CN112695540A - Multilayer co-extrusion EVA resin foamed and crosslinked synthetic leather - Google Patents

Multilayer co-extrusion EVA resin foamed and crosslinked synthetic leather Download PDF

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CN112695540A
CN112695540A CN201911012102.4A CN201911012102A CN112695540A CN 112695540 A CN112695540 A CN 112695540A CN 201911012102 A CN201911012102 A CN 201911012102A CN 112695540 A CN112695540 A CN 112695540A
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layer
eva resin
multilayer
foaming
foamed
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李民
李庆北
蔡相成
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Shanghai HIUV Applied Materials Technology Co Ltd
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Shanghai HIUV Applied Materials Technology Co Ltd
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Priority to CN201911012102.4A priority Critical patent/CN112695540A/en
Priority to CN202210628996.5A priority patent/CN115058904A/en
Priority to PCT/CN2020/070979 priority patent/WO2020143686A1/en
Publication of CN112695540A publication Critical patent/CN112695540A/en
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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
    • 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
    • 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
    • D06N2209/1635—Elasticity
    • 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
    • D06N2209/1642—Hardnes
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Abstract

The invention discloses a synthetic leather foamed and crosslinked by multilayer co-extrusion EVA resin. Wherein the multi-layer co-extrusion EVA resin layer is subjected to cross-linking treatment and comprises at least one foaming layer and at least one modified layer. The synthetic leather foamed and crosslinked by the multilayer co-extrusion EVA resin prepared by the invention has excellent temperature resistance, softness, good resilience, aging resistance and solvent resistance after crosslinking, the EVA resin layer adopts a multilayer co-extrusion mode, the production process is simple, the interlayer adhesive force between the substrate layer and the multilayer co-extrusion EVA resin layer is good, and the interlayer adhesive force can reach more than 5N/cm.

Description

Multilayer co-extrusion EVA resin foamed and crosslinked synthetic leather
Technical Field
The invention relates to the technical field of synthetic leather, in particular to a multilayer co-extruded EVA resin foamed and crosslinked synthetic leather.
Background
With the increasing living standard of people, people put forward higher and higher quality requirements on living goods. Leather, as an article of daily use, has been increasingly demanded not only in the market but also in various requirements (including environmental protection performance, inherent physical strength requirement, durability requirement, solvent resistance requirement, etc.) of customers in recent years. Because the genuine leather can produce a large amount of pollution in the manufacturing process, and meanwhile, the production cost is higher, the durability is relatively poor, the surface physical property is relatively low, the maintenance is difficult and other inherent defects exist, and the potential requirement of high quality of people cannot be met. Synthetic leather has been developed to the present, and because of its advantages such as relatively excellent performance and relatively low cost, it has been used in the manufacture of shoes, bags, sofas, and garments in a large quantity, and the synthetic leather industry has become the support industry of the light industry.
At present, the structure of the whole synthetic leather is built on a base layer which takes Polyurethane (PU) or polyvinyl chloride (PVC) as a main body, a large amount of organic solvents and plasticizers, such as dimethylformamide, methyl ethyl ketone, acetone, toluene, ethyl acetate, o-benzene plasticizers and the like, are used in the production process, and the materials have great harm to human bodies or the environment.
Synthetic leather with EVA as a base material structure has no practical application at present and has few reports. The EVA resin has the advantages of good rebound resilience, flexibility, aging resistance and the like, environmental friendliness, simple process, low cost and the like. This is because EVA is a rubber-like thermoplastic, and has excellent flexibility, low-temperature flexibility, elasticity, stress crack resistance, and good moldability, processability, etc., and is widely used. Ethylene vinyl acetate copolymer (EVA) is a thermoplastic plastic with rubber elasticity, in EVA molecules, due to the existence of a Vinyl Acetate (VA) structural unit, the regularity of a polyethylene molecular chain is greatly reduced, and the crystallinity of the polyethylene molecular chain is reduced, so that the internal rotation movement capability of the molecular chain in thermal movement is greatly improved, the flexibility of the molecular chain is improved, and the ethylene vinyl acetate copolymer (EVA) has high elasticity macroscopically. But because the melting point of the EVA resin is lower than 100 ℃, the EVA resin can hardly be used in the synthetic leather neighborhood if not crosslinked and modified.
