Artificial leather and its manufacturing method

Abstract

The present application relates to an artificial leather and a manufacturing method thereof, the artificial leather comprising a base layer, a polyolefin elastomer composite layer, and a polyurethane resin solution layer, the polyolefin elastomer composite layer being provided on a surface of the base layer, the polyolefin elastomer composite layer comprising at least one foamed layer and at least one modified layer, and the polyurethane resin solution layer being provided on a surface of the polyolefin elastomer composite layer away from the base layer.

Description

[Technical Field]

[0001] This application claims priority to Chinese Patent Application No. 202110774241.1, filed on July 8, 2021, for the invention "Radiation-crosslinked high-peel polyolefin elastomer artificial leather," the entire contents of which are incorporated herein by reference.

[0002] This application claims priority to Chinese Patent Application No. 202110774079.3, filed on July 8, 2021, for the invention "Low-odor polyolefin artificial leather containing rubber components," the entire contents of which are incorporated herein by reference.

[0003] This application claims priority to Chinese Patent Application No. 202110774192.1, filed on July 8, 2021, for the invention entitled "Radiation-Crosslinked Ultra-Soft Foam Polyolefin Elastomer Artificial Leather," the entire contents of which are incorporated herein by reference.

[0004] This application claims priority to Chinese Patent Application No. 202110774564.0, filed on July 8, 2021, for the invention "Multi-layered Leather with High Interfacial Adhesion," the entire contents of which are incorporated herein by reference.

[0005] This application claims priority to Chinese Patent Application No. 202110774653.5, filed on July 8, 2021, for the invention entitled "Environmentally Friendly Leather Suitable for Fine Textures," the entire contents of which are incorporated herein by reference.

[0006] This application claims priority to Chinese Patent Application No. 202110774656.9, filed on July 8, 2021, for the invention entitled "Anti-graffiti Polyurethane Coating Layer," the entire contents of which are incorporated herein by reference.

[0007] This application claims priority to Chinese Patent Application No. 202110774739.8, filed on July 8, 2021, for an invention entitled "Anti-Graffiti Leather Paper," the entire contents of which are incorporated herein by reference.

[0008] This application relates to the technical field of materials, and more particularly to artificial leather and methods for making same. [Background technology]

[0009] As people's living standards improve, they are placing increasingly higher quality demands on daily necessities. As a daily necessities, market demand for leather has grown in recent years, along with increasingly stringent customer requirements (including environmental friendliness, inherent physical strength, durability, and solvent resistance). Genuine leather generates a large amount of pollution during its manufacturing process, and has inherent deficiencies such as high production costs, relatively poor durability, relatively poor surface properties, and difficulty in maintenance, making it unable to meet people's latent needs for high quality. Since its development began, synthetic leather has been widely used in the manufacture of shoes, bags, sofas, clothing, and other products due to its superior performance and relatively low cost. The synthetic leather industry has become a pillar industry in the light industrial sector.

[0010] Currently, the entire structure of synthetic leather is built on a base layer mainly made of polyurethane (PU) or polyvinyl chloride (PVC), and large amounts of organic solvents and plasticizers are used in the production process, such as dimethylformamide, methyl ethyl ketone, acetone, toluene, ethyl acetate, and o-benzene-based plasticizers, which are extremely harmful to the human body and the environment.

[0011] As can be seen from the disclosed technical content, ethylene-vinyl acetate copolymer (EVA) can be used as a base material for synthetic leather. This synthetic leather has advantages such as good resilience, flexibility, and durability, as well as being environmentally friendly, easy to process, and low cost, but its range of use is limited due to its high odor. Summary of the Invention

[0012] The present application provides artificial leather, which has low odor, soft texture, good resilience, and lower cost.

[0013] According to a first aspect, the present application provides an artificial leather, the artificial leather comprising: A base layer; A polyolefin elastomer composite layer provided on the surface of the base layer, comprising at least one foam layer and at least one Performance improvement layer a radiation-crosslinked polyolefin elastomer composite layer comprising: and a polyurethane layer provided on the surface of the polyolefin elastomer composite layer away from the base layer.

[0014] In one embodiment of the present invention, the base layer of the artificial leather is provided with a radiation-crosslinked polyolefin elastomer composite layer, which has no odor and excellent aging resistance and processability, so that the artificial leather of the present invention has low odor, excellent aging resistance, and is easy to process. In addition, the polyolefin elastomer composite layer has at least one foam layer and at least one Performance improvement layer The foam layer softens the texture of the artificial leather, provides excellent resilience, and reduces production costs. Performance improvement layer On the one hand, it can protect the foam layer, and on the other hand, it can improve the performance of the artificial leather, such as aging resistance, UV yellowing resistance, abrasion resistance, etc., and further, the artificial leather of the present application has the above-mentioned excellent performance. In addition, the polyurethane layer is provided on the surface of the polyolefin elastomer composite layer, and can play the role of decorating and protecting the polyolefin elastomer composite layer.

[0015] In some embodiments of the present application, the degree of crosslinking of the foam layer is 15% to 90%.

[0016] In some embodiments of the present application, the raw material ingredients of the foam layer are: 100 parts by mass of a first polyolefin elastomer; 1 part by mass to 15 parts by mass of a foaming agent; First Rubber 0 to 100 parts by mass, preferably 50 to 100 parts by mass, a foaming accelerator of 0 to 10 parts by mass, preferably 2 to 10 parts by mass; a first auxiliary agent and a first filler, The first auxiliary agent contains 0.05 parts by mass to 20 parts by mass of the first cross-linking auxiliary agent.

[0017] In some embodiments of the present application, Performance improvement layer The raw material ingredients are: 100 parts of a second polyolefin elastomer; Second Rubber 0 to 100 parts by mass, preferably 50 to 100 parts by mass, The first tackifier resin is contained in an amount of 0 to 10 parts by mass, preferably 6 to 10 parts by mass.

[0018] In some embodiments of the present application, the first polyolefin elastomer and the second polyolefin elastomer have a melting point of 96°C or less, The first polyolefin elastomer and the second polyolefin elastomer have a Shore A hardness of 91 or less.

[0019] In some embodiments of the present application, the first polyolefin elastomer and the second polyolefin elastomer are at least one selected from polyethylene, ethylene and α-olefin copolymer, polypropylene, and propylene and α-olefin copolymer.

[0020] In some embodiments of the present application, First Rubber and the above Second Rubberare at least one type selected from natural rubber, binary ethylene propylene rubber, ternary ethylene propylene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, cis-1,4-polybutadiene rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer.

[0021] In some embodiments of the present application, the polyurethane layer is a solvent-based, water-based, or solvent-free polyurethane coating layer.

[0022] In some embodiments of the present application, the raw material components of the polyurethane coating layer are 100 parts by mass of polyurethane resin solution, 1 part by mass to 10 parts by mass of organic silicone; 0.2 parts by mass to 2.2 parts by mass of a second crosslinking aid; a second co-agent; The secondary co-agents include chain extenders, thickeners, film formers, slip agents, wetting agents or combinations thereof.

[0023] In some embodiments of the present application, the polyurethane resin solution is obtained by a polymerization reaction using polyisocyanate and polyol as raw materials, and the polyol includes at least one of polyols having a hydroxyl group at the terminal group, polyol polyoxyalkyl ethers, and polyol esters, and the number of carbon atoms linked to the hydroxyl group at the terminal group of the polyol is 6 or more.

[0024] In some embodiments of the present application, the end groups of the organosilicone are either epoxy groups, alkenyl groups, or acrylate groups.

[0025] In some embodiments of the present application, the second crosslinking coagent comprises a second crosslinking coagent and a crosslinking accelerator, and optionally, the second crosslinking coagent is a compound containing multiple functionalities, and the crosslinking accelerator comprises at least one of an organotin compound and a metal oxide.

[0026] In some embodiments of the present application, the second crosslinking coagent is at least one selected from diallylamine, diallyl sulfide, N,N-methylenebisacrylamide, ethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, and tetramethylolmethane tetraacrylate.

[0027] In some embodiments of the present application, the base layer is fabric or paper.

[0028] In some embodiments of the present application, the fabric is at least one selected from a raised fabric, a plain fabric, a polyester fiber, a nylon fabric, a microfiber base, an elastic fabric, and a nonwoven fabric.

