CN114737404A - Composite material for waterborne polyurethane shoes and preparation method thereof - Google Patents

Composite material for waterborne polyurethane shoes and preparation method thereof Download PDF

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Publication number
CN114737404A
CN114737404A CN202210526344.0A CN202210526344A CN114737404A CN 114737404 A CN114737404 A CN 114737404A CN 202210526344 A CN202210526344 A CN 202210526344A CN 114737404 A CN114737404 A CN 114737404A
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layer
aqueous
resin slurry
solvent
oven
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Inventor
戴丽
徐一剡
顾志豪
陈倩
周云峰
金丹
屠银梦
辛世明
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Zhejiang Hexin New Material Co ltd
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Zhejiang Hexin New Material Co ltd
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Priority to CN202210526344.0A priority Critical patent/CN114737404A/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
    • D06N3/146—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 characterised by the macromolecular diols used
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
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    • 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
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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    • 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
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • D—TEXTILES; PAPER
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    • 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
    • D06N3/145—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 two or more layers of 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
    • D06N3/12—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
    • D06N3/147—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 characterised by the isocyanates used
    • 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
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • 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
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
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    • 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
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • D—TEXTILES; PAPER
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a composite material for waterborne polyurethane shoes, which comprises a surface layer, an intermediate layer, a bonding layer and a bottom cloth layer which are sequentially attached from top to bottom; the surface layer is made of aqueous surface resin slurry; the intermediate layer is made of aqueous intermediate layer resin slurry; the adhesion layer is made of a solvent-free resin paste. The composite material for the waterborne polyurethane shoes has higher stripping force and good folding resistance; the use of an organic solvent DMF is avoided, the DMF in the finished product can be controlled not to be contained, and the prepared product meets the requirement that the DMF content of a customer is controlled within 50ppm, and belongs to a green and environment-friendly product. The invention also provides a preparation method of the composite material for the waterborne polyurethane shoes, which reduces the steps of a wet method, directly utilizes the foaming of the solvent-free resin to replace the manufacture of a wet method bass, and achieves the effects of energy conservation and emission reduction.

Description

Composite material for waterborne polyurethane shoes and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a composite material for waterborne polyurethane shoes and a preparation method thereof.
Background
Polyurethane synthetic leather is a product imitating natural leather, and has been used in every corner of our lives for a long time. The solvent type polyurethane resin can realize the production of polyurethane synthetic leather by wet solidification foaming and dry release paper transfer, but DMF solvent is used in the conventional production process, the product has more or less solvent residues, the working procedures are complicated, and a large amount of waste gas and waste water can be generated. In the society with the mainstream of green and environment protection, people pay more and more attention to the health of the people, the requirement on the environmental protection performance of products is higher and higher, and the traditional polyurethane synthetic leather cannot meet the requirement of customers; the common water-based coating process and formula can not meet the requirements of customers on peeling, folding resistance, hydrolysis resistance and the like; the use requirement of brand customers on products is that DMF (dimethyl formamide) is controlled within 50ppm, and the existing formula process cannot meet the use requirement of the customers.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a composite material for waterborne polyurethane shoes and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a composite material for waterborne polyurethane shoes comprises a surface layer, a middle layer, a bonding layer and a bottom cloth layer which are sequentially attached from outside to inside; the surface layer is made of aqueous surface resin slurry; the intermediate layer is made of aqueous intermediate layer resin slurry; the adhesive layer is made of solvent-free resin slurry;
the aqueous surface resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000011
Figure BDA0003644656230000021
the aqueous interlayer resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000022
the solvent-free resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000023
the composite material for the waterborne polyurethane shoe is characterized in that the waterborne layer resin is polyether polyurethane, the polyether polyurethane is a carboxylic acid type or sulfonic acid type waterborne system, and the 100% elongation modulus is 3-6 MPa;
the water-based leveling agent is an organic silicon modified polyether water-based leveling agent;
the water-based defoaming agent is an organic silicon modified bubble-inhibiting assistant;
the aqueous bridging agent is isocyanate aqueous bridging auxiliary agent;
the thickening agent is a thickening agent for waterborne polyurethane;
the waterborne middle layer resin is polyether polyurethane; the polyether polyurethane is a sulfonic acid aqueous system, and the 100% elongation modulus is 1-3 MPa;
the leveling agent is 100 percent of organic silicon modified surfactant;
the color paste is 100 percent of solvent-free pigment.
