Sea-island microstructure master batch, polyolefin artificial leather and preparation method thereof

Abstract

The invention belongs to the technical field of artificial leather, and particularly relates to polyolefin artificial leather, a preparation method thereof and an automobile seat, the polyolefin artificial leather comprises a base cloth layer, a base material layer and a coating layer which are stacked in sequence; the base material layer is prepared from the following raw material components in parts by mass: 135 to 165 parts of island microstructure master batch, 0.4 to 1 part of assistant crosslinking agent, 0.05 to 0.2 part of coupling agent, 0.01 to 0.2 part of ultraviolet absorbent, 0.01 to 0.2 part of light stabilizer and 0.01 to 0.2 part of anti-aging agent; wherein the sea-island microstructure master batch comprises polyolefin and rubber with double bonds; according to the invention, by improving the addition amount and the addition process of the rubber, double bonds in the rubber are protected while the dispersion performance is improved in the form of the sea-island microstructure master batch, on one hand, the master batch structure can prevent the rubber from hardening and embrittling due to the influence of ultraviolet rays after long-time exposure; on the other hand, the rubber content is limited, so that the crack cracking phenomenon caused by swelling is avoided, and the roughness of the artificial leather does not change after the artificial leather is used for a long time in a high-temperature environment.

Description

[0001] This application is a divisional application. The original application has the application number 202510127510.3 and the application date is February 5, 2025. The invention title is: Divisional application for polyolefin artificial leather and its preparation method, and automobile seat. Technical Field

[0002] This invention belongs to the field of artificial leather technology, specifically relating to a polyolefin artificial leather and its preparation method, and automobile seats. Background Technology

[0003] Patent document 202110774131.5 discloses a polyolefin artificial leather substrate and artificial leather containing rubber components, exhibiting excellent resistance to light aging. The artificial leather substrate and artificial leather, from top to bottom, comprise a light-aging-resistant polyolefin layer and a base fabric layer. The light-aging-resistant polyolefin layer contains an appropriate amount of rubber components containing double bonds, forming a cross-linked structure through a suitable method to improve light aging resistance. Simultaneously, a certain amount of ultraviolet absorbers, light stabilizers, and light shielding agents are added. This artificial leather substrate and artificial leather, especially light-colored leather, possess excellent light aging resistance and can be widely used in automotive interiors and other fields. The amount of rubber added in this technical solution is 60-100 parts.

[0004] EPDM has low unsaturation and low polarity. According to the principle of "like dissolves like," polar solvents easily dissolve polar substances, while non-polar solvents dissolve non-polar substances more easily. When EPDM comes into contact with certain solvents, the solvent molecules, being small, diffuse rapidly and preferentially penetrate between EPDM molecules, causing the polymer to swell. After swelling occurs, the polymer may even dissolve. Furthermore, prolonged exposure to ultraviolet light causes EPDM to undergo photo-oxidation, leading to surface cracking, hardening, and even powdering in leather. This is because ultraviolet light can break the unsaturated double bonds in the EPDM molecular chain, initiating free radical reactions and accelerating the aging process.

[0005] Other thermoplastic elastomers, such as TPE, generally have a working temperature not exceeding 80°C, and may soften or deform if exposed to high-temperature environments for a long time; while SEBS has poor low-temperature performance and low elasticity.

[0006] It should be noted that the information disclosed in this background section is only for understanding the background technology of the present application concept, and therefore, the above description is not considered to constitute prior art information. Summary of the Invention

[0007] This disclosure provides at least one polyolefin artificial leather and its preparation method, as well as an automobile seat.

[0008] In a first aspect, embodiments of this disclosure provide a polyolefin artificial leather, comprising: a base fabric layer, a substrate layer, and a coating layer stacked sequentially; the substrate layer comprises the following raw material components in parts by mass: 135-165 parts of island microstructure masterbatch, 0.4-1 parts of crosslinking agent, 0.05-0.2 parts of coupling agent, 0.01-0.2 parts of ultraviolet absorber, 0.01-0.2 parts of light stabilizer, and 0.01-0.2 parts of anti-aging agent; wherein the island microstructure masterbatch comprises polyolefin and rubber with double bonds.

[0009] In one optional embodiment, the island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts of polyolefin and 35-45 parts of EPDM.

[0010] In one alternative embodiment, the island-shaped regions derived from rubber in the island microstructure masterbatch account for 25-50% of the surface area.

