Surface treatment agent with silicone feel, artificial leather and preparation method thereof, automobile
By using materials such as organosilicon-modified aqueous dispersions and propylene-based elastomers, artificial leather with a silicone-like feel was prepared, solving the problems of insufficient tactile feel and environmental friendliness in existing artificial leather technologies, and achieving better tactile feel and environmental performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CANADIAN GENERAL TOWER CHANGSHU CO LTD
- Filing Date
- 2024-03-01
- Publication Date
- 2026-06-19
AI Technical Summary
Existing synthetic leathers fail to meet user needs in terms of feel, softness, and environmental friendliness, and traditional materials have potential negative impacts on health and the environment.
Artificial leather with a silicone-like feel is prepared by using materials such as silicone-modified aqueous dispersions, propylene-based elastomers, and ultra-high melt strength polypropylene through calendering and printing technology, ensuring the material's softness, heat resistance, and recyclability.
It improves the feel and durability of artificial leather, reduces potential health hazards, enhances environmental friendliness, and enables the material to be recycled.
Smart Images
Figure CN118107245B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of artificial leather technology, and more particularly to a surface treatment agent with a silicone-like feel, recyclable artificial leather and its preparation method, and automobiles. Background Technology
[0002] Artificial leather, as a synthetic leather alternative to genuine leather, is increasingly widely used, especially as a surface covering material for automotive interiors, such as seats, door panels, armrests, headrests, and soft-touch materials for the center console. Traditional artificial leather is mainly made of polyvinyl chloride (PVC) and polyurethane (PU), with some using TPO. Initially, these types of artificial leather generally met the requirements for interior decoration. However, as people's demands for automotive interiors have increased, PVC and PU artificial leather have become insufficient in terms of touch and softness. Furthermore, the plasticizers in PVC artificial leather are prone to migration, and TPV artificial leather contains peroxides, both of which are detrimental to human health. PU artificial leather suffers from hydrolysis, affecting its lifespan, and since PU is generally a thermosetting material, it cannot be recycled through heating and melting, posing a potential negative impact on the environment. Summary of the Invention
[0003] Based on the above situation, the main objective of this invention is to provide a surface treatment agent, a silicone-feel artificial leather and its preparation method, and an automobile, which can improve the surface feel of the artificial leather, have a long service life, and be environmentally friendly.
[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0005] A first aspect of the present invention provides a synthetic leather with a silicone-like feel, comprising a surface treatment agent layer, a dense layer, and a base fabric layer stacked together, wherein the surface treatment agent layer is made of a surface treatment agent; and the dense layer is made of a dense layer preform.
[0006] The surface treatment agent comprises: 100 parts of organosilicon-modified aqueous dispersion, 2-8 parts of high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of crosslinking agent, 0.1-1 parts of leveling agent, 0.1-1 parts of defoamer, and 0.1-2 parts of thickener; wherein, the weight percentage of organosilicon in the film-forming surface treatment agent layer is greater than or equal to 60%;
[0007] The main components of the dense layer preform include: propylene-based elastomer, silicone copolymer and ultra-high melt strength polypropylene, wherein the weight percentage of the silicone copolymer is 20% to 45% and the weight percentage of the ultra-high melt strength polypropylene is 4% to 15%.
[0008] Preferably, the solid content of the organosilicon-modified aqueous dispersion is 30% to 50%, and the weight percentage of organosilicon in the surface treatment agent layer forming the film is 60% to 70%.
[0009] Preferably, the high molecular weight polydimethylsiloxane raw material is a mixture comprising water-based silicone oil and high molecular weight polydimethylsiloxane, and the solid content of the mixture is greater than or equal to 80%, and the viscosity is 350,000 cs to 600,000 cs.
[0010] Preferably, at least one of the leveling agent and the defoamer is an organosilicon component.
[0011] Preferably, the leveling agent comprises one or a combination of several of polydimethylsilane, polymethylphenylsiloxane, polydimethylsiloxane, polyether polyester modified organosiloxane, and alkyl modified organosiloxane.
[0012] Preferably, the defoamer includes one or a combination of several of silicone oil-based, emulsion-based, solution-based, and polyether-modified silicone defoamers.
[0013] Preferably, the hollow glass microspheres are mainly composed of sodium-calcium borosilicate glass, with a particle size of 200μm to 500μm and a density of 0.2g / cc to 0.7g / cc.
[0014] Preferably, the crosslinking agent comprises one or a combination of several aqueous end- or unend-capped aliphatic, alicyclic, and aromatic polyisocyanates.
[0015] Preferably, the thickener comprises one or a combination of several of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, and hydroxyethylcellulose.
[0016] Preferably, the dense layer preform comprises: 40-70 parts of propylene-based elastomer, 5-15 parts of ultra-high melt strength polypropylene, 20-40 parts of organosilicon copolymer, and 5-15 parts of other additives.
[0017] A second aspect of the present invention provides a method for preparing artificial leather with a silicone-like feel, comprising the steps of:
[0018] S10: A dense layer is formed using a dense layer preform material by calendering; wherein the main components of the dense layer preform material include: propylene-based elastomer, silicone copolymer and ultra-high melt strength polypropylene, and the weight percentage of the silicone copolymer is 20% to 45% and the weight percentage of the ultra-high melt strength polypropylene is 4% to 15%.