The waterborne polyurethane composite material for shoes, provided by the invention, is characterized in that the solvent-free resin A is a polyether polyol compound mixture; the solvent-free resin B is polyether type isocyanate prepolymer; the catalyst-1 is a gel-promoting metal bismuth catalyst; the catalyst-2 is an amine compound catalyst for promoting curing.
The composite material for the waterborne polyurethane shoes is characterized in that the thickness of the surface layer is 0.02-0.1 mm; the thickness of the middle layer is 0.03-0.2 mm; the thickness of the adhesion layer is 0.08-0.6 mm.
The composite material for the waterborne polyurethane shoes, disclosed by the invention, has the advantages that the viscosity of the waterborne surface layer resin slurry is 3000-10000CPS/25 ℃, and the coating weight is 130-200 g/m; the viscosity of the aqueous middle layer resin sizing agent is 3000-10000CPS/25 ℃, and the coating weight is 130-200 g/m; the viscosity of the solvent-free resin sizing agent is 1000-10000CPS/25 ℃, and the coating weight is 250-350 g/m.
The composite material for the waterborne polyurethane shoe is characterized in that the bottom cloth layer is high-density knitted cloth.
The composite material for the waterborne polyurethane shoes is characterized in that the waterborne surface resin sizing agent is prepared from the following components in parts by weight:
Figure BDA0003644656230000031
the aqueous interlayer resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000032
the solvent-free resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000033
the preparation method of the composite material for the waterborne polyurethane shoe comprises the following steps:
(1) preparing a skin layer: preparing the aqueous surface layer resin slurry according to the proportion, coating the aqueous surface layer resin slurry on release paper, wherein the coating knife position is 0.05-0.15mm, drying the release paper in an oven at the temperature of 70-130 ℃ for 2-3min, and transferring the grains of the release paper to the surface to obtain an epidermal layer;
(2) preparing an intermediate layer: preparing the aqueous interlayer resin slurry according to the proportion, coating the aqueous interlayer resin slurry on the surface layer dried in the step (1), wherein the coating knife position is 0.1-0.5mm, and drying in an oven at 70-130 ℃ for 1-3 min;
(3) preparation of a subsequent layer: blending the solvent-free resin slurry according to the proportion, coating the solvent-free resin slurry on the middle layer dried in the step (2), wherein the coating knife position is 0.2-0.8mm, and drying in an oven at the temperature of 90-130 ℃ for 1-2 min;
(4) attaching: then pre-baking in a baking oven at 90-130 ℃ for 1-2min, and attaching the base fabric to the adhesion layer;
(5) curing: putting the attached base cloth layer, the adhesive layer, the middle layer, the epidermal layer and the release paper into an oven for curing, and drying for 5-15min at the set temperature of 90-140 ℃;
(6) separation: separating and winding the cured finished product and release paper by a guide roller and 2 winding devices; the finished product is on a finished product winding frame, and the release paper is on a release paper winding frame.
The preparation method of the composite material for the waterborne polyurethane shoes, disclosed by the invention, comprises the following steps of (1) drying in an oven at a temperature gradient of 70/90/110/130 ℃; the temperature gradient when drying in the oven in the step (2) is 70/90/110/130 ℃; the temperature gradient when drying in the oven in the step (3) is 90/110/130 ℃; the temperature gradient during drying in the oven in step (4) was 90/110/130 ℃.