Meanwhile, because the hardness of the EVA material is slightly higher than that of the leather material, the EVA material needs to be foamed to reduce the hardness of the EVA material. The foamed EVA can be used for manufacturing high-magnification independent bubble type room temperature foamed plastics, and the material has the advantages of light density, high elasticity, excellent bending resistance and high shock absorption, sound insulation and heat insulation performance, so the foamed EVA is widely used for manufacturing sports equipment, seat cushions, child floors, synthetic leather and the like, is particularly widely applied to sports shoes, case liners and the like, and becomes a hotspot of light material research. However, some disadvantages of the EVA foaming material also limit its application in synthetic leather base materials, such as low temperature hardening, poor mechanical properties, poor resilience, unsatisfactory wear resistance, and the like. Therefore, it is necessary to develop an EVA foamed composite film that can meet the performance requirements of synthetic leather.
Disclosure of Invention
The invention aims to overcome the defects of the technology and provides the synthetic leather foamed and crosslinked by the multi-layer co-extrusion EVA resin, which sequentially comprises a polyurethane layer, a multi-layer co-extrusion EVA resin layer and a substrate layer attached to the resin layer from top to bottom. Wherein the multi-layer co-extrusion EVA resin layer is subjected to cross-linking treatment and comprises at least one foaming layer and at least one modified layer, and the polyurethane layer is tightly attached to the modified layer. The synthetic leather foamed and crosslinked by the multilayer co-extrusion EVA resin prepared by the invention has excellent temperature resistance after crosslinking, softness, good rebound resilience, excellent aging resistance and excellent solvent resistance, the EVA resin layer adopts a multilayer co-extrusion mode, the production process is simple, the interlayer adhesive force between the substrate layer and the multilayer co-extrusion EVA resin layer is good, and the interlayer adhesive force can reach more than 5N/cm.
In order to achieve the purpose, the synthetic leather foamed and crosslinked by the multilayer co-extrusion EVA resin is mainly characterized by comprising a polyurethane layer, a multilayer co-extrusion EVA resin layer and a base layer attached to the resin layer from top to bottom in sequence. The multilayer co-extruded EVA resin layer is foamed and cross-linked and comprises at least one foaming layer and at least one modified layer, and the polyurethane layer is tightly attached to the modified layer.
Preferably, the base layer is any one of knitted elastic napped fabric, plain-knitted napped fabric, knitted plain fabric, woven polyester fabric, nylon fabric, microfiber base fabric, polyester filament elastic fabric, non-woven fabric, various other non-woven fabrics, and various papers.
Preferably, the multilayer co-extruded resin layer with EVA resin as main component includes at least one foaming layer and one modifying layer.
Preferably, the base resin in the foaming layer is EVA, and the foaming layer comprises 100 parts of EVA resin, 1-15 parts of foaming agent, 0-4 parts of cross-linking agent, 0-100 parts of elastomer, 0-200 parts of filler, 0-10 parts of foaming promoter, 0-5 parts of lubricant and 0-20 parts of colorant.
Preferably, the foaming agent in the foaming layer can be a physical foaming agent, a chemical foaming agent and a microsphere foaming agent, and the physical foaming agent includes but is not limited to N2、CO2Pentane, hexane, trichlorotrifluoroethane, and the like. Chemical blowing agents include, but are not limited to, Azodicarbonamide (ADC), azobisisobutyronitrile, N-Dinitrosopentamethylenetetramine (DPT), 4-disulfonylhydrazide diphenyl ether (OBSH), p-benzenesulfonylhydrazide, and the like.
Preferably, the blowing agents are ADC blowing agents, OBSH blowing agents and microsphere blowing agents.
Preferably, the filler in the foaming layer is talcum powder, calcium carbonate, titanium dioxide and the like.