[0019] S20: The dense layer is combined with the base fabric layer to obtain a semi-finished product;
[0020] S30: A surface treatment agent is printed on the surface of the semi-finished product to form a surface treatment agent layer, and then embossed to obtain the finished artificial leather product; wherein, the surface treatment agent comprises: 100 parts of organosilicon-modified aqueous dispersion, 2-8 parts of high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of crosslinking agent, 0.1-1 parts of leveling agent, 0.1-1 parts of defoamer, and 0.1-2 parts of thickener; and the organosilicon content in the film-forming surface treatment agent layer is 60%-70%.
[0021] A third aspect of the present invention provides a surface treatment agent comprising: 100 parts of an organosilicon-modified aqueous dispersion, 2-8 parts of a high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of a crosslinking agent, 0.1-1 parts of a leveling agent, 0.1-1 parts of a defoamer, and 0.1-2 parts of a thickener; the organosilicon content of the surface treatment agent after film formation is 60%-70%.
[0022] A fourth aspect of the present invention provides an automobile, including an interior trim, the interior trim comprising the artificial leather described in any of the preceding claims or the artificial leather obtained by the above preparation method.
[0023] In the artificial leather of the present invention, the main component of the surface treatment agent used in the surface treatment agent layer is an organosilicon-modified aqueous dispersion, and the weight percentage of organosilicon in the film-forming surface treatment agent layer is more than 60%, thereby giving the surface treatment agent layer excellent softness and enabling the artificial leather to achieve a silicone-like feel. At the same time, an appropriate amount of hollow glass microspheres can adjust the smooth feel of the artificial leather surface, thereby further improving the feel of the artificial leather.
[0024] Furthermore, by using propylene-based elastomers, silicone copolymers, and ultra-high melt strength polypropylene, and by controlling the content of these components, the dense layer, which constitutes a significant portion of the resin structure of the artificial leather, also possesses good softness. This results in excellent softness and a better overall feel for the artificial leather. The use of ultra-high melt strength polypropylene also gives the dense layer excellent heat resistance. It acts as a skeletal structure within the dense layer, providing a strong framework, especially in high-temperature environments. This provides excellent support for maintaining the texture of the artificial leather, giving it high-temperature resistance. Therefore, it further improves the abrasion resistance and low-temperature resistance of the artificial leather. Moreover, the artificial leather also exhibits excellent performance in terms of rigidity, softness, and high-temperature resistance. Furthermore, since the dense layer mainly uses propylene-based elastomers and silicone copolymers, which already possess good flexibility, there is no need to add traditional plasticizers. This avoids the large amounts of plasticizers found in traditional PVC dense layers and the potential leaching of small molecules such as white oil in TPE materials, making it more health-friendly. Furthermore, the ultra-high melt strength polypropylene imparts excellent heat resistance to the artificial leather, eliminating the need for peroxides required in traditional TPO artificial leather to address the insufficient high-temperature resistance of materials like TPV. This results in a healthier artificial leather. Simultaneously, the dense layer does not contain non-environmentally friendly substances such as small-molecule plasticizers found in traditional artificial leather, thus avoiding water pollution. Moreover, almost all materials in this application can be recycled through crushing and granulation, resulting in good recyclability and greater environmental friendliness. Compared to artificial leather made from traditional PVC or TPV materials, this significantly improves recyclability and environmental friendliness.
[0025] Other beneficial effects of the present invention will be explained in detail through the introduction of specific technical features and technical solutions in specific embodiments. Those skilled in the art should be able to understand the beneficial technical effects brought about by these technical features and technical solutions through the introduction of these technical features and technical solutions. Attached Figure Description
[0026] Preferred embodiments of the present invention will now be described with reference to the accompanying drawings. In the drawings:
[0027] Figure 1 A schematic diagram of a preferred embodiment of the artificial leather with a silicone feel provided by the present invention;
[0028] Figure 2 A flowchart of a preferred embodiment of the method for preparing artificial leather with a silicone feel provided by the present invention;
[0029] Figure 3 Infrared spectrum of the surface treatment agent layer for artificial leather with a silicone feel provided by the present invention;
[0030] Figures 4-9The images shown are microscopic images of the wear resistance tests performed on Examples 1, 6, and 7 and Comparative Examples 1, 2, and 3 provided by this invention.
[0031] In the picture:
[0032] 100. Surface treatment layer; 200. Dense layer; 300. Base fabric layer. Detailed Implementation
[0033] The present invention is described below based on embodiments, but the present invention is not limited to these embodiments. In the following detailed description of the present invention, some specific details are described in detail, but well-known methods, processes, procedures, and elements are not described in detail in order to avoid obscuring the essence of the present invention.
[0034] Furthermore, those skilled in the art should understand that the accompanying drawings provided herein are for illustrative purposes only and are not necessarily drawn to scale.
[0035] Unless the context explicitly requires it, the words "comprising," "including," and similar terms throughout the specification and claims should be interpreted as encompassing rather than being exclusive or exhaustive; that is, meaning "including but not limited to."
[0036] In the description of this invention, it should be understood that the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance. Furthermore, in the description of this invention, unless otherwise stated, "a plurality of" means two or more. The number of parts of each component mentioned herein refers to parts by weight.