[0011] In one alternative embodiment, the polyolefin includes any one or more combinations of ethylene and α-olefin copolymers, propylene and α-olefin copolymers.

[0012] In an optional embodiment, the island microstructure masterbatch further includes an olefin block copolymer, which is obtained by mixing crystallizable ethylene-octene and amorphous ethylene-octene; and the octene content of the olefin block copolymer is 25-40 mol%.

[0013] In one optional embodiment, the island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts polyolefin, 35-45 parts EPDM, and 5-20 parts olefin block copolymer.

[0014] In one alternative embodiment, the thickness of the substrate layer is 0.15-0.6 mm.

[0015] Secondly, this disclosure also provides a method for preparing polyolefin artificial leather as described above, comprising the following steps: Step S1, dispersing polyolefin and rubber by a screw to form island microstructure masterbatch, wherein the screw has an aspect ratio of 20-25, a compression ratio of 2:1, and a processing temperature of 140-180℃; Step S2, after thorough mixing according to the formula, melt extruding and bonding with a base fabric layer, wherein the processing temperature is 120-200℃ and the bonding pressure is 1-10MPa; Step S3, corona treatment, wherein the corona power is 2-10KWh and the linear velocity is 5-30m / min; Step S4, surface coating and embossing to obtain polyolefin artificial leather.

[0016] In an optional embodiment, step S1 further includes an olefin block copolymer, which is mixed with a polyolefin to form an island-shaped microstructure masterbatch with the rubber.

[0017] Thirdly, embodiments of this disclosure also provide an automobile seat, comprising the polyolefin artificial leather as described above.

[0018] The beneficial effects of this invention are that the polyolefin artificial leather and its preparation method, as well as the automotive seat, improve the dispersion performance by improving the amount and process of rubber addition, and protect the double bonds in the rubber in the form of island microstructure masterbatch, so that it can undergo cross-linking reaction with polyolefin to form a cross-linked structure, thereby improving the processing performance. On the one hand, the masterbatch structure can prevent the rubber from hardening and becoming brittle due to long-term exposure to ultraviolet rays. On the other hand, the limitation of rubber content also avoids cracking caused by swelling, effectively improving the anti-aging performance and ensuring that the roughness of the artificial leather does not change after long-term use in high-temperature environments.

[0019] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention are realized and obtained in accordance with the structures particularly pointed out in the description, claims and drawings.

[0020] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description

[0021] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0022] Figure 1 This is a schematic diagram of the structure of a polyolefin artificial leather provided in an embodiment of the present disclosure;

[0023] Figure 2 The surface pattern of the polyolefin artificial leather provided in Embodiment 3 of this disclosure;

[0024] Figure 3 The surface pattern of the polyolefin artificial leather of Example 7 provided in this disclosure.

[0025] In the picture:

[0026] 1. Base fabric layer; 2. Substrate layer; 3. Coating layer. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Glossary:

[0029] EPDM: Ethylene Propylene Diene Monomer, is a copolymer of ethylene, propylene and a small amount of non-conjugated diene.

[0030] TPE: Thermoplastic elastomer, abbreviated as TPE or TPR, is an abbreviation for Thermoplastic rubber.

[0031] SEBS: A linear triblock copolymer with polystyrene as the end block and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic block. It is an abbreviation for Styrene Ethylene Butylene Styrene.

[0032] As used herein, the phrases “in one embodiment,” “according to one embodiment,” “in some embodiments,” etc., generally refer to the fact that a particular feature, structure, or characteristic following the phrase can be included in at least one embodiment of this disclosure. Therefore, a particular feature, structure, or characteristic can be included in more than one embodiment of this disclosure, such that these phrases do not necessarily refer to the same embodiment. As used herein, the terms “example,” “exemplary,” etc., are used to “serve as an example, instance, or illustration.” Any implementation, aspect, or design described herein as “example” or “exemplary” is not necessarily to be construed as preferred or superior to other implementations, aspects, or designs. Rather, the use of the terms “example,” “exemplary,” etc., is intended to present concepts in a specific manner.

[0033] In this document, exemplary embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. As used herein, expressions such as “at least one of…” modify the entire list of elements when following a list of elements, rather than individual elements in the list. For example, the expression “at least one of a, b, and c” should be understood to include only a, only b, only c, both a and b, both a and c, both b and c, or all of a, b, and c.

