Low-odor PVC artificial leather

Abstract

The invention relates to the field of PVC, and particularly discloses low-odor PVC artificial leather which comprises a surface layer, a surface layer, a middle layer and base cloth, raw materials of the surface layer and the middle layer comprise polyvinyl chloride prepared through suspension polymerization, an acrylonitrile-butadiene copolymer, octyl amyl glycol dibenzoate and polypropylene intercalated sepiolite, and the artificial leather has low odor and high strength.

Description

Technical Field

[0001] The present invention relates to the field of PVC, and more particularly to a low-odor PVC artificial leather. Background Art

[0002] With the progress of science, people's living standards are getting higher and higher, and cars have become an indispensable part of people's lives. PVC, or polyvinyl chloride, has good mechanical properties and low cost, and is widely used to make artificial leather as car interiors. However, due to the existence of free single molecules inside PVC artificial leather, the generation of hydrogen chloride by thermal decomposition, and the volatilization of a large amount of plasticizers, the odor of PVC artificial leather has always hindered its wider application. In order to further improve the quality of PVC artificial leather and improve its health and environmental protection, people reduce the odor of PVC artificial leather by replacing higher-level environmental protection additives, adding water washing steps, etc., but the odor reduction of artificial leather obtained by these methods is limited, and the interlayer strength of artificial leather using environmental protection additives is not high and is easy to crack, and the product strength is insufficient.

[0003] Therefore, how to improve a PVC artificial leather with low odor without reducing its mechanical properties has great economic value for improving its quality and expanding the application scenarios of PVC artificial leather. Summary of the invention

[0004] In order to solve the problem of strong odor of PVC artificial leather, the present application provides a low-odor PVC artificial leather.

[0005] A low-odor PVC artificial leather is characterized by comprising a surface layer, a top layer, an intermediate layer and a base fabric. The raw materials of the surface layer and the intermediate layer include polyvinyl chloride, acrylonitrile-butadiene copolymer and octyl amyl glycol dibenzoate. The polyvinyl chloride is prepared by suspension polymerization.

[0006] By adopting the above technical scheme, the polyvinyl chloride prepared by suspension polymerization has the advantages of simple operation, low production cost, high product quality, safety and environmental protection of acrylonitrile-butadiene copolymer and dibenzoic acid octyl pentyl glycol ester, low VOC content generated in the preparation process, adding acrylonitrile-butadiene copolymer to polyvinyl chloride, the solubility parameters of the two are similar, good compatibility, the product has low rigidity and hardness, the amount of plasticizer in PVC artificial leather is reduced, it is not easy to produce odor, and the prepared paste resin has better compatibility, stability and heat resistance. Adding dibenzoic acid octyl pentyl glycol ester can stably improve the plasticity of the polymer molecular chain, the macromolecules formed in the artificial leather are stable and not easy to volatilize, and the artificial leather has less odor.

[0007] In a specific embodiment, the surface layer comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride, 5-15 parts of acrylonitrile-butadiene copolymer, 5-10 parts of octyl glycol dibenzoate, 0.1-1 parts of isopropylbenzene hydroperoxide, 4-10 parts of carbon black, and 5-15 parts of adsorbent filler; the middle layer comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride, 5-10 parts of acrylonitrile-butadiene copolymer, 5-10 parts of octyl glycol dibenzoate, 0.1-1 parts of isopropylbenzene hydroperoxide, 0.1-1 parts of azodicarbonamide, 4-10 parts of carbon black, and 5-15 parts of adsorbent filler; the surface layer is water-based polyurethane, and the base fabric is cotton cloth.

[0008] By adopting the above technical scheme, the base fabric and the surface layer are non-toxic and environmentally friendly, do not volatilize VOC, have good adhesion to the surface layer and the middle layer, the components of the surface layer and the middle layer are similar, no additional adhesive is needed, the VOC content is reduced, and a certain amount of foaming agent is added to the middle layer, so that the artificial leather feels better.

[0009] In a specific embodiment, the steps of preparing the base fabric include: pre-treatment, dyeing, printing, post-finishing, and washing.

[0010] By adopting the above technical solution, the base fabric is washed after dyeing and printing to reduce the VOC residue in the base fabric.

[0011] Preferably, the base fabric pretreatment step includes: washing and drying.

[0012] Preferably, the post-processing step of the base fabric includes: slitting.

