin is stirred for 30-35min at the normal temperature at the stirring speed of 1000-1500r/min until the coating resin, the dimethyl formamide, the nonionic active agent, the fluorine-free hydrolysis-resistant auxiliary agent, the fluorine-free filler and the color paste are completely dissolved, the stirring speed is reduced to 300 +/-50 r/min after the slurry is stirred uniformly, vacuum defoaming is carried out for 90min at the temperature of 28-32 ℃, and the viscosity is controlled to be 14000-15000 cps.

The specific manufacturing method of the synthetic leather comprises the following steps:

step 1, impregnating the non-woven fabric in an impregnation tank added with an impregnating material, and controlling the pressure of an oil-impregnated press roller to be 5-5.5Kg and the speed to be 9 m/min;

step 2, after impregnation, the non-woven fabric passes through a pre-coagulation tank added with pre-coagulation solid liquid, the pre-coagulation sugar degree is 35-38%, and the pressure of a pre-coagulation oil pressing rod is controlled at 5-5.5 Kg;

step 3, after the treatment of the pre-coagulation tank, ironing the non-woven fabric by an ironing device, wherein the ironing temperature is controlled to be 45-50 ℃; specifically, the nonwoven fabric was ironed by a 6-wheel ironing device.

Step 4, after ironing, the non-woven fabric passes through a coating table device provided with a coating knife, and the prepared coating material is coated on the non-woven fabric along a scraper; wherein, the coating gap between the scraper and the coating is controlled at 225 plus or minus 5 threads, and the coating weight is 1.48 plus or minus 0.05 kg/y;

step 5, conveying the non-woven fabric subjected to blade coating into a solidification tank with the length of 30 meters for solidification, wherein the solidification sugar degree is 16-18%, and the temperature is 28-32 ℃;

step 6, feeding the non-woven fabric solidified by the solidification tank into a washing tank for washing; specifically, 15 groups of water washing tanks are arranged, the water washing sugar degrees of the first six groups are controlled to be 20-10%, the water washing sugar degrees of the middle six groups are controlled to be 10-0%, and the water washing sugar degrees of the last three groups are 0%; the water washing temperature of the last three groups is controlled at 65-75 ℃; specifically, the non-woven fabric is observed firstly before being washed in a water tank after being solidified in a solidification tank, and the thickness and the width are measured.

Step 7, pre-ironing the non-woven fabric after the non-woven fabric is discharged from the water washing tank by an ironing roller at the temperature of 100-; drying the pre-ironed non-woven fabric by using an oven, wherein the temperature of the oven in the first group is 150 ℃, the temperature of the ovens in the second group to the fourth group is 160 ℃, and the temperature of the oven in the fifth group is 140 ℃, so that the production of the synthetic leather is finished; specifically, 8-wheel ironing rollers are adopted for pre-ironing.

And 8, winding the product after drying, wherein the winding thickness is 1.3-1.4mm, and the width is 145-147 cm.

Specifically, in the embodiment, the impregnation material in the step 1 comprises the following components of impregnation resin, dimethyl formamide, a fluorine-free hydrolysis-resistant auxiliary agent and color paste, and the components are sequentially added according to the weight parts of 100:350:1: 3. Stirring the prepared soaking material at the normal temperature at the stirring speed of 1000-1500r/min for 15-20 minutes until the soaking resin, the dimethyl formamide, the fluorine-free hydrolysis-resistant auxiliary agent and the color paste are completely dissolved, and controlling the viscosity at 100-200 cps; the impregnation resin comprises a first hydrolysis-resistant bio-based impregnation resin and a second hydrolysis-resistant bio-based impregnation resin, wherein the first hydrolysis-resistant bio-based impregnation resin is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin II is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II are prepared according to the weight part ratio of 3: 7.

Specifically, in the embodiment, the non-woven fabric adopts a bio-based non-woven fabric with the physical property standards of blasting being more than or equal to 18, 3CM stretching being more than or equal to 350, elongation being more than or equal to 30-70%, and 5CM tearing being more than or equal to 55.

The sugar degree in the invention is the concentration of DMF in DMF water solution, and the data is obtained after measurement by an Abbe refractometer.

Example two

A preparation process of green environment-friendly fluorine-free bio-based space synthetic leather comprises the steps of preparing synthetic leather by coating resin, wherein the coating resin comprises a first polyester-polyether blend resin and a second polyester-polyether blend resin, and the first polyester-polyether blend resin is prepared from the following components in parts by weight:

the second polyester-polyether blended resin is prepared from the following components in parts by weight:

the first polyester-polyether blended resin and the second polyester-polyether blended resin are prepared according to the weight ratio of 5: 6.

