CN111593574A - Environment-friendly EVA synthetic leather subjected to surface grafting treatment and preparation method thereof - Google Patents
Environment-friendly EVA synthetic leather subjected to surface grafting treatment and preparation method thereof Download PDFInfo
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- CN111593574A CN111593574A CN201910125326.XA CN201910125326A CN111593574A CN 111593574 A CN111593574 A CN 111593574A CN 201910125326 A CN201910125326 A CN 201910125326A CN 111593574 A CN111593574 A CN 111593574A
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1664—Releasability
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1685—Wear resistance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses environment-friendly EVA synthetic leather subjected to surface grafting treatment, which sequentially comprises base cloth, an ethylene vinyl acetate copolymer (EVA) layer, a surface grafting treatment layer and a polyurethane layer from bottom to top. Firstly, casting a raw material taking EVA as a main resin on a Base cloth, preparing the environment-friendly EVA synthetic leather Base through radiation crosslinking, then treating a layer of environment-friendly surface grafting treating agent on the surface of the Base, finally coating polyurethane slurry on the surface of the grafting treating layer, and drying and curing to prepare the environment-friendly EVA synthetic leather with high bonding strength, good wear resistance, good scratch resistance and other physical properties. The synthetic leather produced by the process of the invention does not use harmful chemicals such as organic solvents and the like which are not friendly to the environment in the production processes of EVA raw material tape casting film forming, surface grafting treatment, polyurethane layer coating and the like, and eliminates organic pollution from the source.
Description
Technical Field
The invention relates to the technical field of synthetic leather, in particular to environment-friendly EVA synthetic leather subjected to surface grafting treatment and a corresponding preparation method.
Background
In the last 30 years, along with the transfer of industries such as furniture, shoemaking, clothes and the like to China, the domestic synthetic leather industry realizes rapid growth, so that China becomes the largest synthetic leather producing country and export country in the world, and about 70 percent of capacity is concentrated in China. In 2000 to 2014, the domestic synthetic leather yield is rapidly increased from 41 ten thousand tons to 375 ten thousand tons, the annual composite acceleration rate is 17.1 percent, the synthetic leather still stays at the historical high level although the synthetic leather slips under the influence of global economy slowing in 2015 to 2016, the global economy is gradually warmed up in recent years, and the synthetic leather industry is newly stepped into an ascending channel.
At present, the production and processing of the whole synthetic leather industry are mostly established on a base layer taking Polyurethane (PU) or polyvinyl chloride (PVC) as a main body, a large amount of organic solvents and plasticizers are used in the production process, such as dimethylformamide, methyl ethyl ketone, acetone, toluene, ethyl acetate, o-benzene plasticizers and the like, and the materials have great harm to human bodies or the environment.
General PVC synthetic leather becomes very hard when the temperature is lower, and the ability of heat absorption is not enough, and the long-time use of low temperature is very easy to appear crackle, leads to its life to be short. The PVC synthetic leather is a nontoxic material, but residual vinyl chloride monomer in the synthetic leather and an auxiliary agent (particularly an o-benzene plasticizer) used in processing have certain toxicity, so that the PVC synthetic leather not only can be contacted with human skin to cause health influence, but also cannot be recycled, and is a great killer for causing environmental pollution. Therefore, the production line of the common polyvinyl chloride synthetic leather is listed as a restricted development project in China, and the consumption of the PVC synthetic leather is greatly restricted in the countries of 'green ramparts' such as Europe and America and the like.
The solid content of the common polyurethane for synthetic leather is about 30 percent, the organic solvent content reaches 70 percent, and a certain amount of organic solvent is added in the processing process of the synthetic leather, so the organic solvent is used in a large amount in actual production. Solvents which cannot be recovered in the production are discharged into the environment in a gas and wastewater mode, and great harm is caused to the environment and human bodies.