[0013] In one specific embodiment, the adsorbent filler in the surface layer and the middle layer comprises polypropylene intercalated sepiolite.

[0014] By adopting the above technical scheme, sepiolite is a fibrous hydrated magnesium silicate, which is composed of very fine and short fibers or fibrous aggregates, has the characteristics of being pure natural, non-toxic, odorless, asbestos-free, and non-radioactive, and has a porous skeleton with the largest specific surface area and a unique internal pore structure among non-metallic minerals. It is recognized as the clay mineral with the strongest adsorption capacity. By intercalating polypropylene into sepiolite, the interlayer force of sepiolite is enhanced, and the compatibility of sepiolite with an artificial leather matrix is ​​improved. The obtained polypropylene intercalated sepiolite is evenly distributed inside the artificial leather, has a high connection strength with the artificial leather, and continuously adsorbs gas, so that the obtained artificial leather has the characteristics of high strength and low odor.

[0015] In a specific embodiment, the preparation steps of polypropylene intercalated sepiolite include: adding sepiolite to water, adjusting the pH value, heating and stirring, adding hexadecyltrimethylammonium bromide, stirring and reacting, filtering, washing, drying and grinding to obtain modified sepiolite, melt-blending the modified sepiolite with polypropylene, extruding and granulating to obtain polypropylene intercalated sepiolite.

[0016] By adopting the above technical scheme, the preparation method is simple and the intercalation effect is good. The intercalated sepiolite is more evenly distributed in the artificial leather, is more closely connected with the artificial leather, and has a better effect on reducing the odor of the artificial leather.

[0017] Preferably, during the preparation of polypropylene intercalated sepiolite, the average particle size of the sepiolite is 1-0.5 mm.

[0018] Under the above particle size, the prepared polypropylene intercalated sepiolite has good intercalation effect, is evenly distributed in the surface layer and the middle layer, and has good adsorption effect.

[0019] In a specific embodiment, the preparation steps of polyvinyl chloride include: adding polyethylene intercalated sepiolite to polyvinyl alcohol, stirring to obtain a mixture, mixing water and polyvinyl alcohol evenly, degassing under reduced pressure, adding vinyl chloride monomer and azobisisoheptanenitrile, stirring, heating to react, adding acetone thiosemicarbazone, reducing pressure, venting, adding the mixture, stirring evenly, filtering, drying, and obtaining polyvinyl chloride.

[0020] By adopting the above technical scheme, the preparation method is simple, the amount of residual polyethylene monomer is small, the polyethylene intercalated sepiolite participates in the polymerization and is evenly and tightly distributed in the prepared polyvinyl chloride, further improving the adsorption effect.

[0021] Preferably, the average particle size of the sepiolite in the polyethylene intercalated sepiolite is less than 0.5 mm.

[0022] Under the above particle size, the polyethylene intercalated sepiolite obtained has good intercalation effect, good effect of co-suspension polymerization with vinyl chloride monomer, is more tightly combined in the system, and the obtained artificial leather has high strength and good adsorption effect.

[0023] In a specific embodiment, the degree of alcoholysis of the polyvinyl alcohol is 70-78%.

[0024] The alcoholysis degree of polyvinyl alcohol has a great influence on its dispersibility and surface activity. By limiting the alcoholysis degree of polyvinyl alcohol, the polyvinyl alcohol dispersant is suitable for the raw material components of the present application, and has a better dispersing effect on the vinyl chloride monomer and polyethylene intercalated sepiolite of the present application. The polyvinyl chloride prepared by suspension polymerization has greater strength and adsorption, and the prepared artificial leather has better performance.

[0025] In a specific embodiment, the mass ratio of polyvinyl chloride and polypropylene intercalated sepiolite in the surface layer and the middle layer is: (10-12):1.

[0026] By adopting the above technical scheme, polypropylene intercalated sepiolite is evenly distributed in polyvinyl chloride, which can fully adsorb small molecule VOC without reducing the strength of artificial leather, and the obtained artificial leather has relatively excellent comprehensive performance.