[0029] In some embodiments of the present application, the total thickness of the artificial leather is 0.21 mm to 13.1 mm, The thickness of the base layer is 0.1 mm to 6.0 mm, The thickness of the polyolefin elastomer composite layer is 0.1 mm to 7.0 mm, The polyurethane layer has a thickness of 0.01 mm to 0.10 mm.

[0030] In some embodiments of the present application, the film further comprises a polyolefin elastomer adhesive layer disposed between the polyolefin elastomer composite layer and the base layer, the polyolefin elastomer adhesive layer being crosslinked by radiation.

[0031] In some embodiments of the present application, the degree of crosslinking of the polyolefin elastomer adhesive layer is 1% to 90%.

[0032] In some embodiments of the present application, the raw material components of the polyolefin elastomer adhesive layer are 0 to 100 parts by mass, preferably 60 to 100 parts by mass, of a third polyolefin elastomer; 0 to 100 parts by mass, preferably 10 to 100 parts by mass, of a graft-modified polyolefin elastomer; 0.5 parts by mass to 40 parts by mass of a second tackifier resin; 1 part by mass to 10 parts by mass of a third crosslinking aid; a second filler; The total number of parts by mass of the third polyolefin elastomer and the graft-modified polyolefin elastomer is 100 parts by mass.

[0033] In some embodiments of the present application, the graft groups of the graft-modified polyolefin elastomer are selected from (meth)acrylates.

[0034] In some embodiments of the present application, the (meth)acrylate salt is at least one selected from sodium (meth)acrylate, lithium (meth)acrylate, and zinc (meth)acrylate.

[0035] In some embodiments of the present application, the graft group of the graft-modified polyolefin elastomer is at least one selected from acrylic acid, maleic anhydride, glycidyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, and (meth)acrylic acid monomers.

[0036] In some embodiments of the present application, the first tackifying resin and the second tackifying resin both include at least one of rosin and its derivatives, terpene resins, polymeric resins, dicyclopentadiene, and condensation resins.

[0037] In some embodiments of the present application, the first tackifying resin and the second tackifying resin have a softening point of 120° C. or less (≦120° C.).

[0038] In some embodiments of the present application, the degree of crosslinking of the artificial leather is 20% to 90%.

[0039] According to a second aspect, the present application provides a method for producing an artificial leather, the method comprising: At least one foam layer and at least one Performance improvement layer providing a polyolefin elastomer composite layer comprising: and providing a polyurethane layer on the surface of the polyolefin elastomer composite layer away from the base layer, and then subjecting the layer to embossing and radiation crosslinking treatment to obtain the artificial leather.

[0040] In the embodiment of the present application, the manufacturing process is simple and low cost, and by using a radiation crosslinking treatment in the manufacturing method, the obtained artificial leather has better heat resistance, aging resistance, and solvent resistance.

[0041] In some embodiments of the present application, providing a polyolefin elastomer composite layer on the surface of the base layer comprises: providing a base layer; Raw material ingredients of the foam layer and Performance improvement layer After mixing the raw material components, the foam film and Performance improvement layer and forming Foam membrane and Performance improvement layer and coating each of these on the surface of the base layer; and foaming the foamed film on the surface of the base layer to form a polyolefin elastomer composite layer on the surface of the base layer.

[0042] In some embodiments of the present application, providing a polyolefin elastomer composite layer on the surface of the base layer comprises: providing a polyolefin elastomer adhesive layer on the surface of the base layer; and providing a polyolefin elastomer composite layer on the surface of the polyolefin elastomer adhesive layer away from the base layer.

[0043] In some embodiments of the present application, the cross-linking by radiation is carried out by alpha rays, beta rays, gamma rays, X-rays, or neutron rays.

[0044] In order to more clearly describe the embodiments of the present invention or the embodiments in the prior art, the following briefly introduces the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings based on these drawings without requiring creative efforts. [Brief explanation of the drawings]

[0045] [Figure 1] 1 is a schematic diagram of the structure of artificial leather according to some embodiments of the present application. [Figure 2] 1 is a schematic diagram of the structure of artificial leather according to some other embodiments of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0046] Each embodiment or example in this specification is described in an incremental manner, with each embodiment being described by focusing on the differences between other embodiments, and the same or similar parts between the embodiments may be referred to each other.

[0047] In the description herein, the reference words "one embodiment," "some embodiments," "schematic embodiment," "exemplary," "specific examples," or "some examples" mean that the specific features, structures, materials, or characteristics described in the embodiment or example are included in at least one embodiment or example of the present invention. In the description herein, the general expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the described specific features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.

[0048] Additionally, the terms "first" and "second" are for descriptive purposes only and should not be understood as indicating or implying the relative importance or the number of the indicated technical features. Thus, a "first" or "second" feature may explicitly or implicitly include at least one of the feature. In the description of this application, "plurality" means at least two, e.g., two, three, etc., unless otherwise specified.

[0049] As shown in FIG. 1, the present application provides an artificial leather comprising a base layer 10, a polyolefin elastomer composite layer 20, and a polyurethane layer 30, wherein the polyolefin elastomer composite layer 20 is provided on the surface of the base layer 10, and the polyolefin elastomer composite layer 20 comprises at least one foam layer 21 and at least one polyurethane layer 30. Performance improvement layer The polyolefin elastomer composite layer 20 includes a polyurethane layer 30 on the surface of the polyolefin elastomer composite layer 20 that faces away from the base layer 10.

[0050] In the present embodiment, the base layer 10 of the artificial leather is provided with a radiation-crosslinked polyolefin elastomer composite layer 20, which has no odor and has excellent aging resistance and processability, so that the artificial leather of the present application has low odor, excellent aging resistance, and is easy to process. In addition, the polyolefin elastomer composite layer 20 has at least one foam layer 21 and at least one Performance improvement layer 22, and the foam layer 21 makes the artificial leather softer, has good resilience, and can reduce its production cost. Performance improvement layer On the one hand, the polyurethane layer 22 can protect the foam layer 21, and on the other hand, can improve the performance of the artificial leather, such as aging resistance, UV yellowing resistance, abrasion resistance, etc., and the artificial leather of the present application has the above-mentioned excellent performance. In addition, the polyurethane layer 30 is provided on the surface of the polyolefin elastomer composite layer 20, and can serve to decorate and protect the polyolefin elastomer composite layer.

[0051] As described above, the foam layer 21 can improve the flexibility and resilience of the artificial leather, and the degree of crosslinking and the expansion ratio of the foam layer 21 are closely related to the improvement of the flexibility and resilience of the artificial leather. Therefore, in some embodiments of the present application, the degree of crosslinking of the foam layer 21 is set within the range of 15% to 90%, and the expansion ratio is set to 1.2 to 10 times.

[0052] Exemplarily, the crosslinking degree of the foam layer 21 is 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53% , 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, and 90%.

[0053] In order to obtain a foam layer with the degree of crosslinking in the above-described embodiment, a crosslinked foam layer can be obtained by a radiation-assisted method. The degree of crosslinking of the foam layer can also be adjusted by adjusting the radiation dose. In some embodiments of the present application, crosslinking by radiation is carried out using α-rays, β-rays, γ-rays, X-rays, or neutron rays, and the radiation dose is 5 KGy to 200 KGy, preferably 10 KGy to 100 KGy.

[0054] Illustratively, the expansion ratio of the foam layer 21 is 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 2.9 times, 3.0 times, 3.1 times, 3.2 times, 3.3 times, 3.4 times, 3.5 times, 3.6 times, 3.7 times, 3.8 times, 3.9 times, 4.0 times, 4.1 times, 4.2 times, 4.3 times, 4.4 times, 4.5 times, 4.6 times, 4.7 times, 4.8 times, 4.9 times, 5.0 times, 5.1 times, 5.2 times, 5.3 times, 5.4 times, 5.5 times, 5.6 times, 5.7 times, 5.8 times, 5 ... , 5.7 times, 5.8 times, 5.9 times, 6.0 times, 6.1 times, 6.2 times, 6.3 times, 6.4 times, 6.5 times, 6.6 times, 6.7 times, 6.8 times, 6.9 times, 7.0 times, 7.1 times, 7.2 times, 7.3 times, 7.4 times, 7.5 times, 7.6 times, 7.7 times, 7.8 times, 7.9 times, 8.0 times, 8.1 times, 8.2 times, 8.3 times, 8.4 times, 8.5 times, 8.6 times, 8.7 times, 8.8 times, 8.9 times, 9.0 times, 9.1 times, 9.2 times, 9.3 times, 9.4 times, 9.5 times, 9.6 times, 9.7 times, 9.8 times, 9.9 times, and 10.0 times, but are not limited to these.