[0034] The terminology used herein is for the purpose of describing specific exemplary configurations only and is not intended to be limiting. As used herein, the singular articles “a,” “an,” and “the” may also be intended to include plural forms unless otherwise clearly stated herein. The terms “comprising,” “including,” and “having” are inclusive and thus specify the presence of features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof. The method steps, processes, and operations described herein should not be construed as requiring them to be performed in the specific order discussed or shown, unless specifically identified as such. Additional or alternative steps may be employed.

[0035] Existing patent 202110774131.5 discloses a polyolefin artificial leather substrate and artificial leather containing rubber components, exhibiting excellent resistance to light aging. The artificial leather substrate and artificial leather, from top to bottom, comprise a light-aging-resistant polyolefin layer and a base fabric layer. The light-aging-resistant polyolefin layer contains an appropriate amount of rubber components containing double bonds, forming a cross-linked structure through a suitable method to improve light aging resistance. Simultaneously, a certain amount of ultraviolet absorbers, light stabilizers, and light shielding agents are added. This artificial leather substrate and artificial leather, especially light-colored leather, possess excellent light aging resistance and can be widely used in automotive interiors and other fields. The rubber component comprises 60-100 parts.

[0036] EPDM (ethylene propylene diene monomer) has low unsaturation and low polarity. According to the principle of "like dissolves like," polar solvents readily dissolve polar substances, while non-polar solvents dissolve non-polar substances more readily. When EPDM comes into contact with certain solvents, the solvent molecules, being small, diffuse rapidly and preferentially penetrate between EPDM molecules, causing polymer swelling. This swelling can even lead to polymer dissolution. Furthermore, prolonged exposure to ultraviolet light causes photo-oxidation of EPDM, resulting in surface cracking, hardening, and even powdering of the leather. This is because ultraviolet light can break the unsaturated double bonds in the EPDM molecular chain, initiating free radical reactions and accelerating the aging process.

[0037] The effects described above are the results obtained by the inventors after practice and careful research. Therefore, the discovery process of the above problems and the solutions proposed in this disclosure below should be considered as contributions made by the inventors to this disclosure.

[0038] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0039] Please see Figure 1 ,like Figure 1As shown, this disclosure provides a polyolefin artificial leather, comprising: a base fabric layer, a substrate layer, and a coating layer stacked sequentially; the substrate layer comprises the following raw material components in parts by weight: 135-165 parts of island microstructure masterbatch, 0.4-1 parts of crosslinking agent, 0.05-0.2 parts of coupling agent, 0.01-0.2 parts of ultraviolet absorber, 0.01-0.2 parts of light stabilizer, and 0.01-0.2 parts of anti-aging agent; wherein, the island microstructure masterbatch comprises polyolefin and rubber with double bonds.

[0040] In some embodiments, specifically, the island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts of polyolefin and 35-45 parts of EPDM.

[0041] In some embodiments, specifically, the island-shaped regions derived from rubber in the island microstructure masterbatch account for 25-50% of the surface area.

[0042] In some embodiments, specifically, the polyolefin includes any one or more combinations of ethylene and α-olefin copolymers, propylene and α-olefin copolymers.

[0043] In some embodiments, specifically, the island microstructure masterbatch further includes an olefin block copolymer, which is obtained by mixing crystallizable ethylene-octene and amorphous ethylene-octene; and the octene content of the olefin block copolymer is 25-40 mol%.

[0044] In some embodiments, specifically, the island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts polyolefin, 35-45 parts EPDM, and 5-20 parts olefin block copolymer.

[0045] In some embodiments, specifically, the thickness of the substrate layer is 0.15-0.6 mm.

[0046] In some embodiments, specifically, the co-crosslinking agent includes any one or more combinations of monofunctional acrylates, difunctional acrylates, trifunctional acrylates, and polyfunctional acrylates, preferably pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate ethoxylate, pentaerythritol tetraacrylate propoxylate, and trimethylolpropane triacrylate.

[0047] In some embodiments, specifically, the coupling agent comprises one or more of vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and vinyltriisopropoxysilane.

[0048] In some embodiments, specifically, the anti-aging agent includes one or more of antioxidants, heat stabilizers, and free radical scavengers.

[0049] In some embodiments, the light stabilizer specifically includes one or more of the following: salicylic acid derivatives, substituted acrylonitrile derivatives, benzophenone derivatives, benzotriazole derivatives, triazine derivatives, inorganic or organic pigment light shielding agents, and hindered amine derivatives.

[0050] In some embodiments, the ultraviolet absorber specifically includes any one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines.