[0027] In a specific embodiment, the preparation process of artificial leather comprises: S1: uniformly mixing the components of the PVC surface layer to obtain a surface layer paste, and applying the paste on a high-temperature heat-resistant release paper to obtain a PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain the middle layer paste, and apply it on the PVC surface layer obtained in S1 to obtain the PVC composite layer; S3: Laminating the base fabric with the PVC composite layer obtained in S2, and then heating and plasticizing to obtain PVC leather; S4: immersing the PVC leather of S3 in a water bath at 60-80°C, assisted by ultrasonic waves, to obtain low-odor PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by a roller and then dried at 100-120° C. to obtain a low-odor PVC artificial leather.

[0028] By adopting the above technical scheme, the preparation method is simple, the layers of the prepared artificial leather are tightly connected, no additional adhesive is added for bonding, the VOC content is low, the temperature is suitable during the drying process, and the small molecule VOC is further volatilized and removed. The prepared artificial leather has low odor and is not easy to tear and delaminate.

[0029] In a specific embodiment, the plasticizing temperature is 170-175°C.

[0030] By adopting the above technical solution, the artificial leather is fully plasticized, has less residual monomers, is not easy to volatilize VOC, has high strength and low odor.

[0031] In summary, this application has the following beneficial effects: 1. The present application reduces the amount of plasticizer by copolymerizing polyvinyl chloride and acrylonitrile-butadiene copolymer and adding a certain amount of octyl dibenzoate glycol ester as a cohesive plasticizer. The obtained polyvinyl chloride artificial leather contains less plasticizer and residual monomer, and the generated macromolecules are not easy to volatilize. The obtained artificial leather has high strength and low odor. It is further specified that the base fabric is washed after dyeing and printing to further reduce the VOC content in the artificial leather.

[0032] 2. The present application prepares polyvinyl chloride by adding a certain mass of polypropylene intercalated sepiolite as an adsorption filler into the surface layer and the middle layer, and suspending and polymerizing the polyethylene intercalated sepiolite and polyethylene together. The sepiolite in the polypropylene intercalated sepiolite and the polyethylene intercalated sepiolite is limited to a certain size specification, so that the sepiolite is evenly distributed in the prepared artificial leather and is tightly connected to the artificial leather substrate, thereby significantly reducing the odor of the artificial leather. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 : Low odor PVC artificial leather DETAILED DESCRIPTION

[0034] To further help understand the technical solution of the present invention, several specific embodiments are provided to describe the technical solution of the present invention in more detail. All the embodiments described are only partial embodiments of the present invention, not all of them; the embodiments can be combined with each other, and the same or similar concepts or processes may not be described in detail in some embodiments. The following embodiments are further explanations of the present invention, and the present invention is not limited thereto.

[0035] The components of the preparation examples used in the examples of this application all refer to components obtained by the preparation examples. The experimental reagents in the preparation examples, embodiments, and comparative examples, unless otherwise specified, are conventional commercial brands or obtained by conventional preparation processes.

[0036] Preparation Example Preparation Example 1: Base fabric: The cotton cloth is washed, dried, dyed, printed, cut and washed to obtain the base cloth.

[0037] Preparation Example 2: Polypropylene intercalated sepiolite: Add 1000g of sepiolite to 3000ml of water, adjust the pH value to 1, heat to 80°C, stir, add 600g of hexadecyltrimethylammonium bromide after 1 hour, stir and react for 2 hours, filter, wash, dry and grind to obtain modified sepiolite, melt blend the modified sepiolite with 1000g of polypropylene at 180°C for 10 minutes, extrude and granulate to obtain polypropylene intercalated sepiolite.

[0038] In this preparation example, the sepiolite was purchased from Shijiazhuang Tourmaline Mineral Products Co., Ltd., with a specification of 1-0.5 mm and a loose specific gravity of 250.

[0039] Preparation Example 3: Polyethylene intercalated sepiolite: Add 1000g of sepiolite to 3000ml of water, adjust the pH value to 1, heat to 80°C, stir, add 600g of hexadecyltrimethylammonium bromide after 1 hour, stir and react for 2 hours, filter, wash, dry and grind to obtain modified sepiolite, melt blend the modified sepiolite with 1000g of polyethylene at 180°C for 10 minutes, extrude and granulate to obtain polyethylene intercalated sepiolite.

[0040] In this preparation example, the sepiolite was purchased from Shijiazhuang Tourmaline Mineral Products Co., Ltd., with a specification of <0.5 mm and a loose specific gravity of 250.