[0055] In order to obtain the foam layer in the above embodiment, in some embodiments of the present application, the raw material components of the foam layer 21 are: 100 parts by mass of a first polyolefin elastomer; 1 part by mass to 15 parts by mass of a foaming agent; First Rubber 0 to 100 parts by mass, preferably 50 to 100 parts by mass, a foaming accelerator of 0 to 10 parts by mass, preferably 2 to 10 parts by mass; a first auxiliary agent and a first filler, The first auxiliary agent contains 0.05 parts by mass to 20 parts by mass of the first cross-linking auxiliary agent.

[0056] Here, the first polyolefin elastomer has a melting point of 96°C or less and a Shore A hardness of 91 or less, and if the first polyolefin elastomer has a melting point and Shore A hardness within the above ranges, it is advantageous for forming a clear texture.

[0057] In some embodiments of the present application, the first polyolefin elastomer is selected from copolymers and / or homopolymers in which an olefin is a monomer. Specific examples of the first polyolefin elastomer include at least one selected from polyethylene, copolymers of ethylene and α-olefins, polypropylene, and copolymers of propylene and α-olefins.

[0058] In the embodiment of the present application, the foaming agent is not particularly limited, and may be a physical foaming agent, a chemical foaming agent, or a microsphere foaming agent.

[0059] Exemplary physical blowing agents include, but are not limited to, nitrogen (N2), carbon dioxide (CO2), pentane, hexane, and trichlorotrifluoroethane.

[0060] Exemplary chemical blowing agents include, but are not limited to, azodicarbonamide (AC), azobisisobutyronitrile, N,N-dinitrosopentamethylenetetramine (DPT), 4,4-oxydibenzenesulfonyl hydrazide (OBSH), and p-toluenesulfonyl hydrazide.

[0061] In some embodiments of the present application, the blowing agent may be at least one selected from an ADC blowing agent, an OBSH blowing agent, and a bicarbonate blowing agent.

[0062] In some embodiments of the present application, First Rubber is an organic compound containing an unsaturated bond, such as an olefin having a double bond, which allows the foam layer 21 and the polyolefin elastomer composite layer 20 to have an appropriate degree of crosslinking. First Rubberis at least one selected from natural rubber (NR), binary ethylene propylene rubber (EPM), ternary ethylene propylene rubber (EPDM), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), cis-1,4-polybutadiene rubber, styrene butadiene rubber, hydrogenated styrene butadiene block copolymer (SEBS), hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer.

[0063] In some embodiments of the present application, the foaming enhancer may be at least one selected from zinc stearate, zinc oxide, and zinc carbonate.

[0064] In the embodiment of the present application, the components and the number of parts of the first auxiliary agent and the first filler are not specifically limited, and are both ordinary components and addition amounts well known to those skilled in the art.

[0065] In some embodiments of the present application, the first coagent may be selected from a crosslinking coagent, an antioxidant, a colorant, or a combination thereof. Each of the above coagents is added in an appropriate amount, for example, 0.1 to 20 parts, that can achieve its desired function.

[0066] The cross-linking coagent can improve the cross-linking degree of the foam layer 21, and the amount thereof can be adjusted according to actual conditions. In some embodiments of the present application, based on 100 parts by mass of the first polyolefin elastomer, the first cross-linking coagent is added in an amount of 20 parts or less.

[0067] Furthermore, the first cross-linking aid may be at least one selected from diallylamine, diallyl sulfide, N,N-dimethyl-bisacrylamide, ethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, and tetramethylolmethane tetraacrylate.

[0068] In some embodiments of the present application, the raw material component of the first filler in the foamed layer 21 may be at least one selected from calcium carbonate, limestone, white carbon, and talc. Adding the first filler can improve the mechanical properties of the polyolefin elastomer composite layer 20. For example, the amount of the first filler added is 0 to 30 parts, preferably 0.1 to 5 parts, based on 100 parts by mass of the first polyolefin elastomer.

[0069] In the embodiment of the present application, in the polyolefin elastomer composite layer 20 Performance improvement layer 22 has good adhesive properties, resilience, abrasion resistance, flexibility, etc. Performance improvement layer is.

[0070] In some embodiments of the present application, Performance improvement layer The 22 raw ingredients are: 100 parts of a second polyolefin elastomer; Second Rubber 0 to 100 parts by mass, preferably 50 to 100 parts by mass, The first tackifier resin is contained in an amount of 0 to 10 parts by mass, preferably 6 to 10 parts by mass.

[0071] Here, the second polyolefin elastomer has a melting point of 96°C or less and a Shore A hardness of 91 or less, and when the second polyolefin elastomer has a melting point and Shore A hardness within the above ranges, it is advantageous for forming a clear texture.

[0072] In some embodiments of the present application, the second polyolefin elastomer is selected from copolymers and / or homopolymers in which olefins are monomers.

[0073] Exemplarily, the second polyolefin elastomer may be at least one selected from polyethylene, a copolymer of ethylene and an α-olefin, polypropylene, and a copolymer of propylene and an α-olefin.

[0074] In some embodiments of the present application, Second Rubber is an organic compound containing an unsaturated bond, such as an olefin with a double bond, which allows a polyolefin elastomer composite layer 20 to have an appropriate degree of crosslinking.

[0075] For example, Second Rubber is at least one selected from natural rubber (NR), binary ethylene propylene rubber (EPM), ternary ethylene propylene rubber (EPDM), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), cis-1,4-polybutadiene rubber, styrene butadiene rubber, hydrogenated styrene butadiene block copolymer (SEBS), hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer.

[0076] In the embodiment of the present application, the first tackifying resin is used to enhance the adhesion between layers, and the amount of the first tackifying resin added can be adjusted according to the actual situation.

[0077] In some embodiments herein, the first tackifying resin comprises at least one of rosin and its derivatives, terpene resins, polymeric resins, dicyclopentadiene, and condensation resins.

[0078] Illustratively, the rosin may be gum rosin, tall oil rosin, or wood rosin; the rosin derivative may be a resinate, a resinate ester, a rosin amine, a rosin acid anhydride, a rosin alcohol, a hydrogenated rosin, a disproportionated rosin, a polymerized rosin, an esterified rosin, or a maleated rosin; the terpene resin may be an α-terpene resin, a β-terpene resin, or a terpene phenol resin; the polymer resin may be at least one of a C5 petroleum resin, a C9 petroleum resin, a dicyclopentadiene (DCPD) resin, a coumarone-indene resin, or a styrene-based resin; and the condensation resin may be at least one of an alkylphenol resin and a xylene resin.

[0079] In some embodiments of the present application, the softening point of the first tackifying resin is 120° C. or less.

[0080] In the embodiment of the present application, the polyurethane layer 30 not only functions as a decoration but also serves a protective function, which can reduce the residue of dirt on the surface of the artificial leather or make the surface of the artificial leather cleaner.

[0081] In some embodiments of the present application, the polyurethane layer 30 may be formed of a material such as a polyurethane resin, a polyurethane resin layer ... Foam layer It is bonded to 21 surfaces.

[0082] In some embodiments of the present application, polyurethane layer 30 may be a solvent-based, water-based, or solvent-free polyurethane coating layer.

[0083] In some specific embodiments of the present application, polyurethane layer 30 is a solventless or water-based polyurethane coating layer.

[0084] In order to improve the anti-graffiti effect of the polyurethane layer 30, in some embodiments of the present application, the raw material components of the polyurethane coating layer are: 100 parts by mass of polyurethane resin solution, 1 part by mass to 10 parts by mass of organic silicone; 0.2 parts by mass to 2.2 parts by mass of a second crosslinking aid; a second co-agent; The secondary co-agents include chain extenders, thickeners, film formers, slip agents, wetting agents or combinations thereof.

