CN117328274A - A kind of water-based polyurethane coated synthetic leather and preparation method thereof - Google Patents

A kind of water-based polyurethane coated synthetic leather and preparation method thereof Download PDF

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Publication number
CN117328274A
CN117328274A CN202311181159.3A CN202311181159A CN117328274A CN 117328274 A CN117328274 A CN 117328274A CN 202311181159 A CN202311181159 A CN 202311181159A CN 117328274 A CN117328274 A CN 117328274A
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coating
synthetic leather
aqueous polyurethane
polyurethane
waterborne polyurethane
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吴勇
张其斌
孙向浩
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Shanghai Huafeng Super Fiber Technology Co ltd
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Shanghai Huafeng Super Fiber Technology Co ltd
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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
    • D06N3/145—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
    • D06N3/0002—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
    • D06N3/0004—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 ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • 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
    • D06N3/0086—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
    • D06N3/0088—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 directly applying the resin
    • 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
    • D06N3/0086—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
    • 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
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • 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 relates to a waterborne polyurethane coating synthetic leather and a preparation method thereof, wherein the waterborne polyurethane coating synthetic leather has a composite layer structure, and is sequentially provided with a coating B, a coating C and a microfiber base fabric from top to bottom, or further, a coating A is arranged above the coating B; the coating A, the coating B and the coating C are all waterborne polyurethane coatings, and the 100% modulus of the waterborne polyurethane in the coating A, the coating B and the coating C is respectively 1-3MPa, 12-15MPa and 22-25MPa; the preparation method comprises the following steps: coating the coating B slurry on release paper, drying to form a coating B, coating the coating C slurry on the coating B, attaching a microfiber base cloth, drying, stripping from the release paper, and finally treating the coating A slurry on the surface of the coating B in a roller coating or printing mode, and drying to obtain the waterborne polyurethane coating synthetic leather. The synthetic leather disclosed by the invention has excellent low-temperature folding endurance and rebound resilience, and simultaneously has excellent hand feeling.

Description

Waterborne polyurethane coating synthetic leather and preparation method thereof
Technical Field
The invention belongs to the field of polyurethane synthetic leather, relates to waterborne polyurethane coating synthetic leather and a preparation method thereof, and particularly relates to high-strength waterborne polyurethane coating synthetic leather with excellent low-temperature folding resistance and a preparation method thereof.
Background
Polyurethane materials are widely used as coating materials of leather due to good softness and wear resistance, and are key factors influencing the performance of polyurethane synthetic leather and appearance. The polyurethane synthetic leather has good processing performance, leather products with various dermatoglyph and color can be obtained through the development of coating technology, and therefore the polyurethane synthetic leather is widely used in the fields of shoe materials, cladding materials of automotive interiors and the like. In the fields of shoe materials, automotive interiors and daily leather products, the leather is required to be directionally bent during processing, so that the leather is required to have better unilateral folding endurance, and the leather is required to be used in a cold environment, and therefore, the leather has higher requirement on the low-temperature folding endurance.
The prior art generally improves the low-temperature folding endurance of polyurethane by adding soft segments of polyurethane, however, increasing the soft segments of polyurethane reduces the modulus of polyurethane and the stress rebound ability of polyurethane materials, thereby affecting the hand feeling of polyurethane coating.
Compared with the traditional flexible molecular chain, the polybutadiene structure has the characteristic of rubber-like, and can realize elastic deformation rather than viscous flow deformation. For example, patent CN201911263927.3 discloses a low temperature resistant and wear resistant non-yellowing polyurethane resin and superfine fiber synthetic leather prepared by the same, the polyurethane resin prepared by the patent is mainly made of polycarbonate polyol, and hydrogenated hydroxyl-terminated polybutadiene with a special structure is introduced to improve the low temperature folding endurance, however, the hydrophobicity of polyurethane molecules can be increased when the hydrogenated hydroxyl-terminated polybutadiene is added into polyurethane molecules, if the hydrogenated hydroxyl-terminated polybutadiene is connected into water polyurethane molecules, the water polyurethane is unstable in water easily, and the rebound performance of the superfine fiber synthetic leather is affected.