[0037] This invention provides a silicone-feel-like artificial leather that can be used in various scenarios, such as automotive interiors. Figure 1 As shown, the artificial leather includes a surface treatment agent layer 100, a dense layer 200, and a base fabric layer 300 stacked sequentially, i.e., the surface treatment agent layer 100, the dense layer 200, and the base fabric layer are bonded together in sequence. The surface treatment agent layer 100 is made of a surface treatment agent, and the dense layer 200 is made of a dense layer preform.
[0038] The surface treatment agent comprises: 100 parts of silicone-modified aqueous dispersion, 2-8 parts of high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of crosslinking agent, 0.1-1 parts of leveling agent, 0.1-1 parts of defoamer, and 0.1-2 parts of thickener; wherein, the weight percentage of silicone in the surface treatment agent layer 100 forming the film is greater than or equal to 60%. Specifically, in the surface treatment agent, when the weight of the organosilicon-modified aqueous dispersion is 100 parts, the weight of the high molecular weight polydimethylsiloxane raw material can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, or 8 parts, etc.; the weight of the hollow glass microspheres can be 2 parts, 3 parts, 5 parts, 6 parts, 8 parts, 9 parts, or 10 parts, etc.; the weight of the crosslinking agent can be 2 parts, 3 parts, 4 parts, or 5 parts, etc.; the weight of the leveling agent can be 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.9 parts, or 1 part, etc.; the weight of the defoamer can be 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.9 parts, or 1 part, etc.; and the weight of the thickener can be 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.9 parts, 1 part, 1.3 parts, 1.5 parts, 1.7 parts, 1.9 parts, or 2 parts, etc. The weight percentage of organosilicon in the treatment agent layer after film formation reaches 60%, 62%, 64%, 65%, 66%, 68%, 70%, 73%, 75%, 78%, or 80%, etc.
[0039] The main components of the dense layer preform include: propylene-based elastomer, silicone copolymer, and ultra-high melt strength polypropylene. The weight percentage of silicone copolymer is 20% to 45%, and the weight percentage of ultra-high melt strength polypropylene is 4% to 15%. For example, the weight percentage of silicone copolymer is 20%, 22%, 25%, 27%, 30%, 32%, 33%, 35%, 38%, 40%, 43%, or 45%, etc., and the weight percentage of ultra-high melt strength polypropylene is 4%, 5%, 7%, 10%, 12%, 14%, or 15%, etc.
[0040] In the artificial leather of this invention, the main component of the surface treatment agent used in the surface treatment agent layer is a silicone-modified aqueous dispersion, and the weight percentage of silicone in the film-forming surface treatment agent layer exceeds 60%, such as... Figure 3As shown in the figure, from top to bottom, are the infrared spectra of the surface treatment agent layers in Examples 1, 7, and 6 below. It can be seen that the surface treatment agent layer 100 after film formation using the surface treatment agent of the present invention exhibits obvious organosilicon characteristics. By setting the weight percentage of organosilicon after film formation, the problem of poor silicone feel in artificial leather due to too low organosilicon content can be avoided, as well as the problem of reduced wear resistance due to the low strength of the organosilicon color material itself due to too high organosilicon content. Thus, the surface treatment agent layer 100 has excellent softness, enabling artificial leather to achieve a silicone feel. At the same time, an appropriate amount of hollow glass microspheres can adjust the smooth feel of the artificial leather surface, thereby further improving the feel of the artificial leather. Furthermore, a certain amount of high molecular weight polydimethylsiloxane raw material can optimize the silicone feel and wear resistance of the artificial leather.
[0041] Furthermore, by using propylene-based elastomers, silicone copolymers, and ultra-high melt strength polypropylene, and by controlling the content of these components, the dense layer 200, which constitutes a significant portion of the artificial leather resin structure, also possesses excellent softness. This results in superior softness and a better overall feel for the artificial leather. The use of ultra-high melt strength polypropylene also gives the dense layer excellent heat resistance. It acts as a skeletal structure within the dense layer, providing a strong framework, especially in high-temperature environments. This provides excellent support for maintaining the artificial leather's pattern and endows it with high-temperature resistance. Therefore, it further improves the artificial leather's abrasion resistance and low-temperature resistance. The artificial leather also exhibits excellent performance in terms of rigidity, softness, and high-temperature resistance. Moreover, since the dense layer 200 primarily uses propylene-based elastomers and silicone copolymers, which already possess good flexibility, there is no need to add traditional plasticizers. Therefore, it avoids the large amounts of plasticizers found in traditional PVC dense layers and the potential leaching of small molecules such as white oil found in TPE materials, making it more health-friendly. Furthermore, the ultra-high melt strength polypropylene imparts excellent heat resistance to the artificial leather, eliminating the need for peroxides required in traditional TPO artificial leather to address the insufficient high-temperature resistance of materials like TPV. This results in a healthier artificial leather. Simultaneously, the dense layer 200 does not contain non-environmentally friendly substances such as small-molecule plasticizers found in traditional artificial leather, thus avoiding water pollution. Moreover, almost all materials in this application can be recycled through crushing and granulation, resulting in good recyclability and greater environmental friendliness. Compared to artificial leather made from traditional PVC or TPV materials, this significantly improves recyclability and environmental friendliness.