[0085] In one embodiment of the present application, the polyurethane resin solution and the organosilicone undergo a crosslinking reaction with the aid of the second crosslinking coagent and the second coagent to form a three-dimensional network structure, where the carbon chains in the polyurethane resin solution increase the density of active crosslinking points, thereby improving the density of the crosslinked network and resulting in a uniform, tough coating layer. Furthermore, the organosilicone, which provides anti-graffiti properties, is chemically bonded to the polyurethane resin solution, making it less likely to detach from the coating layer, resulting in a polyurethane coating layer with excellent anti-graffiti properties. Furthermore, the raw materials used to produce the polyurethane coating layer do not contain low-boiling, easily volatile organic small molecules, and the polyurethane coating layer does not emit volatile gases, further reducing the odor of the artificial leather.

[0086] The present application provides a method for producing a polyurethane coating layer, in order to obtain the polyurethane coating layer, the method comprising: mixing a polyurethane resin solution, an organic silicone, a second crosslinking aid, and a second aid in a certain ratio, and then adding and mixing a solvent to obtain a slurry; applying the slurry to a substrate, and after the slurry has dried, crosslinking the slurry by radiation to obtain the polyurethane coating layer of the present invention.

[0087] In some embodiments of the present application, the polyurethane resin solution is obtained by carrying out a polymerization reaction using polyisocyanate and polyol as raw materials, wherein the polyisocyanate is at least one selected from aromatic diisocyanates and aliphatic diisocyanates. Illustratively, the aromatic diisocyanate may be 4,4'-methylenebisphenylisocyanate (MDI), m-xylene diisocyanate (XDI), benzene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, and tolylene diisocyanate (TDI), and the aliphatic diisocyanate may be isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI).

[0088] In some embodiments of the present application, the polyol includes at least one of a polyol having a terminal hydroxyl group, a polyol polyoxyalkyl ether, and a polyol ester, wherein the number of carbon atoms linked to the hydroxyl group in the terminal group of the polyol is 6 or more. Note that the polyol refers to an organic compound containing two or more hydroxyl groups, such as a diol or triol.

[0089] In one embodiment of the present invention, the soft segment structure of the polyurethane resin molecule has six or more carbon atoms, and radiation-induced crosslinking begins with the long carbon chains in the soft segment structure of the polyurethane resin molecule as active crosslinking points, which then undergo a crosslinking reaction with the active groups in the organosilicon to form a three-dimensional network structure. The long carbon chain structure increases the density of the active crosslinking points, thereby improving the density of the crosslinked network and resulting in a uniform, tough coating film. The organosilicon, which provides anti-graffiti properties, is chemically bonded to the polyurethane resin solution and is therefore less likely to detach from the coating layer, resulting in a polyurethane coating layer with excellent anti-graffiti properties.

[0090] In some embodiments of the present application, the polyol is a diol, and the diol may be an aliphatic diol or a cycloaliphatic diol. Exemplary diols include 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, 1,12-octadecanediol, 1,3-cyclohexanediol, 1,4-dimethylolcyclohexane, 1,4-cyclohexanediol, and 1,3-dimethylolcyclohexane.

[0091] In some embodiments of the present application, the polyol polyoxyalkyl ether is obtained by addition polymerization of an initiator with one or more of ethylene oxide, propylene oxide, and tetrahydrofuran, wherein the initiator is selected from the diols in the above embodiments, i.e., the initiator may be 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, 1,12-octadecanediol, 1,3-cyclohexanediol, 1,4-dimethylolcyclohexane, 1,4-cyclohexanediol, or 1,3-dimethylolcyclohexane.

[0092] In some embodiments of the present application, the polyol ester may be polyethylene glycol adipate, polycaprolactone, polypropylene glycol pimelate, polysuccinic acid dodecanedioic acid ester, polyhexanediol isophthalate, or polyethylene glycol cyclohexanedicarboxylic acid ester.

[0093] In an embodiment of the present application, the second crosslinking coagent includes a second crosslinking coagent and a crosslinking accelerator.

[0094] Exemplarily, the second crosslinking coagent is a compound having multiple functionalities, and the compound may contain an unsaturated bond. For example, the second crosslinking coagent is at least one selected from triallyl isocyanurate, triallyl cyanurate, divinylbenzene, diallylamine, diallyl sulfide, N,N-methylenebisacrylamide, ethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, and tetramethylolmethane tetraacrylate.

[0095] For example, the crosslinking accelerator is at least one selected from organotin compounds and metal oxides. Here, the organotin compounds are at least one selected from dibutyltin dilaurate, stannous octoate, and dibutylbis(laurylthio)tin. The metal oxide is at least one selected from zinc oxide, zirconium oxide, aluminum oxide, and magnesium oxide.

[0096] In an embodiment of the present application, in addition to the second crosslinking coagent, the polyurethane coating layer may include other coagents used in coating layers known to those skilled in the art, such as one or more of a chain extender, a thickener, a film-forming agent, a slip agent, a wetting agent, a curing agent, and a catalyst.

[0097] Illustratively, the chain extender is at least one selected from a diol, a dibasic acid, and a diamine.

[0098] Illustratively, the thickener may be selected from associative polyurethane-based thickeners.

[0099] For example, the film-forming agent may be at least one selected from ethylene glycol, propylene glycol, hexylene glycol, dodecanol ester, ethylene glycol butyl ether, dipropylene glycol monobutyl ether, tripropylene glycol-n-butyl ether, and propylene glycol phenyl ether, thereby improving the application and leveling performance of the slurry.

[0100] For example, the slip agent may be selected from an organic siloxane emulsion, preferably an anionic, cationic, or nonionic organic silicone microemulsion, which can provide the artificial leather with a smooth feel, while also enhancing the artificial leather's waterproof, mildew-resistant, wet abrasion resistance, and other properties, and also solving the problem of stickiness.

[0101] Illustratively, the wetting agent may be selected from polyoxyethylene ether-modified organosilicones, which can improve the penetration performance of the water-based polyurethane into the substrate.

[0102] Each of the above auxiliary agents is added to the polyurethane coating layer in an appropriate amount to achieve its desired function, and the amount of each auxiliary agent added can be, for example, 0.1 to 20 parts by mass per 100 parts by mass of the polyurethane resin.

[0103] In some embodiments of the present application, the end group of the organosilicone is either an epoxy group, an alkenyl group, or an acrylate group, such as divinyl-terminated phenylsilicone oil, modified polysiloxane, or epoxy-terminated polysiloxane.

[0104] In some embodiments of the present application, the base layer 10 is a fabric or paper. Illustratively, the fabric is at least one selected from a raised fabric, a plain fabric, a polyester fiber, a nylon fabric, a microfiber-based fabric, an elastic fabric, and a nonwoven fabric.

[0105] In some embodiments of the present application, the total thickness of the artificial leather is 0.21 mm to 13.1 mm, the thickness of the base layer 10 is 0.1 mm to 6.0 mm, the thickness of the polyolefin elastomer composite layer 20 is 0.1 mm to 7.0 mm, and the thickness of the polyurethane layer is 0.01 mm to 0.10 mm.

[0106] In order to improve the adhesive strength and peel strength between the polyolefin elastomer composite layer 20 and the base layer 10, in some embodiments of the present application, the artificial leather further includes a polyolefin elastomer adhesive layer 40 provided between the polyolefin elastomer composite layer 20 and the base layer 10, as shown in FIG. 2.

[0107] In some embodiments of the present application, the degree of crosslinking of the polyolefin elastomer adhesive layer 40 is 1% to 90%.

[0108] In some embodiments of the present application, the raw material components of the polyolefin elastomer adhesive layer 40 include: 0 to 100 parts by mass, preferably 60 to 100 parts by mass, of a third polyolefin elastomer; 0 to 100 parts by mass, preferably 10 to 100 parts by mass, of a graft-modified polyolefin elastomer; 0.5 parts by mass to 40 parts by mass of a second tackifier resin; 1 part by mass to 10 parts by mass of a third crosslinking aid; a second filler; The total number of parts by mass of the third polyolefin elastomer and the graft-modified polyolefin elastomer is 100 parts by mass.

[0109] In some embodiments of the present application, the third polyolefin elastomer is selected from copolymers and / or homopolymers in which olefins are the monomers.