The method also comprises the preparation of a coating material, wherein the coating material comprises coating resin, dimethyl formamide, a nonionic active agent, a fluorine-free hydrolysis-resistant auxiliary agent, a fluorine-free filler and color paste, and the components are added in the following weight parts of 95:55:1.5:0.3:1.8: 2. The coating resin is stirred at the normal temperature at the stirring speed of 1000-1500r/min for 30-35min until the coating resin, the dimethyl formamide, the nonionic active agent, the fluorine-free hydrolysis-resistant auxiliary agent, the fluorine-free filler and the color paste are completely dissolved, the stirring speed is reduced to 300 +/-50 r/min after the slurry is stirred uniformly, vacuum deaeration is carried out for 90min, the temperature is 28-32 ℃, and the viscosity is controlled to be 14000-15000 cps.

The specific manufacturing method of the synthetic leather comprises the following steps:

step 1, impregnating the non-woven fabric in an impregnation tank added with an impregnating material, and controlling the pressure of an oil-impregnated press roller to be 5-5.5Kg and the speed to be 9 m/min;

step 2, after impregnation, the non-woven fabric passes through a pre-coagulation tank added with pre-coagulation solid liquid, the pre-coagulation sugar degree is 35-38%, and the pressure of a pre-coagulation oil pressing rod is controlled at 5-5.5 Kg;

step 3, after the treatment of the pre-coagulation tank, ironing the non-woven fabric by an ironing device, wherein the ironing temperature is controlled to be 45-50 ℃; specifically, the nonwoven fabric was ironed by a 6-wheel ironing device.

Step 4, after ironing, the non-woven fabric passes through a coating table device provided with a coating knife, and the prepared coating material is coated on the non-woven fabric along a scraper; wherein, the coating gap between the scraper and the coating is controlled at 225 plus or minus 5 threads, and the coating weight is 1.48 plus or minus 0.05 kg/y;

step 5, conveying the non-woven fabric subjected to blade coating into a solidification tank with the length of 30 meters for solidification, wherein the solidification sugar degree is 16-18%, and the temperature is 28-32 ℃;

step 6, feeding the non-woven fabric solidified by the solidification tank into a washing tank for washing; specifically, 15 groups of water washing tanks are arranged, the water washing sugar degrees of the first six groups are controlled to be 20-10%, the water washing sugar degrees of the middle six groups are controlled to be 10-0%, and the water washing sugar degrees of the last three groups are 0%; the water washing temperature of the last three groups is controlled at 65-75 ℃; specifically, the non-woven fabric is observed firstly before being washed in a water tank after being solidified in a solidification tank, and the thickness and the width are measured.

Step 7, pre-ironing the non-woven fabric after the non-woven fabric is discharged from the water washing tank by an ironing roller at the temperature of 100-; drying the pre-ironed non-woven fabric by using an oven, wherein the temperature of the oven in the first group is 150 ℃, the temperature of the ovens in the second group to the fourth group is 160 ℃, and the temperature of the oven in the fifth group is 140 ℃, so that the production of the synthetic leather is finished; specifically, 8-wheel ironing rollers are adopted for pre-ironing.

And 8, winding the product after drying, wherein the winding thickness is 1.3-1.4mm, and the width is 145-147 cm.

Specifically, in this embodiment, the impregnation material in step 1 includes the following components: the color paste comprises an impregnating resin, dimethyl formamide, a fluorine-free hydrolysis-resistant auxiliary agent and color paste, wherein the components are sequentially added according to the weight parts of 95:345:2: 4. Stirring the prepared soaking material at the normal temperature at the stirring speed of 1000-1500r/min for 15-20 minutes until the soaking resin, the dimethyl formamide, the fluorine-free hydrolysis-resistant auxiliary agent and the color paste are completely dissolved, and controlling the viscosity at 100-200 cps; the impregnation resin comprises a first hydrolysis-resistant bio-based impregnation resin and a second hydrolysis-resistant bio-based impregnation resin, wherein the first hydrolysis-resistant bio-based impregnation resin is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin II is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II are prepared according to the weight part ratio of 2: 8.

Specifically, in the embodiment, the non-woven fabric adopts a bio-based non-woven fabric with the physical property standards of blasting being more than or equal to 18, 3CM stretching being more than or equal to 350, elongation being more than or equal to 30-70%, and 5CM tearing being more than or equal to 55.

The sugar degree in the invention is the concentration of DMF in DMF water solution, and the data is obtained after measurement by an Abbe refractometer.

EXAMPLE III

A preparation process of green environment-friendly fluorine-free bio-based space synthetic leather comprises the steps of preparing synthetic leather by coating resin, wherein the coating resin comprises a first polyester-polyether blend resin and a second polyester-polyether blend resin, and the first polyester-polyether blend resin is prepared from the following components in parts by weight:

the second polyester-polyether blended resin is prepared from the following components in parts by weight:

the first polyester-polyether blended resin and the second polyester-polyether blended resin are prepared according to the weight portion of 6: 5.