The invention has the beneficial effects that:
according to the composite material for the waterborne polyurethane shoes, waterborne polyurethane selected by the surface layer has fine wrinkles, meets the requirement on flexing resistance and the requirement on smooth surface, and enables a finished product to have more comfortable touch and good folding resistance. The middle layer adopts low-modulus (100% elongation modulus is 1-3MPa) water-based polyether polyurethane resin to connect the surface layer and the adhesive layer, so that the solvent-free layer has good curing performance and the resin is tightly combined; the product is soft and comfortable and has good bonding and shaping performance. The optimized selection of the solvent-free resin of the next layer is combined with the middle layer and the cloth layer, so that the product has higher peeling force and has proper hand feeling. The aqueous polyurethane resin and the solvent-free resin adopted by the invention do not contain harmful solvent, so that the use of organic solvent DMF is avoided, the DMF in the finished product can be controlled not to be contained, and the prepared product meets the requirement that the DMF content of a client is controlled within 50ppm, and belongs to a green and environment-friendly product.
According to the composite material for the waterborne polyurethane shoe, disclosed by the invention, the water resistance and the thermal stability of the waterborne polyurethane shoe are improved by introducing organic silicon into a waterborne polyurethane structure, the waterborne bridging agent adopts isocyanate waterborne bridging auxiliary agents, the groups can generate silicon hydroxyl groups, and the silicon hydroxyl groups are rapidly condensed in the film forming and drying process to form a net structure, so that the water resistance of the waterborne polyurethane can be improved, the thermal stability of the waterborne polyurethane can be greatly improved, the wear resistance and the water washing resistance of the synthetic leather are further obviously improved, the blocking resistance and the wear resistance are obviously improved, and the service life is prolonged.
According to the composite material for the waterborne polyurethane shoes, disclosed by the invention, superfine hydrophilic silicon dioxide is added into the solvent-free slurry, so that superfine and uniform holes are endowed to the product, the water vapor permeability is improved, the air permeability of the product is improved, and meanwhile, the antibacterial and deodorizing performance is improved by adding the nonionic organic antibacterial auxiliary agent, so that the wearing comfort is ensured.
The preparation method of the composite material for the waterborne polyurethane shoes reduces the steps of a wet method, directly utilizes the foaming of the solvent-free resin to replace the manufacture of a wet method bass, and achieves the effects of energy conservation and emission reduction. The invention utilizes the similarity of polyether molecular structures and the crosslinking reaction of solvent-free resin, and the prepared waterborne polyurethane composite material for shoes has higher stripping force and good folding resistance.
The present invention will be further described with reference to the following specific examples.
Detailed Description
The sources of the raw materials in the following examples are: the aqueous layer resin is polyether type aqueous polyurethane, and the modulus of the polyether type aqueous polyurethane is 3-6MPa (100% elongation); the aqueous bridging agent is isocyanate aqueous bridging auxiliary agent; the waterborne middle layer resin is polyether waterborne polyurethane, has the modulus of 1-3MPa (100% elongation), and is prepared from Corsik corporation, Inc.
The waterborne leveling agent is organosilicon modified polyether waterborne leveling agents BYK-346 and BYK-348, the waterborne defoaming agent is organosilicon modified bubble suppression aids BYK-024 and BYK-054, and the leveling agent is 100% solid organosilicon modified surfactant BYK-348 which are from Picker chemical Co.
The thickener is a thickener U-605 (association type) for water-based polyurethane, and is from Wanhua chemical Co.
The solvent-free resin A and the solvent-free resin B are respectively solvent-free resin HX-NS-8002A and solvent-free resin HX-NS-8002B; the catalyst-1 and the catalyst-2 are respectively a gel-promoting metal bismuth catalyst and a curing-promoting amine compound catalyst, and are respectively a catalyst HX-512 and a catalyst HX-606 which are all from Hexixin science and technology Co.
The color paste is 100 percent of solid solvent-free pigment and is from deep blue technology limited company.
Example 1
A composite material for waterborne polyurethane shoes comprises a surface layer, a middle layer, a bonding layer and a bottom cloth layer which are sequentially attached from outside to inside; the surface layer is made of aqueous surface resin slurry; the intermediate layer is made of aqueous intermediate layer resin slurry; the adhesive layer is prepared from solvent-free resin slurry;
the aqueous surface resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000061
the aqueous interlayer resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000062
the solvent-free resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000063
the viscosity of the aqueous surface resin sizing agent is 5500CPS/25 ℃, and the coating weight is 180 g/m; the viscosity of the aqueous intermediate layer resin slurry is 4500CPS/25 ℃, and the coating weight is 150 g/m; the viscosity of the solvent-free resin slurry is 3500CPS/25 ℃, and the coating weight is 280 g/m.