[0110] Illustratively, the third polyolefin elastomer may be at least one selected from polyethylene, a copolymer of ethylene and an α-olefin, polypropylene, and a copolymer of propylene and an α-olefin.

[0111] In some embodiments of the present application, the graft groups of the graft-modified polyolefin elastomer are selected from (meth)acrylates.

[0112] Illustratively, the (meth)acrylate salt is at least one selected from sodium (meth)acrylate, lithium (meth)acrylate, and zinc (meth)acrylate.

[0113] In some embodiments of the present application, the graft group of the graft-modified polyolefin elastomer may be at least one selected from the group consisting of acrylic acid, maleic anhydride, glycidyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, and (meth)acrylic acid monomers other than (meth)acrylate salts.

[0114] In the present embodiment, the second tackifying resin can enhance the adhesiveness of the polyolefin elastomer adhesive layer 40. The amount of the second tackifying resin added can be adjusted according to the actual situation.

[0115] In some embodiments herein, the second tackifying resin comprises at least one of rosin and its derivatives, terpene resins, polymeric resins, dicyclopentadiene and condensation resins.

[0116] Illustratively, the rosin may be gum rosin, tall oil rosin, or wood rosin; the rosin derivative may be a resinate, a resinate ester, a rosin amine, a rosin acid anhydride, a rosin alcohol, a hydrogenated rosin, a disproportionated rosin, a polymerized rosin, an esterified rosin, or a maleated rosin; the terpene resin may be an α-terpene resin, a β-terpene resin, or a terpene phenol resin; the polymer resin may be at least one of a C5 petroleum resin, a C9 petroleum resin, a dicyclopentadiene (DCPD) resin, a coumarone-indene resin, or a styrene-based resin; and the condensation resin may be at least one of an alkylphenol resin and a xylene resin.

[0117] In some embodiments of the present application, the softening point of the second tackifying resin is 120° C. or less.

[0118] In some embodiments of the present application, the raw material component of the second filler may be at least one selected from calcium carbonate, limestone, white carbon, and talc. Addition of the second filler can improve the mechanical properties of the polyolefin elastomer adhesive layer 40. For example, the amount of the second filler added is 0 to 30 parts, preferably 0.1 to 5 parts, per 100 parts by mass of the base resin (i.e., the third polyolefin elastomer and / or the graft-modified polyolefin elastomer).

[0119] According to a second aspect, the present application provides a method for producing an artificial leather, the method comprising: At least one foam layer and at least one Performance improvement layer Step S10 of providing a polyolefin elastomer composite layer comprising: and step S20 of providing a polyurethane layer on the surface of the polyolefin elastomer composite layer away from the base layer, followed by embossing and crosslinking treatment by radiation to obtain artificial leather.

[0120] Specifically, in some embodiments, step S10 comprises: a step S11 of providing a base layer; Raw material ingredients of the foam layer and Performance improvement layer After mixing the raw material components, the foam film and Performance improvement layer Step S12 of forming Foam membrane and Performance improvement layer a step S13 of coating the surface of the base layer with the above; and step S14 of foaming the foam film on the surface of the base layer to form a polyolefin elastomer composite layer on the surface of the base layer.

[0121] Specifically, in some embodiments, step 20 comprises: A step S21 of preparing a polyurethane layer slurry, 1) Add polyisocyanate and dehydrated polyol to a stirring vessel and stir. The temperature of the stirring vessel is 40°C to 60°C. After uniform stirring, gradually increase the temperature to 120°C to continue the reaction. After the reaction is complete, decrease the temperature to 50°C. 2) adding acetone, organic silicone, crosslinking agent, crosslinking accelerator, and second auxiliary agent, and then continuing to stir to allow the mixture to react sufficiently; 3) Adding a solvent to adjust the viscosity of the system and allowing the system to react sufficiently to obtain a polyurethane slurry; Step S21 including: The above slurry is applied to the surface of the polyolefin elastomer composite layer, the slurry is dried, and then crosslinking by radiation is carried out to obtain the artificial leather of the present application, wherein the crosslinking by radiation includes S22 carried out by alpha rays, beta rays, gamma rays, X-rays or neutron rays.

[0122] In some embodiments of the present application, step S10 comprises: a step S11 of providing a base layer; Raw material ingredients of the foam layer, Performance improvement layer The raw material components of the adhesive layer and the polyolefin elastomer layer are mixed together, and then co-extruded to form a foamed film. Performance improvement layer and step S12 of forming a polyolefin elastomer adhesive layer; Polyolefin elastomer adhesive layer, foam film and Performance improvement layer a step S13 of coating the surface of the base layer with the above; and step S14 of foaming the foam film on the surface of the polyolefin elastomer adhesive layer to form a polyolefin elastomer composite layer on the surface of the polyolefin elastomer adhesive layer.

[0123] According to an embodiment of the present application, the manufacturing process of artificial leather is simple and low cost, and the manufacturing method uses a radiation crosslinking treatment, so that the manufactured artificial leather has better heat resistance, aging resistance, and solvent resistance.

[0124] The artificial leather and the method for producing the same of the present invention will be described in detail below with reference to specific embodiments.

[0125] Example 1 In this example, the polyurethane resin solution layer in the artificial leather is a slurry composition of a conventional solvent-free polyurethane resin solution. The polyolefin elastomer composite layer is a foam layer. Performance improvement layer The foam layer is bonded to the base layer, and the raw material composition is as shown in Table 1. The foaming agent is an ADC foaming agent (Yifang Yaxing L-C2).

[0126] Performance improvement layer The components are in parts by weight and include the following raw materials: 100 parts of a second polyolefin elastomer (Mitsui Chemicals DF740, melting point 96°C, Shore A hardness 91), Second Rubber (EPDM, Dow 3745P) 0 parts.

[0127] The polyurethane resin solution layer contains the following raw material components in parts by weight: 100 parts of solvent-free polyurethane prepolymer (Asahikawa Chemical XCJ10A) 66.5 parts of hardener (Asahikawa Chemical XCJ10B), 0.7 parts catalyst (Bayer Chemical T12).

[0128] Here, the isocyanate content of the polyurethane prepolymer is 2.3%, and the hydroxyl value of the curing agent is 40 mgKOH / g.

[0129] The present embodiment further provides a method for producing artificial leather, the method comprising the steps of: 1) Providing a base layer. 2) Raw material components of the foam layer Performance improvement layer After mixing the raw material components, a foamed film is formed by co-extrusion. Performance improvement layer To form. 3) A foam film is applied to the surface of the base layer. Performance improvement layer and covering. 4) The film formed on the surface of the base layer is subjected to a foaming treatment to form a polyolefin elastomer composite layer on the surface of the base layer, and the foaming temperature is 100°C to 230°C. 5) Preparation of polyurethane slurry: The polyisocyanate and the dehydrated polyol are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40 to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction. After the reaction is complete, the temperature is lowered to 50°C. After adding acetone, organosilicon, crosslinking agent and crosslinking accelerator, continue stirring to allow the mixture to react thoroughly. A solvent is added depending on the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained. 6) Applying polyurethane slurry to the surface of the polyolefin elastomer composite layer away from the base layer, and then embossing and crosslinking by radiation to obtain artificial leather.

[0130] Example 2 In this example, the polyurethane layer in the artificial leather is the same as the polyurethane layer in Example 1, and the polyolefin elastomer composite layer is the foam layer and Performance improvement layer The foam layer is bonded to the base layer, and the raw material composition is as shown in Table 1. The foaming agent is an ADC foaming agent (Yifang Yaxing L-C2).

[0131] Performance improvement layer The components are in parts by weight and include the following raw materials: 100 parts of second polyolefin elastomer (Mitsui Chemicals DF740) Second Rubber (EPDM, Dow 3745P) 100 parts.

[0132] The method for producing the artificial leather in this example is the same as that in Example 1.

[0133] Example 3 In this example, the polyurethane layer in the artificial leather is the same as in Example 1. The polyolefin elastomer composite layer is Performance improvement layer , foam layer and second Performance improvement layer It has a three-layer structure including the second Performance improvement layer The foam layer is laminated to the base layer, and the raw material composition ratio of the foam layer is as shown in Table 1. The foaming agent is an ADC foaming agent (Yifang Yaxing L-C2).