[0041] Preparation Example 4: Polyvinyl chloride: 1 kg of polyethylene intercalated sepiolite prepared in Preparation Example 3 was mixed evenly with 1 kg of water and 15 g of polyvinyl alcohol to obtain a polyethylene intercalated sepiolite mixture for use; 100 kg of water and 40 g of polyvinyl alcohol were mixed evenly, degassed, 70 kg of vinyl chloride monomer and 15 g of azobisisoheptonitrile were added, stirred, heated at 55 ° C for reaction, acetone thiosemicarbazone was added after 10 hours, and the pressure was reduced to 7.0 kg / cm 2 The mixture was vented, polyethylene intercalated sepiolite was added, stirred evenly, filtered and dried to obtain polyvinyl chloride. The alcoholysis degree of polyvinyl alcohol in this preparation example was 78%.

[0042] Preparation Example 5: Polyvinyl chloride: 1 kg of polyethylene intercalated sepiolite prepared in Preparation Example 3 was mixed evenly with 1 kg of water and 15 g of polyvinyl alcohol to obtain a polyethylene intercalated sepiolite mixture for use; 100 kg of water and 40 g of polyvinyl alcohol were mixed evenly, degassed, 70 kg of vinyl chloride monomer and 15 g of azobisisoheptonitrile were added, stirred, heated at 55 ° C for reaction, acetone thiosemicarbazone was added after 10 hours, and the pressure was reduced to 7.0 kg / cm 2 The mixture was vented, polyethylene intercalated sepiolite was added, stirred evenly, filtered and dried to obtain polyvinyl chloride. The alcoholysis degree of polyvinyl alcohol in this preparation example was 88%.

[0043] Preparation Example 6: Polyvinyl chloride: Mix 100 kg water and 40 g polyvinyl alcohol evenly, degas, add 70 kg vinyl chloride monomer and 15 g azobisisoheptanenitrile, stir, heat to 55 ° C for reaction, add acetone thiosemicarbazone after 10 hours, and reduce the pressure to 7.0 kg / cm 2 The polyvinyl chloride was obtained by exhausting, filtering and drying. The alcoholysis degree of polyvinyl alcohol in this preparation example was 78%.

[0044] Preparation Example 7: Polyvinyl chloride: 1 kg of polypropylene intercalated sepiolite prepared in Preparation Example 2 was mixed evenly with 1 kg of water and 15 g of polyvinyl alcohol to obtain a polypropylene intercalated sepiolite mixture for use; 100 kg of water and 40 g of polyvinyl alcohol were mixed evenly, degassed, 70 kg of vinyl chloride monomer and 15 g of azobisisoheptonitrile were added, stirred, heated at 55 ° C for reaction, acetone thiosemicarbazone was added after 10 hours, and the pressure was reduced to 7.0 kg / cm 2 The mixture was vented, and polypropylene intercalated sepiolite was added, stirred evenly, filtered, and dried to obtain polyvinyl chloride. The alcoholysis degree of polyvinyl alcohol in this preparation example was 78%.

[0045] Preparation Example 8: Polyethylene intercalated sepiolite: Add 1000g of sepiolite to 3000ml of water, adjust the pH value to 1, heat to 80°C, stir, add 600g of hexadecyltrimethylammonium bromide after 1 hour, stir and react for 2 hours, filter, wash, dry and grind to obtain modified sepiolite, melt blend the modified sepiolite with 1000g of polyethylene at 180°C for 10 minutes, extrude and granulate to obtain polyethylene intercalated sepiolite.

[0046] In this preparation example, the sepiolite was purchased from Shijiazhuang Tourmaline Mineral Products Co., Ltd., with a specification of 1-0.5 mm and a loose specific gravity of 250.

[0047] Preparation Example 9: Polyvinyl chloride: 1 kg of polyethylene intercalated sepiolite prepared in Preparation Example 8 was mixed evenly with 1 kg of water and 15 g of polyvinyl alcohol to obtain a polyethylene intercalated sepiolite mixture for use; 100 kg of water and 40 g of polyvinyl alcohol were mixed evenly, degassed, 70 kg of vinyl chloride monomer and 15 g of azobisisoheptanenitrile were added, stirred, heated at 55 ° C for reaction, acetone thiosemicarbazone was added after 10 hours, and the pressure was reduced to 7.0 kg / cm 2 The mixture was vented, polyethylene intercalated sepiolite was added, stirred evenly, filtered and dried to obtain polyvinyl chloride. The alcoholysis degree of polyvinyl alcohol in this preparation example was 78%. Example