[0042] Preferably, the weight percentage of organosilicon in the surface treatment agent layer is 60% to 70%. Controlling the weight ratio of organosilicon in the surface treatment agent layer within this range can make the artificial leather exhibit a better silicone feel, prevent the surface treatment agent layer from becoming too soft, and improve the adhesion between the surface treatment agent layer and the dense layer.
[0043] The organosilicon-modified aqueous dispersion can be selected as needed. In a preferred embodiment, the solid content of the organosilicon-modified aqueous dispersion is 30% to 50%, such as 30%, 35%, 40%, 45%, or 50%. By selecting an organosilicon-modified aqueous dispersion with this solid content, the organosilicon weight percentage of the surface treatment agent layer can be better achieved to reach 60% to 70% even when other components do not contain organosilicon. Moreover, organosilicon-modified aqueous dispersions with this solid content are easy to purchase, which can reduce costs.
[0044] Specifically, the high molecular weight polydimethylsiloxane raw material is a mixture, including water-based silicone oil and high molecular weight polydimethylsiloxane, and the solid content of the mixture is greater than or equal to 80%, and the viscosity is 350,000 cs to 600,000 cs. For example, the solid content of the mixture is 80, 82, 85, 88, 90, 93 or 95, and the viscosity of the mixture is 350,000, 380,000, 400,000, 450,000, 500,000, 550,000 or 600,000, etc. The solids in the mixture are mainly silicone components. Using the above solid content and range can increase the silicone content in the surface treatment agent, improve the silicone feel of the prepared artificial leather, and increase the adhesion between the surface treatment agent layer and the dense layer, so that the distribution of each component in the surface treatment agent on the surface of the dense layer is more uniform, and improve the smooth touch of the artificial leather surface.
[0045] In a preferred embodiment, at least one of the leveling agent and defoamer in the surface treatment agent is an organosilicon component. That is, in addition to the organosilicon-modified aqueous dispersion containing organosilicon, the leveling agent or defoamer in the surface treatment agent can also be a raw material containing organosilicon, or both the leveling agent and defoamer can be raw materials containing organosilicon. Further, preferably, in addition to the organosilicon-modified aqueous dispersion containing organosilicon, both the leveling agent and defoamer in the surface treatment agent are selected from raw materials containing organosilicon. In this way, even when the solid content of the organosilicon-modified aqueous dispersion is relatively low, or when the weight part of the organosilicon-modified aqueous dispersion is slightly small, it can still be ensured that the weight percentage of organosilicon in the surface treatment agent film reaches more than 60%, thereby increasing the selection range of organosilicon-modified aqueous dispersion.
[0046] Specifically, the leveling agent may include one or a combination of several of the following: polydimethylsilane, polymethylphenylsiloxane, polydimethylsiloxane, polyether polyester modified organosiloxane, and alkyl modified organosiloxane. For example, the leveling agent may be only polydimethylsilane, polymethylphenylsiloxane, polydimethylsiloxane, polyether polyester modified organosiloxane, or alkyl modified organosiloxane, or it may be a mixture of two, three, or four of these raw materials. Of course, it may also be a mixture of dimethylsilane, polymethylphenylsiloxane, polydimethylsiloxane, polyether polyester modified organosiloxane, and alkyl modified organosiloxane.
[0047] Defoamers include one or a combination of several of the following silicone-based defoamers: silicone oil-based, emulsion-based, solution-based, and polyether-modified. For example, a defoamer may only include silicone oil-based silicone defoamers, emulsion-based silicone defoamers, solution-based silicone defoamers, or polyether-modified silicone defoamers. Defoamers can also be a mixture of any two of the following: silicone oil-based silicone defoamers, emulsion-based silicone defoamers, solution-based silicone defoamers, and polyether-modified silicone defoamers; or a mixture of any three of these. For example, a mixture of silicone oil-based silicone defoamers and emulsion-based silicone defoamers... The defoamer can be a mixture of liquid silicone defoamers, or a mixture of silicone oil-based silicone defoamers and solution-based silicone defoamers, or a mixture of silicone oil-based silicone defoamers and polyether-modified silicone defoamers, or silicone oil-based silicone defoamers, emulsion-based silicone defoamers, solution-based silicone defoamers, or polyether-modified silicone defoamers, etc.; of course, the defoamer can also be a mixture of silicone oil-based silicone defoamers, emulsion-based silicone defoamers, solution-based silicone defoamers, and polyether-modified silicone defoamers.
[0048] In a preferred embodiment, the main component of the hollow glass microspheres is sodium-calcium borosilicate glass, with a particle size of 200 μm to 500 μm and a density of 0.2 g / cc to 0.7 g / cc. For example, the particle sizes of the hollow glass microspheres are 200 μm, 230 μm, 250 μm, 280 μm, 300 μm, 320 μm, 350 μm, 380 μm, 400 μm, 420 μm, 450 μm, 480 μm, or 500 μm, etc., and the densities are 0.2 g / cc, 0.3 g / cc, 0.4 g / cc, 0.5 g / cc, 0.6 g / cc, or 0.7 g / cc, etc. Using hollow glass microspheres within this range allows the surface treatment agent to better encapsulate the microspheres, thereby maintaining the mechanical properties of the formed surface treatment agent layer.