The EVA synthetic leather is leather with an EVA material as a main substrate, has good low-temperature formability, flexibility, hydrolysis resistance, aging resistance and other properties, can be processed in an environment-friendly mode of extrusion casting film forming, and has controllable relative cost, so the EVA leather has strong development advantages.
In the production process of the EVA synthetic leather, the synthetic leather prepared by plasticizing and forming has single surface color and slightly insufficient hand feeling, so that the surface of the EVA synthetic leather is usually subjected to surface treatments such as color changing, color increasing/extinction, brightening, slipping, embossing, topping, grain dyeing, ironing, polishing, coke wiping, hand feeling improvement and the like so as to obtain rich color, soft luster and other surface effects and hand feeling similar to natural leather in order to make the color of the EVA synthetic leather richer and the hand feeling closer to real leather. In the leather production process, the surface is generally selected from materials with better physical properties. Among them, polyurethane is widely used and has been proved to be a very effective and cost-effective material.
Because of the incompatibility of polyurethane and EVA in structure and components, if the polyurethane is directly coated on the surface of an EVA film, the polyurethane has low adhesion strength and is relatively easy to fall off from the surface, so that the physical property of the film formed on the surface cannot meet the general requirement of practical use of leather, the surface of the EVA film needs to be modified to generate a coupling effect, so that the subsequent coating can generate sufficient adhesion strength on the surface to form a guarantee foundation for the improvement of the final physical property index, and related reports at present do not find the polyurethane and EVA film.
Disclosure of Invention
The invention aims to overcome the defects of the technology and provides the environment-friendly EVA synthetic leather subjected to surface grafting treatment and the corresponding preparation method. The EVA synthetic leather produced by the preparation method provided by the invention does not use harmful chemicals such as organic solvents and the like which are not friendly to the environment in the production processes of EVA raw material casting film forming, surface grafting treatment, polyurethane layer coating and the like, and eliminates organic pollution from the source.
In order to achieve the purpose, the environment-friendly EVA synthetic leather subjected to surface grafting treatment and the corresponding preparation method are mainly characterized in that firstly, a raw material taking EVA as a main resin is cast on a Base cloth, the environment-friendly EVA synthetic leather Base is prepared through radiation crosslinking, secondly, a layer of environment-friendly surface grafting treatment agent is pretreated on the Base surface, finally, polyurethane slurry is coated on the surface of the grafting treatment layer, and the environment-friendly EVA synthetic leather with high bonding strength, wear resistance, scratch resistance and other physical properties can be prepared through drying and curing.
Preferably, the content of the ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer (EVA) layer is more than 50 wt%, and the other comprises one or more of a combination of a cross-linking agent, an antioxidant, a coloring agent, a flame retardant, a mold release agent, a flame retardant, a filler and other modifiers.
Preferably, the ethylene vinyl acetate copolymer (EVA) layer is subjected to radiation crosslinking, and the crosslinking degree is more than 20%.
Preferably, the degree of crosslinking of the Ethylene Vinyl Acetate (EVA) layer can be adjusted by the amount of the crosslinking agent or the radiation dose.
Preferably, the environment-friendly surface grafting treating agent is a solvent-free or water-based polyurethane surface grafting treating agent.
Preferably, the solvent-free surface grafting treatment agent main body resin comprises a polyether polyurethane prepolymer with an end group of isocyanate and a polyester polyurethane prepolymer with an end group of isocyanate.
Preferably, the solvent-free surface grafting treating agent main body resin is a polyether polyurethane prepolymer with an end group of isocyanate.
Preferably, the solvent-free polyurethane surface grafting treating agent comprises 36-80 wt% of polyurethane prepolymer with isocyanate as a terminal group, 14-58 wt% of polyol prepolymer with hydroxyl as a terminal group, 0.1 wt% of dibutyltin dilaurate catalyst, 0.5 wt% of leveling agent, 0.5 wt% of wetting viscosity reducer, 4.9 wt% of plasticizer and the like.