[0048] Example 1 This example includes the following qualities of raw materials: Surface layer: 600 g of polyvinyl chloride obtained in Preparation Example 6, 150 g of acrylonitrile-butadiene copolymer, 50 g of octyl amyl glycol dibenzoate, 1 g of cumene hydroperoxide, 100 g of carbon black, and 100 g of sepiolite; Middle layer: 600 g of polyvinyl chloride obtained in Preparation Example 6, 150 g of acrylonitrile-butadiene copolymer, 50 g of octyl amyl glycol dibenzoate, 1 g of isopropylbenzene hydroperoxide, 100 g of carbon black, 100 g of sepiolite, and 1 g of azodicarbonamide.

[0049] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by a roller and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0050] Example 2 This example includes the following qualities of raw materials: Surface layer: 800 g of polyvinyl chloride obtained in Preparation Example 6, 50 g of acrylonitrile-butadiene copolymer, 50 g of octyl amyl glycol dibenzoate, 10 g of cumene hydroperoxide, 40 g of carbon black, and 133 g of sepiolite; Middle layer: 800 g of polyvinyl chloride obtained in Preparation Example 6, 50 g of acrylonitrile-butadiene copolymer, 50 g of octyl amyl glycol dibenzoate, 10 g of isopropylbenzene hydroperoxide, 40 g of carbon black, 133 g of sepiolite, and 10 g of azodicarbonamide.

[0051] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0052] Example 3 This example includes the following qualities of raw materials: Surface layer: 700 g of polyvinyl chloride obtained in Preparation Example 6, 100 g of acrylonitrile-butadiene copolymer, 70 g of octyl amyl glycol dibenzoate, 8 g of cumene hydroperoxide, 70 g of carbon black, and 117 g of sepiolite; Middle layer: 700 g of polyvinyl chloride obtained in Preparation Example 6, 100 g of acrylonitrile-butadiene copolymer, 70 g of octyl amyl glycol dibenzoate, 8 g of isopropylbenzene hydroperoxide, 70 g of carbon black, 117 g of sepiolite, and 8 g of azodicarbonamide.

[0053] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0054] Example 4 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 6, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 6, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8g of azodicarbonamide.

[0055] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0056] Example 5 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 6, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 117g of polyethylene intercalated sepiolite prepared in Preparation Example 3; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 6, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 117g of polyethylene intercalated sepiolite prepared in Preparation Example 3, and 8g of azodicarbonamide.

[0057] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0058] Example 6 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 4, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 4, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8g of azodicarbonamide.

[0059] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0060] Example 7 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 5, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 5, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8g of azodicarbonamide.

[0061] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0062] Example 8 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 4, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 70g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 4, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 70g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8g of azodicarbonamide.

[0063] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0064] Example 9 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 4, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 50g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: polyvinyl chloride prepared in Preparation Example 4, 100 g of acrylonitrile-butadiene copolymer, 70 g of octyl amyl glycol dibenzoate, 8 g of isopropylbenzene hydroperoxide, 70 g of carbon black, 50 g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8 g of azodicarbonamide.

[0065] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0066] Example 10 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 7, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 7, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8g of azodicarbonamide.

[0067] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0068] Embodiment 11 This example includes the following qualities of raw materials: Surface layer: 700g of polyvinyl chloride prepared in Preparation Example 9, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of cumene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2; Middle layer: 700g of polyvinyl chloride prepared in Preparation Example 9, 100g of acrylonitrile-butadiene copolymer, 70g of octyl amyl glycol dibenzoate, 8g of isopropylbenzene hydroperoxide, 70g of carbon black, 117g of polypropylene intercalated sepiolite prepared in Preparation Example 2, and 8g of azodicarbonamide.