[0049] In the above embodiments, the crosslinking agent includes one or more of aqueous-terminated or unterminated aliphatic, alicyclic, and aromatic polyisocyanates. For example, the crosslinking agent may include only one of aqueous-terminated aliphatic, alicyclic, and aromatic polyisocyanates, or only one of unterminated aliphatic, alicyclic, and aromatic polyisocyanates. It may also include two, three, four, or more of these raw materials. That is, the crosslinking agent may also be a mixture of two, three, or more raw materials.
[0050] Thickeners include one or more of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, and hydroxyethylcellulose. For example, thickeners may include only methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, or hydroxyethylcellulose, or combinations of two, three, or more of these raw materials.
[0051] Specifically, the dense layer preform material includes: 40-70 parts of propylene-based elastomer, 5-15 parts of ultra-high melt strength polypropylene (HMSPP), 20-40 parts of silicone copolymer, and 5-15 parts of other additives. Specifically, the propylene-based elastomer, HMSPP, silicone copolymer, and other additives can be selected according to their respective weight ranges mentioned above. For example, the propylene-based elastomer can be 40, 50, 60, 65, or 70 parts, the HMSPP can be 5, 7, 10, 12, 13, or 15 parts, the silicone copolymer can be 20, 25, 30, 35, or 40 parts, and the other additives can be 5, 7, 10, 12, 13, or 15 parts. Using this composition allows the artificial leather to achieve a silicone-like feel while improving its overall mechanical properties.
[0052] In the dense layer preform, the propylene-based elastomer is a propylene-ethylene copolymer with a Shore A hardness between 50A and 70A. Preferably, the propylene-based elastomer has a Shore A hardness of 50A, 55A, 60A, 65A, or 70A to optimize the flexibility of the prepared dense layer 200 and the artificial leather, avoiding both excessively high Shore A hardness leading to a stiff artificial leather and excessively low Shore A hardness leading to a soft artificial leather. Of course, within this range, readily available commercially available propylene-based elastomers can be selected as needed, such as those from ExxonMobil-Vitamax.
[0053] Preferably, the organosilicon copolymer contains silane components with a weight ratio greater than or equal to 90%, that is, the weight of silane is more than 90% of the total weight of the organosilicon copolymer. For example, the weight ratio of silane components in the organosilicon copolymer reaches 90%, 92%, 93%, 94%, 95%, 96%, or 97%, etc. Using such organosilicon copolymers with high silane content can better improve the low-temperature resistance of artificial leather.
[0054] In one embodiment, the ultra-high melt strength polypropylene has a melting point of 170°C to 190°C, such as 170°C, 175°C, 180°C, 185°C, or 190°C. Using ultra-high melt strength polypropylene within this melting point range provides superior heat resistance, thereby better ensuring the skeletal structure in high-temperature environments. Of course, within this range, readily available commercially available ultra-high melt strength polypropylene, such as that from ExxonMobil, can be selected as needed.
[0055] Other additives in the dense layer may be added as needed, and may include at least one of compatibilizers, stabilizers, lubricants and color masterbatches, or may include only compatibilizers, stabilizers, lubricants or color masterbatches.
[0056] In the above embodiments, the base fabric layer 300 can be a four-way stretch base fabric with a thickness of 0.6cm to 0.8cm, such as 0.6cm, 0.65cm, 0.7cm, 0.75cm, or 0.8cm, to better increase the flexibility of the artificial leather. Specifically, the base fabric layer 300 can be selected from readily available knitted fabrics within this range as needed.
[0057] The base fabric layer 300 and the dense layer 200 can be directly bonded together by hot pressing. In a preferred embodiment, the artificial leather also includes an adhesive layer, and the dense layer 200 and the base fabric layer 300 are bonded together by the adhesive layer. The adhesive layer is a high-temperature resistant hot melt adhesive, which can be a commercially available high-temperature resistant hot melt adhesive.
[0058] This invention also provides a method for preparing artificial leather with a silicone-like feel, such as... Figure 2 As shown, the steps include:
[0059] S10: Dense layer 200 is formed by calendering using dense layer preform material;
[0060] S20: Composite the dense layer 200 with the base fabric layer 300 to obtain a semi-finished product;
[0061] S30: A surface treatment agent is printed on the surface of the semi-finished product to form a surface treatment agent layer 100, and then embossed to obtain the finished artificial leather product. Specifically, a surface treatment agent is printed on the side of the dense layer 200 of the semi-finished product that is away from the base fabric 300 to form a surface treatment agent layer 100.
[0062] The components of the dense layer preform and the surface treatment agent are as described in the aforementioned embodiments, and will not be repeated here. Specifically, the dense layer preform and the surface treatment agent can be prepared in advance before steps S10 to S30, or the dense layer preform can be prepared before step S10, and the surface treatment agent can be prepared before or after any step before step S30, such as after step S20 and before step S30.
[0063] In this invention, considering that the components in the dense layer preform are mainly granular solids, it is preferable to use a calendering method to form the dense layer 200. Moreover, by using a calendering method, release paper is not used in the production process, and the recycling of release paper can also be avoided. The production process also has better recyclability and environmental friendliness, thereby increasing the environmental friendliness of artificial leather from the production process.