The bottom cloth layer is high-density knitted cloth.
The preparation method of the composite material for the waterborne polyurethane shoe comprises the following steps:
(1) preparing a skin layer: preparing the aqueous surface resin slurry according to a ratio, coating the aqueous surface resin slurry on release paper, drying the release paper in an oven with a temperature gradient of 70/90/110/130 ℃ for 2min at a coating knife position of 0.1mm, transferring the lines of the release paper to the surface, and drying the surface layer to form a film with the thickness of 0.03mm to obtain the surface layer;
(2) preparing an intermediate layer: preparing the aqueous intermediate layer resin slurry according to the proportion, coating the aqueous intermediate layer resin slurry on the surface layer dried in the step (1), coating the surface layer with a cutter position of 0.15mm, drying the surface layer in a drying oven with a temperature gradient of 70/90/110/130 ℃ for 2min, and drying the intermediate layer to form a film with a thickness of 0.04 mm;
(3) preparation of a subsequent layer: blending solvent-free resin slurry according to a ratio, coating the solvent-free resin slurry on the middle layer dried in the step (2), wherein the coating knife position is 0.3mm, and drying in an oven with the temperature gradient of 90/110/130 ℃ for 1min to form a film with the thickness of 0.2 mm; the optimized and selected polyether type solvent-free resin group is subjected to a film forming principle (the solvent-free resin has slow intermolecular reaction in the initial stage of reaction, some physical bubbles are eliminated in the process, the intermediate temperature gradient reaches a set value of 110 ℃, the intermediate temperature gradient is subjected to crosslinking and fast reaction to form a reticular molecular structure, and the film is formed, and the intermediate temperature gradient is subjected to crosslinking and curing at the temperature of 130 ℃ in the later stage), so that the smooth and fine crease effect of the surface of a finished product is realized, the cells are compact, and the polyether type solvent-free resin group is tightly combined with the polyether type waterborne polyurethane resin in the middle layer by utilizing the similarity of the polyether molecular structure of the finished product;
(4) attaching: then pre-baking for 1min in an oven with the temperature gradient of 90/110/130 ℃, and attaching the base fabric on the adhesion layer;
(5) curing: putting the attached base cloth layer, the adhesive layer, the middle layer, the epidermal layer and the release paper into an oven for curing, wherein the curing time is 6min at the set temperature of 130 ℃;
(6) separation: separating and winding the cured finished product and release paper by a guide roller and 2 winding devices; the finished product is on a finished product winding frame, and the release paper is on a release paper winding frame.
Example 2
A composite material for waterborne polyurethane shoes comprises a surface layer, a middle layer, a bonding layer and a bottom cloth layer which are sequentially attached from outside to inside; the surface layer is made of aqueous surface resin slurry; the intermediate layer is made of aqueous intermediate layer resin slurry; the adhesive layer is prepared from solvent-free resin slurry;
the aqueous surface resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000071
the aqueous interlayer resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000081
the solvent-free resin slurry is prepared from the following components in parts by weight:
Figure BDA0003644656230000082
the viscosity of the aqueous surface resin sizing agent is 5500CPS/25 ℃, and the coating weight is 180 g/m; the viscosity of the aqueous intermediate layer resin slurry is 4500CPS/25 ℃, and the coating weight is 150 g/m; the viscosity of the solvent-free resin slurry is 3500CPS/25 ℃, and the coating weight is 280 g/m.
The bottom cloth layer is high-density knitted cloth.