From the above, it is known that the conventional aqueous polyurethane has some difficulty in obtaining the polyurethane with rebound resilience and low-temperature folding endurance by modifying the molecular structure.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides waterborne polyurethane coating synthetic leather and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the waterborne polyurethane coating synthetic leather has a composite layer structure, and is sequentially provided with a coating B, a coating C and a microfiber base fabric from top to bottom, or further provided with a coating A above the coating B;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the 100% modulus of the aqueous polyurethane in the coating A is 1-3MPa, the 100% modulus of the aqueous polyurethane in the coating B is 12-15MPa, and the 100% modulus of the aqueous polyurethane in the coating C is 22-25MPa;
the thickness of the microfiber base cloth is 1.0-1.3mm, the total thickness of the microfiber base cloth and the coating C is less than or equal to 1.5mm, the total thickness of the microfiber base cloth, the coating C and the coating B is less than or equal to 1.8mm, and the total thickness of the microfiber base cloth, the coating C, the coating B and the coating A is less than or equal to 2.0mm.
As a preferable technical scheme:
the aqueous polyurethane coating synthetic leather is one or more of conventional polyester type aqueous polyurethane, polyether type aqueous polyurethane, polycarbon polyester type aqueous polyurethane, polycarbon polyether type aqueous polyurethane and polyester polyether type polyurethane, and does not contain polyolefin type aqueous polyurethane.
According to the waterborne polyurethane coating synthetic leather, the auxiliary agent is further dispersed in the waterborne polyurethane coating.
The water-based polyurethane coating synthetic leather has the advantages that the auxiliary agent is more than one of a small molecular lubricant, such as tributyl phosphate (an embodiment with small solubility in water and small addition amount), propylene carbonate, triethyl phosphate, polyethylene glycol (PEG-200) with the number average molecular weight of 200 and the like, the auxiliary agent is more than one of a leveling agent, such as BYK-346 of Pick Germany and the like, which can improve the ductility of the material, and a thickening agent, such as stahl of a large number of commercial products on the market, which is used as an auxiliary agent for improving the flow property of a wet filmEVO RM-4417、EVO RM-4456 for increasing waterAn auxiliary agent for viscosity of the polyurethane coating.
The total thickness of the coating A, the coating B and the coating C of the waterborne polyurethane coating synthetic leather is 0.6-1mm, and the control is to meet the hand feeling requirement; the thickness of coating C is at least 30% of the total thickness of coating A, coating B and coating C, and the sum of the thicknesses of coating C and coating B is 80-100% of the total thickness of coating A, coating B and coating C.
The water-based polyurethane coating synthetic leather has the advantages that the single-side bending resistance frequency of the water-based polyurethane coating synthetic leather is not less than 3 ten thousand times at the temperature of minus 40 ℃; the residual deformation of the waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under 150N tensile force is less than or equal to 5%, and the smaller the residual deformation is, the better the rebound resilience is.
The invention also provides a method for preparing the aqueous polyurethane coating synthetic leather, which comprises the following steps:
(1) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
the release paper method for preparing the coating is a dry transfer film technology in the field of synthetic leather, and engineering personnel in the field can obtain the required coating thickness by adjusting the coating amount according to related technical information and combining the target coating thickness;
(2) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(3) Forming a coating A;
coating A sizing agent is processed on the surface of coating B by adopting a roller coating or printing mode, and drying is carried out, thus obtaining the waterborne polyurethane coating synthetic leather;
the mode of preparing the coating by the release paper method and the technology of preparing the top coating by the roller coating or printing method are also common treatment modes in the synthetic leather industry, and engineering technicians in the field can obtain the coating required by the invention by combining the target coating thickness according to related technical information and adjusting the coating amount and the drying process;
the preparation method of the aqueous polyurethane coating synthetic leather is not limited to the method, and the coating C, the coating B and the coating A can be directly coated on the microfiber base cloth in sequence, or the coating A, the coating B, the coating C and the microfiber base cloth can be directly coated on the release paper in sequence.
The mechanism of the invention is as follows:
the chain segment of polyurethane resin consists of hard segments and soft segments, wherein the hard segments are chain segments formed by the reaction of isocyanate, chain extender and cross-linking agent on the main chain of polyurethane molecules, and the cohesive energy of the groups is larger, the space volume is larger and the rigidity is larger; the soft segment refers to a carbon-carbon main chain polymer polyol which has better flexibility and is a soft segment in a polyurethane main chain. The more hard segments the greater the polyurethane 100% modulus and the more soft segments the less polyurethane 100% modulus.