[0069] The preparation method is as follows: S1: uniformly mixing the components of the PVC surface layer to obtain a surface layer paste, and applying the paste on a high-temperature heat-resistant release paper to obtain a PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain the middle layer paste, and apply it on the PVC surface layer obtained in S1 to obtain the PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0070] Comparative Example Comparative Example 1 This comparative example includes the following raw materials: Surface layer: 700 g of polyvinyl chloride obtained in Preparation Example 6, 70 g of octyl amyl glycol dibenzoate, 8 g of cumene hydroperoxide, 70 g of carbon black, and 117 g of sepiolite; Middle layer: 700 g of polyvinyl chloride obtained in Preparation Example 6, 100 g of acrylonitrile-butadiene copolymer, 70 g of octyl amyl glycol dibenzoate, 8 g of isopropylbenzene hydroperoxide, 70 g of carbon black, 117 g of sepiolite, and 8 g of azodicarbonamide.

[0071] The preparation method is as follows: S1: uniformly mixing the components of the PVC surface layer to obtain a surface layer paste, and applying the paste on a high-temperature heat-resistant release paper to obtain a PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain the middle layer paste, and apply it on the PVC surface layer obtained in S1 to obtain the PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0072] Comparative Example 2 This comparative example includes the following raw materials: Surface layer: 700 g of polyvinyl chloride obtained in Preparation Example 6, 100 g of acrylonitrile-butadiene copolymer, 70 g of chlorinated paraffin, 8 g of cumene hydroperoxide, 70 g of carbon black, and 117 g of sepiolite; Middle layer: 700 g of polyvinyl chloride obtained in Preparation Example 6, 100 g of acrylonitrile-butadiene copolymer, 70 g of octyl amyl glycol dibenzoate, 8 g of isopropylbenzene hydroperoxide, 70 g of carbon black, 117 g of sepiolite, and 8 g of azodicarbonamide.

[0073] The preparation method is as follows: S1: uniformly mix the components of the PVC surface layer to obtain a surface layer paste, and apply the paste on the high-temperature heat-resistant release paper to obtain the PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain an middle layer paste, and apply the paste on the PVC surface layer obtained in S1 to obtain a PVC composite layer; S3: Laminating the base fabric prepared in Preparation Example 1 with the PVC composite layer prepared in S2, and then removing the release paper and heating and plasticizing at 170°C to obtain PVC leather; S4: immersing the PVC leather of S3 in a 60°C water bath, assisted by ultrasonic waves, to obtain PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by roller coating and then dried at 100° C. to obtain a low-odor PVC artificial leather.

[0074] Performance Test Test 1: The tensile strength of the artificial leathers prepared in the embodiments and comparative examples was tested with reference to the standard QB / T 3812.5-99 "Determination of tensile strength and elongation of leather". The test results are shown in Table 1.

[0075] Test 2: Tested with reference to Volkswagen odor test standard PV3900C3, temperature 80°C, 2 hours. The odor rating system is divided into 6 levels: 1 = no odor; 2 = odor but not disturbing; 3 = obvious odor but no disturbing odor; 4 = disturbing odor; 5 = strong disturbing odor; 6 = unbearable odor. The odor levels of the artificial leathers prepared in each embodiment and comparative example were tested. The test results are shown in Table 1.

[0076] Table 1 In combination with Examples 1-3, Comparative Examples 1-2 and Table 1, the present application adds a certain mass of acrylonitrile-butadiene copolymer and octyl amyl glycol dibenzoate to suspension polymerized polyvinyl chloride, and further adds a certain mass of adsorbent filler, especially sepiolite, to obtain artificial leather with low odor and high strength.

[0077] In combination with Examples 3-5 and Table 1, the present application inserts polypropylene into sepiolite and limits the specifications of sepiolite to make it more compatible and bonded with the artificial leather substrate, thereby achieving better adsorption and enhancement effects.

[0078] In combination with Examples 3, 6-7, and 10 and Table 1, the present application adds a certain mass of polyethylene intercalated sepiolite in the process of preparing polyvinyl chloride by suspension polymerization, and further limits the alcoholysis degree of polyvinyl alcohol, so that its surface tension and dispersion effect are suitable for the components of the suspension polymerization of the present application, the vinyl chloride monomer and the polyvinyl ene intercalated sepiolite are better dispersed in the system, and the obtained artificial leather has lower odor and higher strength.

[0079] In combination with Examples 3, 6, and 11 and Table 1, the present application further improves the performance of artificial leather by limiting the specifications of sepiolite in the suspension polymerization of polyvinyl chloride.

[0080] In combination with Examples 3, 8-9 and Table 1, the present application limits the mass ratio of polyvinyl chloride and polypropylene intercalated sepiolite, so that the fibrous sepiolite uniformly forms a better reinforcement and adsorption network in the prepared PVC artificial leather, further improving the performance of the artificial leather.