The preparation method of the composite material for the waterborne polyurethane shoe comprises the following steps:
(1) preparing a skin layer: preparing the aqueous surface resin slurry according to a ratio, coating the aqueous surface resin slurry on release paper, drying the release paper in an oven with a temperature gradient of 70/90/110/130 ℃ for 2min at a coating knife position of 0.1mm, transferring the lines of the release paper to the surface, and drying the surface layer to form a film with the thickness of 0.03mm to obtain the surface layer;
(2) preparing an intermediate layer: preparing the aqueous intermediate layer resin slurry according to a ratio, coating the aqueous intermediate layer resin slurry on the surface layer dried in the step (1), wherein the coating knife position is 0.15mm, drying the aqueous intermediate layer resin slurry in a drying oven with a temperature gradient of 70/90/110/130 ℃ for 2min, and the thickness of the intermediate layer after drying is 0.04 mm;
(3) preparation of a subsequent layer: preparing a bonding layer according to the proportion, coating the bonding layer on the middle layer dried in the step (2), coating a cutter position: 0.3mm, drying in an oven with the temperature gradient of 90/110/130 ℃ for 1min to form a film with the thickness of 0.2 mm; the optimized and selected polyether type solvent-free resin group is subjected to a film forming principle (the solvent-free resin has slow intermolecular reaction in the initial stage of reaction, some physical bubbles are eliminated in the process, the intermediate temperature gradient reaches a set value of 110 ℃, the intermediate temperature gradient is subjected to crosslinking and fast reaction to form a reticular molecular structure, and the film is formed, and the intermediate temperature gradient is subjected to crosslinking and curing at the temperature of 130 ℃ in the later stage), so that the smooth and fine crease effect of the surface of a finished product is realized, the cells are compact, and the polyether type solvent-free resin group is tightly combined with the polyether type waterborne polyurethane resin in the middle layer by utilizing the similarity of the polyether molecular structure of the finished product;
(4) attaching: then pre-baking for 1min in an oven with the temperature gradient of 90/110/130 ℃, and attaching the base fabric on the adhesion layer;
(5) curing: putting the attached base cloth layer, the adhesive layer, the middle layer, the epidermal layer and the release paper into an oven for curing, wherein the set temperature is 130/130/130/130/130 ℃, and the drying time is 6 min;
(6) separation: separating and winding the cured finished product and release paper by a guide roller and 2 winding devices; the finished product is on a finished product winding frame, and the release paper is on a release paper winding frame.
Comparative example 1
A composite material for aqueous polyurethane footwear, which is the same as in examples 1 and 2, except that 0 part of the aqueous bridging agent and 0 part of the ultra-fine hydrophilic silica were used.
The performance of the waterborne polyurethane ecological clothing leather prepared in the above examples 1-2 and comparative example 1 was tested, and the test method and results are shown in table 1.
TABLE 1 results of performance test of the aqueous polyurethane shoe composites prepared in examples 1-2 and comparative example 1
Figure BDA0003644656230000091
As can be seen from Table 1, compared with comparative example 1, the blocking resistance and wear resistance of the waterborne polyurethane composite material for shoes prepared in examples 1-2 are obviously improved after the silane coupling agent is added; after the superfine hydrophilic silicon dioxide is added, the micropores are fine and uniform, and the thickness of the coating can be ensured.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims (9)

1. The composite material for the waterborne polyurethane shoes is characterized in that: the fabric comprises a surface layer, an intermediate layer, a bonding layer and a bottom cloth layer which are sequentially attached from outside to inside; the surface layer is made of aqueous surface resin slurry; the intermediate layer is made of aqueous intermediate layer resin slurry; the adhesive layer is made of solvent-free resin slurry;
the aqueous surface resin slurry is prepared from the following components in parts by weight:
Figure FDA0003644656220000011
the aqueous interlayer resin slurry is prepared from the following components in parts by weight:
Figure FDA0003644656220000012
the solvent-free resin slurry is prepared from the following components in parts by weight:
Figure FDA0003644656220000013
2. the aqueous polyurethane footwear composite of claim 1, wherein: the water-based layer resin is polyether polyurethane, the polyether polyurethane is a carboxylic acid type or sulfonic acid type water-based system, and the 100% elongation modulus is 3-6 MPa;
the water-based leveling agent is an organic silicon modified polyether water-based leveling agent;
the water-based defoaming agent is an organic silicon modified bubble-inhibiting assistant;
the aqueous bridging agent is isocyanate aqueous bridging auxiliary agent;
the thickening agent is a thickening agent for waterborne polyurethane;
the waterborne middle layer resin is polyether polyurethane; the polyether polyurethane is a sulfonic acid aqueous system, and the 100% elongation modulus is 1-3 MPa;
the leveling agent is 100 percent of organic silicon modified surfactant;
the color paste is 100 percent of solvent-free pigment.