[0064] In one embodiment, in step S10, the dense layer preform is melt-blended in an internal mixer. The components in the dense layer preform are mixed in the internal mixer according to the above-mentioned weight parts. Then, the mixture is sequentially passed through a two-roll mill, filtered by an extruder, and rolled into a thin sheet by a four-roll mill to obtain a dense layer 200, thereby making the thickness of the dense layer more uniform. The internal mixer temperature is 190℃~220℃, the open mill temperature is 180℃~200℃, the extruder temperature is 200℃~220℃, and the four-roll temperature is 175℃~230℃. For example, the internal mixer temperature can be 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, or 220℃, the open mill temperature can be 180℃, 185℃, 190℃, 195℃, or 200℃, the extruder temperature can be 200℃, 205℃, 210℃, 215℃, or 220℃, and the four-roll temperature can be 175℃, 180℃, 190℃, 200℃, 210℃, 220℃, 225℃, or 230℃.
[0065] In step S20, the base fabric layer 300, the adhesive layer and the dense layer 200 are laminated by a composite roller, and then a semi-finished product is obtained after passing through a cooling roller.
[0066] In step S30, a surface treatment agent is printed onto the surface of the semi-finished product using gravure printing. After drying, a surface treatment agent layer is obtained, followed by high-temperature printing to obtain the finished artificial leather product. Preferably, the drying temperature is 110℃, 115℃, 120℃, 125℃, or 130℃, etc.
[0067] The surface treatment agent can be obtained by mechanical stirring according to the weight parts of each raw material. The mechanical stirring speed is 1000 to 1500 rpm, the stirring time is 40 to 60 minutes, and the drying temperature is 110°C to 130°C. For example, the mechanical stirring speed can be 1000 rpm, 1100 rpm, 1200 rpm, 1300 rpm, 1400 rpm, or 1500 rpm, the stirring time can be 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes, and the drying temperature can be 110°C, 115°C, 120°C, 125°C, or 130°C.
[0068] The present invention also provides an automobile, including an interior trim, such as automobile seats, soft-touch materials for the automobile center console, etc., wherein the interior trim includes the recyclable artificial leather described in any of the above embodiments.
[0069] Several specific embodiments of the artificial leather of the present invention are given below, along with some comparative examples.
[0070] Example 1
[0071] S01: Preparation of surface treatment agent: Take 100 parts of organosilicon modified water-based dispersion, 3 parts of high molecular weight polydimethylsiloxane raw material, 7 parts of hollow glass microspheres, 3 parts of crosslinking agent, 0.3 parts of siloxane-containing leveling agent, 0.5 parts of organosilicon defoamer, and 1 part of thickener, and mix them evenly by mechanical stirring to obtain the surface treatment agent.
[0072] S02: Preparation of dense layer preform: Take 60 parts of propylene-based elastomer, 5 parts of ultra-high melt strength polypropylene, 35 parts of organosilicon copolymer, and 10 parts of other additives, and melt-blend them in an internal mixer to obtain dense layer preform.
[0073] S10: Dense layer 200 is formed by calendering using dense layer preform material;
[0074] S20: Composite the dense layer 200 with the base fabric layer 300 to obtain a semi-finished product;
[0075] S30: A surface treatment agent is printed on the surface of the semi-finished product to form a surface treatment agent layer 100, and then embossed to obtain the finished artificial leather product. Specifically, a surface treatment agent is printed on the side of the dense layer 200 of the semi-finished product that is away from the base fabric 300 to form a surface treatment agent layer 100.
[0076] Example 2
[0077] Unlike Example 1, the surface treatment agent contains 2 parts of high molecular weight polydimethylsiloxane raw material and 5 parts of hollow glass microspheres.
[0078] Example 3
[0079] Unlike Example 1, the surface treatment agent contains 8 parts of high molecular weight polydimethylsiloxane raw material and 8 parts of hollow glass microspheres.
[0080] Example 4
[0081] Unlike Example 1, the surface treatment agent contains 5 parts of high molecular weight polydimethylsiloxane raw material and 10 parts of hollow glass microspheres.
[0082] Example 5
[0083] Unlike Example 1, in the surface treatment agent, 0.3 parts of the leveling agent containing siloxane were replaced with 0.3 parts of the leveling agent without siloxane, and 0.5 parts of the silicone defoamer were replaced with the non-silicone defoamer.
[0084] Example 6
[0085] Unlike Example 1, the components of the surface treatment agent and the dense layer preform are different. In Example 6, the surface treatment agent consists of 100 parts of silicone-modified aqueous dispersion, 6 parts of high molecular weight polydimethylsiloxane raw material, 3 parts of hollow glass microspheres, 3 parts of crosslinking agent, 0.3 parts of siloxane-containing leveling agent, 0.5 parts of silicone defoamer, and 1 part of thickener. The dense layer preform consists of 60 parts of propylene-based elastomer, 15 parts of ultra-high melt strength polypropylene, 25 parts of silicone copolymer, and 10 parts of other additives.
[0086] Example 7
[0087] Unlike Example 1, the composition of the dense layer preform is different. In Example 7, the composition of the dense layer preform includes 70 parts of propylene-based elastomer, 5 parts of ultra-high melt strength polypropylene, 25 parts of organosilicon copolymer, and 10 parts of other additives.
[0088] Comparative Example 1
[0089] Unlike Example 1, the surface treatment agent has a different composition. In Comparative Example 1, the surface treatment agent consists of 100 parts of silicone-modified aqueous dispersion, 6 parts of high molecular weight polydimethylsiloxane raw material, 15 parts of hollow glass microspheres, 3 parts of crosslinking agent, 0.3 parts of leveling agent, 0.5 parts of defoamer, and 1 part of thickener.