Preferably, the foaming aid is a metal oxide such as zinc oxide.
Preferably, the lubricant is stearic acid or zinc stearate, or the like.
Preferably, the elastomer includes rubber elastomers such as Natural Rubber (NR), Ethylene Propylene Diene Monomer (EPDM), hydrogenated styrene butadiene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and polyolefin elastomers. Polyolefin elastomers such as ethylene-octene copolymers (POE) and the like.
Preferably, the crosslinking agent includes, but is not limited to, dicumyl peroxide, di-tert-butylperoxy-dicumyl peroxide, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-di (tert-butylperoxy) -2, 5-dimethylhexane, or n-butyl 4, 4-di (tert-butylperoxy) valerate.
Preferably, the modified layer comprises 100 parts of EVA resin, 0-100 parts of elastomer, 0-200 parts of filler, 0-4 parts of crosslinking agent, 0-4 parts of auxiliary crosslinking agent and 0-20 parts of colorant. The modified layer is a modified layer with special performances such as adhesion, rebound resilience, wear resistance, flexibility and the like.
The polyurethane layer is closely attached to the modified layer, and the polyurethane layer can be a solvent type, water-based or solvent-free polyurethane coating.
Preferably, the polyurethane layer adopts an environment-friendly solvent-free or water-based polyurethane coating.
Preferably, the multi-layer co-extruded EVA resin layer is subjected to foaming and crosslinking treatment, the foaming multiplying power of the multi-layer co-extruded EVA resin layer is 1.2-10 times, the crosslinking degree is 3-95%, and the foaming and crosslinking treatment is free foaming and crosslinking through a crosslinking agent and/or radiation crosslinking treatment. The crosslinking agent can be used for crosslinking in the foaming process, the crosslinking agent can be not used for crosslinking in the foaming process, the crosslinking agent is used for radiation crosslinking after foaming, a certain crosslinking degree exists in the foaming process, and then the crosslinking degree is further improved through radiation crosslinking, or the crosslinking agent is used for radiation crosslinking before foaming.
Preferably, the total thickness of the synthetic leather is 0.21-5.3 mm, the thickness of the base layer is 0.1-2.2 mm, the thickness of the multi-layer co-extrusion foaming EVA resin layer is 0.1-3.0 mm, the thickness of the modified layer is 0.01-1.0 mm, the thickness of the polyurethane layer is 0.01-0.10 mm, and the thickness of each layer inside can be adjusted according to needs.
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 polyurethane layer in the synthetic leather foamed and crosslinked by the multi-layer co-extrusion EVA resin is a conventional solvent-free polyurethane slurry formula, the multi-layer co-extrusion EVA resin layer includes a foaming layer and a modification layer, wherein the foaming layer is in contact with the base fabric layer, and the raw material ratios of the foaming layer, the modification layer and the polyurethane layer slurry are respectively:
foaming layer
Ethylene vinyl acetate copolymer (EVA)100 parts
ADC foaming agent 1 part
Modified layer
Figure BDA0002244508450000041
Polyurethane layer
100 parts of solvent-free polyurethane prepolymer
66.5 parts of curing agent
Catalyst 1.7 parts
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 invention also provides a preparation method of the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather, which comprises the following steps:
1) preparing related raw materials of a foaming layer and a modification layer;
2) fully mixing the raw materials of the foaming layer and the modification layer, respectively adding the raw materials into an extruder, extruding the mixture to form a film, casting the film on a substrate, and rolling the film to form the film, wherein the thickness of the substrate layer is 0.1 mm;
3) foaming the multilayer co-extruded EVA resin in a high-temperature furnace, wherein the foaming temperature range is 100-230 ℃, the total thickness after foaming is 0.1mm, and the thickness of the modified layer is 0.01 mm;
4) and coating a polyurethane layer on the foamed multi-layer co-extruded EVA resin layer, wherein the thickness of the polyurethane layer is 0.01 mm.
Finally, the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather is prepared by post-embossing and other treatments.