[0051] In some embodiments, specifically, the base fabric layer includes any one or more combinations of wool fabric, plain weave, polyester fabric, nylon fabric, microfiber base fabric, elastic fabric, and nonwoven fabric.

[0052] In some embodiments, specifically, the coating layer includes any one of polyurethane coatings, acrylic coatings, and silicone coatings; the polyurethane coating includes any one or a combination of acrylic polyurethane, alkyd polyurethane, polyester polyurethane, polyether polyurethane, epoxy polyurethane, and waterborne polyurethane; the acrylic coating includes any one or a combination of acrylic resin and modified acrylic resin; and the silicone coating includes any one or a combination of anionic, cationic, and nonionic silicone coatings.

[0053] This disclosure also provides a method for preparing polyolefin artificial leather as described above, comprising the following steps: Step S1, dispersing polyolefin and rubber by a screw to form island microstructure masterbatch, wherein the screw has an aspect ratio of 20-25, a compression ratio of 2:1, and a processing temperature of 140-180℃; Step S2, after thorough mixing according to the formula, melt extruding and bonding with a base fabric layer, wherein the processing temperature is 120-200℃ and the bonding pressure is 1-10MPa; Step S3, corona treatment, wherein the corona power is 2-10KWh and the linear velocity is 5-30m / min; Step S4, surface coating and embossing to obtain polyolefin artificial leather.

[0054] This disclosure also provides an automotive seat comprising the polyolefin synthetic leather as described above.

[0055] Example 1

[0056] Step S1: Polyolefin and rubber are dispersed by a screw to form a sea-island microstructure masterbatch made of 100 parts polyolefin and 35 parts EPDM. The screw has an aspect ratio of 20, a compression ratio of 2:1, and a processing temperature of 150°C.

[0057] Step S2: After fully mixing according to the formula, melt extrusion is applied to the base fabric layer. The processing temperature is 170℃ and the bonding pressure is 8MPa.

[0058] Step S3: Corona treatment, with a corona power of 8 kWh and a linear velocity of 25 m / min.

[0059] Step S4, surface coating and embossing, to obtain polyolefin artificial leather.

[0060] Specifically, the parameter models for steps S2 and S4 are shown in Table 1 below.

[0061] Table 1

[0062]

[0063]

[0064] Specifically, by changing some parameters in Example 1, the component parameters and performance parameters in Examples 1-7, as shown in Tables 2 and 3, were obtained.

[0065] Softness: QB / T5155-2017 "Test Methods for Determination of Softness of Artificial Leather and Synthetic Leather".

[0066] Tensile strength and elongation at break: GB / T1040.3-2006 "Determination of tensile properties of plastics - Part 3: Test conditions for films and sheets".

[0067] Heat aging resistance: The samples were placed in an oven at 110℃±2℃ for 168 hours, and the color change grade was evaluated according to GB / T 250-2008.

[0068] UV aging performance: Irradiation temperature 60℃, UV radiation of 280nm to 400nm 15kwh / ㎡, of which UV radiation of wavelength 280nm to 320nm accounts for at least 3% and not more than 10%, and the color change level is evaluated according to GB / T 250-2008.

[0069] Table 2

[0070]

[0071] Table 3

[0072]

[0073] Specifically, comparing the data of Examples 1, 2, and 3 shows that Examples 2 and 3 have better pattern retention and better aging effect after adding olefin block copolymer OBC. In the island microstructure, the "sea" formed by mixing olefin block copolymer and polyolefin can further enhance the anti-aging effect.

[0074] Specifically, comparing the data of Examples 1, 4, and 5 shows that Example 4 has a high EPDM content and good softness, while Example 5 has more than 50 parts of EPDM added, resulting in a high swelling rate and poor anti-aging performance.

[0075] Specifically, comparing the data from Examples 2, 6, and 7, it is shown that the OBC in Example 7 did not incorporate an island structure, resulting in poor tensile strength.

[0076] Please see Figure 2 The polyolefin artificial leather provided in Example 3 is a preferred embodiment. In addition to having excellent tensile strength and softness, it also has an extremely high extreme temperature embossing retention rate. This is because the rubber in the island microstructure masterbatch provides anti-aging properties, and the rubber in the island microstructure does not exhibit swelling.

[0077] like Figure 3 As shown, the polyolefin artificial leather provided in Example 7 serves as a comparative example. Because its olefin block copolymer was not added to the island microstructure masterbatch, its tensile strength decreased, and it could not form a combination with the island microstructure masterbatch, which in turn led to a decrease in the retention rate of embossing, and the surface pattern tended to flatten under extreme temperatures.