3. The aqueous polyurethane footwear composite of claim 1, wherein: the solvent-free resin A is a polyether polyol compound mixture; the solvent-free resin B is polyether type isocyanate prepolymer; the catalyst-1 is a gel-promoting metal bismuth catalyst; the catalyst-2 is an amine compound catalyst for promoting curing.
4. The aqueous polyurethane footwear composite of claim 1, wherein: the thickness of the skin layer is 0.02-0.1 mm; the thickness of the middle layer is 0.03-0.2 mm; the thickness of the adhesion layer is 0.08-0.6 mm.
5. The aqueous polyurethane footwear composite of claim 1, wherein: the viscosity of the aqueous surface resin slurry is 3000-10000CPS/25 ℃, and the coating weight is 130-200 g/m; the viscosity of the aqueous middle layer resin sizing agent is 3000-10000CPS/25 ℃, and the coating weight is 130-200 g/m; the viscosity of the solvent-free resin sizing agent is 1000-10000CPS/25 ℃, and the coating weight is 250-350 g/m.
6. The aqueous polyurethane footwear composite of claim 1, wherein: the bottom cloth layer is high-density knitted cloth.
7. The aqueous polyurethane footwear composite of any one of claims 1-6, wherein: the aqueous surface resin slurry is prepared from the following components in parts by weight:
Figure FDA0003644656220000021
the aqueous interlayer resin slurry is prepared from the following components in parts by weight:
Figure FDA0003644656220000022
Figure FDA0003644656220000031
the solvent-free resin slurry is prepared from the following components in parts by weight:
Figure FDA0003644656220000032
8. the method of preparing the aqueous polyurethane footwear composite of any one of claims 1-7, wherein: the method comprises the following steps:
(1) preparing a skin layer: preparing the aqueous surface resin slurry according to the proportion, coating the aqueous surface resin slurry on release paper with a coating knife position of 0.05-0.15mm, drying the release paper in an oven at the temperature of 70-130 ℃ for 2-3min, and transferring the lines of the release paper to the surface to obtain an epidermal layer;
(2) preparing an intermediate layer: preparing the aqueous interlayer resin slurry according to the proportion, coating the aqueous interlayer resin slurry on the surface layer dried in the step (1), wherein the coating knife position is 0.1-0.5mm, and drying in an oven at 70-130 ℃ for 1-3 min;
(3) preparation of a subsequent layer: and (3) preparing the solvent-free resin slurry according to the proportion, coating the solvent-free resin slurry on the middle layer dried in the step (2), and coating a cutter position: 0.2-0.8mm, and drying in an oven at 90-130 deg.C for 1-2 min;
(4) attaching: then pre-baking in a baking oven at 90-130 ℃ for 1-2min, and attaching the base fabric to the adhesion layer;
(5) curing: putting the attached base cloth layer, the adhesive layer, the middle layer, the epidermal layer and the release paper into an oven for curing, setting the temperature at 90-140 ℃, and drying for 5-15 min;
(6) separation: separating and winding the cured finished product and release paper by a guide roller and 2 winding devices; the finished product is on a finished product winding frame, and the release paper is on a release paper winding frame.
9. The method of preparing the aqueous polyurethane footwear composite according to claim 8, wherein: the temperature gradient when drying in the oven in the step (1) is 70/90/110/130 ℃; the temperature gradient when drying in the oven in the step (2) is 70/90/110/130 ℃; the temperature gradient when drying in the oven in the step (3) is 90/110/130 ℃; the temperature gradient during drying in the oven in step (4) was 90/110/130 ℃.
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