Example 2
In this embodiment, the ratio of the slurry for the polyurethane layer in the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin is the same as that in embodiment 1, the multilayer co-extruded EVA resin layer includes a foaming layer and a modified layer, wherein the foaming layer is in contact with the base fabric layer, and the raw material ratios of the foaming layer and the modified layer are respectively:
foaming layer
Figure BDA0002244508450000042
Modified layer
Figure BDA0002244508450000051
The invention also provides a preparation method of the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather, which comprises the following steps:
1) preparing related raw materials of a foaming layer and a modification layer;
2) fully mixing the raw materials of the foaming layer and the modification layer, respectively adding the raw materials into an extruder, extruding the mixture to form a film, casting the film on a substrate, and rolling the film to form the film, wherein the thickness of the substrate layer is 1.0 mm;
3) foaming the multilayer co-extruded EVA resin in a high-temperature furnace, wherein the foaming temperature range is 100-230 ℃, the total thickness after foaming is 1.0mm, and the thickness of the modified layer is 0.1 mm;
4) carrying out radiation crosslinking on the foamed multi-layer co-extruded EVA resin layer, wherein the radiation dose is 20 KGy;
5) and coating a polyurethane layer on the multi-layer co-extrusion EVA resin layer which is foamed and subjected to radiation crosslinking, wherein the thickness of the polyurethane layer is 0.05 mm.
Finally, the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather is prepared by post-embossing and other treatments.
Example 3
In this embodiment, the ratio of the slurry for the polyurethane layer in the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin is the same as that in embodiment 1, the multilayer co-extruded EVA resin layer includes a foaming layer and a modified layer, wherein the foaming layer is in contact with the base fabric layer, the ratio of the raw materials for the modified layer, the thickness of each layer, and the preparation method are the same as those in embodiment 2, and the ratio of the raw materials for the foaming layer is:
foaming layer
Figure BDA0002244508450000052
Example 4
In this embodiment, the ratio of the slurry for the polyurethane layer in the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin is the same as that in embodiment 1, the multilayer co-extruded EVA resin layer includes a foaming layer and a modified layer, wherein the foaming layer is in contact with the base fabric layer, the ratio of the raw materials for the modified layer, the thickness of each layer, and the preparation method are the same as those in embodiment 2, and the ratio of the raw materials for the foaming layer is:
foaming layer
Figure BDA0002244508450000061
Example 5
In this embodiment, the ratio of the slurry for the polyurethane layer in the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin is the same as that in embodiment 1, the multilayer co-extruded EVA resin layer includes a foaming layer and a modified layer, wherein the foaming layer is in contact with the base fabric layer, the ratio of the raw materials of the modified layer is the same as that in embodiment 2, and the ratio of the raw materials of the foaming layer is:
foaming layer
Figure BDA0002244508450000062
The invention also provides a preparation method of the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather, which comprises the following steps:
1) preparing related raw materials of a foaming layer and a modification layer;
2) fully mixing the raw materials of the foaming layer and the modification layer, respectively adding the raw materials into an extruder, extruding the mixture to form a film, casting the film on a substrate, and rolling the film to form the film, wherein the thickness of the substrate layer is 2.2 mm;
3) foaming the multilayer co-extruded EVA resin in a high-temperature furnace, wherein the foaming temperature range is 100-230 ℃, the total thickness after foaming is 3.0mm, and the thickness of the modified layer is 1.0 mm;
4) carrying out radiation crosslinking on the foamed multi-layer co-extruded EVA resin layer, wherein the radiation dose is 90 KGy;
5) and coating a polyurethane layer on the multi-layer co-extrusion EVA resin layer which is foamed and subjected to radiation crosslinking, wherein the thickness of the polyurethane layer is 0.1 mm.
Finally, the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather is prepared by post-embossing and other treatments.