Preferably, the aqueous surface grafting treating agent main body resin comprises aqueous polyurethane with a hydroxyl end group, aqueous polyurethane with a carboxyl end group and aqueous polyurethane with an amino end group.
Preferably, the aqueous surface grafting treatment agent main body resin is aqueous polyurethane with a hydroxyl end group.
Preferably, the waterborne polyurethane surface grafting treatment agent comprises 40-70 wt% of waterborne polyurethane with a hydroxyl end group, 2-7 wt% of prepolymer cross-linking agent with an isocyanate end group, 21.8-56.8 wt% of water, 0.3 wt% of thickening agent, 0.3 wt% of wetting agent, 0.1 wt% of defoaming agent, 0.5 wt% of film forming agent and the like.
Preferably, the polyurethane layer main body resin is water-based polyurethane or solvent-free polyurethane.
Preferably, the thickness of the surface grafting treatment layer is 5 to 40 μm.
Preferably, the thickness of the polyurethane layer is 15 to 100 μm.
The invention provides a preparation method of environment-friendly EVA synthetic leather subjected to surface grafting treatment, which comprises the following steps:
preparing related raw materials of an EVA layer;
fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a Base cloth, and performing radiation crosslinking to obtain an environment-friendly EVA synthetic leather Base;
treating the surface of the EVA synthetic leather Base by using an environment-friendly surface grafting treating agent, forming a film by means of anilox transfer printing or roll coating, and forming the surface grafting treatment layer by one or more of the processes of heating pre-crosslinking, cooling, film coating, curing or film uncovering;
and coating polyurethane slurry on the surface of the surface grafting treatment layer, and drying and curing to obtain the environment-friendly EVA synthetic leather with high bonding strength and better wear resistance and scratch resistance.
By adopting the environment-friendly EVA synthetic leather subjected to surface grafting treatment and the corresponding preparation method, harmful chemicals such as organic solvents and the like which are not friendly to the environment are not used in the production processes of EVA raw material casting film forming, surface grafting treatment, polyurethane layer coating and the like, so that organic pollution is eliminated from the source, and the EVA synthetic leather has high bonding strength, better physical properties such as wear resistance, scratch resistance and the like.
Drawings
FIG. 1 is a schematic structural diagram of the environmentally-friendly EVA synthetic leather subjected to surface grafting treatment.
Reference numerals
1 base cloth
2 Ethylene Vinyl Acetate (EVA) layer
3 surface graft treatment layer
4 polyurethane layer
Detailed Description
In order to more clearly describe the technical contents of the present invention, the following further description is given in conjunction with specific embodiments.
Example 1
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight:
wherein the isocyanate content of the polyurethane prepolymer is 14.5 percent, and the hydroxyl value of the curing agent is 80 mgKOH/g;
the conventional formula of the surface layer polyurethane slurry comprises the following raw materials in percentage by weight:
solvent-free polyurethane prepolymer: 60.0 wt%
Curing agent: 39.9 wt.%
Catalyst: 0.1 wt%
Wherein the isocyanate ester content of the polyurethane prepolymer is 2.3 percent, and the hydroxyl value of the curing agent is 40 mgKOH/g;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 50 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 20%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, laminating, curing, uncovering and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with solvent-free polyurethane slurry according to the formula of the conventional formula, and the solvent-free polyurethane slurry is dried and cured to obtain the environment-friendly EVA synthetic leather with high bonding strength, wear resistance, scratch resistance and other physical properties, wherein the thickness of the polyurethane layer is 50 mu m.