[0134] No. 1 Performance improvement layer The components are in parts by weight and include the following raw materials: 100 parts of second polyolefin elastomer (Mitsui Chemicals DF740) Second Rubber (EPDM, Dow 3745P) 70 parts.

[0135] No. 2 Performance improvement layer The components are in parts by weight and include the following raw materials: 100 parts of second polyolefin elastomer (Mitsui Chemicals DF740) 6 parts of No. 1 tackifying resin (terpene resin, model number T100).

[0136] The method for producing the artificial leather in this example is the same as that in Example 1.

[0137] Example 4 In this example, the polyurethane layer in the artificial leather is the same as in Example 1, and the polyolefin elastomer composite layer is the first Performance improvement layer , foam layer and second Performance improvement layer It has a three-layer structure including the second Performance improvement layer The foam layer is laminated to the base layer, and the raw material composition ratio of the foam layer is as shown in Table 1. The foaming agent is an ADC foaming agent (Yifang Yaxing L-C2).

[0138] No. 1 Performance improvement layer The components are in parts by weight and include the following raw materials: 100 parts of second polyolefin elastomer (Mitsui Chemicals DF740) Second Rubber (EPDM, Dow 3745P) 50 parts.

[0139] No. 2 Performance improvement layer The components are in parts by weight and include the following raw materials: 100 parts of second polyolefin elastomer (Mitsui Chemicals DF740) 6 parts of No. 1 tackifying resin (terpene resin, model number T100).

[0140] The method for producing the artificial leather in this example is the same as that in Example 1.

[0141] Example 5 In this example, the first Performance improvement layer , 2nd Performance improvement layer The compounding ratio of the polyurethane layer slurry was the same as in Example 4, and the polyolefin elastomer composite layer was Performance improvement layer , foam layer and second Performance improvement layer It has a three-layer structure including the second Performance improvement layer is bonded to the base layer, the raw material composition ratio of the foam layer is as shown in Table 1, and the foaming agent is OBSH foaming agent (Shijiazhuang Duoyi Chemical, OBSH-75).

[0142] The difference between the manufacturing method of this example and Example 4 is that the foaming temperature is adjusted to 100°C to 160°C.

[0143] Example 6 In this example, the first artificial leather Performance improvement layer , 2nd Performance improvement layer The compounding ratio of the polyurethane layer slurry was the same as in Example 4, and the polyolefin elastomer composite layer was Performance improvement layer , foam layer and second Performance improvement layer It has a three-layer structure including the second Performance improvement layer is bonded to the base layer, the raw material composition ratio of the foam layer is as shown in Table 1, and the foaming agent is sodium bicarbonate foaming agent (Kunshan Yayang Technology, TR60A).

[0144] The difference between the manufacturing method of this example and Example 4 is that the foaming temperature is adjusted to 100°C to 200°C.

[0145] Example 7 The difference between the artificial leather of this example and Example 4 is that the first polyolefin elastomer and Performance improvement layer The second polyolefin elastomer in the raw material components is LG Chemical LF100, which has a melting point of 96°C and a Shore A hardness of 91.

[0146] Example 8 The difference between the artificial leather of this example and Example 4 is that the first polyolefin elastomer and Performance improvement layer The second polyolefin elastomer in the raw material components is Mitsui Chemicals DF640, which has a melting point of less than 50°C and a Shore A hardness of 56.

[0147] Comparative Example 1 The difference between the comparative example and Example 4 is that the artificial leather produced was not subjected to foaming and radiation treatment.

[0148] Comparative Example 2 The difference between the comparative example and Example 4 is that the artificial leather produced was not subjected to radiation treatment.

[0149] The data shown in Table 1 are the raw material components and contents of the foamed layer in the artificial leathers produced in Examples 1 to 8 and Comparative Examples 1 and 2 of the present application.

[0150] [Table 1]

[0151] The data shown in Table 2 are the thicknesses of the base layer, polyolefin elastomer composite layer, and polyurethane layer in the artificial leathers produced in Examples 1 to 8 and Comparative Examples 1 and 2 of the present application, as well as the total thickness of the three layers and the radiation dose.

[0152] [Table 2]

[0153] The data shown in Table 3 are data on the degree of crosslinking of the foam layer in the artificial leathers produced in Examples 1 to 8 and Comparative Examples 1 and 2, as well as the Shore hardness and abrasion resistance of the artificial leathers. The degree of crosslinking of the foam layer was tested using the xylene extraction method in GB / T 29848-2018-5.5.3, the Shore A hardness of the foam layer was tested using GB / T 2411-2008, and the abrasion resistance of the artificial leathers was tested using ASTM D1242-1995.

[0154] [Table 3]

[0155] Example 9 The difference between this example and Example 1 is that the raw material components of the polyurethane layer, their contents, and radiation dose are different. The raw material component contents and radiation dose are as shown in Table 4.

[0156] The present invention also provides a method for producing artificial leather, which includes the following steps: 1) Providing a base layer. 2) Raw material components of the foam layer and Performance improvement layer After mixing the raw material components, the foam film and Performance improvement layer To form. 3) A foam film is applied to the surface of the base layer. Performance improvement layer and covering. 4) The film formed on the surface of the base layer is subjected to a foaming treatment to form a polyolefin elastomer composite layer on the surface of the base layer, and the foaming temperature is 100°C to 230°C. 5) Preparation of polyurethane slurry: The polyurethane layer slurry was specifically prepared as follows. (1) Diphenylmethane diisocyanate (Wanhua Chemical, MDI-100) and 1,6-hexanediol (BASF, HBO) are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40°C to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction. After the reaction is complete, the temperature is lowered to 50°C. (2) Add acetone, divinyl-terminated phenylsilicone oil (Anhui Isopropyl Ether, IOTA253), triallyl isocyanurate (TAIC), zinc oxide, and a second auxiliary agent (for example, 0.5 to 2 parts of a thickener, 5 to 20 parts of a film-forming agent, 0.1 to 2 parts of a wetting agent, and 0.3 to 5 parts of a slip agent), and then continue stirring to allow the mixture to react sufficiently. (3) A solvent is added to adjust the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained. 6) Applying polyurethane slurry to the surface of the polyolefin elastomer composite layer away from the base layer, and obtaining artificial leather after embossing and crosslinking treatment by radiation.

[0157] Example 10 The difference between this example and Example 1 is that the raw material components of the polyurethane layer, their contents, and radiation dose are different. The raw material component contents and radiation dose are as shown in Table 4.

[0158] The polyurethane layer slurry was specifically prepared as follows. 1) Toluene diisocyanate (Dow Chemical, VORANATE® T-80) and 1,10-decanediol (Shandong Li Sheng Chemical Industry) are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40°C to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction, and after the reaction is complete, the temperature is lowered to 50°C. 2) Add acetone, modified polysiloxane (Anhui Isopropyl Ether, IOTA2031), triallyl isocyanurate (TAIC), zinc oxide, and a second auxiliary (for example, 0.5 to 2 parts of a thickener, 5 to 20 parts of a film-forming agent, 0.1 to 2 parts of a wetting agent, and 0.3 to 5 parts of a slip agent) and continue stirring to allow the mixture to react thoroughly. 3) A solvent is added depending on the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained.

[0159] Example 11 The difference between this example and Example 1 is that the raw material components of the polyurethane layer, their contents, and radiation dose are different. The raw material component contents and radiation dose are as shown in Table 4.

[0160] The polyurethane layer slurry was specifically prepared as follows. 1) Hexamethylene diisocyanate (BASF, BASONTA® HI 100AP) and diethylene glycol hexyl ether (Dow Chemical, HECB) are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40°C to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction. After the reaction is complete, the temperature is lowered to 50°C. 2) Add acetone, epoxy group mono-terminated polysiloxane (Anhui SiO2, IOTA150-4), triallyl isocyanurate (TAIC), zinc oxide, and a second auxiliary (for example, 0.5 to 2 parts of a thickener, 5 to 20 parts of a film-forming agent, 0.1 to 2 parts of a wetting agent, and 0.3 to 5 parts of a slip agent) and continue stirring to allow the mixture to react sufficiently. 3) A solvent is added to adjust the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained.