The invention was based on the investigation of 100% modulus and ultimate thickness. The smaller the 100% modulus, the more inversely proportional the elastic resilience contribution it makes, the more the material deforms when subjected to an external force, and the more the surface material is deformed under an equivalent stress, the more the external stress is easily consumed by molecular chain displacement adjustment rather than being stored as internal stress, and the less the elastic resilience after withdrawal of the external stress becomes when the stress is consumed. The composite coating needs to have high rebound resilience and high deformability, and 100% modulus of the aqueous polyurethane in the coating A (outermost layer), the coating B (middle layer) and the coating C (innermost layer) needs to be reasonably set.
If the 100% modulus of the aqueous polyurethane in the coating A, the coating B and the coating C is larger, the molecular chain structure of the product is more easy to generate energy storage deformation and has high rebound resilience, but the product is also difficult to consume and crack when the stress is over the limit due to lack of proper viscous flow deformation, and the product is easy to crack and is poor in appearance of being bent; if the 100% modulus of the aqueous polyurethane in coating A, coating B, coating C is small, the rebound is poor, although the composite coating has high deformability. Considering that the deformation of the outer layer is the largest and the deformation of the inner layer is the smallest in the bending process, the invention controls the 100% modulus of the aqueous polyurethane in the coating A, the coating B and the coating C to gradually increase, namely the polyurethane film gradually softens from inside to outside, and a soft-hard gradient structure is formed.
Experiments show that the composite coating needs to strictly control the magnitude and thickness ratio of the modulus gradient difference in order to obtain low-temperature folding endurance under the ideal rebound resilience.
The 100% modulus of the aqueous polyurethane in the coating A is 1-3MPa, and the deformation force received by the coating A is maximum because the coating A is positioned at the outermost layer, so that the total thickness of the microfiber base cloth, the coating C, the coating B and the coating A is required to be controlled to be less than or equal to 2.0mm, and the deformation capability of the coating A can be matched with the deformation size actually received by the coating A; the total thickness of the microfiber base cloth, the coating C, the coating B and the coating A determines how much high-elastic deformation is carried out on the coating A in the bending process, and when the total thickness is too large, the coating film cracks due to the too large deformation carried out on the coating A;
the 100% modulus of the aqueous polyurethane in the coating B is 12-15MPa, the deformation force received by the coating B is moderate because the coating B is positioned in the middle layer, the total thickness of the microfiber base cloth, the coating C and the coating B determines how much high-elastic deformation the coating B is subjected to in the bending process, and when the total thickness is too large, the coating film is also induced to crack because the deformation of the coating B is too large. The total thickness of the microfiber base cloth, the coating C and the coating B is required to be controlled to be less than or equal to 1.8mm, so that the deformability of the coating B can be ensured to be matched with the deformation actually received.
The 100% modulus of the aqueous polyurethane in the coating C is 22-25MPa, and the total thickness of the microfiber base cloth and the coating C is controlled to be less than or equal to 1.5mm because the coating C is positioned in the innermost layer and receives the smallest deformation force. The total thickness determines how much high the coating C will undergo during bending, and when the total thickness is too large, white streaks appear due to the excessive deformation to which the coating C is subjected.
The general thickness of the microfiber base cloth is at least 1mm so as to ensure that a rigid framework structure is obtained, and 1-2mm is generally selected, and the thickness of the microfiber base cloth is controlled to be 1-1.3mm so as to reduce the whole thick bottom of the synthetic leather as much as possible, and further the thickness ratio of the coating C can be relatively increased; when the thickness of the microfiber base cloth exceeds 1.3mm, this means that the thickness of the coating layer C having a high modulus may be less than 0.2mm, and it is difficult to obtain a suitable elastic energy storage under the action of an external force; when the thickness exceeds 1.5mm, even a coating C having a high modulus cannot be established.
The total thickness of the coating A, the coating B and the coating C is 0.6-1mm, and the control is to meet the hand feeling requirement; the thickness of coating C is at least 30% of the total thickness of coating A, coating B and coating C, and the sum of the thicknesses of coating C and coating B is 80-100% of the total thickness of coating A, coating B and coating C to ensure proper elastic recovery of the film.
The beneficial effects are that:
(1) The composite coating of the waterborne polyurethane coating synthetic leather prepared by the invention has a certain gradient change of softness and hardness from outside to inside, and improves the rebound resilience of the material on the premise of meeting the low-temperature folding endurance of a coating film; or has better low-temperature folding endurance under the same rebound resilience.