[0078] In summary, this polyolefin artificial leather and its preparation method, as well as the automotive seat, improve the dispersion performance by improving the amount and process of rubber addition, and protect the double bonds in the rubber in the form of island microstructure masterbatch. On the one hand, the masterbatch structure can prevent the rubber from hardening and becoming brittle due to long-term exposure to ultraviolet rays. On the other hand, the limitation of rubber content also avoids cracking caused by swelling, effectively improving the anti-aging performance and ensuring that the roughness of the artificial leather does not change after long-term use in high-temperature environments.

[0079] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A microstructured island masterbatch, characterized in that, The island microstructure masterbatch is formed by dispersing polyolefins and rubber. The island microstructure masterbatch also includes an olefin block copolymer, which is obtained by mixing crystallizable ethylene-octene and amorphous ethylene-octene. Furthermore, the octene content of the olefin block copolymer is 25-40 mol%; The island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts polyolefin, 35-45 parts EPDM, and 5-20 parts olefin block copolymer.

2. The island microstructure masterbatch as described in claim 1, characterized in that, In the island-shaped microstructure masterbatch, the island-shaped regions obtained from rubber account for 25-50% of the surface area.

3. The island microstructure masterbatch as described in claim 1, characterized in that, The polyolefin includes any one or more combinations of ethylene and α-olefin copolymers, propylene and α-olefin copolymers.

4. A method for preparing a microstructured island masterbatch as described in any one of claims 1-3, characterized in that, The process includes the following steps: dispersing polyolefins and rubber using a screw to form island-shaped microstructure masterbatch, wherein the screw has an aspect ratio of 20-25, a compression ratio of 2:1, and a processing temperature of 140-180℃.

5. A type of polyolefin artificial leather, characterized in that, include: A base fabric layer, a substrate layer, and a coating layer are stacked sequentially. The substrate layer comprises the following raw material components in parts by weight: The mixture contains 135-165 parts of island microstructure masterbatch, 0.4-1 parts of crosslinking agent, 0.05-0.2 parts of coupling agent, 0.01-0.2 parts of ultraviolet absorber, 0.01-0.2 parts of light stabilizer, and 0.01-0.2 parts of anti-aging agent.

6. The polyolefin artificial leather as described in claim 5, characterized in that, The thickness of the substrate layer is 0.15-0.6 mm.

7. The polyolefin artificial leather as described in claim 5, characterized in that, The co-crosslinking agent includes any one or more combinations of monofunctional acrylates, difunctional acrylates, trifunctional acrylates and polyfunctional acrylates, preferably pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate ethoxylate, pentaerythritol tetraacrylate propoxylate and trimethylolpropane triacrylate. The coupling agent includes one or more of vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriisopropoxysilane; The anti-aging agent includes one or more of antioxidants, heat stabilizers, and free radical scavengers; The light stabilizer includes one or more of the following: salicylic acid derivatives, substituted acrylonitrile derivatives, benzophenone derivatives, benzotriazole derivatives, triazine derivatives, inorganic or organic pigment light shielding agents, and hindered amine derivatives. The ultraviolet absorber includes any one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines.

8. The polyolefin artificial leather as described in claim 5, characterized in that, The base fabric layer includes any one or more combinations of wool fabric, plain weave, polyester fabric, nylon fabric, microfiber base fabric, elastic fabric and non-woven fabric; The coating layer includes any one of polyurethane coatings, acrylic coatings, and silicone coatings; the polyurethane coating includes any one or a combination of acrylic polyurethane, alkyd polyurethane, polyester polyurethane, polyether polyurethane, epoxy polyurethane, and waterborne polyurethane; the acrylic coating includes any one or a combination of acrylic resin and modified acrylic resin; the silicone coating includes any one or a combination of anionic, cationic, and nonionic silicone coatings.

9. A method for preparing polyolefin artificial leather as described in any one of claims 5-8, characterized in that, Includes the following steps: Step S1: Prepare island microstructure masterbatch; Step S2: After thoroughly mixing according to the formula, melt extrude and bond with the base fabric layer; Step S3, corona treatment; Step S4, surface coating and embossing, to obtain polyolefin artificial leather.

10. A car seat, characterized in that, Including the polyolefin artificial leather as described in any one of claims 5-8.

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