The method also comprises the preparation of a coating material, wherein the coating material comprises coating resin, dimethyl formamide, a nonionic active agent, a fluorine-free hydrolysis-resistant auxiliary agent, a fluorine-free filler and color paste, and the components are added in a weight ratio of 105:63:2:1:2.5:1.5 in sequence. The coating resin is stirred for 30-35min at the normal temperature at the stirring speed of 1000-1500r/min until the coating resin, the dimethyl formamide, the nonionic active agent, the fluorine-free hydrolysis-resistant auxiliary agent, the fluorine-free filler and the color paste are completely dissolved, the stirring speed is reduced to 300 +/-50 r/min after the slurry is stirred uniformly, vacuum defoaming is carried out for 90min at the temperature of 28-32 ℃, and the viscosity is controlled to be 14000-15000 cps.

The specific manufacturing method of the synthetic leather comprises the following steps:

step 1, impregnating the non-woven fabric in an impregnation tank added with an impregnating material, and controlling the pressure of an oil-impregnated press roller to be 5-5.5Kg and the speed to be 9 m/min;

step 2, after impregnation, the non-woven fabric passes through a pre-coagulation tank added with pre-coagulation solid liquid, the pre-coagulation sugar degree is 35-38%, and the pressure of a pre-coagulation oil pressing rod is controlled at 5-5.5 Kg;

step 3, after the treatment of the pre-coagulation tank, ironing the non-woven fabric by an ironing device, wherein the ironing temperature is controlled to be 45-50 ℃; specifically, the nonwoven fabric was ironed by a 6-wheel ironing device.

Step 4, after ironing, the non-woven fabric passes through a coating table device provided with a coating knife, and the prepared coating material is coated on the non-woven fabric along a scraper; wherein, the coating gap between the scraper and the coating is controlled at 225 plus or minus 5 threads, and the coating weight is 1.48 plus or minus 0.05 kg/y;

step 5, conveying the non-woven fabric subjected to blade coating into a solidification tank with the length of 30 meters for solidification, wherein the solidification sugar degree is 16-18%, and the temperature is 28-32 ℃;

step 6, feeding the non-woven fabric solidified by the solidification tank into a washing tank for washing; specifically, 15 groups of water washing tanks are arranged, the water washing sugar degrees of the first six groups are controlled to be 20-10%, the water washing sugar degrees of the middle six groups are controlled to be 10-0%, and the water washing sugar degrees of the last three groups are 0%; the water washing temperature of the last three groups is controlled at 65-75 ℃; specifically, the non-woven fabric is observed firstly before being washed in a water tank after being solidified in a solidification tank, and the thickness and the width are measured.

Step 7, pre-ironing the non-woven fabric after the non-woven fabric is discharged from the water washing tank by an ironing roller at the temperature of 100-; drying the pre-ironed non-woven fabric by using an oven, wherein the temperature of the oven in the first group is 150 ℃, the temperature of the ovens in the second group to the fourth group is 160 ℃, and the temperature of the oven in the fifth group is 140 ℃, so that the production of the synthetic leather is finished; specifically, 8-wheel ironing rollers are adopted for pre-ironing.

And 8, winding the product after drying, wherein the winding thickness is 1.3-1.4mm, and the width is 145-147 cm.

Specifically, in this embodiment, the impregnation material in step 1 includes the following components: the color paste comprises an impregnating resin, dimethyl formamide, a fluorine-free hydrolysis-resistant auxiliary agent and color paste, wherein the components are sequentially added according to the weight ratio of 105:355:1.5: 8. Stirring the prepared soaking material at the normal temperature at the stirring speed of 1000-1500r/min for 15-20 minutes until the soaking resin, the dimethyl formamide, the fluorine-free hydrolysis-resistant auxiliary agent and the color paste are completely dissolved, and controlling the viscosity at 100-200 cps; the impregnation resin comprises a first hydrolysis-resistant bio-based impregnation resin and a second hydrolysis-resistant bio-based impregnation resin, wherein the first hydrolysis-resistant bio-based impregnation resin is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin II is prepared from the following components in parts by weight:

the hydrolysis-resistant bio-based impregnating resin I and the hydrolysis-resistant bio-based impregnating resin II are prepared according to the weight part ratio of 3: 8.

Specifically, in the embodiment, the non-woven fabric adopts a bio-based non-woven fabric with the physical property standards of blasting being more than or equal to 18, 3CM stretching being more than or equal to 350, elongation being more than or equal to 30-70%, and 5CM tearing being more than or equal to 55.

The sugar degree in the invention is the concentration of DMF in DMF water solution, and the data is obtained after measurement by an Abbe refractometer.

The physical properties of the products produced in examples 1 to 3 of the present invention were tested, and the specific test results were as follows:

table 1 data of experimental test results of finished products

According to the experimental results of the physical property test of the product produced by the invention, the product has good physical properties without affecting the physical properties of leather materials on the premise of environmental protection; compared with the common space synthetic leather, the physical performance of the product is superior to that of the common space synthetic leather on the whole, particularly in the items of tensile load, pants type tearing, conventional peeling load, hydrolysis-resistant peeling load and the like, the physical performance of the product is far superior to that of the common space synthetic leather, and the leather material is firmer.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.