(2) The total thickness of the coating of the waterborne polyurethane coating synthetic leather prepared by the invention is controlled within the range of 0.6-1mm, so that the synthetic leather has excellent hand feeling.
Drawings
FIG. 1 is a schematic illustration of a composite layer structure of the present invention;
wherein, 1-coating A, 2-coating B, 3-coating C, 4-microfiber base cloth.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following is a method for testing performance in each example:
single-side bending resistance: the temperature is-40 ℃ and the bending times are 3 ten thousand times according to the measurement of ISO 5402-1-2017, if the steel is cracked, the steel is unqualified; otherwise, the product is qualified;
100% modulus: according to GB/T13022-1991, the tensile strength of a material is measured when the elongation reaches 100%, namely the corresponding tensile strength when the elongation of the polyurethane film is 100% is divided by the cross-sectional area of a polyurethane film sample before stretching;
residual deformation: the aqueous polyurethane coated synthetic leather prepared in the following examples was cut into a size of 200 mm. Times.50 mm, and the length L of the synthetic leather between the two jigs was measured before the test according to the test by the tester in GB/T13022-1991 standard 0 And marked with a test site, then the synthetic leather was stretched for 30 minutes with a tension of 150N, then the tension was removed, left for 10 minutes, and then the length L of the marked site was measured 1 Residual deformation rate of synthetic leather= (L 1 -L 0 )/L 0 ×100％。
Example 1
The waterborne polyurethane coating synthetic leather has a composite layer structure, and is sequentially provided with a coating A1, a coating B2, a coating C3 and a microfiber base cloth 4 from top to bottom as shown in figure 1;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the manufacturer of the aqueous polyurethane in the coating A is Colorgea Polymer (China Co., ltd.) with the trade name ofDAH,100% modulus of 1MPa;
the manufacturer of the aqueous polyurethane in coating B is Stoul fine paint (Suzhou Co., ltd.) and is given the brand name:d RU-94-226, 100% modulus of 12MPa;
the manufacturer of the aqueous polyurethane in coating C is Stoul fine paint (Suzhou Co., ltd.) and is given the brand name:d EX-RU-94-424, 100% modulus 23MPa;
the thickness of the coating A is 0.1mm, the thickness of the coating B is 0.3mm, and the thickness of the coating C is 0.2mm; the total thickness of the coating A, the coating B and the coating C is 0.6mm, the thickness of the coating C accounts for 33% of the total thickness of the coating A, the coating B and the coating C, and the sum of the thicknesses of the coating C and the coating B accounts for 83% of the total thickness of the coating A, the coating B and the coating C;
microfiber base cloth was manufactured by Toray Industries, incSeries 500Z products (1.7 mm in thickness) were obtained by skin milling and 1.3mm in thickness.
The preparation method of the aqueous polyurethane coating synthetic leather comprises the following steps:
(1) Preparation of raw materials:
aqueous polyurethane in the coating A;
the coating B is water-borne polyurethane;
the aqueous polyurethane in the coating C;
microfiber base cloth;
release paper;
(2) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
(3) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(4) Forming a coating A;
and (3) treating the slurry of the coating A on the surface of the coating B in a roller coating mode, and drying to obtain the waterborne polyurethane coating synthetic leather.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 4.82 percent.
Comparative example 1
An aqueous polyurethane coated synthetic leather, substantially identical to example 1, except that: the manufacturer of the aqueous polyurethane in the coating B is Colorgea Polymer (China Co., ltd.) with the trade name ofDL 519, 100% modulus7MPa.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 1.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 17.99 percent.
As is clear from comparison of comparative example 1 and example 1, since the 100% modulus of the aqueous polyurethane in the coating layer B of comparative example 1 is too small, it is difficult to store stress, which may result in deterioration of the rebound resilience of the finally produced aqueous polyurethane coated synthetic leather, and the coating layer B and the coating layer C may also result in swelling of the coating layer due to excessively large difference in elongation and recovery after bending.
Comparative example 2
An aqueous polyurethane coated synthetic leather, substantially identical to example 1, except that: the manufacturer of the aqueous polyurethane in the coating B is Colorgea Polymer (China Co., ltd.) with the trade name ofDL 1007, 100% modulus was 18MPa.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 1.
The single-side bending resistance of the finally prepared waterborne polyurethane coating synthetic leather is not qualified at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 4.31 percent.