[0161] Example 12 The difference between this example and Example 1 is that the raw material components of the polyurethane layer, their contents, and radiation dose are different. The raw material component contents and radiation dose are as shown in Table 4.

[0162] The polyurethane layer slurry was specifically prepared as follows. 1) Isophorone diisocyanate (Jinan Weizhen Chemical Industry, IPDI) and polycaprolactone (Jiangsu Renjiang Chemical Industry, PCL) are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40 to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction, and after the reaction is complete, the temperature is lowered to 50°C. 2) Add acetone, divinyl-terminated phenyl silicone oil (Anhui Isopropyl Ether, IOTA253), triallyl isocyanurate (TAIC), zinc oxide, and a second auxiliary agent (for example, 0.5 to 2 parts of a thickener, 5 to 20 parts of a film-forming agent, 0.1 to 2 parts of a wetting agent, and 0.3 to 5 parts of a slip agent), and then continue stirring to allow the mixture to react thoroughly. 3) A solvent is added depending on the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained.

[0163] Example 13 The difference between this example and Example 1 is that the raw material components of the polyurethane layer, their contents, and radiation dose are different. The raw material component contents and radiation dose are as shown in Table 4.

[0164] The polyurethane layer slurry was specifically prepared as follows. 1) Cyclohexane-1,4-diisocyanate (Hubei Jinrue Da Chemical Co., Ltd., CHDI) and 1,6-hexanediol (BASF, HDO) are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40°C to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction. After the reaction is complete, the temperature is lowered to 50°C. 2) Add acetone, modified polysiloxane (Anhui Isopropyl Ether, IOTA2031), triallyl isocyanurate (TAIC), zinc oxide, and a second auxiliary (for example, 0.5 to 2 parts of a thickener, 5 to 20 parts of a film-forming agent, 0.1 to 2 parts of a wetting agent, and 0.3 to 5 parts of a slip agent) and continue stirring to allow the mixture to react thoroughly. 3) Add a solvent to adjust the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained.

[0165] Comparative Example 3 The difference between this comparative example and Example 13 is that the polyol in the raw material components of the polyurethane resin solution layer was different. The contents of the raw material components and the radiation doses are as shown in Table 4.

[0166] The polyurethane layer slurry was specifically prepared as follows. 1) Cyclohexane-1,4-diisocyanate (Hubei Jinrue Da Chemical Industry Co., Ltd., CHDI) and polyhexylene glycol are added to a stirring vessel and stirred. The temperature of the stirring vessel is 40°C to 60°C. After uniform stirring, the temperature is gradually increased to 120°C to continue the reaction. After the reaction is complete, the temperature is lowered to 50°C. 2) Add acetone, modified polysiloxane (Anhui Isopropyl Ether, IOTA2031), triallyl isocyanurate (TAIC), zinc oxide, and a second auxiliary (for example, 0.5 to 2 parts of a thickener, 5 to 20 parts of a film-forming agent, 0.1 to 2 parts of a wetting agent, and 0.3 to 5 parts of a slip agent) and continue stirring to allow the mixture to react thoroughly. 3) A solvent is added depending on the viscosity of the system, and after sufficient reaction, a polyurethane slurry is obtained.

[0167] Comparative Example 4 The difference between this comparative example and Example 11 is the radiation dose. The contents of the raw material components and the radiation dose are as shown in Table 4.

[0168] [Table 4]

[0169] Graffiti prevention performance test The artificial leather samples provided with the polyurethane coating layer were subjected to an anti-graffiti performance test, and the results are shown in Table 5. The test is carried out according to the following method. Graffiti prevention performance test method: Under conditions of 20°C and 50% humidity, the symbol "#" was written on the leather coating layer using a regular oil-based marking pen, and after the symbol dried, it was wiped off with a dry pure cotton cloth and the results after wiping were recorded.

[0170] [Table 5]

[0171] As can be seen from the data in Table 5, the polyurethane coating layer of the present invention allows the artificial leather product to have excellent anti-graffiti properties.

[0172] Example 14 This embodiment is based on the first embodiment, and adds a polyolefin elastomer adhesive layer between the base layer and the polyolefin elastomer composite layer, and the manufacturing method of the adhesive layer includes the following: Ethylene-α-olefin copolymer elastomer, graft polyolefin elastomer in which the graft group is glycidyl methacrylate (GMA), and C5 petroleum resin were mixed in the blending ratios shown in Table 6, and then the raw material components of the foam layer, Performance improvement layer Co-extrusion with the raw material components of polyolefin elastomer adhesive layer, foam layer and Performance improvement layer are formed, and these are coated on the surface of the base layer.

[0173] Here, the contents of the raw material components of the polyolefin elastomer adhesive layer and the radiation doses for crosslinking by radiation are as shown in Table 6.

[0174] Example 15 The difference between this example and Example 14 is that the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation are different, and as shown in Table 6, the second tackifying resin is rosin.

[0175] Example 16 The difference between this example and Example 14 is the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation. As shown in Table 6, the graft group of the grafted polyolefin elastomer is methyl acrylate (MA), and the second tackifying resin is terpene resin (T100).

[0176] Example 17 The difference between this example and Example 14 is the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation. As shown in Table 6, the graft group of the grafted polyolefin elastomer is acrylic acid (AA), and the second tackifying resin is C5 petroleum resin.

[0177] Example 18 The difference between this example and Example 14 is the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation. As shown in Table 6, the graft group of the grafted polyolefin elastomer is glycidyl methacrylate (GMA), and the second tackifying resin is rosin.

[0178] Example 19 The difference between this example and Example 14 is the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation. As shown in Table 6, the graft group of the grafted polyolefin elastomer is maleic anhydride (MAH), and the second tackifying resin is terpene resin (T100).

[0179] Example 20 The difference between this example and Example 19 is that the second tackifier resin is a terpene resin (T90) and the radiation dose is 50 KGy.

[0180] Example 21 The difference between this example and Example 19 is that the radiation dose is 50 KGy.

[0181] Example 22 The difference between this example and Example 19 is that the tackifier resin is a terpene resin (T110).

[0182] Example 23 The difference between this example and Example 19 is that the tackifier resin is a terpene resin (T120).

[0183] Example 24 The difference between this example and Example 19 is that the tackifying resin is a Surlyn resin.

[0184] Comparative Example 5 The difference between this comparative example and Example 19 is, as shown in Table 6, that the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation are different.

[0185] Comparative Example 6 The difference between this comparative example and Example 19 is, as shown in Table 6, that the content of the raw material components of the polyolefin elastomer adhesive layer and the radiation dose for crosslinking by radiation are different.

[0186] [Table 6]

[0187] The crosslinking degree of the polyolefin elastomer adhesive layer and the interlayer peel strength between the polyolefin elastomer adhesive layer and the base layer in the artificial leathers produced in Examples 14 to 24 and Comparative Examples 5 and 6 were tested. The test results are shown in Table 7, where the crosslinking degree of the polyolefin elastomer adhesive layer was tested in accordance with the xylene extraction method in GB / T 29848-2018-5.5.3, and the interlayer peel strength was tested in accordance with GB / T 14905-2009.

[0188] [Table 7]

[0189] As can be seen from the data in Table 7, the adhesive strength between the polyolefin elastomer composite layer and the base layer was improved by adding one polyolefin elastomer adhesive layer between the polyolefin elastomer composite layer and the base layer and performing a crosslinking treatment using radiation.

[0190] Finally, it should be noted that the above examples are for illustrating the embodiments of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the above examples, those skilled in the art may still make modifications to the embodiments described in the above examples, or may make equivalent substitutions for some or all of the technical features thereof, and these modifications or substitutions should not depart from the essence of the corresponding embodiments and the scope of the embodiments of the present invention. [Explanation of symbols]

[0191] 10: base layer; 20: Polyolefin elastomer composite layer; 21: foam layer; twenty two: Performance improvement layer ; 30: Polyurethane layer; 40: Polyolefin elastomer adhesive layer.