Example 2
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight:
wherein the isocyanate content of the polyurethane prepolymer is 15.0 percent, and the hydroxyl value of the curing agent is 210 mgKOH/g;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 72%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, laminating, curing, uncovering and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with solvent-free polyurethane slurry, the formula is the same as that of example 1, and after drying and curing, the thickness of the polyurethane layer is 50 microns, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 3
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight:
wherein the isocyanate content of the polyurethane prepolymer is 10.5 percent, and the hydroxyl value of the curing agent is 400 mgKOH/g;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 78 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 90%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, laminating, curing, uncovering and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with solvent-free polyurethane slurry, the formula is the same as that of example 1, and after drying and curing, the thickness of the polyurethane layer is 50 microns, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 4
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight:
wherein the isocyanate content of the polyurethane prepolymer is 15.0 percent, and the hydroxyl value of the curing agent is 210 mgKOH/g;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 95 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 34%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, laminating, curing, uncovering and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with solvent-free polyurethane slurry, the formula is the same as that of example 1, and after drying and curing, the thickness of the polyurethane layer is 50 microns, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 5
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight:
wherein the isocyanate content of the polyurethane prepolymer is 15.0 percent, and the hydroxyl value of the curing agent is 210 mgKOH/g;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 40%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, laminating, curing, uncovering and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with solvent-free polyurethane slurry, the formula is the same as that of example 1, and after drying and curing, the thickness of the polyurethane layer is 50 microns, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 6
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight:
wherein the isocyanate content of the polyurethane prepolymer is 15.0 percent, and the hydroxyl value of the curing agent is 210 mgKOH/g;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 40%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of the environment-friendly EVA synthetic leather Base, forming a film by means of anilox transfer printing or roll coating, and then carrying out the working procedures of heating pre-crosslinking, cooling, laminating, curing, uncovering and the like, wherein the thickness of the grafting treating layer is 40 mu m.
5) The surface of the grafting treatment layer is coated or treated with solvent-free polyurethane slurry, the formula is the same as that of example 1, and the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared by drying and curing, wherein the thickness of the polyurethane layer is 15 micrometers.
Example 7
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight: :
wherein the waterborne polyurethane 1 is aliphatic polyurethane with solid content of 35 percent; the cross-linking agent 1 is isocyanate type;
the surface coating polyurethane slurry comprises the following raw materials in percentage by weight:
wherein the aqueous polyurethane 2 is aliphatic polyurethane with solid content of 35 percent; the cross-linking agent 2 is aziridine type;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 40%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, curing and the like, wherein the thickness of the grafting treatment layer is 10 mu m.
5) The surface of the grafting treatment layer is coated or treated with the aqueous polyurethane slurry, and the aqueous polyurethane slurry is dried and dried according to the conventional formula, so that the thickness of the polyurethane layer is 50 mu m, and the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 8
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight: :
wherein the waterborne polyurethane 3 is aromatic, and the solid content is 40 percent; the cross-linking agent 1 is isocyanate type;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 40%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, curing and the like, wherein the thickness of a grafting treatment layer is 5 mu m.
5) The surface of the grafting treatment layer is coated or treated with the aqueous polyurethane slurry, the formula is the same as that in example 7, and the polyurethane layer is dried and cured to have a thickness of 100 microns, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 9
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight: :
wherein the aqueous polyurethane 4 is an aliphatic polyurethane aqueous emulsion with a solid content of 25 percent; the cross-linking agent 1 is isocyanate type;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 40%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, curing and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with the aqueous polyurethane slurry, the formula is the same as that in example 7, and the polyurethane layer is dried and cured to have a thickness of 50 μm, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Example 10
In this embodiment, the surface grafting treatment agent includes the following raw materials in percentage by weight: :
wherein the aqueous polyurethane 5 is acrylate modified polyurethane, and the solid content is 32 percent; the cross-linking agent 1 is isocyanate type;
the preparation method of the environment-friendly EVA synthetic leather subjected to surface grafting treatment comprises the following steps:
1) preparing related raw materials of an EVA layer, wherein the content of EVA is 60 wt%;
2) fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a base fabric, flattening and rolling;
3) carrying out radiation crosslinking, wherein the crosslinking degree of the EVA layer is 40%, and obtaining an environment-friendly EVA synthetic leather Base;
4) the method comprises the steps of pretreating a layer of environment-friendly surface grafting treating agent on the surface of an environment-friendly EVA synthetic leather Base, forming a film in a reticulate pattern transfer printing or roll coating mode, and then carrying out the working procedures of heating pre-crosslinking, cooling, curing and the like, wherein the thickness of a grafting treatment layer is 20 micrometers.