As can be seen from the comparison of comparative example 2 and example 1, the 100% modulus of the aqueous polyurethane in coating B of comparative example 2 is too high, which results in a rapid decrease in the number of low temperature folding endurance.
Example 2
A waterborne polyurethane coating synthetic leather has a composite layer structure, and comprises a coating A, a coating B, a coating C and microfiber base cloth from top to bottom in sequence;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the manufacturer of the aqueous polyurethane in the coating A is Zhejiang Huafeng synthetic resin Co., ltd, the brand is JF-PDY-836HY, and the 100% modulus is 3MPa;
the manufacturer of the aqueous polyurethane in coating B is Stoul fine paint (Suzhou Co., ltd.) and is given the brand name:d RU-94-226, 100% modulus of 12MPa;
the manufacturer of the aqueous polyurethane in coating C is Stoul fine paint (Suzhou Co., ltd.) and is given the brand name:d EX-RU-94-424, 100% modulus 23MPa;
the thickness of the coating A is 0mm, the thickness of the coating B is 0.35mm, and the thickness of the coating C is 0.25mm; the total thickness of the coating A, the coating B and the coating C is 0.6mm, the thickness of the coating C accounts for 42% of the total thickness of the coating A, the coating B and the coating C, and the sum of the thicknesses of the coating C and the coating B accounts for 100% of the total thickness of the coating A, the coating B and the coating C;
microfiber base cloth was manufactured by Toray Industries, incSeries 500Z products (1.7 mm in thickness) were obtained by skin milling and 1.2mm in thickness.
The preparation method of the aqueous polyurethane coating synthetic leather comprises the following steps:
(1) Preparation of raw materials:
aqueous polyurethane in the coating A;
the coating B is water-borne polyurethane;
the aqueous polyurethane in the coating C;
microfiber base cloth;
release paper;
(2) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
(3) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(4) Forming a coating A;
and (3) treating the slurry of the coating A on the surface of the coating B in a roller coating mode, and drying to obtain the waterborne polyurethane coating synthetic leather.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 3.55 percent.
Comparative example 3
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the manufacturer of the aqueous polyurethane in the coating C is Colorgea Polymer (China Co., ltd.) with the trade name ofDL 1007, 100% modulus was 18MPa.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 13.21 percent.
Comparing comparative example 3 with example 2, it is seen that the 100% modulus of the aqueous polyurethane in coating C of comparative example 3 is too low, resulting in a material that stores too little energy under stress and has poor rebound resilience.
Comparative example 4
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the manufacturer of the aqueous polyurethane in coating C is Shanghai Zhanzhan New Material technology Co., ltd, brand ML3003, 100% modulus 44MPa.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The single-side bending resistance of the finally prepared waterborne polyurethane coating synthetic leather is not qualified at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 2.91 percent.
Comparing comparative example 4 with example 2, it is seen that the 100% modulus of the aqueous polyurethane in coating C of comparative example 4 is too high, resulting in a rapid decrease in the number of low temperature folding endurance.
Comparative example 5
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the thickness of the coating C was 0.5mm and the thickness of B was 0.1mm.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The single-side bending resistance of the finally prepared waterborne polyurethane coating synthetic leather is not qualified at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 3.24 percent.
Comparing comparative example 5 with example 2, it is known that, since the total thickness of the microfiber base cloth of comparative example 5 and the coating C is greater than 1.5mm, the coating C is deformed too much during bending, so that cracking occurs when the coating C is bent for 3 ten thousand times at-40 ℃.
Comparative example 6
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the thickness of the coating C was 0.15mm, and the thickness of the coating B was 0.45mm.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 10.96 percent.
Comparing comparative example 6 with example 2, it is known that the poor rebound resilience is caused by the too small thickness ratio of the coating C of comparative example 6, because the relatively thin thickness of the coating C with the energy storage contribution makes the overall rebound resilience of the coating less desirable.
Comparative example 7
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the thickness of coating B was 0.5mm.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The single-side bending resistance of the finally prepared waterborne polyurethane coating synthetic leather is not qualified at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 5.05 percent.
Comparing the comparative example 7 with the example 2, it is known that the excessive total thickness of the microfiber base cloth, the coating C and the coating B of the comparative example 7 can cause the coating B to deform excessively in the bending process, so that the finally prepared waterborne polyurethane coating synthetic leather is subjected to unilateral bending for 3 ten thousand times at the temperature of minus 40 ℃ to generate cracking.