[0090] Comparative Example 2
[0091] Unlike Example 1, the composition of the dense layer preform is different. In Comparative Example 2, the composition of the dense layer preform includes 25 parts of propylene-based elastomer, 5 parts of ultra-high melt strength polypropylene, 70 parts of organosilicon copolymer, and 10 parts of other additives.
[0092] Comparative Example 3
[0093] Unlike Example 1, the composition of the dense layer preform is different. In Comparative Example 3, the composition of the dense layer preform includes 45 parts of propylene-based elastomer, 30 parts of ultra-high melt strength polypropylene, 25 parts of organosilicon copolymer, and 10 parts of other additives.
[0094] Comparative Example 4
[0095] Comparative Example 4 is a commercially available PVC artificial leather, comprising a surface treatment agent layer, a dense layer, a foaming layer, an adhesive layer, and a base fabric layer stacked sequentially. The main components of the surface treatment agent layer are one or both of polyurethane and acrylic acid; the main components of the dense layer are PVC resin and phthalic plasticizers, with a weight ratio of 100:70 to 100:100; the main components of the foaming layer are PVC resin, phthalic plasticizers, and foaming agents, with a weight ratio of 100:70:0.1 to 100:100:5; and the main components of the adhesive layer are PVC resin and phthalic plasticizers, with a weight ratio of 100:40 to 100:80.
[0096] Comparative Example 5
[0097] Comparative Example 5 is a commercially available TPO artificial leather, comprising a surface treatment agent layer, a dense layer and a base fabric layer stacked sequentially. The main components of the surface treatment agent layer are one or both of polyurethane and acrylic acid; the main components of the dense layer are one or more of TPV resin, TPO resin, polypropylene and polyethylene, wherein TPV is obtained by crosslinking EPDM with PP and peroxide.
[0098] Performance tests were conducted on the artificial leathers of the above embodiments and comparative examples. The test results are shown in Table 1. The hand feel evaluation was a subjective evaluation, meaning the tester directly touched the product to assess its feel. The stiffness / softness evaluation was conducted according to the GMW3390 method; a higher test value indicates higher hardness. The Taber abrasion resistance performance evaluation was conducted according to GMW... The 3208 method was used for testing. The artificial leather from the above embodiments and comparative examples was cut to the same size and placed on a Taber abrasion tester for testing. Specifically, 1 kg of leather was used for 4000 abrasion cycles, and the samples were rated, with a maximum rating of 5. The flexural strength evaluation was conducted according to ISO 5402. The artificial leather from the above embodiments and comparative examples was cut to the same size and placed on a flexural strength tester at room temperature for testing. Specifically, it was bent 100,000 times, and the samples were rated, with a maximum rating of 5. The low-temperature strength evaluation was conducted according to ISO 5402. The artificial leather from the above embodiments and comparative examples was cut to the same size and placed on a flexural strength tester at -20°C for testing. Specifically, it was bent 30,000 times, and the samples were rated, with a maximum rating of 5.
[0099] Table 1
[0100]
[0101]
[0102] The test data above shows that Examples 1 through 7 all achieve a silicone-like feel. Examples 1 and 7 also achieve a smooth silicone-like feel, and exhibit excellent performance in terms of rigidity, abrasion resistance, bending resistance, and low-temperature resistance. Combined with... Figures 4-9 The images shown are microscopic images of the abrasion resistance after tests for Examples 1, 6, and 7, and Comparative Examples 1, 2, and 3, respectively. While Comparative Example 1 also achieved a smooth silicone feel, the excessive use of hollow glass microspheres did not significantly improve the smoothness compared to Example 1. On the contrary, the excessive use of hollow microspheres led to a deterioration in the film-forming properties of the surface treatment agent. After the abrasion test, the surface treatment agent peeled off. After the bending test, the artificial leather surface turned noticeably white due to stress, and the treatment agent cracked. Although Comparative Example 2 also had a silicone feel, the increased weight percentage of the organosilicon copolymer in its dense layer made the material significantly softer. However, the organosilicon copolymer itself had low strength and a relatively lower dyne value, resulting in decreased adhesion of the surface treatment agent layer. The abrasion resistance test showed extremely poor performance, failing to meet the abrasion resistance requirements. Comparative Example 3, due to its increased HMSPP weight ratio, resulted in a significantly harder material feel, similar to that of typical PVC artificial leather. The increased HMSPP content also led to increased material rigidity, causing a sharp decline in its bending resistance. Surface cracks appeared after bending at room temperature, and the dense layer showed obvious cracking after bending at low temperatures. Comparative Example 4, while exhibiting better surface properties in terms of rigidity, abrasion resistance, bending resistance, and low-temperature resistance, had a plastic feel and was less health- and environmentally friendly than Examples 1-7. Comparative Example 5 possessed extremely high rigidity and lacked the flexibility of typical artificial leather, making it unsuitable for use in soft areas such as seats, thus limiting its current applications.
[0103] It should be noted that the use of step numbers (letters or numbers) to refer to certain specific method steps in this invention is merely for the purpose of convenience and brevity in description, and is by no means intended to restrict the order of these method steps. Those skilled in the art will understand that the order of the relevant method steps should be determined by the technology itself and should not be unduly restricted by the existence of step numbers. Those skilled in the art can determine various permissible and reasonable orderings of steps based on the technology itself.