5) The surface of the grafting treatment layer is coated or treated with the aqueous polyurethane slurry, the formula is the same as that in example 7, and the polyurethane layer is dried and cured to have a thickness of 50 μm, so that the environment-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like can be prepared.
Comparative example 1
In this comparative example, the EVA synthetic leather was not subjected to irradiation crosslinking, and the surface was not coated with the surface graft treatment layer and the polyurethane layer, wherein the EVA content in the EVA layer was 60 wt%, and the other preparation methods were the same as in example 5.
Comparative example 2
In this comparative example, the EVA synthetic leather was not subjected to irradiation crosslinking, and the surface was not coated with a surface graft treatment layer, and only the polyurethane layer was coated on the Base surface of the environmentally friendly EVA synthetic leather, wherein the EVA content in the EVA layer was 60 wt%, and the other preparation methods and polyurethane layer were the same as in example 5.
Comparative example 3
In this comparative example, the EVA synthetic leather has irradiation crosslinking with a crosslinking degree of 40%, and the surface is not coated with the surface graft treatment layer and the polyurethane layer, in which the EVA content in the EVA layer is 60 wt%, and the other method is the same as in example 5.
Comparative example 4
In this comparative example, the EVA synthetic leather has irradiation crosslinking, the degree of crosslinking is 40%, and the surface is not coated with a surface graft treatment layer, and only the polyurethane layer is coated on the surface of the Base of the environmentally friendly EVA synthetic leather, wherein the EVA content in the EVA layer is 60 wt%, other preparation methods and polyurethane layers are the same as those in example 5.
Comparative example 5
In this comparative example, the EVA synthetic leather was not subjected to irradiation crosslinking, and the surface was not coated with a polyurethane layer, and only the surface of the environmentally friendly EVA synthetic leather Base was grafted with a treatment layer having a thickness of 20 μm, wherein the EVA content in the EVA layer was 60 wt%, and the other preparation methods and surface grafting treatment layers were the same as in example 5.
Comparative example 6
In this comparative example, the EVA synthetic leather was not subjected to irradiation crosslinking, and the surface was coated with a surface graft treatment layer and a polyurethane layer, in which the EVA layer had an EVA content of 60 wt%, and the other preparation methods and the surface treatment layer and the polyurethane layer were the same as in example 5.
Comparative example 7
In this comparative example, the EVA synthetic leather was irradiated and crosslinked with a crosslinking degree of 40%, and the surface was not coated with a polyurethane layer, and only the surface of the Base of the EVA synthetic leather was grafted with a treatment layer having a thickness of 20 μm, wherein the EVA content in the EVA layer was 60 wt%, and other preparation methods and surface graft treatment layers were the same as those of example 5.
The properties of the synthetic leathers prepared in examples 1 to 10 and comparative examples 1 to 7 were measured, the peel strength was measured according to the specification of GB/T8949-.
Table-table of performance data of synthetic leather
Note: in the peel strength, comparative examples 2 and 4 are data of the peel strength of the polyurethane layer and the EVA layer, and the peel strength of the other examples and comparative examples is actually data of the peel strength of the base fabric and the EVA layer, which shows that the adhesive strength of the polyurethane layer and the EVA layer after the surface grafting treatment is greater than the adhesive strength of the EVA layer and the base fabric.
As can be seen from the data in the table, the environmentally-friendly EVA synthetic leather subjected to surface grafting treatment and the synthetic leather produced by the corresponding preparation method do not use harmful chemicals such as organic solvents and the like which are not friendly to the environment in the production processes of EVA raw material casting film forming, surface grafting treatment, polyurethane layer coating and the like, eliminate organic pollution from the source, and have the environmentally-friendly EVA synthetic leather with high bonding strength, better physical properties such as wear resistance, scratch resistance and the like.