Example 6
In this embodiment, the polyurethane layer in the synthetic leather foamed and crosslinked by the multi-layer co-extrusion EVA resin is a conventional aqueous polyurethane slurry formula, the multi-layer co-extrusion EVA resin layer includes a modified layer 1 (mainly playing a role of bonding with the base fabric layer), a foamed layer and a modified layer 2, wherein the modified layer 1 contacts with the base fabric layer, and the foaming layer, the modified layer and the polyurethane layer are prepared from the following raw materials in proportion:
modified layer 1
Ethylene vinyl acetate copolymer (EVA)100 parts
Foaming layer
Figure BDA0002244508450000071
Modified layer 2
Figure BDA0002244508450000072
Polyurethane layer
Figure BDA0002244508450000081
Wherein the water-based polyurethane is aliphatic polyurethane, and the solid content is 35 percent; the cross-linking agent is aziridine type;
the invention also provides a preparation method of the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather, which comprises the following steps:
1) preparing related raw materials of a foaming layer and a modification layer;
2) fully mixing the raw materials of the foaming layer and the modification layer, respectively adding the raw materials into an extruder, extruding the mixture to form a film, casting the film on a substrate, and rolling the film to form the film, wherein the thickness of the substrate layer is 1.0 mm;
3) foaming the multilayer co-extruded EVA resin in a high-temperature furnace, wherein the foaming temperature range is 100-230 ℃, the total thickness after foaming is 1.0mm, the thickness of the modified layer 1 is 0.04mm, and the thickness of the modified layer 2 is 0.1 mm;
4) carrying out radiation crosslinking on the foamed multi-layer co-extruded EVA resin layer, wherein the radiation dose is 90 KGy;
5) and coating a polyurethane layer on the multi-layer co-extrusion EVA resin layer which is foamed and subjected to radiation crosslinking, wherein the thickness of the polyurethane layer is 0.05 mm.
Finally, the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather is prepared by post-embossing and other treatments.
Example 7
In this embodiment, the ratio of the polyurethane layer slurry in the synthetic leather foamed and crosslinked by the multi-layer co-extrusion EVA resin is the same as that in embodiment 6, the thicknesses and the preparation methods of the modified layer 1, the modified layer 2 and the multi-layer co-extrusion EVA resin layer are the same as those in embodiment 6, only the formula of the modified layer 2 is adjusted, and the raw material ratio of the modified layer 2 is as follows:
modified layer 2
Figure BDA0002244508450000082
Example 8
In this embodiment, the ratio of the polyurethane layer slurry in the synthetic leather foamed and crosslinked by the multilayer co-extrusion EVA resin is the same as that in embodiment 6, the thicknesses of the modified layer 1, the modified layer 2 and the multilayer co-extrusion EVA resin layer are the same as those in embodiment 6, the foaming temperature in the preparation method is adjusted to 100-160 ℃, other preparation methods are the same as those in embodiment 6, the ADC foaming agent in the foaming layer is replaced by the OBSH foaming agent, and the raw material ratio of the foaming layer is as follows:
foaming layer
Figure BDA0002244508450000091
Example 9
In this embodiment, the ratio of the polyurethane layer slurry in the synthetic leather foamed and crosslinked by the multilayer co-extrusion EVA resin is the same as that in embodiment 6, the thicknesses of the modified layer 1, the modified layer 2 and the multilayer co-extrusion EVA resin layer are the same as those in embodiment 6, the foaming temperature in the preparation method is adjusted to 100 to 180 ℃, other preparation methods are the same as those in embodiment 6, the ADC foaming agent in the foaming layer is replaced by the microsphere foaming agent, and the raw material ratio of the foaming layer is as follows:
foaming layer
Figure BDA0002244508450000092
Example 10
In this embodiment, the polyurethane layer slurry ratio in the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin is the same as that in embodiment 6, the multilayer co-extruded EVA resin layer includes a modified layer 1, a foamed layer 2 and a modified layer 2, wherein the modified layer 1 is in contact with the base fabric layer, and the raw material ratios of the foamed layer and the modified layer are respectively:
modified layer 1
Ethylene vinyl acetate copolymer (EVA)100 parts
Foaming layer 1
Ethylene vinyl acetate copolymer (EVA)100 parts
ADC foaming agent 1 part
0.2 part of cross-linking agent
Foaming layer 2
Figure BDA0002244508450000101
Modified layer 2
Figure BDA0002244508450000102
The invention also provides a preparation method of the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather, which comprises the following steps:
1) preparing related raw materials of a foaming layer and a modification layer;
2) fully mixing the raw materials of the foaming layer and the modification layer, respectively adding the raw materials into an extruder, extruding the mixture to form a film, casting the film on a substrate, and rolling the film to form the film, wherein the thickness of the substrate layer is 1.0 mm;
3) foaming the multilayer co-extruded EVA resin in a high-temperature furnace, wherein the foaming temperature range is 100-230 ℃, the total thickness after foaming is 1.0mm, the thickness of the modified layer 1 is 0.04mm, and the thickness of the modified layer 2 is 0.1 mm;
4) carrying out radiation crosslinking on the foamed multi-layer co-extruded EVA resin layer, wherein the radiation dose is 90 KGy;
5) and coating a polyurethane layer on the multi-layer co-extrusion EVA resin layer which is foamed and subjected to radiation crosslinking, wherein the thickness of the polyurethane layer is 0.05 mm.