Comparative example 8
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the thickness of the coating B was 0.15mm, and the thickness of the coating A was 0.2mm.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 18.51 percent.
Comparing comparative example 8 with example 2, it is known that the coating of comparative example 8 partially replaces the thickness of coating B, resulting in the final aqueous polyurethane coated synthetic leather having poor resilience due to the energy storage under stress.
Comparative example 9
An aqueous polyurethane coated synthetic leather, substantially identical to example 2, except that: the thickness of the coating A was 0.3mm.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially the same as in example 2.
The single-side bending resistance of the finally prepared waterborne polyurethane coating synthetic leather is not qualified at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 21.74%.
As can be seen from comparison of comparative example 9 and example 2, since the total thickness of the microfiber base cloth, the coating C, the coating B, and the coating a of comparative example 9 is greater than 2.0mm, the coating a is cracked at-40 ℃ for 3 ten thousand times due to excessive deformation during bending, and the rebound resilience is deteriorated due to excessive thickness of the coating a.
Example 3
A waterborne polyurethane coating synthetic leather has a composite layer structure, and comprises a coating A, a coating B, a coating C and microfiber base cloth from top to bottom in sequence;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the manufacturer of the aqueous polyurethane in the coating A is Zhejiang Huafeng synthetic resin Co., ltd, the brand is JF-PDY-S820W, and the 100% modulus is 2MPa;
the manufacturer of the aqueous polyurethane in coating B is Dakai ink chemical company (DIC) and is given the brand name: HYDRAN APX-101h,100% modulus 14MPa;
the manufacturer of the aqueous polyurethane in the coating C is Colorgea Polymer (China Co., ltd.) with the trade name of2077 100% modulus 25MPa;
the thickness of the coating A is 0.1mm, the thickness of the coating B is 0.2mm, and the thickness of the coating C is 0.4mm; the total thickness of the coating A, the coating B and the coating C is 0.7mm, the thickness of the coating C accounts for 57% of the total thickness of the coating A, the coating B and the coating C, and the sum of the thicknesses of the coating C and the coating B accounts for 86% of the total thickness of the coating A, the coating B and the coating C;
microfiber base cloth was manufactured by Toray Industries, incSeries 500Z products (1.7 mm in thickness) were obtained by skin milling and 1.1mm in thickness.
The preparation method of the aqueous polyurethane coating synthetic leather comprises the following steps:
(1) Preparation of raw materials:
aqueous polyurethane in the coating A;
the coating B is water-borne polyurethane;
the aqueous polyurethane in the coating C;
microfiber base cloth;
release paper;
(2) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
(3) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(4) Forming a coating A;
and (3) treating the slurry of the coating A on the surface of the coating B in a printing mode, and drying to obtain the waterborne polyurethane coating synthetic leather.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 1.73 percent.
Example 4
A waterborne polyurethane coating synthetic leather has a composite layer structure, and comprises a coating A, a coating B, a coating C and microfiber base cloth from top to bottom in sequence;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the manufacturer of the aqueous polyurethane in the coating A is Zhejiang Huafeng synthetic resin Co., ltd, the brand is JF-PDY-515Y, and the 100% modulus is 1.5MPa;
the manufacturer of the aqueous polyurethane in coating B is Dakai ink chemical company (DIC) and is given the brand name: HYDRAN APX-101h,100% modulus 14MPa;
the manufacturer of the aqueous polyurethane in the coating C is Shanghai Zhanzhan new material science and technology Co., ltd, the brand is ML3010, and the 100% modulus is 24MPa;
the thickness of the coating A is 0.2mm, the thickness of the coating B is 0.3mm, and the thickness of the coating C is 0.5mm; the total thickness of the coating A, the coating B and the coating C is 1mm, the thickness of the coating C accounts for 50% of the total thickness of the coating A, the coating B and the coating C, and the sum of the thicknesses of the coating C and the coating B accounts for 80% of the total thickness of the coating A, the coating B and the coating C;
microfiber base cloth was manufactured by Toray Industries, incSeries 500Z products (1.7 mm in thickness) were obtained by skin milling and 1mm in thickness.
The preparation method of the aqueous polyurethane coating synthetic leather comprises the following steps:
(1) Preparation of raw materials:
aqueous polyurethane in the coating A;
the coating B is water-borne polyurethane;
the aqueous polyurethane in the coating C;
microfiber base cloth;
release paper;
(2) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
(3) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(4) Forming a coating A;
and (3) treating the slurry of the coating A on the surface of the coating B in a printing mode, and drying to obtain the waterborne polyurethane coating synthetic leather.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 2.28 percent.