In this specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.
Claims (8)
1. The environment-friendly EVA synthetic leather subjected to surface grafting treatment is characterized by sequentially comprising a base cloth, an EVA layer, a surface grafting treatment layer and a polyurethane layer from bottom to top.
2. The environment-friendly surface-grafted EVA synthetic leather according to claim 1, wherein the EVA layer contains more than 50 wt% of ethylene-vinyl acetate copolymer, and the EVA layer is subjected to radiation crosslinking treatment, and the crosslinking degree is more than 20%.
3. The environmentally friendly surface graft treated EVA synthetic leather of claim 1, wherein the surface graft treatment layer is formed by a water-based or solvent-free polyurethane surface graft treatment agent.
4. The environmentally friendly surface graft processed EVA synthetic leather of claim 1 or 3, wherein the surface graft processing layer is formed by a solvent-free polyurethane surface graft processing agent, and the solvent-free polyurethane surface graft processing agent comprises 36-80 wt% of a polyurethane prepolymer with an isocyanate end group, 14-58 wt% of a polyol prepolymer with a hydroxyl end group, 0.1 wt% of dibutyltin dilaurate catalyst, 0.5 wt% of a leveling agent, 0.5 wt% of a wetting viscosity reducer and 4.9 wt% of a plasticizer.
5. The environment-friendly surface-grafted EVA synthetic leather according to claim 1 or 3, wherein the surface-grafted layer is formed by an aqueous polyurethane surface grafting agent, and the aqueous polyurethane surface grafting agent comprises 40-70 wt% of aqueous polyurethane with a hydroxyl end group, 2-7 wt% of a prepolymer cross-linking agent with an isocyanate end group, 21.8-56.8 wt% of water, 0.3 wt% of a thickening agent, 0.3 wt% of a wetting agent, 0.1 wt% of a defoaming agent and 0.5 wt% of a film forming agent.
6. The environmentally-friendly surface-grafted EVA synthetic leather of claim 1, wherein the main resin of the polyurethane layer is water-based polyurethane or solvent-free polyurethane.
7. The environment-friendly surface-grafted EVA synthetic leather according to claim 1, wherein the surface-grafted layer has a thickness of 5 to 40 μm and the polyurethane layer has a thickness of 15 to 100 μm.
8. A method for preparing the environment-friendly surface-grafted EVA synthetic leather according to any one of claims 1 to 7, wherein the method comprises the following steps:
preparing related raw materials of an EVA layer;
fully mixing the raw materials, adding the mixture into an extruder, extruding the mixture into a film, casting the film on a Base cloth, and performing radiation crosslinking to obtain an environment-friendly EVA synthetic leather Base;
treating the surface of the EVA synthetic leather Base by using an environment-friendly surface grafting treating agent, forming a film by means of anilox transfer printing or roll coating, and forming the surface grafting treatment layer by one or more of the processes of heating pre-crosslinking, cooling, film coating, curing or film uncovering;
and coating polyurethane slurry on the surface of the surface grafting treatment layer, and drying and curing to obtain the environment-friendly EVA synthetic leather with high bonding strength and better wear resistance and scratch resistance.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910125326.XA CN111593574A (en) | 2019-02-20 | 2019-02-20 | Environment-friendly EVA synthetic leather subjected to surface grafting treatment and preparation method thereof |
| PCT/CN2020/070979 WO2020143686A1 (en) | 2019-01-09 | 2020-01-08 | Ethylene-vinyl acetate synthetic leather substrate, ethylene-vinyl acetate synthetic leather, and surface grafting treatment agent for ethylene-vinyl acetate synthetic leather |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910125326.XA CN111593574A (en) | 2019-02-20 | 2019-02-20 | Environment-friendly EVA synthetic leather subjected to surface grafting treatment and preparation method thereof |
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