Finally, the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather is prepared by post-embossing and other treatments.
Example 11
In this embodiment, the polyurethane layer slurry ratio in the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin is the same as that in embodiment 6, the multilayer co-extruded EVA resin layer includes a modified layer 1, a foamed layer 1, a modified layer 2, a foamed layer 2 and a modified layer 3, wherein the modified layer 1 is in contact with the base fabric layer, and the foaming layer and the modified layer are prepared from the following raw materials in proportion:
modified layer 1
Ethylene vinyl acetate copolymer (EVA)100 parts
Foamed layers 1 and 2
Figure BDA0002244508450000111
Modified layers 2 and 3
Figure BDA0002244508450000112
The invention also provides a preparation method of the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather, which comprises the following steps:
1) preparing related raw materials of a foaming layer and a modification layer;
2) fully mixing the raw materials of the foaming layer and the modification layer, respectively adding the raw materials into an extruder, extruding the mixture to form a film, casting the film on a substrate, and rolling the film to form the film, wherein the thickness of the substrate layer is 1.0 mm;
3) foaming the multilayer co-extruded EVA resin in a high-temperature furnace, wherein the foaming temperature range is 100-230 ℃, the total thickness after foaming is 1.5mm, the thickness of the modified layer 1 is 0.04mm, and the thicknesses of the modified layers 2 and 3 are respectively 0.1 mm;
4) carrying out radiation crosslinking on the foamed multi-layer co-extruded EVA resin layer, wherein the radiation dose is 90 KGy;
5) and coating a polyurethane layer on the multi-layer co-extrusion EVA resin layer which is foamed and subjected to radiation crosslinking, wherein the thickness of the polyurethane layer is 0.05 mm.
Finally, the multilayer co-extruded EVA resin foamed and crosslinked synthetic leather is prepared by post-embossing and other treatments.
Comparative example 1
The layer formulations and preparation were the same as in example 2, except that no foaming was present.
Comparative example 2
The layer formulations and preparation were the same as in example 6, except that no foaming was present.
The adhesive force between the base layer and the multi-layer co-extruded EVA resin layer in the multi-layer co-extruded EVA resin foamed and cross-linked synthetic leather prepared in examples 1 to 11 and comparative examples 1 and 2, the cross-linking degree and shore hardness of the multi-layer co-extruded EVA resin layer, and the wear resistance data of the synthetic leather are shown in the following table one: the interlayer adhesion force is tested according to GB/T14905-2009, the crosslinking degree of the EVA layer is tested according to GB/T29848-2018-5.5.3 xylene extraction method, the abrasion resistance is tested according to ASTM D1242-1995, and the Shore hardness is tested according to GB/T2411-2008.
Table-performance parameter table of multi-layer co-extruded EVA resin foamed and cross-linked synthetic leather
Figure BDA0002244508450000121
Note: in the examples, the expansion ratios of all samples were controlled in the range of 2 to 2.5 times.