Comparative example 10
An aqueous polyurethane coated synthetic leather, substantially as in example 4, except that: the manufacturer of the aqueous polyurethane in the coating A is Colorgea Polymer (China Co., ltd.) with the trade name of1030 The 100% modulus is 0.5MPa.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially as described in example 4.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 19.47 percent.
As can be seen from comparing comparative example 10 with example 4, the 100% modulus of the aqueous polyurethane in coating a of comparative example 10 is too small, resulting in the consumption of stress by coating a, and the resulting aqueous polyurethane coated synthetic leather has poor rebound resilience when the stress is removed.
Comparative example 11
An aqueous polyurethane coated synthetic leather, substantially as in example 4, except that: the manufacturer of the aqueous polyurethane in the coating A is Colorgea Polymer (China Co., ltd.) with the trade name of3040 The 100% modulus is 5MPa.
A method of preparing an aqueous polyurethane coated synthetic leather as described above was substantially as described in example 4.
The single-side bending resistance of the finally prepared waterborne polyurethane coating synthetic leather is not qualified at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 3.98 percent.
As is clear from the comparison between comparative example 11 and example 1, the 100% modulus of the aqueous polyurethane in the coating A of comparative example 11 is too high, which results in a rapid decrease in the number of times of low-temperature folding endurance of the produced aqueous polyurethane coated synthetic leather.
Example 5
A waterborne polyurethane coating synthetic leather has a composite layer structure, and comprises a coating A, a coating B, a coating C and microfiber base cloth from top to bottom in sequence;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the manufacturer of the aqueous polyurethane in the coating A is Colorgea Polymer (China Co., ltd.) with the trade name ofDL1537, 100% modulus of 2MPa;
the manufacturer of the aqueous polyurethane in coating B is Dakai ink chemical company (DIC) and is given the brand name: HYDRAN APX-101h,100% modulus 14MPa;
the manufacturer of the aqueous polyurethane in the coating C is Colorgea Polymer (China Co., ltd.) with the trade name of2077 100% modulus 25MPa;
the thickness of the coating A is 0.2mm, the thickness of the coating B is 0.5mm, and the thickness of the coating C is 0.3mm; the total thickness of the coating A, the coating B and the coating C is 1mm, the thickness of the coating C accounts for 30% of the total thickness of the coating A, the coating B and the coating C, and the sum of the thicknesses of the coating C and the coating B accounts for 80% of the total thickness of the coating A, the coating B and the coating C;
microfiber base cloth was manufactured by Toray Industries, incSeries 500Z products (1.7 mm in thickness) were obtained by skin milling and 1mm in thickness.
The preparation method of the aqueous polyurethane coating synthetic leather comprises the following steps:
(1) Preparation of raw materials:
aqueous polyurethane in the coating A;
the coating B is water-borne polyurethane;
the aqueous polyurethane in the coating C;
microfiber base cloth;
release paper;
(2) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
(3) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(4) Forming a coating A;
and (3) treating the slurry of the coating A on the surface of the coating B in a printing mode, and drying to obtain the waterborne polyurethane coating synthetic leather.
The finally prepared waterborne polyurethane coating synthetic leather has qualified unilateral bending resistance at the temperature of minus 40 ℃, and the residual deformation of the finally prepared waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under the tensile force of 150N is 5.17 percent.

Claims (7)

1. The waterborne polyurethane coating synthetic leather is characterized by having a composite layer structure, wherein a coating B, a coating C and a microfiber base fabric are sequentially arranged from top to bottom, or further, a coating A is arranged above the coating B;
the coating A, the coating B and the coating C are all waterborne polyurethane coatings;
the 100% modulus of the aqueous polyurethane in the coating A is 1-3MPa, the 100% modulus of the aqueous polyurethane in the coating B is 12-15MPa, and the 100% modulus of the aqueous polyurethane in the coating C is 22-25MPa;
the thickness of the microfiber base cloth is 1.0-1.3mm, the total thickness of the microfiber base cloth and the coating C is less than or equal to 1.5mm, the total thickness of the microfiber base cloth, the coating C and the coating B is less than or equal to 1.8mm, and the total thickness of the microfiber base cloth, the coating C, the coating B and the coating A is less than or equal to 2.0mm.