Claims

1. A base layer; a polyolefin elastomer composite layer provided on a surface of the base layer, the polyolefin elastomer composite layer including at least one foam layer and at least one performance-improving layer, the entire polyolefin elastomer composite layer being crosslinked by radiation; a polyurethane resin solution layer provided on a surface of the polyolefin elastomer composite layer away from the base layer; and Including, The raw material components of the foam layer are 100 parts by mass of a first polyolefin elastomer; 1 to 15 parts by mass of a blowing agent; 0 to 100 parts by mass of a first rubber; 0 to 10 parts by mass of a foaming accelerator; A first auxiliary agent; A first filler; The first coagent comprises 0.05 parts by mass to 20 parts by mass of a first crosslinking coagent; The raw material components of the performance improving layer are 100 parts by mass of a second polyolefin elastomer; 0 to 100 parts by mass of a second rubber; 0 to 10 parts by mass of a first tackifier resin; Including, However, the performance-improving layer does not contain the foaming agent, The polyurethane resin solution layer is a solvent-based, aqueous-based or solventless polyurethane coating layer.

2. The crosslinking degree of the foam layer is 15% to 90%. The artificial leather according to claim 1.

3. the amount of the first rubber in the raw material components of the foam layer is 50 parts by mass to 100 parts by mass; The amount of the foaming accelerator is 2 parts by mass to 10 parts by mass. The artificial leather according to claim 1.

4. The raw material components of the performance improving layer The amount of the second rubber is 50 parts by mass to 100 parts by mass, The artificial leather according to any one of claims 1 to 3, wherein the amount of the first tackifier resin is 6 parts by mass to 10 parts by mass.

5. the first polyolefin elastomer and the second polyolefin elastomer have a melting point of 96°C or less, the first polyolefin elastomer and the second polyolefin elastomer have a Shore A hardness of 91 or less; The artificial leather according to any one of claims 1 to 3.

6. The first polyolefin elastomer and the second polyolefin elastomer are at least one selected from the group consisting of polyethylene, ethylene and α-olefin copolymer, polypropylene, and propylene and α-olefin copolymer. The artificial leather according to any one of claims 1 to 3.

7. Each of the first rubber and the second rubber is at least one selected from natural rubber, binary ethylene propylene rubber, ternary ethylene propylene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, cis-1,4-polybutadiene rubber, styrene butadiene rubber, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer. The artificial leather according to any one of claims 1 to 3.

8. The raw material components of the polyurethane coating layer are: 100 parts by mass of polyurethane resin solution; 1 to 10 parts by mass of an organic silicone; 0.2 parts by mass to 2.2 parts by mass of a second crosslinking aid; A second auxiliary agent; and Including, The secondary co-agent comprises a chain extender, a thickener, a film former, a slip agent, a wetting agent or a combination thereof; The artificial leather according to any one of claims 1 to 3.

9. The polyurethane resin solution is obtained by a polymerization reaction using polyisocyanate and polyol as raw materials, the polyol includes at least one of a polyol having a hydroxyl group at a terminal group, a polyol polyoxyalkyl ether, and a polyol ester, and the number of carbon atoms linked to the hydroxyl group at the terminal group of the polyol is 6 or more; The artificial leather according to claim 8.

10. The terminal group of the organosilicone is either an epoxy group, an alkenyl group, or an acrylate group. The artificial leather according to claim 8.

11. the second cross-linking coagent includes a second cross-linking coagent and a cross-linking accelerator, Optionally, the second crosslinking coagent is a compound having multiple functionalities, and the crosslinking accelerator comprises at least one of an organotin compound and a metal oxide. The artificial leather according to claim 8.

12. the second cross-linking aid is at least one selected from diallylamine, diallyl sulfide, N,N-methylenebisacrylamide, ethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, and tetramethylolmethane tetraacrylate; The artificial leather according to claim 11.

13. The base layer is fabric or paper. The artificial leather according to claim 1.

14. The fabric is at least one selected from a raised fabric, a plain fabric, a polyester fiber, a nylon fabric, a microfiber base, an elastic fabric, and a nonwoven fabric. The artificial leather according to claim 13.

15. The total thickness of the artificial leather is 0.21 mm to 13.1 mm, The thickness of the base layer is 0.1 mm to 6.0 mm, the thickness of the polyolefin elastomer composite layer is 0.1 mm to 7.0 mm; The thickness of the polyurethane resin solution layer is 0.01 mm to 0.10 mm. The artificial leather according to claim 1.

16. The polyolefin elastomer adhesive layer is provided between the polyolefin elastomer composite layer and the base layer and is crosslinked by radiation. The artificial leather according to claim 1.

17. The crosslinking degree of the polyolefin elastomer adhesive layer is 1% to 90%. The artificial leather according to claim 16.

18. The raw material components of the polyolefin elastomer adhesive layer are 0 to 100 parts by mass of a third polyolefin elastomer; 0 to 100 parts by mass of a graft-modified polyolefin elastomer; 0.5 parts by mass to 40 parts by mass of a second tackifier resin; 1 part by mass to 10 parts by mass of a third crosslinking aid; A second filler; Including, The total mass parts of the third polyolefin elastomer and the graft-modified polyolefin elastomer is 100 mass parts. The artificial leather according to claim 17.

19. the third polyolefin elastomer is 60 parts by mass to 100 parts by mass, The graft-modified polyolefin elastomer is 10 parts by mass to 100 parts by mass. The artificial leather according to claim 18.

20. The graft group of the graft-modified polyolefin elastomer is selected from (meth)acrylates; The artificial leather according to claim 18.

21. The (meth)acrylate salt is at least one selected from sodium (meth)acrylate, lithium (meth)acrylate, and zinc (meth)acrylate. The artificial leather according to claim 20.

22. The graft group of the graft-modified polyolefin elastomer is at least one selected from acrylic acid, maleic anhydride, glycidyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, and (meth)acrylic acid monomers; The artificial leather according to claim 18.

23. the first tackifier resin includes at least one of rosin and its derivatives, terpene resin, polymer resin, dicyclopentadiene, and condensation resin, and the softening point of the first tackifier resin is 120°C or lower; The artificial leather according to claim 1.

24. the second tackifier resin includes at least one of rosin and its derivatives, terpene resin, polymer resin, dicyclopentadiene, and condensation resin, and the softening point of the second tackifier resin is 120°C or lower; The artificial leather according to claim 18.

25. The crosslinking degree of the artificial leather is 20% to 90%. The artificial leather according to claim 1.

26. providing a polyolefin elastomer composite layer on a surface of the base layer, the polyolefin elastomer composite layer including at least one foam layer and at least one performance-improving layer; providing a polyurethane resin solution layer on a surface of the polyolefin elastomer composite layer away from the base layer, drying the polyurethane resin solution layer, and then embossing and crosslinking the polyolefin elastomer composite layer and the polyurethane resin solution layer by radiation to obtain an artificial leather; Including, The raw material components of the foam layer are 100 parts by mass of a first polyolefin elastomer; 1 to 15 parts by mass of a blowing agent; 0 to 100 parts by mass of a first rubber; 0 to 10 parts by mass of a foaming accelerator; A first auxiliary agent; A first filler; The first coagent comprises 0.05 parts by mass to 20 parts by mass of a first crosslinking coagent; The raw material components of the performance improving layer are 100 parts by mass of a second polyolefin elastomer; 0 to 100 parts by mass of a second rubber; 0 to 10 parts by mass of a first tackifier resin; Including, However, the performance-improving layer does not contain the foaming agent, The method for producing artificial leather, wherein the polyurethane resin solution layer is a solvent-based, aqueous-based or solventless polyurethane coating layer.

27. Providing a polyolefin elastomer composite layer on the surface of the base layer providing a base layer; mixing raw material components of the foam layer and raw material components of the performance-improving layer, respectively, and then forming a foam film and a performance-improving layer by co-extrusion; applying a foam membrane and a performance-improving layer to the surface of the base layer; foaming the foamed film on the surface of the base layer to form a polyolefin elastomer composite layer on the surface of the base layer; The method for producing the artificial leather according to claim 26, comprising:

28. Providing a polyolefin elastomer composite layer on the surface of the base layer providing a polyolefin elastomer adhesive layer on the surface of the base layer; providing a polyolefin elastomer composite layer on a surface of the polyolefin elastomer adhesive layer away from the base layer; The method for producing the artificial leather according to claim 26, comprising:

29. The crosslinking by radiation is carried out by α rays, β rays, γ rays, X-rays or neutron rays. A method for producing the artificial leather according to any one of claims 26 to 28.

Images