As can be seen from the performance data of the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin shown in the table, the crosslinking degree of the foamed EVA resin layer can be adjusted by adjusting the amount of the crosslinking agent, the radiation dose and the foaming time by adopting the synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin prepared by the invention.
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 description is thus to be regarded as illustrative instead of limiting.

Claims (8)

1. The utility model provides a synthetic leather that multilayer is crowded EVA resin altogether and is foamed and crosslinked which characterized in that, synthetic leather from the top down include polyurethane layer, multilayer crowded EVA resin layer altogether and the laminating is in multilayer crowded EVA resin layer on the stratum basale altogether in proper order, multilayer crowded EVA resin layer altogether through foaming and cross-linking treatment and including at least one deck modified layer and at least one deck foaming layer, the modified layer is hugged closely on the polyurethane layer.
2. The multilayer co-extrusion EVA resin foamed and crosslinked synthetic leather according to claim 1, wherein the foamed layer comprises 100 parts of EVA resin, 1-15 parts of foaming agent, 0-4 parts of crosslinking agent, 0-100 parts of elastomer, 0-200 parts of filler, 0-10 parts of foaming promoter, 0-5 parts of lubricant and 0-20 parts of colorant.
3. The multilayer co-extrusion EVA resin foamed and crosslinked synthetic leather according to claim 1, wherein the modified layer comprises 100 parts of EVA resin, 0-100 parts of elastomer, 0-200 parts of filler, 0-4 parts of crosslinking agent, 0-4 parts of auxiliary crosslinking agent and 0-20 parts of colorant.
4. A synthetic leather foamed and crosslinked with multi-layer co-extruded EVA resins according to claim 2 or 3, characterised in that the crosslinking agent includes but is not limited to one or more of dicumyl peroxide, di-tert-butylperoxy-dicumyl, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-di (tert-butylperoxy) -2, 5-dimethylhexane or n-butyl-4, 4-di (tert-butylperoxy) valerate.
5. The synthetic leather foamed and crosslinked by the multilayer co-extruded EVA resin according to claim 1, wherein the crosslinking degree of the multilayer co-extruded EVA resin layer is 3-95%.
6. The multilayer co-extruded EVA resin foamed and cross-linked synthetic leather of claim 1, characterised in that the foaming and cross-linking treatment is free foaming and cross-linking by a cross-linking agent and/or cross-linking by radiation.
7. The multilayer co-extruded EVA resin foamed and crosslinked synthetic leather of claim 1, wherein the polyurethane layer is a solvent-based, water-based or solvent-free polyurethane coating.
8. The synthetic leather foamed and crosslinked by the multilayer co-extrusion EVA resin of claim 1, wherein the total thickness of the synthetic leather is 0.21-5.3 mm, the thickness of the base layer is 0.1-2.2 mm, the thickness of the multilayer co-extrusion foamed EVA resin layer is 0.1-3.0 mm, the thickness of the modification layer is 0.01-1.0 mm, and the thickness of the polyurethane layer is 0.01-0.10 mm.
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CN101538802A (en) * 2009-04-23 2009-09-23 朱守诚 High-performance fiber reinforced film composite material
CN101538800A (en) * 2009-04-23 2009-09-23 合肥市东方美捷分子材料技术有限公司 Thermoplastic resin coating film material and preparation method thereof
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CN103696274B (en) * 2013-12-27 2015-11-18 四川大学 A kind of foaming synthetic leather manufacture method based on water-base resin and TPU resin

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CN1130224A (en) * 1995-02-28 1996-09-04 南亚塑胶工业股份有限公司 Method for producing plastic artificial leather (cloth) through calendering ethylene-vinylacetate copoly resin
CN101538802A (en) * 2009-04-23 2009-09-23 朱守诚 High-performance fiber reinforced film composite material
CN101538800A (en) * 2009-04-23 2009-09-23 合肥市东方美捷分子材料技术有限公司 Thermoplastic resin coating film material and preparation method thereof
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