2. The aqueous polyurethane coating synthetic leather according to claim 1, wherein the aqueous polyurethane is one or more of polyester-type aqueous polyurethane, polyether-type aqueous polyurethane, polycarbon-polyester-type aqueous polyurethane, polycarbon-polyether-type aqueous polyurethane and polyester-polyether-type polyurethane.
3. The aqueous polyurethane coated synthetic leather of claim 1, wherein an auxiliary agent is further dispersed in the aqueous polyurethane coating.
4. The aqueous polyurethane coating synthetic leather according to claim 3, wherein the auxiliary agent is more than one of a small molecular lubricant, a leveling agent, a thickener and color paste.
5. The aqueous polyurethane coated synthetic leather according to claim 1, wherein the total thickness of the coating A, the coating B and the coating C is 0.6-1mm, the thickness of the coating C is at least 30% of the total thickness of the coating A, the coating B and the coating C, and the sum of the thicknesses of the coating C and the coating B is 80-100% of the total thickness of the coating A, the coating B and the coating C.
6. The aqueous polyurethane coating synthetic leather according to any one of claims 1 to 5, wherein the aqueous polyurethane coating synthetic leather has a single-side bending resistance of not less than 3 ten thousand times at-40 ℃; the residual deformation of the waterborne polyurethane coating synthetic leather after the tensile force is removed after the waterborne polyurethane coating synthetic leather is acted for 30 minutes under 150N tensile force is less than or equal to 5 percent.
7. A method for preparing the aqueous polyurethane coating synthetic leather according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Forming a coating B;
coating the coating B slurry on release paper, and drying to form a coating B;
(2) Forming a coating layer C;
coating the coating B with the coating C slurry, attaching a microfiber base cloth, drying, and stripping from the release paper;
(3) Forming a coating A;
and (3) treating the slurry of the coating A on the surface of the coating B by adopting a roller coating or printing mode, and drying to obtain the waterborne polyurethane coating synthetic leather.
CN202311181159.3A 2023-09-13 2023-09-13 A kind of water-based polyurethane coated synthetic leather and preparation method thereof Pending CN117328274A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH055280A (en) * 1990-11-20 1993-01-14 Asahi Chem Ind Co Ltd Synthetic leather
JP2004250809A (en) * 2003-02-19 2004-09-09 Kuraray Co Ltd Leather-like sheet
JP2013189736A (en) * 2012-02-14 2013-09-26 Toyo Cloth Co Ltd Synthetic leather
CN104179030A (en) * 2014-07-02 2014-12-03 合肥冠怡涂层织物有限公司 High-quality microfiber-type waterborne synthetic leather and preparation method thereof
CN105408543A (en) * 2013-07-25 2016-03-16 世联株式会社 Synthetic leather and method for manufacturing same
JP2020023761A (en) * 2018-08-06 2020-02-13 三菱ケミカル株式会社 Artificial leather, or synthetic leather
CN215104234U (en) * 2020-12-31 2021-12-10 浙江聚得利合成革有限公司 Soft and folding-resistant artificial leather for Martin boots
CN114232357A (en) * 2021-12-25 2022-03-25 华伦皮塑（苏州）有限公司 Water-based solvent-free automobile interior material and processing technology thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH055280A (en) * 1990-11-20 1993-01-14 Asahi Chem Ind Co Ltd Synthetic leather
JP2004250809A (en) * 2003-02-19 2004-09-09 Kuraray Co Ltd Leather-like sheet
JP2013189736A (en) * 2012-02-14 2013-09-26 Toyo Cloth Co Ltd Synthetic leather
CN105408543A (en) * 2013-07-25 2016-03-16 世联株式会社 Synthetic leather and method for manufacturing same
CN104179030A (en) * 2014-07-02 2014-12-03 合肥冠怡涂层织物有限公司 High-quality microfiber-type waterborne synthetic leather and preparation method thereof
JP2020023761A (en) * 2018-08-06 2020-02-13 三菱ケミカル株式会社 Artificial leather, or synthetic leather
CN215104234U (en) * 2020-12-31 2021-12-10 浙江聚得利合成革有限公司 Soft and folding-resistant artificial leather for Martin boots
CN114232357A (en) * 2021-12-25 2022-03-25 华伦皮塑（苏州）有限公司 Water-based solvent-free automobile interior material and processing technology thereof

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