[0104] It is particularly important to emphasize that the specific numerical selection of the various parameters involved in this invention requires not only a theoretical foundation far exceeding that of those skilled in the art, but also creative experimentation and selection based on the expected design results, supplemented by several arduous trials, before the desired target results can be obtained. The determination of these values cannot be achieved by those skilled in the art without creative effort.
[0105] Those skilled in the art will understand that, without conflict, the above-mentioned preferred solutions can be freely combined and superimposed.
[0106] It should be understood that the above embodiments are merely exemplary and not restrictive. Various obvious or equivalent modifications or substitutions that can be made by those skilled in the art regarding the above details without departing from the basic principles of the present invention will be included within the scope of the claims of the present invention.
Claims
1. A type of artificial leather with a silicone-like feel, characterized in that, It comprises a surface treatment agent layer, a dense layer, and a base fabric layer stacked together, wherein the surface treatment agent layer is made of a surface treatment agent; and the dense layer is made of a dense layer preform. The surface treatment agent comprises: 100 parts of silicone-modified aqueous dispersion, 2-8 parts of high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of crosslinking agent, 0.1-1 parts of leveling agent, 0.1-1 parts of defoamer, and 0.1-2 parts of thickener; wherein, the weight percentage of silicone in the film-forming surface treatment agent layer is greater than or equal to 60%; The main components of the dense layer preform include: propylene-based elastomer, silicone copolymer and ultra-high melt strength polypropylene, wherein the weight percentage of the silicone copolymer is 20% to 45% and the weight percentage of the ultra-high melt strength polypropylene is 4% to 15%.
2. The artificial leather according to claim 1, characterized by, The solid content of the organosilicon-modified aqueous dispersion is 30% to 50%, and the weight percentage of organosilicon in the surface treatment agent layer forming the film is 60% to 70%.
3. The artificial leather according to claim 1, characterized in that, The high molecular weight polydimethylsiloxane raw material is a mixture, including water-based silicone oil and high molecular weight polydimethylsiloxane, and the solid content of the mixture is greater than or equal to 80%, and the viscosity is 350,000 cs to 600,000 cs.
4. The artificial leather according to claim 1, characterized by, At least one of the leveling agent and the defoamer is an organosilicon component.
5. The artificial leather according to claim 4, characterized in that, The leveling agent includes one or a combination of several of the following: polydimethylsilane, polymethylphenylsiloxane, polydimethylsiloxane, polyether polyester modified organosiloxane, and alkyl modified organosiloxane.
6. The artificial leather according to claim 4, characterized in that, The defoamer includes one or a combination of several of the following: silicone oil type, emulsion type, solution type, and polyether modified silicone defoamer.
7. The artificial leather according to claim 1, characterized by, The hollow glass microspheres are mainly composed of sodium calcium borosilicate glass, with a particle size of 200μm~500μm and a density of 0.2 g / cc~0.7g / cc.
8. The artificial leather according to claim 1, characterized by, The crosslinking agent includes one or a combination of several aqueous-terminated or unterminated aliphatic, alicyclic, and aromatic polyisocyanates.
9. The artificial leather according to claim 1, characterized by, The thickener includes one or a combination of several of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, and hydroxyethylcellulose.
10. The artificial leather according to any one of claims 1 to 9, characterized in that, The dense layer preform material includes: 40-70 parts of propylene-based elastomer, 5-15 parts of ultra-high melt strength polypropylene, 20-40 parts of organosilicon copolymer, and 5-15 parts of other additives.
11. A method for producing artificial leather having a silicone gel hand, characterized by, Including the following steps: S10: A dense layer is formed using a dense layer preform material via calendering; wherein the main components of the dense layer preform material include: a propylene-based elastomer, an organosilicon copolymer, and ultra-high melt strength polypropylene, and the organosilicon copolymer accounts for 20% to 45% by weight, and the ultra-high melt strength polypropylene accounts for 4% to 15% by weight; S20: The dense layer is combined with the base fabric layer to obtain a semi-finished product; S30: A surface treatment agent is printed on the surface of the semi-finished product to form a surface treatment agent layer, and then embossed to obtain the finished artificial leather product; wherein, the surface treatment agent includes: 100 parts of silicone-modified aqueous dispersion, 2-8 parts of high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of crosslinking agent, 0.1-1 parts of leveling agent, 0.1-1 parts of defoamer, and 0.1-2 parts of thickener; and the proportion of silicone in the film-forming surface treatment agent layer is 60%-70%.
12. A surface treatment agent with a silicone-like feel, used for artificial leather; characterized in that, include: The film consists of 100 parts of an organosilicon-modified aqueous dispersion, 2-8 parts of high molecular weight polydimethylsiloxane raw material, 2-10 parts of hollow glass microspheres, 2-5 parts of a crosslinking agent, 0.1-1 parts of a leveling agent, 0.1-1 parts of a defoamer, and 0.1-2 parts of a thickener; the weight percentage of organosilicon in the surface treatment agent layer is greater than or equal to 60%.
13. An automobile characterized by comprising: The invention includes automotive interiors, which include the artificial leather as described in any one of claims 1-10 or the artificial leather prepared by the method of claim 11.