[0081] The specific embodiment adopted in this application is only an explanation of this application, and it is not a limitation of this application. After reading this specification, technical personnel in this field can make non-creative modifications to this embodiment as needed, but as long as it is within the scope of the claims of this application, it is protected by the patent law.

Claims

1. Low odor PVC artificial leather, characterized by: The invention comprises a surface layer, a surface layer, an intermediate layer and a base fabric. The raw materials of the surface layer and the intermediate layer include polyvinyl chloride, acrylonitrile-butadiene copolymer and octyl amyl glycol dibenzoate. The polyvinyl chloride is prepared by suspension polymerization.

2. The low-odor PVC artificial leather according to claim 1, characterized in that: The surface layer comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride, 5-15 parts of acrylonitrile-butadiene copolymer, 5-10 parts of octyl amyl glycol dibenzoate, 0.1-1 parts of isopropylbenzene hydroperoxide, 4-10 parts of carbon black, and 5-15 parts of adsorbent filler; the middle layer comprises the following raw materials in parts by weight: 60-80 parts of polyvinyl chloride, 5-10 parts of acrylonitrile-butadiene copolymer, 5-10 parts of octyl amyl glycol dibenzoate, 0.1-1 parts of isopropylbenzene hydroperoxide, 0.1-1 parts of azodicarbonamide, 4-10 parts of carbon black, and 5-15 parts of adsorbent filler; the surface layer is waterborne polyurethane, and the base fabric is cotton fabric.

3. The low-odor PVC artificial leather according to claim 2, characterized in that: The preparation steps of the base fabric include: pre-treatment, dyeing, printing, post-finishing and washing.

4. The low-odor PVC artificial leather according to claim 2, characterized in that: The adsorbent filler in the surface layer and the middle layer includes polypropylene intercalated sepiolite.

5. The low-odor PVC artificial leather according to claim 4, characterized in that: The preparation steps of the polypropylene intercalated sepiolite include: adding sepiolite into water, adjusting pH value, heating and stirring, adding hexadecyltrimethylammonium bromide, stirring and reacting, filtering, washing, drying and grinding to obtain modified sepiolite, and melt-blending the modified sepiolite with polypropylene, extruding and granulating to obtain the polypropylene intercalated sepiolite.

6. The low-odor PVC artificial leather according to claim 2, characterized in that: The preparation steps of the polyvinyl chloride include: adding polyethylene intercalated sepiolite to polyvinyl alcohol, stirring to obtain a mixture, mixing water and polyvinyl alcohol evenly, degassing under reduced pressure, adding vinyl chloride monomer and azobisisoheptanenitrile, stirring, heating for reaction, adding acetone thiosemicarbazone, reducing pressure, exhausting, adding the mixture, stirring evenly, filtering, drying, and obtaining polyvinyl chloride.

7. The low-odor PVC artificial leather according to claim 6, characterized in that: The alcoholysis degree of the polyvinyl alcohol is 70-78%.

8. The low-odor PVC artificial leather according to claim 4, characterized in that: The mass ratio of polyvinyl chloride and polypropylene intercalated sepiolite in the surface layer and the middle layer is: (10-12):

1.

9. The low-odor PVC artificial leather according to any one of claims 1 to 8, characterized in that: The preparation process of the artificial leather comprises: S1: uniformly mixing the components of the PVC surface layer to obtain a surface layer paste, and applying the paste on a high-temperature heat-resistant release paper to obtain a PVC surface layer; S2: uniformly mix the components of the PVC middle layer to obtain the middle layer paste, and apply it on the PVC surface layer obtained in S1 to obtain the PVC composite layer; S3: Laminating the base fabric with the PVC composite layer obtained in S2, and then heating and plasticizing to obtain PVC leather; S4: immersing the PVC leather of S3 in a water bath at 60-80°C, assisted by ultrasonic waves, to obtain low-odor PVC artificial leather; S5: The surface of the PVC artificial leather of S4 is coated with a polyurethane coating by a roller and then dried at 100-120° C. to obtain a low-odor PVC artificial leather.

10. The low-odor PVC artificial leather according to claim 9, characterized in that: The plasticizing temperature is 170-175°C.

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